Hydrogen-absorbing alloy

BACKGROUND OF THE INVENTION
This invention relates to a hydrogen-absorbing alloy and to a secondary battery comprising a negative electrode comprising the hydrogen-absorbing alloy.
Hydrogen-absorbing alloy has been noticed as being capable of safely and easily storing hydrogen as an energy source, and also as being useful as an energy exchange material or an energy storage material. Therefore, there have being proposed various applications of hydrogen-absorbing alloy as a new functional raw material. For example, hydrogen-absorbing alloy has been proposed to employ for the storage and transport of hydrogen, the storage and transport of heat, the conversion of heat energy to mechanical energy, the separation and purification of hydrogen, the separation of hydrogen isotope, a battery employing hydrogen as an active material, a catalyst in synthetic chemistry, and a temperature sensor.
Recently, a nickel-hydrogen secondary battery where a hydrogen-absorbing alloy is employed as a negative electrode material has been attracting many attentions as a public-use battery of next generation, because the battery is advantageous in various aspects, e.g. it is high in capacity, highly resistive to over charging and over discharging, capable of performing a high rate charge/discharge, free from environmental pollution, and interchangeable with a nickel-cadmium battery. Accordingly, many attempts have been intensively made at present for the application and actual use of the nickel-hydrogen battery.
As evident from these facts, the hydrogen-absorbing alloy has many possibilities for various applications in view of its physical and chemical characteristics, so that the hydrogen-absorbing alloy is now considered as being one of important raw materials in future industries.
The metal capable of absorbing hydrogen may be in the form of single substance which reacts exothermically with hydrogen, i.e., a metal element capable of forming a stable compound together with hydrogen (for example, Pd, Ti, Zr, V, rare earth elements and alkaline earth elements); or in the form of an alloy comprising an above-mentioned metal alloyed with other kinds of metal.
One of the advantages of the alloying is that the bonding strength between a metal and hydrogen can be suitably weakened so that not only the absorption reaction but also the desorption (releasing) reaction can be performed comparatively easily. Second advantage of the alloying is that the absorption and desorption characteristics of the alloy such as the magnitude of hydrogen gas pressure required for the reaction (equilibrium pressure; plateau pressure), the extent of equilibrium region (plateau region), the change (flatness) of equilibrium pressure during the process of absorbing hydrogen, etc. can be improved. Third advantage of the alloying is the improvement in chemical and physical stability of the alloy.
The composition of the conventional hydrogen-absorbing alloy may be classified into the following types;
(1) a rare earth element type (for example, LaNi.sub.5, MmNi.sub.5, etc.);
(2) a Laves type (for example, ZrV.sub.2, ZrMn.sub.2, etc.);
(3) a titanium type (for example, TiNi, TiFe, etc.);
(4) a magnesium type (for example, Mg.sub.2 Ni, MgNi.sub.2, etc.); and
(5) other types (for example, cluster, etc.).
Among them, the rare earth element type hydrogen-absorbing alloy represented by the aforementioned type (1) is now put to practical use as an electrode material. However, the discharge capacity of the alkaline battery comprising this electrode material now reaches to as high as 80% or more of the theoretical capacity, so that any further increase in discharge capacity would be difficult.
By the way, the rare earth element-Ni based intermetallic compound represented by the aforementioned type (1) includes many number of compounds other than an AB.sub.5 type compound (A=a metal element which is capable of exothermically reacting with hydrogen, and B=another kind of metal). For example, Mat. Res. Bull., 11, (1976) 1241 describes that an intermetallic compound containing a larger quantity of rare earth element as compared with the AB.sub.5 type compound is capable of absorbing a larger quantity of hydrogen in the vicinity of normal temperature as compared with the AB.sub.5 type compound. It is also reported that a magnesium-rare earth element based alloy, which is a magnesium-substituted rare earth-Ni based alloy, is capable of absorbing a large quantity of hydrogen gas (Y. Ohsumi, "Soda and Chlorine", 34, 447 (1983)).
It is pointed out by H. Oesterreicher et al in J. Lee-Common Met, 73,339 (1980) that La.sub.1-x Mg.sub.x Ni.sub.2 type alloys for example among the alloys having such compositions are accompanied with a problem that the hydrogen-releasing rate thereof is very low due to the high stability thereof to hydrogen.
There is also a report on a PuNi.sub.3 type hydrogen-absorbing alloy having a composition of Mg.sub.2 LaNi.sub.9, which was made by K. Kadir et al as described in a summary of lecture in the 120th Spring Meeting of Japan Metallic Society, p.289 (1997).
However, the magnesium-rare earth element based alloys having the aforementioned compositions are accompanied with a problem that even though the quantity of hydrogen absorption in a gaseous phase is large, the electrode comprising this alloy scarcely works in an alkaline electrolyte at normal temperature.
Japanese Patent Unexamined Publication S/62-271348 discloses a hydrogen absorption electrode comprising a hydrogen-absorbing alloy represented by a general formula Mm.sub.1-x A.sub.x Ni.sub.a Co.sub.b M.sub.c, while Japanese Patent Unexamined Publication S/62-271349 discloses a hydrogen absorption electrode comprising a hydrogen-absorbing alloy represented by a general formula La.sub.1-x A.sub.x Ni.sub.a Co.sub.b M.sub.c.
However, a metal oxide-hydrogen secondary battery comprising any of these hydrogen absorption electrodes is low in discharge capacity and short in charge/discharge cycle life.
Further, PCT Re-Publication No. WO97/03213 discloses a hydrogen absorption electrode containing a hydrogen-absorbing alloy having a composition represented by a general formula (i); (R.sub.1-x L.sub.x)(Ni.sub.1-y M.sub.y).sub.z, a specific antiphase boundary and a LaNi.sub.5 crystal structure. This hydrogen-absorbing alloy is manufactured by allowing a melt of the alloy represented by the general formula (i) to drop on the surface of a roll, whereby cooling and solidifying the melt under cooling conditions: 50 to 500.degree. C. in supercooling temperature and 1,000 to 10,000.degree. C./sec. in cooling rate, thus obtaining flakes having a thickness of 0.1 to 2.0 mm, which is then heat-treated. This publication also mentions that if the aforementioned manufacturing conditions are not met, the resultant alloy may have two phases, i.e. a LaNi.sub.5 type crystal phase and a Ce.sub.2 Ni.sub.7 type crystal phase, and hence it is impossible to obtain an alloy constituted by the LaNi.sub.5 type crystal phase.
However, a metal oxide-hydrogen secondary battery, which comprises a negative electrode containing this hydrogen-absorbing alloy having a composition represented by the general formula (i), a specific antiphase boundary and a LaNi.sub.5 crystal structure, is accompanied with a problem that not only the discharge capacity but also the cycle life thereof are not satisfiable.
BRIEF SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to overcome the problem that the aforementioned magnesium-rare earth element type hydrogen-absorbing alloy is too high in stability to hydrogen to release hydrogen, and hence to provide a hydrogen-absorbing alloy which is capable of easily realizing a hydrogen absorption electrode having a large discharge capacity.
A further object of this invention is to provide a secondary battery which is high in capacity and excellent in charge/discharge cycle life.
Namely, according to the present invention, there is provided a hydrogen-absorbing alloy which contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot, and the alloy ingot being represented by the following general formula (1);
(Mg.sub.1-a-b R1.sub.a M1.sub.b)Ni.sub.z (1)
wherein R1 is at least one element selected from rare earth elements (including Y); M1 is at least one element selected from elements having a larger electronegativity than that of Mg (excluding the elements of R1, Cr, Mn, Fe, Co, Cu, Zn and Ni); and a, b and z are respectively a number satisfying conditions: 0.1.ltoreq.a.ltoreq.0.8, 0<b.ltoreq.0.9, 1-a-b>0, and 3.ltoreq.z.ltoreq.3.8.
According to the present invention, there is further provided a hydrogen-absorbing alloy which contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot, and the alloy ingot being represented by the following general formula (2);
Mg.sub.1-a R1.sub.a (Ni.sub.1-x M2.sub.x).sub.z (2)
wherein R1 is at least one element selected from rare earth elements (including Y); M2 is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Cu and Zn; and a, x and z are respectively a number satisfying conditions: 0.1.ltoreq.a.ltoreq.0.8, 0.ltoreq.x.ltoreq.0.9, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a hydrogen-absorbing alloy which contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot, and the alloy ingot being represented by the following general formula (3);
Mg.sub.1-a-b R1.sub.a M1.sub.b (Ni.sub.1-x M2.sub.x).sub.z (3)
wherein R1 is at least one element selected from rare earth elements (including Y); M2 is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Cu and Zn; M1 is at least one element selected from elements having a larger electronegativity than that of Mg (excluding the elements of R1, the elements of M1 and Ni); and a, b, x and z are respectively a number satisfying conditions: 0.1.ltoreq.a.ltoreq.0.8, 0<b.ltoreq.0.9, 1-a-b>0, 0<x.ltoreq.0.9, and 3.ltoreq.z.ltoreq.3.8.
According to the present invention, there is further provided a hydrogen-absorbing alloy which contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot, and the alloy ingot being represented by the following general formula (4);
Mg.sub.1-a R1.sub.a (Ni.sub.1-x M3.sub.x).sub.z (4)
wherein R1 is at least one element selected from rare earth elements (including Y); M3 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B; and a, x and z are respectively a number satisfying conditions: 0.65.ltoreq.a.ltoreq.0.8, 0<x.ltoreq.0.6, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a hydrogen-absorbing alloy which contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot, and the alloy ingot being represented by the following general formula (5);
Mg.sub.1-a-b R1.sub.a T1.sub.b (Ni.sub.1-x M3.sub.x).sub.z (5)
wherein R1 is at least one element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M3 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B; and a, b, x and z are respectively a number satisfying conditions: 0.65.ltoreq.a<0.8, 0<b.ltoreq.0.3, 0.65<(a+b).ltoreq.0.8, 0<x.ltoreq.0.6, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a hydrogen-absorbing alloy which contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot, and the alloy ingot being represented by the following general formula (6);
Mg.sub.a R1.sub.1-a (Ni.sub.1-x-y Co.sub.x M4.sub.y).sub.z (6)
wherein R1 is at least one element selected from rare earth elements (including Y); M4 is at least one element selected from the group consisting of Mn, Fe, V, Cr, Nb, Al, Ga, Zn, Sn, Cu, Si, P and B; and a, x, y and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0<x.ltoreq.0.5, 0.ltoreq.y.ltoreq.0.2, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a hydrogen-absorbing alloy which contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot, and the alloy ingot being represented by the following general formula (7);
Mg.sub.a R1.sub.1-a-b T2.sub.b (Ni.sub.1-x-y Co.sub.x M4.sub.y).sub.z(7)
wherein R1 is at least one element selected from rare earth elements (including Y); T2 is at least one element selected from the group consisting of Ca, Ti and Zr; M4 is at least one element selected from the group consisting of Mn, Fe, V, Cr, Nb, Al, Ga, Zn, Sn, Cu, Si, P and B; and a, b, x, y and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0<b.ltoreq.0.3, 0<x.ltoreq.0.5, 0.ltoreq.y.ltoreq.0.2, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a hydrogen-absorbing alloy which contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot, and the alloy ingot being represented by the following general formula (8);
Mg.sub.a (La.sub.1-b R1.sub.b).sub.1-a Ni.sub.z (8)
wherein R1 is at least one element selected from rare earth elements (including Y) but is not La; and a, b and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0.01.ltoreq.b<0.5, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a hydrogen-absorbing alloy which contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot, and the alloy ingot being represented by the following general formula (9);
Mg.sub.a (La.sub.1-b R1.sub.b).sub.1-a (Ni.sub.1-x M3.sub.x).sub.z(9)
wherein R1 is at least one element selected from rare earth elements (including Y) but is not La; M3 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B; and a, b, x and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0.01.ltoreq.b<0.5, 0.1.ltoreq.x.ltoreq.0.6, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a hydrogen-absorbing alloy containing an alloy represented by the following general formula (10);
Mg.sub.a R2.sub.1-a-b T1.sub.b (Ni.sub.1-x M3.sub.x).sub.z (10)
wherein R2 is two or more kinds of element selected from rare earth elements (including Y), the content of Ce constituting the R2 being less than 20% by weight; T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M3 is at least one element selected from the group consisting of Mn, Fe, Co, Al, Ga, Zn, Sn, Cu, Si and B; and a, b, x and z are respectively a number satisfying conditions: 0<a.ltoreq.0.5, 0.ltoreq.b.ltoreq.0.3, 0.ltoreq.x.ltoreq.0.9, and 3.ltoreq.z<4.
Further, according to the present invention, there is also provided a hydrogen-absorbing alloy containing an alloy represented by the following general formula (11);
Mg.sub.a R3.sub.1-a-b T1.sub.b (Ni.sub.1-x-y M5.sub.x Co.sub.y).sub.z(11)
wherein R3 is two or more kinds of element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M5 is at least one element selected from the group consisting of Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B; a, b, x, y and z are respectively a number satisfying conditions: 0<a.ltoreq.0.5, 0.ltoreq.b.ltoreq.0.3, 0.ltoreq.x.ltoreq.0.9, 0<y.ltoreq.0.4, x+y.ltoreq.0.9, and 3.ltoreq.z<4, the content of Ce constituting the R3 being less than m % by weight where m is represented by the following formula (I);
m=125y+20 (I)
wherein y is a quantity of Co in the aforementioned general formula (11).
Further, according to the present invention, there is also provided a hydrogen-absorbing alloy comprising an alloy represented by the following general formula (12), the alloy containing a principal phase having a composition where the a and z in the general formula (12) meet the following formula (II), and the alloy having a plane defect in the principal phase which is not more than 20 in number per 100 nm;
Mg.sub.a R1.sub.1-a-b T1.sub.b (Ni.sub.1-x M6.sub.x).sub.z (12)
wherein R1 is at least one element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M6 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si, B, Nb, W, Mo, V, Cr, Ta, P and S; and a, b, x and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0.ltoreq.b.ltoreq.0.3, 0<x.ltoreq.0.6, and 3.ltoreq.z.ltoreq.3.8;
z=-6.times.a+.delta. (II)
wherein .delta. is: 5-0.2.ltoreq..delta..ltoreq.5+0.2.
Further, according to the present invention, there is also provided a hydrogen-absorbing alloy comprising an alloy represented by the following general formula (13), the alloy containing more than 70% by volume of crystal grain having a plane defect of not more than 20 in number per 100 nm and a principal phase having a composition where the a and z in the general formula (13) meet the following formula (II);
Mg.sub.a R1.sub.1-a-b T1.sub.b (Ni.sub.1-x M6.sub.x).sub.z (13)
wherein R1 is at least one element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M6 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si, B, Nb, W, Mo, V, Cr, Ta, P and S; and a, b, x and z are respectively a number satisfying conditions: ##EQU1##
Further, according to the present invention, there is also provided a hydrogen-absorbing alloy comprising an alloy represented by the following general formula (14), the alloy containing a principal phase having a composition where the a and z in the general formula (14) meet the following formula (II), not more than 20% by volume of a phase having a CaCu.sub.5 type crystal structure and not more than 10% by volume of a phase having a MgCu.sub.2 type crystal structure;
Mg.sub.a R1.sub.1-a-b T1.sub.b (Ni.sub.1-x M6.sub.x).sub.z (14)
wherein R1 is at least one element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M6 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si, B, Nb, W, Mo, V, Cr, Ta, P and S; and a, b, x and z are respectively a number satisfying conditions: ##EQU2##
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing hydrogen-absorbing alloy particles comprising a pulverized product of an alloy ingot manufactured by means of a casting or sintering method and the alloy ingot being represented by the following general formula (1);
(Mg.sub.1-a-b R1.sub.a M1.sub.b)Ni.sub.z (1)
wherein R1 is at least one element selected from rare earth elements (including Y); M1 is at least one element selected from elements having a larger electronegativity than that of Mg (excluding the elements of R1, Cr, Mn, Fe, Co, Cu, Zn and Ni); and a, b and z are respectively a number satisfying conditions: 0.1.ltoreq.a.ltoreq.0.8, 0<b.ltoreq.0.9, 1-a-b>0, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing hydrogen-absorbing alloy particles comprising a pulverized product of an alloy ingot manufactured by means of a casting or sintering method and the alloy ingot being represented by the following general formula (2);
Mg.sub.1-a R1.sub.a (Ni.sub.1-x M2.sub.x).sub.z (2)
wherein R1 is at least one element selected from rare earth elements (including Y); M2 is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Cu and Zn; and a, x and z are respectively a number satisfying conditions: 0.1.ltoreq.a.ltoreq.0.8, 0<x.ltoreq.0.9, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing hydrogen-absorbing alloy particles comprising a pulverized product of an alloy ingot manufactured by means of a casting or sintering method and the alloy ingot being represented by the following general formula (3);
Mg.sub.1-a-b R1.sub.a M1.sub.b (Ni.sub.1-x M2.sub.x).sub.z (3)
wherein R1 is at least one element selected from rare earth elements (including Y); M2 is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Cu and Zn; M1 is at least one element selected from elements having a larger electronegativity than that of Mg (excluding the elements of R1, the elements of M1 and Ni); and a, b, x and z are respectively a number satisfying conditions: 0.1.ltoreq.a.ltoreq.0.8, 0<b.ltoreq.0.9, 1-a-b>0, 0<x.ltoreq.0.9, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing hydrogen-absorbing alloy particles comprising a pulverized product of an alloy ingot manufactured by means of a casting or sintering method and the alloy ingot being represented by the following general formula (4);
Mg.sub.1-a R1.sub.a (Ni.sub.1-x M3.sub.x).sub.z (4)
wherein R1 is at least one element selected from rare earth elements (including Y); M3 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B; and a, x and z are respectively a number satisfying conditions: 0.65.ltoreq.a.ltoreq.0.8, 0<x.ltoreq.0.6, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing hydrogen-absorbing alloy particles comprising a pulverized product of an alloy ingot manufactured by means of a casting or sintering method and the alloy ingot being represented by the following general formula (5);
Mg.sub.1-a-b R1.sub.a T1.sub.b (Ni.sub.1-x M3.sub.x).sub.z (5)
wherein R1 is at least one element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M3 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B; and a, b, x and z are respectively a number satisfying conditions: 0.65.ltoreq.a<0.8, 0<b.ltoreq.0.3, 0.65<(a+b).ltoreq.0.8, 0<x.ltoreq.0.6, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing hydrogen-absorbing alloy particles comprising a pulverized product of an alloy ingot manufactured by means of a casting or sintering method and the alloy ingot being represented by the following general formula (6);
Mg.sub.a R1.sub.1-a (Ni.sub.1-x-y Co.sub.x M4.sub.y).sub.z (6)
wherein R1 is at least one element selected from rare earth elements (including Y); M4 is at least one element selected from the group consisting of Mn, Fe, V, Cr, Nb, Al, Ga, Zn, Sn, Cu, Si, P and B; and a, x, y and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0<x.ltoreq.0.5, 0.ltoreq.y.ltoreq.0.2, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing hydrogen-absorbing alloy particles comprising a pulverized product of an alloy ingot manufactured by means of a casting or sintering method and the alloy ingot being represented by the following general formula (7);
Mg.sub.a R1.sub.1-a-b T2.sub.b (Ni.sub.1-x-y Co.sub.x M4.sub.y).sub.z(7)
wherein R1 is at least one element selected from rare earth elements (including Y); T2 is at least one element selected from the group consisting of Ca, Ti and Zr; M4 is at least one element selected from the group consisting of Mn, Fe, V, Cr, Nb, Al, Ga, Zn, Sn, Cu, Si, P and B; and a, b, x, y and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0<b.ltoreq.0.3, 0<x.ltoreq.0.5, 0.ltoreq.y.ltoreq.0.2, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing hydrogen-absorbing alloy particles comprising a pulverized product of an alloy ingot manufactured by means of a casting or sintering method and the alloy ingot being represented by the following general formula (8);
Mg.sub.a (La.sub.1-b R1.sub.b).sub.1-a Ni.sub.z (8)
wherein R1 is at least one element selected from rare earth elements (including Y) but is not La; and a, b and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0.01.ltoreq.b<0.5, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing hydrogen-absorbing alloy particles comprising a pulverized product of an alloy ingot manufactured by means of a casting or sintering method and the alloy ingot being represented by the following general formula (9);
Mg.sub.a (La.sub.1-b R1.sub.b).sub.1-a (Ni.sub.1-x M3.sub.x).sub.z(9)
wherein R1 is at least one element selected from rare earth elements (including Y) but is not La; M3 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B; and a, b, x and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0.01.ltoreq.b<0.5, 0.1.ltoreq.x.ltoreq.0.6, and 3.ltoreq.z.ltoreq.3.8.
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing a hydrogen-absorbing alloy comprising an alloy represented by the following general formula (10);
Mg.sub.a R2.sub.1-a-b T1.sub.b (Ni.sub.1-x M3.sub.x).sub.z (10)
wherein R2 is two or more kinds of element selected from rare earth elements (including Y), the content of Ce constituting the R2 being less than 20% by weight; T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M3 is at least one element selected from the group consisting of Mn, Fe, Co, Al, Ga, Zn, Sn, Cu, Si and B; and a, b, x and z are respectively a number satisfying conditions: 0<a.ltoreq.0.5, 0.ltoreq.b.ltoreq.0. 3, 0.ltoreq.x.ltoreq.0.9, and 3.ltoreq.z<4.
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing a hydrogen-absorbing alloy comprising an alloy represented by the following general formula (11);
Mg.sub.a R3.sub.1-a-b T1.sub.b (Ni.sub.1-x-y M5.sub.x Co.sub.y).sub.z(11)
wherein R3 is two or more kinds of element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M5 is at least one element selected from the group consisting of Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B; a, b, x, y and z are respectively a number satisfying conditions: 0<a.ltoreq.0.5, 0.ltoreq.b.ltoreq.0.3, 0.ltoreq.x.ltoreq.0.9, 0<y.ltoreq.0.4, x+y.ltoreq.0.9, and 3.ltoreq.z<4, the content of Ce constituting the R3 being less than m % by weight where m is represented by the following formula (I);
m=125y+20 (I)
wherein y is a quantity of Co in the aforementioned general formula (11).
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing a hydrogen-absorbing alloy comprising an alloy represented by the following general formula (12), the alloy containing a principal phase having a composition where the a and z in the general formula (12) meet the formula (II), and the alloy having a plane defect in the principal phase which is not more than 20 in number per 100 nm;
Mg.sub.a R1.sub.1-a-b T1.sub.b (Ni.sub.1-x M6.sub.x).sub.z (12)
wherein R1 is at least one element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M6 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si, B, Nb, W, Mo, V, Cr, Ta, P and S; and a, b, x and z are respectively a number satisfying conditions: ##EQU3##
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing a hydrogen-absorbing alloy comprising an alloy represented by the following general formula (13), the alloy containing more than 70% by volume of crystal grain having a plane defect of not more than 20 in number per 100 nm and a principal phase having a composition where the a and z in the general formula (13) meet the following formula (II);
Mg.sub.a R1.sub.1-a-b T1.sub.b (Ni.sub.1-x M6.sub.x).sub.z (13)
wherein R1 is at least one element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M6 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si, B, Nb, W, Mo, V, Cr, Ta, P and S; and a, b, x and z are respectively a number satisfying conditions: ##EQU4##
Further, according to the present invention, there is also provided a secondary battery comprising a negative electrode containing a hydrogen-absorbing alloy comprising an alloy represented by the following general formula (14), the alloy containing a principal phase having a composition where the a and z in the general formula (14) meet the following formula (II), not more than 20% by volume of a phase having a CaCu.sub.5 type crystal structure and not more than 10% by volume of a phase having a MgCu.sub.2 type crystal structure;
Mg.sub.a R1.sub.1-a-b T1.sub.b (Ni.sub.1-x M6.sub.x).sub.z (14)
wherein R1 is at least one element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M6 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si, B, Nb, W, Mo, V, Cr, Ta, P and S; and a, b, x and z are respectively a number satisfying conditions: ##EQU5##
Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinbefore.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate presently preferred embodiments of the invention, and together with the general description given above and the detailed description of the preferred embodiments given below, serve to explain the principles of the invention.
FIG. 1 is a graph showing a relationship between the content of Ce and the content of Co in R3 in a hydrogen-absorbing alloy according to this invention;
FIG. 2 is a partially sectioned perspective view showing a cylindrical nickel-hydrogen secondary battery representing one embodiment of an alkaline secondary battery of this invention;
FIG. 3 is a schematic view of a temperature-scanning type hydrogen absorption/desorption property-evaluating apparatus to be employed in an example of this invention; and
FIG. 4 is a microphotograph illustrating a transmission electron microscopic image of the principal phase of a hydrogen-absorbing alloy according one example of this invention.

DETAILED DESCRIPTION OF THE INVENTION
Next, fourteen kinds of hydrogen-absorbing alloy according to this invention will be explained in detail as follows.
(A) A First Hydrogen-Absorbing Alloy
This hydrogen-absorbing alloy contains an alloy ingot manufactured by means of a casting or sintering method or contains a pulverized product of the alloy ingot. The alloy ingot has a composition represented by the following general formula (1);
(Mg.sub.1-a-b R1.sub.a M1.sub.b)Ni.sub.z (1)
wherein R1 is at least one element selected from rare earth elements (including Y); M1 is at least one element selected from elements having a larger electronegativity than that of Mg (excluding the elements of R1, Cr, Mn, Fe, Co, Cu, Zn and Ni); and a, b and z are respectively a number satisfying conditions: 0.1.ltoreq.a.ltoreq.0.8, 0<b.ltoreq.0.9, 1-a-b>0, and 3.ltoreq.z.ltoreq.3.8.
In view of saving the manufacturing cost of a hydrogen-absorbing alloy, the aforementioned element R1 should preferably be at least one kind of element selected from the group consisting of La, Ce, Pr, Nd and Y. Among them, it is preferable to employ a misch metal which is mixture of rare earth elements. This misch metal should preferably be an alloy where the content of La, Ce, Pr and Nd accounts for 99 wt % or more. Specific examples of such a misch metal are a Ce-rich misch metal (Mm) containing 50 wt % or more of Ce and not more than 30 wt % of La, or a La-rich misch metal (Lm) where the content of La is larger than that of the aforementioned Mm.
The reason for limiting the range of (a) is as follows. Namely, if the value of (a) is less than 0.1, it may become difficult to enhance the hydrogen absorption rate of the alloy. o n the other hand, if the value of (a) exceeds over 0.8, it may become difficult to improve the rechargeable hydrogen storage capacity of the alloy, so that the properties inherent to the Mg-based alloy may be vanished. A more preferable range of the (a) is 0.35.ltoreq.a.ltoreq.0.8.
The aforementioned M1 may be Al:1.5, Ta:1.5, V:1.6, Nb:1.6, Ga:1.6, In:1.7, Ge:1.8, Pb:1.8, Mo:1.8, Sn:1.8, Si:1.8, Re:1.9, Ag:1.9, B:2.0, C:2.5, P:2.1, Ir:2.2, Rh:2.2, Ru:2.2, Os:2.2, Pt:2.2, Au:2.4, Se:2.4 and S:2.5. This M1 can be one or more than one kinds of these elements. The numerical value following the symbol ":" in each element denotes an electronegativity of a metal as the value of polling is employed. By the way, the electronegativity of Mg as the value of polling is employed is 1.2.
It is possible to increase the hydrogen equilibrium pressure of the alloy by substituting the M1 for a portion of Mg by the aforementioned quantity (0<b.ltoreq.0.9). As a result of this substitution, it is possible to enhance the working voltage of the alkaline secondary battery comprising a negative electrode containing the aforementioned alloy, whereby the discharge capacity and charge/discharge cycle life of the battery can be improved.
Further, the alloy having such a composition is capable of improving the hydrogen absorption/desorption rate assumably due to the following mechanism. Namely, there is a correlation in many of hydride of simple metal that the larger the difference in electro-negativity between a metal and hydrogen is, the larger is the bonding force between a metal and hydrogen. When the change in bonding force between the alloy and hydrogen by substituting another element for a portion of Mg is examined from the viewpoint of electro-negativity, it is assumed that the larger the difference in electronegativity between a metal and hydrogen is, the larger the ionic bond becomes between the metal and hydrogen, thus enhancing the bond between the metal and hydrogen, and increasingly stabilizing the hydrogen absorbed therein.
Therefore, when the aforementioned M1 is selected from those having a larger electronegativity than that of Mg, the difference in electronegativity between the hydrogen-absorbing alloy and hydrogen can be minimized, and hence the hydrogen inside the crystal lattice of the alloy is assumed to be made unstable, thus resulting in an improvement in hydrogen absorption/desorption property of the hydrogen-absorbing alloy.
Especially, when Al or Ag, or both are employed as the M1, the crystal lattice of the hydrogen-absorbing alloy can be expanded, thus improving the hydrogen absorption/desorption property of the hydrogen-absorbing alloy.
Further, when the value of "b" exceeds over 0.9, the crystal structure of the hydrogen-absorbing alloy may be prominently altered, thus deteriorating the properties inherent to the Mg-based alloy. Additionally, the hydrogen-absorbing alloy of this composition would be sharply deteriorated in catalytic activity at the moment of hydrogen absorption. More preferable range of the "b" is 0.1.ltoreq.b.ltoreq.0.8.
The reason for limiting the range of (z) is as follows. Namely, if the value of (z) is less than 3.0, the hydrogen inside the alloy is highly stabilized, thus minimizing the desorption of hydrogen from the alloy. On the other hand, if the value of (z) exceeds over 3.8, the hydrogen site in the alloy would be reduced, thus possibly decreasing the quantity of hydrogen absorption. A more preferable range of the (z) is 3.0.ltoreq.z.ltoreq.3.6.
This first hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This first hydrogen-absorbing alloy can be manufactured by means of a casting or sintering method as explained below.
(Casting method)
(a) Each element was weighed to obtain a predetermined mixture, which was then melted by means of an induction furnace in an argon atmosphere for instance, and cast in a mold to obtain an alloy ingot having an aimed composition.
(b) Mother alloys such as an RNi.sub.5 -type alloy, an R.sub.2 Ni.sub.7 -type alloy, an RNi.sub.3 -type alloy, an RNi.sub.2 -type alloy, an Mg.sub.2 Ni-type alloy, and an MgNi.sub.2 -type alloy were prepared by means of an induction furnace. Then, each mother alloy was weighed to obtain a predetermined mixture and then melted by means of an induction furnace, the resultant melt being cast in a mold to obtain an alloy ingot having an aimed composition.
(Sintering method)
(a) Each element was weighed to obtain a predetermined mixture, which was then sintered in an argon atmosphere for instance, the resultant sintered product being subsequently heat-treated at around the melting point thereof to obtain an alloy ingot having an aimed composition.
(b) Mother alloys having a relatively high melting point, such as an RNi.sub.5 -type alloy, an R.sub.2 Ni.sub.7 -type alloy, an RNi.sub.3 -type alloy, an RNi.sub.2 -type alloy, and an RNi-type alloy were prepared by means of an induction furnace. At the same time, another kind of mother alloy such as an Mg.sub.2 Ni-type alloy and an MgNi.sub.2 -type alloy were prepared by means of an induction furnace. Then, each powder of mother alloy was weighed and mixed to obtain a predetermined composition, which was then heat-treated at around the melting point thereof to obtain an alloy ingot having an aimed composition.
The alloy ingot thus obtained is then preferably heat-treated in vacuum or in an inert atmosphere at a temperature ranging from 300.degree. C. to less than melting point thereof for a time period ranging from 0.1 to 500 hours. It is possible through this heat treatment to alleviate the distortion in lattice of the alloy, so that the hydrogen absorption/desorption characteristics such as the hydrogen absorption/desorption rate of the alloy can be improved. The heat treatment temperature should preferably be in the range from 750 to 1,050.degree. C., more preferably in the range from 800 to 1,000.degree. C. Further, the heat treatment period should preferably be in the range from 0.5 to 100 hours, more preferably in the range from 1 to 20 hours.
(B) A Second Hydrogen-Absorbing Alloy
This hydrogen-absorbing alloy contains an alloy ingot manufactured by means of a casting or sintering method or contains a pulverized product of the alloy ingot. The alloy ingot has a composition represented by the following general formula (2);
Mg.sub.1-a R1.sub.a (Ni.sub.1-x M2.sub.x).sub.z (2)
wherein R1 is at least one element selected from rare earth elements (including Y); M2 is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Cu and Zn; and a, x and z are respectively a number satisfying conditions:
0.1.ltoreq.a.ltoreq.0.8, 0<x.ltoreq.0.9, and 3.ltoreq.z.ltoreq.3.8.
Specific examples of the element R1 may be the same as explained with reference to the aforementioned first alloy.
The reason for limiting the range of (a) is as follows. Namely, if the value of (a) is less than 0.1, it may become difficult to improve the hydrogen desorption property of the alloy. On the other hand, if the value of (a) exceeds over 0.8, it may become difficult to improve the rechargeable hydrogen storage capacity of the alloy, so that the properties inherent to the Mg-based alloy may be vanished. A more preferable range of (a) is 0.65.ltoreq.a.ltoreq.0.80.
It is possible to improve the hydrogen absorption/desorption rate of the alloy by substituting the M2 for a portion of Ni by the aforementioned quantity (0<x.ltoreq.0.9). This may be attributed to the fact that the M2 is an element which is incapable of thermally reacting with hydrogen, i.e. an element which is hardly capable of spontaneously producing a hydride, so that the hydrogen absorption and desorption of the hydrogen-absorbing alloy can be facilitated by the addition of the M2.
Further, an alkaline secondary battery comprising a negative electrode containing this alloy enables the charge/discharge cycle property thereof to be remarkably improved. It is preferably that this M2 is Co or Mn, or both of Co and Mn.
Further, when the value of "x" exceeds over 0.9, the crystal structure of the hydrogen-absorbing alloy may be prominently altered, thus deteriorating the properties inherent to the Mg-based alloy. More preferable range of the "x" is 0.1.ltoreq.x.ltoreq.0.8.
The reason for limiting the range of (z) is as follows. Namely, if the value of (z) is less than 3.0, the hydrogen inside the alloy is highly stabilized, thus minimizing the desorption of hydrogen from the alloy. On the other hand, if the value of (z) exceeds over 3.8, the hydrogen site in the alloy would be reduced, thus possibly decreasing the quantity of hydrogen absorption. A more preferable range of the content (z) is 3.0.ltoreq.z.ltoreq.3.6.
This second hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This second hydrogen-absorbing alloy can be manufactured by means of a casting or sintering method as explained above.
The alloy ingot thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
(C) A Third Hydrogen-Absorbing Alloy
This hydrogen-absorbing alloy contains an alloy ingot manufactured by means of a casting or sintering method or contains a pulverized product of the alloy ingot. The alloy ingot has a composition represented by the following general formula (3);
Mg.sub.1-a-b R1.sub.a M1.sub.b (Ni.sub.1-x M2.sub.x).sub.z (3)
wherein R1 is at least one element selected from rare earth elements (including Y); M2 is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Cu and Zn; M1 is at least one element selected from elements having a larger electronegativity than that of Mg (excluding the elements of R1, the elements of M1 and Ni); and a, b, x and z are respectively a number satisfying conditions: 0.1.ltoreq.a.ltoreq.0.8, 0<b.ltoreq.0.9, 1-a-b>0, 0<x.ltoreq.0.9, and 3.ltoreq.z.ltoreq.3.8.
Specific examples of the element R1 may be the same as explained with reference to the aforementioned first alloy.
The reason for limiting the range of (a) is as follows. Namely, if the value of (a) is less than 0.1, it may become difficult to enhance the hydrogen absorption rate of the alloy. On the other hand, if the value of (a) exceeds over 0.8, it may become difficult to improve the rechargeable hydrogen storage capacity of the alloy, so that the properties inherent to the Mg-based alloy may be vanished. A more preferable range of the (a) is 0.35.ltoreq.a.ltoreq.0.8.
As for the element M1 of this alloy, the same kinds of element as explained with reference to the aforementioned first alloy can be employed. Especially, it is preferable to employ Al or Ag, or both as the M1. Because, a hydrogen-absorbing alloy containing such an M1 is capable of expanding the crystal lattice of the hydrogen-absorbing alloy, thus further improving the hydrogen absorption/desorption property thereof.
It is possible to increase the hydrogen equilibrium pressure of the alloy by limiting the range of (b) to the aforementioned range. As a result, it is possible to enhance the working voltage of the alkaline secondary battery comprising a negative electrode containing the aforementioned alloy, whereby the discharge capacity and charge/discharge cycle life of the battery can be improved.
Further, when the value of "b" exceeds over 0.9, the crystal structure of the hydrogen-absorbing alloy may be prominently altered, thus deteriorating the properties inherent to the Mg-based alloy. More preferable range of "b" is 0.1.ltoreq.b.ltoreq.0.8.
It is possible to improve the hydrogen absorption/desorption rate of the alloy by substituting the M2 for a portion of Ni by the aforementioned quantity (0<x.ltoreq.0.9). Further, an alkaline secondary battery comprising a negative electrode containing this alloy enables the charge/discharge cycle property thereof to be remarkably improved.
Further, when the value of "x" exceeds over 0.9, the crystal structure of the hydrogen-absorbing alloy may be prominently altered, thus deteriorating the properties inherent to the Mg-based alloy. It is preferably that this M2 is Co or Mn, or both of Co and Mn. More preferable range of "x" is 0.1.ltoreq.x.ltoreq.0.8.
The reason for limiting the range of (z) is as follows. Namely, if the value of (z) is less than 3.0, the hydrogen inside the alloy is highly stabilized, thus minimizing the desorption of hydrogen from the alloy. On the other hand, if the value of (z) exceeds over 3.8, the hydrogen site in the alloy would be reduced, thus possibly decreasing the quantity of hydrogen absorption. A more preferable range of the (z) is 3.0.ltoreq.z.ltoreq.3.6.
This third hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This third hydrogen-absorbing alloy can be manufactured by means of a casting or sintering method as explained above.
The alloy ingot thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
(D) A Fourth Hydrogen-Absorbing Alloy
This hydrogen-absorbing alloy contains an alloy ingot manufactured by means of a casting or sintering method or contains a pulverized product of the alloy ingot. The alloy ingot has a composition represented by the following general formula (4);
Mg.sub.1-a R1.sub.a (Ni.sub.1-x M3.sub.x).sub.z (4)
wherein R1 is at least one element selected from rare earth elements (including Y); M3 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B; and a, x and z are respectively a number satisfying conditions: 0.65.ltoreq.a.ltoreq.0.8, 0<x.ltoreq.0.6, and 3.ltoreq.z.ltoreq.3.8.
Specific examples of the element R1 in the general formula (4) may be the same as explained with reference to the aforementioned first alloy.
The reason for limiting the range of "a" is as follows. Namely, if the value of "a" is less than 0.65, the crystal structure of the alloy may be altered, so that the quantity of hydrogen absorption may be decreased. On the other hand, if the value of "a" exceeds over 0.8, it may become difficult to improve the hydrogen desorption property of the alloy.
It is possible to improve the hydrogen absorption/desorption property such as the hydrogen absorption/desorption rate of the alloy by selecting at least one kind of element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B as the element M3 in the general formula (4). This may be attributed to the fact that the M3 is an element which is incapable of thermally reacting with hydrogen, i.e. an element which is hardly capable of spontaneously producing a hydride, so that the hydrogen absorption and desorption of the hydrogen-absorbing alloy can be facilitated by substituting the M3 for a portion of Ni. Further, a metal oxide-hydrogen secondary battery comprising a negative electrode containing this alloy enables the charge/discharge cycle property thereof to be remarkably improved.
When the value of (x) exceeds over 0.6, the discharge capacity of a metal oxide-hydrogen secondary battery comprising a negative electrode containing this alloy would be lowered. A more preferable range of the (x) is 0.01.ltoreq.x.ltoreq.0.5.
The reason for limiting the range of (z) is as follows. Namely, if the value of (z) is less than 3.0, the hydrogen inside the alloy is highly stabilized, thus minimizing the desorption of hydrogen from the alloy. When the value of (z) is made not less than 3, the hydrogen absorption/desorption property such as the hydrogen absorption/desorption rate of the alloy can be sufficiently improved, thus making it possible to realize a metal oxide-hydrogen secondary battery improved in discharge capacity and in charge/discharge cycle property. However, if the value of (z) exceeds over 3.8, the hydrogen site in the alloy would be reduced, thus possibly decreasing the quantity of hydrogen absorption. A more preferable range of the (z) is 3.0.ltoreq.z.ltoreq.3.6.
This fourth hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This fourth hydrogen-absorbing alloy can be manufactured by means of a casting or sintering method as explained above.
The alloy ingot thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
(E) A Fifth Hydrogen-Absorbing Alloy
This hydrogen-absorbing alloy contains an alloy ingot manufactured by means of a casting or sintering method or contains a pulverized product of the alloy ingot. The alloy ingot has a composition represented by the following general formula (5);
Mg.sub.1-a-b R1.sub.a T1.sub.b (Ni.sub.1-x M3.sub.x).sub.z (5)
wherein R1 is at least one element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M3 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B; and a, b, x and z are respectively a number satisfying conditions: 0.65.ltoreq.a<0.8, 0<b.ltoreq.0.3, 0.65<(a+b).ltoreq.0.8, 0<x.ltoreq.0.6, and 3.ltoreq.z.ltoreq.3.8.
Specific examples of the element R1 in the general formula (5) may be the same as explained with reference to the aforementioned first alloy.
The reason for limiting the range of "a" is as follows. Namely, if the value of "a" is less than 0.65, the crystal structure of the alloy may be altered, so that the quantity of hydrogen absorption may be decreased. On the other hand, if the value of "a" is 0.8 or more, it may become difficult to improve the hydrogen desorption property of the alloy.
It is possible to improve the property of the alloy such as the hydrogen absorption/desorption rate without greatly decreasing the hydrogen absorption quantity of the alloy by selecting at least one kind of element selected from the group consisting of Ca, Ti, Zr and Hf as the T1. At the same time, the pulverization of the alloy resulting from the absorption and desorption of hydrogen can be suppressed.
When the value of (b) exceeds over 0.3, the aforementioned effects, i.e. the improvement of desorption property and the suppression of pulverization cannot be realized, thus deteriorating the discharge capacity and charge/discharge cycle life of the secondary battery. There is a tendency that the smaller the value of (b) is, the longer would be the charge/discharge cycle life. In view of ensuring a long cycle life, the value of (b) should preferably be 0.2 or less.
The reason for limiting the total (a+b) of the (a) and (b) to the aforementioned range is as follows. Namely, if the total (a+b) is not more than 0.65, the crystal structure of the alloy may be altered, so that the quantity of hydrogen absorption may be decreased. On the other hand, if the total (a+b) exceeds over 0.8, it may become difficult to improve the hydrogen desorption property of the alloy.
It is possible to improve the hydrogen absorption/desorption property such as the hydrogen absorption/desorption rate of the alloy by selecting at least one kind of element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B as the element M3. This may be attributed to the fact that the M3 is an element which is incapable of thermally reacting with hydrogen, i.e. an element which is hardly capable of spontaneously producing a hydride, so that the hydrogen absorption and desorption of the hydrogen-absorbing alloy can be facilitated by substituting the M3 for a portion of Ni. Further, a metal oxide-hydrogen secondary battery comprising a negative electrode containing this alloy enables the charge/discharge cycle property thereof to be remarkably improved.
When the value of (x) exceeds over 0.6, the discharge capacity of a metal oxide-hydrogen secondary battery comprising a negative electrode containing this alloy would be lowered. A more preferable range of the (x) is 0.01.ltoreq.x.ltoreq.0.5.
The reason for limiting the range of (z) is as follows. Namely, if the value of (z) is less than 3.0, the hydrogen inside the alloy is highly stabilized, thus minimizing the desorption of hydrogen from the alloy. When the value of (z) is made not less than 3, the hydrogen absorption/desorption property such as the hydrogen absorption/desorption rate of the alloy can be sufficiently improved, thus making it possible to realize a metal oxide-hydrogen secondary battery improved in discharge capacity and in charge/discharge cycle property. However, if the value of (z) exceeds over 3.8, the hydrogen site in the alloy would be reduced, thus possibly decreasing the quantity of hydrogen absorption. A more preferable range of the (z) is 3.0.ltoreq.z.ltoreq.3.6.
This fifth hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This fifth hydrogen-absorbing alloy can be manufactured by means of a casting or sintering method as explained above.
The alloy ingot thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
(F) A Sixth Hydrogen-Absorbing Alloy
This hydrogen-absorbing alloy contains an alloy ingot manufactured by means of a casting or sintering method or contains a pulverized product of the alloy ingot. The alloy ingot has a composition represented by the following general formula (6);
Mg.sub.a R1.sub.1-a (Ni.sub.1-x-y Co.sub.x M4.sub.y).sub.z (6)
wherein R1 is at least one element selected from rare earth elements (including Y); M4 is at least one element selected from the group consisting of Mn, Fe, V, Cr, Nb, Al, Ga, Zn, Sn, Cu, Si, P and B; and a, x, y and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0<x.ltoreq.0.5, 0.ltoreq.y.ltoreq.0.2, and 3.ltoreq.z.ltoreq.3.8.
Specific examples of the element R1 in the general formula (6) may be the same as explained with reference to the aforementioned first alloy.
The reason for limiting the range of (a) is as follows. Namely, if the value of (a) is less than 0.2, it may become difficult to improve the hydrogen desorption property of the alloy. On the other hand, if the value of (a) exceeds over 0.35, the crystal structure of the alloy may be altered, so that the quantity of hydrogen absorption may be decreased.
When the quantity of Co is limited to the aforementioned range, the reversibility in the absorption-desorption of hydrogen can be improved, thus extremely improving the charge/discharge cycle property of a secondary battery. Further, this alloy is small in plateau slope, and moreover, is capable of minimizing the hysteresis and improving the static hydrogen absorption property thereof. However, if the quantity of Co (x) is more than 0.5, it may lead to a lowering in quantity of hydrogen absorption, and at the same time, the oxidation and reduction reaction of Co would be caused to generate if a secondary battery is fabricated using a negative electrode containing this alloy, thus making it difficult to expect a large discharge capacity. A more preferably range of the quantity of Co (x) is 0.03.ltoreq.x.ltoreq.0.35.
It is possible to improve the hydrogen absorption/desorption property of the alloy such as the hydrogen absorption/desorption rate by selecting at least one kind of element selected from the group consisting of Mn, Fe, V, Cr, Nb, Al, Ga, Zn, Sn, Cu, Si, P and B as the M4. This may be attributed to the facts that the diffusion of hydrogen penetrated into the alloy as well as the absorption/desorption of hydrogen can be facilitated by the substituting the M4 for a portion of Ni. Further, it is possible, when a metal oxide-hydrogen secondary battery is fabricated using a negative electrode containing this alloy, to prominently improve the charge/discharge cycle property of the battery.
If the value of (y) is more than 0.2, it will lead to a deterioration of discharge capacity in a metal oxide-hydrogen secondary battery which is fabricated using a negative electrode containing this alloy. A more preferable range of the (y) is 0.01.ltoreq.y.ltoreq.0.15.
The reason for limiting the range of (z) is as follows. Namely, if the value of (z) is less than 3.0, the hydrogen inside the alloy is highly stabilized, thus minimizing the desorption of hydrogen from the alloy. When the value of (z) is made not less than 3, the hydrogen absorption/desorption property such as the hydrogen absorption/desorption rate of the alloy can be sufficiently improved, thus making it possible to realize a metal oxide-hydrogen secondary battery improved in discharge capacity and in charge/discharge cycle property. However, if the value of (z) exceeds over 3.8, the hydrogen site in the alloy would be reduced, thus possibly decreasing the quantity of hydrogen absorption. A more preferable range of the (z) is 3.0.ltoreq.z.ltoreq.3.6.
This sixth hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This sixth hydrogen-absorbing alloy can be manufactured by means of a casting or sintering method as explained above.
The alloy ingot thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
(G) A Seventh Hydrogen-Absorbing Alloy
This hydrogen-absorbing alloy contains an alloy ingot manufactured by means of a casting or sintering method or contains a pulverized product of said alloy ingot. The alloy ingot has a composition represented by the following general formula (7);
Mg.sub.a R1.sub.1-a-b T2.sub.b (Ni.sub.1-x-y Co.sub.x M4.sub.y).sub.z(7)
wherein R1 is at least one element selected from rare earth elements (including Y); T2 is at least one element selected from the group consisting of Ca, Ti and Zr; M4 is at least one element selected from the group consisting of Mn, Fe, V, Cr, Nb, Al, Ga, Zn, Sn, Cu, Si, P and B; and a, b, x, y and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0<b.ltoreq.0.3, 0<x.ltoreq.0.5, 0.ltoreq.y.ltoreq.0.2, and 3.ltoreq.z.ltoreq.3.8.
Specific examples of the element R1 in the general formula (7) may be the same as explained with reference to the aforementioned first alloy.
The reason for limiting the range of (a) is as follows. Namely, if the value of (a) is less than 0.2, it may become difficult to improve the hydrogen desorption property of the alloy. On the other hand, if the value of (a) exceeds over 0.35, the crystal structure of the alloy may be altered, so that the quantity of hydrogen absorption may be decreased.
It is possible to improve the property of the alloy such as the hydrogen desorption rate without greatly decreasing the hydrogen absorption quantity of the alloy by limiting the range of (b), and at the same time, the pulverization of the alloy resulting from the absorption and desorption of hydrogen can be suppressed.
When the value of (b) exceeds over 0.3, the aforementioned effects, i.e. the improvement of desorption property and the suppression of pulverization cannot be realized, thus deteriorating the discharge capacity and charge/discharge cycle life of the secondary battery. There is a tendency that the smaller the value of (b) is, the longer would be the charge/discharge cycle life. In view of ensuring a long cycle life, the value of (b) should preferably be 0.2 or less.
When the quantity of Co is limited to the aforementioned range, the reversibility in the absorption-desorption of hydrogen can be improved, thus extremely improving the charge/discharge cycle property of a secondary battery. Further, this alloy is small in plateau slope, and moreover, is capable of minimizing the hysteresis and improving the static hydrogen absorption property thereof. However, if the quantity of Co (x) is more than 0.5, it may lead to a lowering in quantity of hydrogen absorption, and at the same time, the oxidation and reduction reaction of Co would be caused to generate if a secondary battery is fabricated using a negative electrode containing this alloy, thus making it difficult to expect a large discharge capacity A more preferably range of the quantity of Co (x) is 0.03.ltoreq.x.ltoreq.0.35.
It is possible to improve the hydrogen absorption/desorption property of the alloy such as the hydrogen absorption/desorption rate by limiting the range of (y). This may be attributed to the facts that the diffusion of hydrogen penetrated into the alloy as well as the absorption/desorption of hydrogen can be facilitated by the substituting the M4 for a portion of Ni. Further, it is possible, when a metal oxide-hydrogen secondary battery is fabricated using a negative electrode containing this alloy, to prominently improve the charge/discharge cycle property of the battery.
If the value of (y) is more than 0.2, it will lead to a deterioration of discharge capacity in a metal oxide-hydrogen secondary battery which is fabricated using a negative electrode containing this alloy. A more preferable range of the (y) is 0.01.ltoreq.y.ltoreq.0.15.
The reason for limiting the range of (z) is as follows. Namely, if the value of (z) is less than 3.0, the hydrogen inside the alloy is highly stabilized, thus minimizing the desorption of hydrogen from the alloy. When the value of (z) is made not less than 3, the hydrogen absorption/desorption property such as the hydrogen absorption/desorption rate of the alloy can be sufficiently improved, thus making it possible to realize a metal oxide-hydrogen secondary battery improved in discharge capacity and in charge/discharge cycle property. However, if the value of (z) exceeds over 3.8, the hydrogen site in the alloy would be reduced, thus possibly decreasing the quantity of hydrogen absorption. A more preferable range of the (z) is 3.0.ltoreq.z.ltoreq.3.6.
This seventh hydrogen-absorbing alloy may contain an element such as C, N, O or F as a n impurity as far as the content of such an element is within a range which does not hinder the property of the alloy.
However, it is pre ferable that the content of these impurities should be not more than 1 wt % respectively.
This seventh hydrogen-absorbing alloy can be manufactured by means of a casting or sintering method as explained above.
The alloy ingot thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
(H) A Eighth Hydrogen-Absorbing Alloy
This hydrogen-absorbing alloy contains an alloy ingot manufactured by means of a casting or sintering method or contains a pulverized product of the alloy ingot. The alloy ingot has a composition represented by the following general formula (8);
Mg.sub.a (La.sub.1-b R1.sub.b).sub.1-a Ni.sub.z (8)
wherein R1 is at least one element selected from rare earth elements (including Y) but is not La; and a, b and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0.01.ltoreq.b<0.5, and 3.ltoreq.z.ltoreq.3.8.
Specific examples of the element R1 in the general formula (8) may be the same as explained with reference to the aforementioned first alloy.
The reason for limiting the range of (a) is as follows. Namely, if the value of (a) is less than 0.2, it may become difficult to improve the hydrogen desorption property of the alloy. On the other hand, if the value of (a) exceeds over 0.35, the crystal structure of the alloy may be altered, so that the quantity of hydrogen absorption may be decreased.
The reason for limiting the range of (b) is as follows. Namely, if the value of (b) is less than 0.01, it may become difficult to enhance the hydrogen equilibrium pressure of the alloy and the working voltage of the secondary battery. Although it is possible to enhance the hydrogen equilibrium pressure of the alloy by increasing the value of (b), the quantity of hydrogen absorption may be decreased if the value of the (b) becomes 0.5 or more.
The reason for limiting the range of (z) is as follows. Namely, if the value of (z) is less than 3, the hydrogen that has been adsorbed becomes very stable, thus making it difficult to desorb the hydrogen. Therefore, a secondary battery comprising a negative electrode containing this alloy would be deteriorated in its discharge capacity. On the other hand, if the value of (z) exceeds over 3.8, the site for allowing hydrogen to enter therein in the hydrogen-absorbing alloy may be decreased. A more preferable range of the (z) is therefore 3.0.ltoreq.z.ltoreq.3.6.
This alloy should desirably be less than 700 (kgf/mm.sup.2) in Vickers hardness (Hv). Because, if the Vickers hardness (Hv) of the alloy is 700 or more, the charge/discharge cycle life of a secondary battery comprising a negative electrode containing this alloy would prominently deteriorated. This may be attributed to the facts that, if the Vickers hardness (Hv) of a hydrogen-absorbing alloy is 700 or more, the fracture toughness (K.sub.IC) thereof becomes smaller, thus making it brittle, so that the crack of the alloy is accelerated by the absorption and desorption of hydrogen, and hence the current-collecting efficiency of the negative electrode would be deteriorated. Therefore, a preferable range of Vickers hardness (Hv) of the alloy is less than 650 (kgf/mm.sup.2), more preferably less than 600 (kgf/mm.sup.2).
This eighth hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This eighth hydrogen-absorbing alloy can be manufactured by means of a casting or sintering method as explained above.
The alloy ingot thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
(I) A Ninth Hydrogen-Absorbing Alloy
This hydrogen-absorbing alloy contains an alloy ingot manufactured by means of a casting or sintering method or contains a pulverized product of the alloy ingot. The alloy ingot has a composition represented by the following general formula (9);
Mg.sub.a (La.sub.1-b R1.sub.b).sub.1-a (Ni.sub.1-x M3.sub.x).sub.z(9)
wherein R1 is at least one element selected from rare earth elements (including Y) but is not La; M3 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B; and a, b, x and z are respectively a number satisfying conditions: 0.2.ltoreq.a.ltoreq.0.35, 0.01.ltoreq.b<0.5, 0.1.ltoreq.x.ltoreq.0.6, and 3.ltoreq.z.ltoreq.3.8.
Specific examples of the element R1 in the general formula (8) may be the same as explained with reference to the aforementioned first alloy.
The reason for limiting the range of (a) is as follows. Namely, if the value of (a) is less than 0.2, it may become difficult to improve the hydrogen desorption property of the alloy. On the other hand, if the value of (a) exceeds over 0.35, the crystal structure of the alloy may be altered, so that the quantity of hydrogen absorption may be decreased.
The reason for limiting the value (b) in this alloy to the aforementioned range is as follows. Namely, if the value of (b) is less than 0.01, it may become difficult to enhance the hydrogen equilibrium pressure of the alloy and the working voltage of the secondary battery. Although it is possible to enhance the hydrogen equilibrium pressure of the alloy by increasing the value of (b), the quantity of hydrogen absorption may be decreased if the value of the (b) becomes 0.5 or more.
When the value of (x) in the alloy is confined to the aforementioned range, the absorption and desorption of hydrogen can be facilitated, thus making it possible to improve the discharge capacity of the secondary battery. At the same time, the corrosion resistance of the alloy would be enhanced, thus improving the charge/discharge cycle life thereof. A more preferable range of the (x) is 0.1.ltoreq.x.ltoreq.0.5.
The reason for limiting the value of (z) in the alloy to the aforementioned range is as follows. Namely, if the value of (z) is less than 3, the hydrogen that has been adsorbed becomes very stable, thus making it difficult to desorb the hydrogen. Therefore, a secondary battery comprising a negative electrode containing this alloy would be deteriorated in its discharge capacity. On the other hand, if the value of (z) exceeds over 3.8, the site for allowing hydrogen to enter therein in the hydrogen-absorbing alloy may be decreased. A more preferable range of the (z) is therefore 3.0.ltoreq.z.ltoreq.3.6.
This alloy should desirably be less than 700 (kgf/mm.sup.2) in Vickers hardness (Hv) for the same reasons as explained with reference to the aforementioned eighth alloy. Therefore, a preferable range of Vickers hardness (Hv) of the alloy is less than 650 (kgf/mm.sup.2), more preferably less than 600 (kgf/mm.sup.2).
This ninth hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This ninth hydrogen-absorbing alloy can be manufactured by means of a casting or sintering method as explained above.
The alloy ingot thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
(K) A Tenth Hydrogen-Absorbing Alloy
This tenth hydrogen-absorbing alloy contains an alloy having a composition represented by the following general formula (10);
Mg.sub.a R2.sub.1-a-b T1.sub.b (Ni.sub.1-x M3.sub.x).sub.z (10)
wherein R2 is two or more kinds of element selected from rare earth elements (including Y), the content of Ce constituting said R2 being less than 20% by weight; T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M3 is at least one element selected from the group consisting of Mn, Fe, Co, Al, Ga, Zn, Sn, Cu, Si and B; and a, b, x and z are respectively a number satisfying conditions: 0<a.ltoreq.0.5, 0.ltoreq.b.ltoreq.0.3, 0.ltoreq.x.ltoreq.0.9, and 3.ltoreq.z<4.
The reason for limiting the value of (a) to the aforementioned range is as follows. Namely, if the value of (a) exceeds over 0.5, the crystal structure of the alloy may be altered, so that the quantity of hydrogen absorption may be decreased. Therefore, a secondary battery comprising a negative electrode containing this alloy would be deteriorated in its discharge capacity. A more preferable range of the (a) is 0.1.ltoreq.a.ltoreq.0.4, most preferably in the range of 0.2.ltoreq.a.ltoreq.0.35.
The corrosion resistance of the alloy may be improved by the inclusion of Ce in the alloy. However, if the content of Ce in the R2 is 20 wt % or more, the high temperature property of the alloy may be deteriorated due to the presence in large quantity of a phase having a different crystal structure other than the aimed crystal structure. Furthermore, a secondary battery comprising a negative electrode containing this alloy may be deteriorated in its charge/discharge property under a high temperature environment. There is a tendency that the high temperature property of the alloy and the charge/discharge property of the secondary battery in a high temperature condition can be improved by decreasing the content of Ce in the R2. A more preferable range of Ce content in R2 is less than 18 wt %, most preferably less than 16 wt %.
It is preferable that the aforementioned R2 contains La. However, if the R2 is constituted exclusively by La, the corrosion resistance of the alloy may be deteriorated thereby lowering the charge/discharge cycle life of the secondary battery though the discharge capacity of the secondary battery may be improved. Preferably, the content of La in the R2 should be more than 70 wt %. When the content of La is controlled within the aforementioned range in an R2 where the content of Ce is less than 20 wt %, the discharge capacity of the battery can be improved without deteriorating the corrosion resistance of the hydrogen-absorbing alloy.
It is preferable in view of lowering the manufacturing cost of a hydrogen-absorbing alloy and of hydrogen-absorbing electrode that the R2 is constituted by La, Ce, Pr and Nd.
The T1 functions to suppress the progress of pulverization of hydrogen-absorbing alloy without excessively lowering the discharge capacity of the secondary battery. Preferably, the T1 should be Ca and Zr.
The reason for limiting the range of (b) is as follows. Namely, if the value of (b) is more than 0.3, the discharge capacity of the secondary battery may be lowered and at the same time, the effect of suppressing the pulverization may be weakened. A more preferable range of the (b) is 0.ltoreq.b.ltoreq.0.2, most preferably 0.ltoreq.b.ltoreq.0.1.
Although the M3 is at least one element selected from the group consisting of Mn, Fe, Co, Al, Ga, Zn, Sn, Cu, Si and B, it is more preferable that the M3 is selected from Mn, Co and Al. When the value of (x) is limited to the aforementioned range, the hydrogen absorption-desorption rate of hydrogen-absorbing alloy can be improved, and at the same time, the discharge capacity of the battery can be improved since the absorption-desorption of hydrogen can be facilitated. Additionally, due to an improvement of the corrosion resistance of the hydrogen-absorbing alloy, the charge/discharge cycle property of the battery can be improved. A more preferable range of the (x) is 0.01.ltoreq.x.ltoreq.0.6, most preferably 0.01.ltoreq.x.ltoreq.0.5.
The reason for limiting the value of (z) in the alloy to the aforementioned range is as follows. Namely, if the value of (z) is less than 3, the hydrogen that has been adsorbed becomes very stable, thus making it difficult to desorb the hydrogen. Therefore, a secondary battery comprising a negative electrode containing this alloy would be deteriorated in its discharge capacity. On the other hand, if the value of (z) exceeds over 4, the site for allowing hydrogen to enter therein in the hydrogen-absorbing alloy may be decreased. A more preferable range of the (z) is therefore in the range of 3.0.ltoreq.z.ltoreq.3.8, most preferably 3.0.ltoreq.z.ltoreq.3.6.
This tenth hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This tenth hydrogen-absorbing alloy can be manufactured by means of a casting method, a sintering method, a melt-quenching method such as a single roll method or a double roll method, an ultra-quenching method such as a gas-atomizing method. The alloy thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
The reason for enabling a secondary battery having an excellent charge/discharge property to be obtained even if this tenth hydrogen-absorbing alloy is manufactured by means of the aforementioned melt-quenching method or ultra-quenching method can be assumedly attributed to the fact that the tenth hydrogen-absorbing alloy manufactured by means of the aforementioned melt-quenching method or ultra-quenching method is minimal in plane defect.
(L) A Eleventh Hydrogen-Absorbing Alloy
This eleventh hydrogen-absorbing alloy contains an alloy having a composition represented by the following general formula (11);
Mg.sub.a R3.sub.1-a-b T1.sub.b (Ni.sub.1-x-y M5.sub.x Co.sub.y).sub.z(11)
wherein R3 is two or more kinds of element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M5 is at least one element selected from the group consisting of Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B; a, b, x, y and z are respectively a number satisfying conditions: 0<a.ltoreq.0.5, 0.ltoreq.b.ltoreq.0.3, 0.ltoreq.x.ltoreq.0.9, 0<y.ltoreq.0.4, x+y.ltoreq.0.9, and 3.ltoreq.z<4, the content of Ce constituting the R3 being less than m % by weight where m is represented by the following formula (I);
m=125y+20 (I)
wherein y is a quantity of Co in the aforementioned general formula (11).
The reason for limiting the value of (a) in this alloy to the aforementioned range is as follows. Namely, if the value of (a) exceeds over 0.5, the crystal structure of the alloy may be altered, so that the quantity of hydrogen absorption may be decreased. Therefore, a secondary battery comprising a negative electrode containing this alloy would be deteriorated in its discharge capacity. A more preferable range of the (a) is 0.1.ltoreq.a.ltoreq.0.4, most preferably in the range of 0.2.ltoreq.a.ltoreq.0.35.
The reason for limiting the content of Ce in R3 to the range as defined by the above formula (I) is as follows. This formula (I) has been created by the present inventors. Namely, it has been found by the present inventors after repeated experiments that there is correlation between the Co content and Ce content in the hydrogen-absorbing alloy. Specifically, the corrosion resistance of the hydrogen-absorbing alloy (particularly, the alloy containing La) may be improved by the inclusion of Ce in the alloy. However, if the content of Ce in the R3 is increased, a phase having a different crystal structure other than the aimed crystal structure is increased. However, when Co is added to this alloy, the generation of a phase having a different crystal structure other than the aimed crystal structure can be suppressed. Accordingly, it is possible, by suitably changing the Ce content in R3 in conformity with the Co content in the alloy, to obtain a hydrogen-absorbing alloy having an improved corrosion resistance while maintaining a preferable crystal structure. More specifically, as shown in FIG. 1, when the Ce content in the R3 is made equal to or larger than the value calculated from the aforementioned formula (I): m=125y+20, the crystal structure of the hydrogen-absorbing alloy would become different from the aimed crystal structure, so that the high temperature characteristic of the alloy as well as the charge/discharge property of the secondary battery in a high temperature environment would be deteriorated.
However, when the Ce content in the R3 is made smaller than the value calculated from the aforementioned formula (I) as suggested by this invention, it is possible to maintain a preferable crystal structure of the hydrogen-absorbing alloy, and to improve, in particular, the high temperature characteristic of the alloy as well as the charge/discharge property of the secondary battery in a high temperature environment.
It is preferable that the aforementioned R3 further contains La. It is more preferable in view of lowering the manufacturing cost of a hydrogen-absorbing alloy and of hydrogen-absorbing electrode that the R3 is constituted by La, Ce, Pr and Nd.
The T1 functions to suppress the progress of pulverization of hydrogen-absorbing alloy without excessively lowering the discharge capacity of the secondary battery. Preferably, the T1 should be constituted by Ca and Zr.
The reason for limiting the value of (b) to the aforementioned range is as follows. Namely, if the value of (b) is more than 0.3, the discharge capacity of the secondary battery may be lowered and at the same time, the effect of suppressing the pulverization may be weakened. A more preferable range of the (b) is 0.ltoreq.b.ltoreq.0.2, most preferably 0.ltoreq.b.ltoreq.0.1.
Although the M5 is at least one element selected from the group consisting of Mn, Fe, Al, Ga, Zn, Sn, Cu, Si and B, it is more preferable that the M5 is selected from Mn, Co and Al. When the value of (x) is limited to the aforementioned range, the hydrogen absorption-desorption rate of hydrogen-absorbing alloy can be improved, and at the same time, the discharge capacity of the battery can be improved since the absorption-desorption of hydrogen can be facilitated. Additionally, due to an improvement of the corrosion resistance of the hydrogen-absorbing alloy, the charge/discharge cycle property of the battery can be improved. A more preferable range of the (x) is 0.01.ltoreq.x.ltoreq.0.6, most preferably 0.01.ltoreq.x.ltoreq.0.5.
The reason for limiting the Co content (y) in the alloy to the aforementioned range is as follows. Namely, if the Co content (y) is more than 0.4, the quantity of hydrogen absorption of the alloy may be lowered, so that the discharge capacity of the secondary battery may be lowered. This may be attributed to the fact that as the Co content (y) is increased, the tolerance in Ce content in the R3, which is calculated from the aforementioned formula (I), becomes higher. A more preferable quantity of the Co content (y) is in the range of 0<y<0.35.
By limiting the value of (x+y) of this alloy to the aforementioned range, the charge/discharge cycle life of the battery can be improved. A more preferable range of the (x+y) is 0<x+y.ltoreq.0.6.
The reason for limiting the value of (z) in the alloy to the aforementioned range is as follows. Namely, if the value of (z) is less than 3, the hydrogen that has been adsorbed becomes very stable, thus making it difficult to desorb the hydrogen. Therefore, a secondary battery comprising a negative electrode containing this alloy would be deteriorated in its discharge capacity. On the other hand, if the value of (z) exceeds over 4, the site for allowing hydrogen to enter therein in the hydrogen-absorbing alloy may be decreased. A more preferable range of the (z) is therefore in the range of 3.0.ltoreq.z.ltoreq.3.8, most preferably 3.0.ltoreq.z.ltoreq.3.6.
This eleventh hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This eleventh hydrogen-absorbing alloy can be manufactured by means of a casting method, a sintering method, a melt-quenching method such as a single roll method or a double roll method, an ultra-quenching method such as a gas-atomizing method. The alloy thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
The reason for enabling a secondary battery having an excellent charge/discharge property to be obtained even if this eleventh hydrogen-absorbing alloy is manufactured by means of the aforementioned melt-quenching method or ultra-quenching method can be assumedly attributed to the fact that the eleventh hydrogen-absorbing alloy manufactured by means of the aforementioned melt-quenching method or ultra-quenching method is minimal in plane defect.
(M) A Twelfth Hydrogen-Absorbing Alloy
This twelfth hydrogen-absorbing alloy contains an alloy represented by the following general formula (12). The alloy contains as a principal phase a crystal phase having a composition where the a and z in the general formula (12) meet the following formula (II), and has a plane defect in the principal phase which is not more than 20 in number per 100 nm.
Mg.sub.a R1.sub.1-a-b T1.sub.b (Ni.sub.1-x M6.sub.x).sub.z (12)
wherein R1 is at least one element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M6 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si, B, Nb, W, Mo, V, Cr, Ta, P and S; and a, b, x and z are respectively a number satisfying conditions: ##EQU6##
The term "principal phase" noted above denotes a crystal phase in the alloy which is highest in existing ratio.
The .delta. is desirably 5 and should fall within a range of between 4.8 and 5.2.
The component analysis of each crystal phase of the alloy can be performed using an EDX analyzer (Energy Dispersive X-ray Spectrometer) of transmission electron microscope and setting the diameter of the beam to 4 nm. The plane defect in crystal phase of alloy is a linear defect which can be observed by taking a picture of the transmission electron microscopic image of crystal grains constituting the crystal phase. The measurement of the plane defect in crystal phase of alloy can be performed by the following method (a) or (b).
(a) A picture of transmission electron microscopic image of crystal grains, magnified by 10,000 to 100,000 times, is taken using a transmission electron microscope, and the number of plane defect per unit length is counted.
(b) Through an observation of (1,0,0) plane of the crystal grain of the alloy, the number of plane defect existing perpendicular to the C-axis of the crystal grain is counted.
An alloy containing, as a principal phase, a crystal phase where values of "a" and "z" in the general formula (12) do not meet the aforementioned formula (II) is poor in hydrogen absorption/desorption characteristics. The reason for limiting the number of plane defect in the principal phase of the hydrogen-absorbing alloy to the aforementioned range is as follows. Namely, if the number of the plane defect in the principal phase exceeds over 20 per 100 nm, it may become difficult to improve the hydrogen desorption property and the cycle characteristics of the alloy, so that it may become difficult to realize a secondary battery having a large discharge capacity and exhibiting an excellent charge/discharge cycle life. When the number of the plane defect in the principal phase can be limited within 10 per 100 nm, it would become possible to further improve the hydrogen absorption-desorption characteristic of the alloy and in particular the cycle characteristic of the alloy, and hence it is possible to realize a metal oxide-hydrogen secondary battery having an improved discharge capacity and an improved charge/discharge cycle life.
Specific examples of the element R1 in the general formula (12) may be the same as explained with reference to the aforementioned first alloy.
It is possible, by substituting T1 for a portion of the R1, to improve the property of the alloy such as the hydrogen desorption rate without greatly decreasing the hydrogen absorption quantity of the alloy, and at the same time, to suppress the pulverization of the alloy resulting from the absorption and desorption of hydrogen.
However, when the value of (b) exceeds over 0.3, the aforementioned effects, i.e. the improvement of desorption property and the suppression of pulverization cannot be realized, thus deteriorating the discharge capacity of the secondary battery. There is a tendency that the smaller the value of (b) is, the longer the charge/discharge cycle life would become. In view of ensuring a long cycle life therefore, the value of (b) should preferably be 0.2 or less.
It is possible to improve the hydrogen absorption/desorption property of the alloy such as the hydrogen absorption/desorption rate by substituting M6 for a portion of the Ni. This may be attributed to the facts that the diffusion of hydrogen penetrated into the alloy as well as the absorption/desorption of hydrogen can be facilitated by the substitution of the M6 for a portion of the Ni. Further, it is possible, when a metal oxide-hydrogen secondary battery is fabricated using a negative electrode containing this alloy, to prominently improve the charge/discharge cycle life of the battery.
However, if the value of (x) is more than 0.6, it will lead to a deterioration of discharge capacity in the secondary battery, so that the range of (x) should preferably be 0.ltoreq.x.ltoreq.0.6. A more preferable range of the (x) is 0.01.ltoreq.y.ltoreq.0.5.
The reason for limiting the range of (a) and the range of (z) in the aforementioned general formula (12) is as explained below. If the value of (a) falls outside the range of 0.2.ltoreq.a.ltoreq.0.35 and at the same time, the value of (z) falls outside the range of 3.ltoreq.z.ltoreq.3.8, the number of the plane defect in the principal phase of the alloy may exceed over 20 per 100 nm. More preferable range of the (z) is 3.ltoreq.z.ltoreq.3.6.
This twelfth hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This twelfth hydrogen-absorbing alloy can be manufactured by means of a casting method, a sintering method, a melt-quenching method such as a single roll method or a double roll method, an ultra-quenching method such as a gas-atomizing method. The alloy thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
If the hydrogen-absorbing alloy according to this invention is to be manufactured by means of the melt-quenching method or the ultra-quenching method, the R1 should preferably contain less than 20 wt % of Ce. If the content of Ce in the R1 is 20 wt % or more, the number of plane defect in the principal phase may exceed over 20 per 100 nm. The alloy composition which can be manufactured by means of the melt-quenching method or the ultra-quenching method, i.e. the allowable range of Ce content in the R1 would be influenced depending on the kind and quantity of substituting element to be included in the Ni site. For example, when Co is included as a substituting element in the Ni site, the acceptable limit of Ce content in the R1 is likely to be expanded with an increase in Co content. Specifically, when the Co content (x) is 0.2, the Ce content in the R1 can be less than 45 wt %.
(N) A Thirteenth Hydrogen-Absorbing Alloy
This thirteenth hydrogen-absorbing alloy comprises an alloy represented by the following general formula (13). The alloy contains as a principal phase a crystal phase having a composition where the a and z in the general formula (13) meet the following formula (II), and further contains more than 70% by volume of crystal grain having a plane defect of not more than 20 in number per 100 nm.
Mg.sub.a R1.sub.1-a-b T1.sub.b (Ni.sub.1-x M6.sub.x).sub.z (13)
wherein R1 is at least one element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M6 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si, B, Nb, W, Mo, V, Cr, Ta, P and S; and a, b, x and z are respectively a number satisfying conditions: ##EQU7##
The term "principal phase" noted above denotes a crystal phase in the alloy which is highest in existing ratio.
The .delta. is desirably 5 and should fall within a range of between 4.8 and 5.2.
The component analysis of each crystal phase of the alloy and the plane defect in the crystal grain can be performed in the same manner as explained with reference to the aforementioned twelfth hydrogen-absorbing alloy.
An alloy containing, as a principal phase, a crystal phase where values of "a" and "z" in the general formula (13) do not meet the aforementioned formula (II) is poor in hydrogen absorption/desorption characteristics. The reason for limiting the volume ratio of the crystal phase where the plane defect of the crystal grain is not more than 20 in number per 100 nm in this hydrogen-absorbing alloy is as follows. Namely, if the ratio of the crystal phase is not more than 70 wt %, it may become difficult to improve the hydrogen desorption property and the cycle characteristics of the alloy, so that it may become difficult to realize a secondary battery having a large discharge capacity and exhibiting an excellent charge/discharge cycle life. When the alloy contains more than 70% by volume of a crystal phase where the number of the plane defect in crystal grain is 10 or less per 100 nm, it would become possible to further improve the hydrogen absorption-desorption characteristic of the alloy and to prominently improve the charge/discharge cycle characteristic in particular, and hence it is possible to realize a metal oxide-hydrogen secondary battery having an improved discharge capacity and an improved charge/discharge cycle life.
Specific examples of the element R1 in the general formula (13) may be the same as explained with reference to the aforementioned first alloy. When the R1 contains La, the content of La in the R1 should preferably be 50 wt % or more.
It is possible, by substituting T1 for a portion of the R1, to improve the property of the alloy such as the hydrogen desorption rate without greatly decreasing the hydrogen absorption quantity of the alloy, and at the same time, to suppress the pulverization of the alloy resulting from the absorption and desorption of hydrogen.
However, when the value of (b) exceeds over 0.3, the aforementioned effects, i.e. the improvement of desorption property and the suppression of pulverization cannot be realized, thus deteriorating the discharge capacity of the secondary battery. There is a tendency that the smaller the value of (b) is, the longer the charge/discharge cycle life would become. In view of ensuring a long cycle life therefore, the value of (b) should preferably be 0.2 or less.
It is possible to improve the hydrogen absorption/desorption property of the alloy such as the hydrogen absorption/desorption rate by substituting M6 for a portion of the Ni. This may be attributed to the facts that the diffusion of hydrogen penetrated into the alloy as well as the absorption/desorption of hydrogen can be facilitated by the substitution of the M6 for a portion of the Ni. Further, it is possible, when a metal oxide-hydrogen secondary battery is fabricated using a negative electrode containing this alloy, to prominently improve the charge/discharge cycle life of the battery.
However, if the value of (x) is more than 0.6, it will lead to a deterioration of discharge capacity in the secondary battery, so that the range of (x) should preferably be 0.ltoreq.x.ltoreq.0.6. A more preferable range of the (x) is 0.01.ltoreq.y.ltoreq.0.5.
The reason for limiting the range of (a) and the range of (z) in the aforementioned general formula (13) is as explained below. If the value of (a) falls outside the range of 0.2.ltoreq.a.ltoreq.0.35 and at the same time, the value of (z) falls outside the range of 3.ltoreq.z.ltoreq.3.8, the quantity of crystal grains where the number of the plane defect therein is more than 20 per 100 nm may not less than 30% by volume. More preferable ranges of the (z) is 3.ltoreq.z.ltoreq.3.6.
This thirteenth hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This thirteenth hydrogen-absorbing alloy can be manufactured by means of a casting method, a sintering method, a melt-quenching method such as a single roll method or a double roll method, an ultra-quenching method such as a gas-atomizing method. The alloy thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
If the hydrogen-absorbing alloy according to this invention is to be manufactured by means of the melt-quenching method or the ultra-quenching method, the R1 should preferably contain less than 20 wt % of Ce. If the content of Ce in the R1 is 20 wt % or more, the quantity of crystal grains where the number of the plane defect therein is not more than 20 per 100 nm may not exceed over 70% by volume. The alloy composition which can be manufactured by means of the melt-quenching method or the ultra-quenching method, i.e. the allowable range of Ce content in the R1 would be influenced depending on the kind and quantity of substituting element to be included in the Ni site. For example, when Co is included as a substituting element in the Ni site, the acceptable limit of Ce content in the R1 is likely to be expanded with an increase in Co content. Specifically, when the Co content (x) is 0.2, the Ce content in the R1 can be less than 45 wt %.
(O) A Fourteenth Hydrogen-Absorbing Alloy
This fourteenth hydrogen-absorbing alloy comprises an alloy represented by the following general formula (14). The alloy contains as a principal phase a crystal phase having a composition where the a and z in the general formula (14) meet the following formula (II), and further contains not more than 20% by volume of a crystal phase having a CaCu.sub.5 type crystal structure and not more than 10% by volume of a crystal phase having a MgCu.sub.2 type crystal structure.
Mg.sub.a R1.sub.1-a-b T1.sub.b (Ni.sub.1-x M6.sub.x).sub.z (14)
wherein R1 is at least one element selected from rare earth elements (including Y); T1 is at least one element selected from the group consisting of Ca, Ti, Zr and Hf; M6 is at least one element selected from the group consisting of Co, Mn, Fe, Al, Ga, Zn, Sn, Cu, Si, B, Nb, W, Mo, V, Cr, Ta, P and S; and a, b, x and z are respectively a number satisfying conditions: ##EQU8##
The term "principal phase" noted above denotes a crystal phase in the alloy which is highest in existing ratio.
The .delta. is desirably 5 and should fall within a range of between 4.8 and 5.2.
The determination in quantity of the principal phase, a crystal phase having a CaCu.sub.5 type crystal structure, and a crystal phase having a MgCu.sub.2 type crystal structure can be performed by taking the pictures of the secondary electronic image and the back scattered electronic image by making use of a scanning electronic microscope (SEM), and then by performing the component analysis of each phase by making use of an EDX analyzer (Energy Dispersive X-ray Spectrometer) of transmission electron microscope. By further performing an X-ray analysis of the alloy, the crystal type of each phase can be further confirmed.
The reason for limiting the quantity of each crystal phase is as explained below. Namely, an alloy containing, as a principal phase, a crystal phase where values of "a" and "z" in the general formula (14) do not meet the aforementioned formula (II) is poor in hydrogen absorption/desorption characteristics. Further, it contains a crystal phase where the values of "a" and "z" in the general formula (14) meet the aforementioned formula (II), the alloy will be poor in hydrogen absorption quantity if containing more than 20% by volume of a crystal phase having a CaCu.sub.5 type crystal structure. On the other hand, it contains a crystal phase where the values of "a" and "z" in the general formula (14) meet the aforementioned formula (II), the alloy will be poor in hydrogen desorption property if containing more than 10% by volume of a crystal phase having a MgCu.sub.2 type crystal structure. More preferably, the content of the crystal phase having a CaCu.sub.5 type crystal structure in the alloy should be not more than 10% by volume. On the other hand, the content of the crystal phase having a MgCu.sub.2 type crystal structure in the alloy should more preferably be not more than 5% by volume.
Specific examples of the element R1 in the general formula (12) may be the same as explained with reference to the aforementioned first alloy. When the R1 contains La, the content of La in the R1 should preferably be 50 wt % or more.
It is possible, by substituting T1 for a portion of the R1, to improve the property of the alloy such as the hydrogen desorption rate without greatly decreasing the hydrogen absorption quantity of the alloy, and at the same time, to suppress the pulverization of the alloy resulting from the absorption and desorption of hydrogen.
However, when the value of (b) exceeds over 0.3, the aforementioned effects, i.e. the improvement of desorption property and the suppression of pulverization cannot be realized, thus deteriorating the discharge capacity of the secondary battery. There is a tendency that the smaller the value of (b) is, the longer the charge/discharge cycle life would become. In view of ensuring a long cycle life therefore, the value of (b) should preferably be 0.2 or less.
It is possible to improve the hydrogen absorption/desorption property of the alloy such as the hydrogen absorption/desorption rate by substituting M6 for a portion of the Ni. This may be attributed to the facts that the diffusion of hydrogen penetrated into the alloy as well as the absorption/desorption of hydrogen can be facilitated by the substitution of the M6 for a portion of the Ni. Further, it is possible, when a metal oxide-hydrogen secondary battery is fabricated using a negative electrode containing this alloy, to prominently improve the charge/discharge cycle life of the battery.
However, if the value of (x) is more than 0.6, it will lead to a deterioration of discharge capacity in the secondary battery, so that the range of (x) should preferably be 0.ltoreq.x.ltoreq.0.6. A more preferable range of the (x) is 0.01.ltoreq.y.ltoreq.0.5.
This fourteenth hydrogen-absorbing alloy may contain an element such as C, N, O or F as an impurity as far as the content of such an element is within a range which does not hinder the property of the alloy. However, it is preferable that the content of these impurities should be not more than 1 wt % respectively.
This fourteenth hydrogen-absorbing alloy can be manufactured by means of a casting method, a sintering method, a melt-quenching method such as a single roll method or a double roll method, an ultra-quenching method such as a gas-atomizing method. The alloy thus obtained is then preferably heat-treated in the same manner as explained with reference to the aforementioned first hydrogen-absorbing alloy.
If the hydrogen-absorbing alloy according to this invention is to be manufactured by means of the melt-quenching method or the ultra-quenching method, the R1 should preferably contain less than 20 wt % of Ce. Because, if the content of Ce in the R1 is 20 wt % or more, either the quantity of the crystal phase having a CaCu.sub.5 type crystal structure in the alloy may become higher than 20% by volume, or the quantity of the crystal phase having a MgCu.sub.2 type crystal structure in the alloy may become higher than 10% by volume.
The alloy composition which can be manufactured by means of the melt-quenching method or the ultra-quenching method, i.e. the allowable range of Ce content in the R1 would be influenced depending on the kind and quantity of substituting element to be included in the Ni site. For example, when Co is included as a substituting element in the Ni site, the acceptable limit of Ce content in the R1 is likely to be expanded with an increase in Co content. Specifically, when the Co content (x) is 0.2, the Ce content in the R1 can be less than 45 wt %.
This invention will be explained further with reference to FIG. 2 showing a cylindrical metal oxide-hydrogen secondary battery embodying a secondary battery of this invention.
Referring to FIG. 2, a bottomed cylindrical case 1 is accommodated therein with an electrode group 5 which has been manufactured by stacking a positive electrode 2, a separator 3 and a negative electrode 4, and then by spirally winding the stacked body. The negative electrode 4 is disposed at the outermost periphery of the electrode group 5 so as to electrically contact with the cylindrical case 1. The cylindrical case 1 contains an alkaline electrolyte. A first sealing plate 7 formed of a disk having an opening 6 at the center is disposed on the upper opening of the cylindrical case 1. An insulating gasket 8 having a ring-like shape is interposed between the periphery of the first sealing plate 7 and the upper inner wall surface of the opening of the cylindrical case 1. The peripheral fringe portion of the opening of the cylindrical case 1 is caulked inward so that the first sealing plate 7 is hermetically fixed via the gasket 8 to cylindrical case 1. The positive electrode lead 9 is connected through its one end to the positive electrode 2 and through its other end to the lower surface of the first sealing plate 7. A positive electrode terminal 10 having a hat-like shape is mounted over the first sealing plate 7 in such a manner as to cover the opening 6. A rubber safety valve 11 is disposed in a space surrounded by the first sealing plate 7 and the positive electrode terminal 10 in such a manner as to seal the opening 6. A holding plate 12 formed of an insulating disk having an opening at the center is disposed over the positive electrode terminal 10 in such a manner that the projected portion of the positive electrode terminal 10 is protruded out through the opening of the holding plate 12. An envelope tube 13 is disposed to cover all of the periphery of the holding plate 12, the side wall of the cylindrical case 1 and the periphery of the bottom of the cylindrical case 1.
Next, the details of the positive electrode 2, the negative electrode 4, the separator 3 and the electrolyte will be explained.
(1) The Positive Electrode 2
This positive electrode 2 can be manufactured by adding a conductive material to an active material, i.e. nickel hydroxide powder, and the resultant mixture is kneaded together with a polymeric binder and water to prepare a paste, which is then stuffed into an electroconductive substrate and, after being dried, molded into a predetermined shape.
The nickel hydroxide powder may contain at least one oxide or hydroxide of metal selected from the group consisting of zinc and cobalt.
As for the conductive material, cobalt oxide, cobalt hydroxide, metallic cobalt, metallic nickel and carbon can be used.
Examples of binder are carboxymethyl cellulose, methyl cellulose, sodium polyacrylate, polytetrafluoroethylene and polyvinyl alcohol (PVA).
The electroconductive substrate may be formed of a mesh-like, sponge-like, fibrous or felt-like metallic porous body which is made of a metal such as nickel, stainless steel or a nickel-plated metal.
(2) The Negative Electrode 4
This negative electrode 4 can be manufactured by the following methods (1) and (2).
(1) A conductive material is added at first to a hydrogen-absorbing alloy powder and then kneaded together with a binder and water to prepare a paste, which is then stuffed into an electroconductive substrate and, after being dried, molded into a predetermined shape, thereby forming the negative electrode.
(2) A conductive material is added at first to a hydrogen-absorbing alloy powder and then kneaded together with a binder to prepare a mixed material, which is then stuffed into an electroconductive substrate and, after being dried, molded into a predetermined shape, thereby forming the negative electrode.
As for the hydrogen-absorbing alloy, at least one of the aforementioned first to fourteenth hydrogen-absorbing alloys can be employed. As for the pulverizing method of the hydrogen-absorbing alloy, a mechanical pulverizing method such as a ball mill, a pulverizer, a jet mill, etc. or a method of allowing the alloy to absorb and desorb a high pressure hydrogen, whereby effecting an expansion of volume in the alloy, thus pulverizing the alloy may be employed.
The particle distribution of this hydrogen-absorbing alloy powder should preferably be such that particles having a particle diameter of 100 .mu.m or more is less than 10 wt %, and particles having a particle diameter of 10 .mu.m or less is less than 15 wt %, and an average diameter thereof is 35 to 55 .mu.m. It is possible with a hydrogen-absorbing alloy powder having such a particle distribution to perform the activation thereof within a short period of time and at the same time, to realize a metal oxide-hydrogen secondary battery having a long charge/discharge cycle life.
As for the binder, the same materials as employed for the positive electrode 2 can be used. By the way, if this negative electrode is to be manufactured by making use of the aforementioned item (2), it is preferable to employ a binder containing polytetrafluoroethylene (PTFE).
As for the conductive material, carbon black for example can be used.
The electroconductive substrate may be formed from a two-dimensional substrate such as a punched metal, an expanded metal and a nickel net; or a three-dimensional substrate such as a felt-like metallic porous body or a sponge-like metallic substrate.
(3) The Separator 3
The separator 3 may be formed of a nonwoven fabric such as a polypropylene nonwoven fabric, a nylon nonwoven fabric or a nonwoven fabric comprising polypropylene fiber and nylon fiber. In particular, a polypropylene nonwoven fabric treated to have a hydrophilic surface is preferable as a separator.
(4) Alkaline Electrolyte
Examples of the alkaline electrolyte which are useful in this invention include an aqueous solution of sodium hydroxide (NaOH), an aqueous solution of lithium hydroxide (LiOH), an aqueous solution of potassium hydroxide (KOH), a mixed solution of sodium hydroxide (NaOH) and lithium hydroxide (LiOH), a mixed solution of potassium hydroxide (KOH) and lithium hydroxide (LiOH), and a mixed solution of NaOH, KOH and LiOH.
Although this invention has been explained about a cylindrical alkaline secondary battery, it is also possible according to this invention to apply it to a rectangular alkaline secondary battery, wherein a closed-end rectangular case is accommodated therein with an electrode group consisting of a laminated body comprising positive electrodes and negative electrodes which are alternately superimposed one upon another with a separator being interposed therebetween, and with an alkali electrolyte.
The first hydrogen-absorbing alloy according to this invention contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot and the alloy ingot is represented by the general formula (1). It is possible with this hydrogen-absorbing alloy to increase the hydrogen equilibrium pressure of the alloy, and at the same time, to improve the hydrogen absorption/desorption rate.
Accordingly, a secondary battery which comprises a negative electrode comprising hydrogen-absorbing alloy particles containing a pulverized product of the alloy ingot is capable of enhancing the working voltage thereof, whereby the discharge capacity thereof can be remarkably enhanced and the charge/discharge cycle life thereof can be improved. Furthermore, the discharge characteristic at high temperatures of the secondary battery can also be improved.
The second hydrogen-absorbing alloy according to this invention contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot and the alloy ingot is represented by the general formula (2). It is possible with this hydrogen-absorbing alloy to improve the hydrogen absorption/desorption rate.
Accordingly, a secondary battery which comprises a negative electrode comprising hydrogen-absorbing alloy particles containing a pulverized product of the alloy ingot is capable of prominently enhancing the charge/discharge cycle life thereof. Furthermore, the discharge characteristic at high temperatures of the secondary battery can also be improved.
The third hydrogen-absorbing alloy according to this invention contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot and the alloy ingot is represented by the general formula (3). It is possible with this hydrogen-absorbing alloy to prominently improve the hydrogen absorption/desorption rate, and at the same time, to increase the hydrogen equilibrium pressure of the alloy.
Accordingly, a secondary battery which comprises a negative electrode comprising hydrogen-absorbing alloy particles containing a pulverized product of the alloy ingot is capable of prominently enhancing both of the discharge capacity and the charge/discharge cycle life. At the same time, the discharge characteristic at high temperatures of the secondary battery can also be improved.
The fourth hydrogen-absorbing alloy according to this invention contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot and the alloy ingot is represented by the general formula (4). It is possible with this hydrogen-absorbing alloy to improve the hydrogen absorption/desorption property thereof, and in particular, to prominently improve the hydrogen absorption/desorption rate of the alloy.
Accordingly, a secondary battery which comprises a negative electrode comprising hydrogen-absorbing alloy particles containing a pulverized product of the alloy ingot is large in discharge capacity and is capable of improving the charge/discharge cycle life.
The fifth hydrogen-absorbing alloy according to this invention contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot and the alloy ingot is represented by the general formula (5). It is possible with this hydrogen-absorbing alloy to improve the hydrogen absorption/desorption property thereof, and in particular, to prominently improve the hydrogen absorption/desorption rate of the alloy.
Accordingly, a secondary battery which comprises a negative electrode comprising hydrogen-absorbing alloy particles containing a pulverized product of the alloy ingot is capable of prominently improving the discharge capacity and the charge/discharge cycle life.
The sixth hydrogen-absorbing alloy according to this invention contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot and the alloy ingot is represented by the general formula (6). Since a portion of nickel component is substituted by Co in this hydrogen-absorbing alloy, it is possible to prominently improve the hydrogen absorption/desorption property such as the hydrogen absorption/desorption rate of the alloy. At the same time, the quantity of hydrogen absorption in the plateau region can be stabilized.
Accordingly, a secondary battery which comprises a negative electrode comprising hydrogen-absorbing alloy particles containing a pulverized product of the alloy ingot is capable of stabilizing the voltage at the discharging, thus making it possible to realize a large discharge capacity and an improved charge/discharge cycle life of the battery.
The seventh hydrogen-absorbing alloy according to this invention contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot and the alloy ingot is represented by the general formula (7). According to this hydrogen-absorbing alloy, it is possible to prominently improve the hydrogen absorption/desorption property such as the hydrogen absorption/desorption rate of the alloy. At the same time, the quantity of hydrogen absorption in the plateau region can be stabilized.
Accordingly, a secondary battery which comprises a negative electrode comprising hydrogen-absorbing alloy particles containing a pulverized product of the alloy ingot is capable of stabilizing the voltage at the discharging, thus making it possible to realize a large discharge capacity and an improved charge/discharge cycle life of the battery.
The eighth hydrogen-absorbing alloy according to this invention contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot and the alloy ingot is represented by the general formula (8). Since a portion of Mg component is substituted by La in this hydrogen-absorbing alloy, it is possible to enhance the hydrogen equilibrium pressure to a desired value and at the same time, to prominently improve the hydrogen absorption/desorption property of the alloy. At the same time, the quantity of hydrogen absorption in the plateau region can be stabilized.
Accordingly, a secondary battery which comprises a negative electrode comprising hydrogen-absorbing alloy particles containing a pulverized product of the alloy ingot is capable of improving the working voltage, so that it is possible to improve the discharge capacity and charge/discharge cycle life of the battery.
The ninth hydrogen-absorbing alloy according to this invention contains an alloy ingot manufactured by means of a casting or sintering method or a pulverized product of the alloy ingot and the alloy ingot is represented by the general formula (9). Since a predetermined quantity of rare earth element component R1 is substituted by La and at the same time, a predetermined quantity of Ni component is substituted by M3 in this hydrogen-absorbing alloy, it is possible to improve all of the hydrogen equilibrium pressure, the hydrogen absorption/desorption property and the corrosion resistance of the alloy.
Accordingly, a secondary battery which comprises a negative electrode comprising hydrogen-absorbing alloy particles containing a pulverized product of the alloy ingot is capable of prominently improving the charge/discharge cycle life owing to the synergistic effects by the rare earth element component R1 containing La and by the Ni component containing M3.
The tenth hydrogen-absorbing alloy according to this invention contains an alloy represented by the general formula (10). Since the Ce content in the R2 is less than 20 wt %, it is possible to improve the corrosion resistance thereof while ensuring an excellent crystal structure, and at the same time, to maintain an excellent hydrogen absorption/desorption property even in a high temperature environment.
Accordingly, it is possible, with a secondary battery comprising a negative electrode containing this hydrogen-absorbing alloy, to realize a high capacity and long life even in a high temperature environment.
Further, when La is included as the R2 in this tenth hydrogen-absorbing alloy and the La content in the R2 is larger than 70 wt %, the hydrogen absorption/desorption quantity can be improved without sacrificing the corrosion resistance of the alloy.
Accordingly, a secondary battery comprising a negative electrode containing this alloy is capable of prominently improving the discharge capacity and charge/discharge cycle life.
The eleventh hydrogen-absorbing alloy according to this invention contains an alloy represented by the general formula (11). According to this hydrogen-absorbing alloy, since the upper limit of the Ce content is limited depending on the Co content according to the aforementioned formula (I), it is possible to improve the corrosion resistance of the alloy while maintaining a preferable crystal structure, and to assure an excellent hydrogen absorption/ desorption property even in a high temperature environment.
Accordingly, it is possible, with a secondary battery comprising a negative electrode containing this hydrogen-absorbing alloy, to realize a high capacity and long life even in a high temperature environment.
The twelfth hydrogen-absorbing alloy according to this invention comprises an alloy represented by the general formula (12). The alloy contains a principal phase having a composition where the a and z in the general formula (12) meet the formula (II), and have a plane defect in the principal phase which is not more than 20 in number per 100 nm. Accordingly, it is possible to ensure a high hydrogen absorption quantity and at the same time, to overcome the problem that hydrogen is hardly desorbed. As a result, it is possible to prominently improve the hydrogen absorption/desorption property such as the hydrogen absorption/desorption rate.
Accordingly, it is possible, with a secondary battery comprising a negative electrode containing this hydrogen-absorbing alloy, to realize a high capacity and an improved charge/discharge cycle property thereof.
The thirteenth hydrogen-absorbing alloy according to this invention comprises an alloy represented by the general formula (13). The alloy contains a principal phase having a composition where the a and z in the general formula (13) meet the formula (II), and more than 70% by volume of crystal grains where the number of the plane defect therein is not more than 20 per 100 nm. Accordingly, it is possible to ensure a high hydrogen absorption quantity and at the same time, to overcome the problem that hydrogen is hardly desorbed. As a result, it is possible to prominently improve the hydrogen absorption/desorption property such as the hydrogen absorption/desorption rate.
Accordingly, it is possible, with a secondary battery comprising a negative electrode containing this hydrogen-absorbing alloy, to realize a high capacity and an improved charge/discharge cycle property.
The fourteenth hydrogen-absorbing alloy according to this invention comprises an alloy represented by the general formula (14). The alloy contains a principal phase having a composition where the a and z in the general formula (14) meet the formula (II), not more than 20% by volume of a crystal phase having a CaCu.sub.5 type crystal structure and not more than 10% by volume of a crystal phase having a MgCu.sub.2 type crystal structure. Accordingly, this hydrogen-absorbing alloy can improve the hydrogen absorption/desorption property such as the hydrogen absorption/desorption rate.
Accordingly, it is possible, with a secondary battery comprising a negative electrode containing this hydrogen-absorbing alloy, to realize a high capacity and an improved charge/discharge cycle property.
Furthermore, when the content of the crystal phase having a CaCu.sub.5 type crystal structure is not more than 10% by volume, and at the same time, the content of the crystal phase having a MgCu.sub.2 type crystal structure is not more than 5% by volume in this fourteenth hydrogen-absorbing alloy, the hydrogen absorption/desorption characteristic of the alloy can be prominently improved, in particular, the cycle characteristic of the alloy can be prominently improved. Accordingly, it is possible to realize a metal oxide-hydrogen secondary battery which is prominently improved in both discharge capacity and charge/discharge cycle life.
Followings are preferred embodiments of this invention.
FIG. 3 is a schematic view illustrating a temperature scanning type hydrogen absorption/desorption property-evaluating apparatus employed in the evaluation of hydrogen-absorbing alloys obtained in the following Examples and Comparative Examples. Referring to FIG. 3, a hydrogen gas cylinder 31 is connected via a pipe 32 to a test sample vessel 33. The middle portion of the pipe 32 is branched, and a distal end of the branched pipe 34 is connected to a vacuum pump 35. A manometer 36 is mounted on a pipe portion 34a branched from the branched pipe 34. On the pipe 32 interposed between the hydrogen gas cylinder 31 and the test sample vessel 33, there are mounted a first valve 37.sub.1 and a second valve 37.sub.2 in the mentioned order starting from the hydrogen gas cylinder 31. A pressure accumulator 38 is attached to a portion of the pipe 32 which is located between the first valve 37.sub.1 and the second valve 37.sub.2. Further, the vacuum pump 35 is connected via a third valve 37.sub.3 with the branched pipe 34a.
The test sample vessel 33 is provided with a heater 39. A thermocouple 40 is disposed inside the test sample vessel 33. A temperature controller 42 to be controlled by a computer 41 is connected to the thermocouple 40 as well as to the heater 39 so as to control the temperature of the heater 39 on the basis of a temperature detected from the thermocouple 40. A recorder 43 to be controlled by the computer 41 is connected to the manometer 36 as well as to the temperature controller 42.
Examples 1-8 and Comparative Examples 1-2
Each element was weighed so as to obtain the compositions shown in Table 1 shown below, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere, thereby preparing various kinds of hydrogen-absorbing alloy ingot. These alloy ingots were respectively pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 125 .mu.m or less.
Comparative Example 3
Each element was weighed so as to obtain the composition shown in Table 1 shown below, and the resultant composition was melted in an induction furnace filled with an argon gas atmosphere, thereby preparing an alloy ingot.
Then, the alloy ingot was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 890.degree. C. for 12 hours in an argon atmosphere and then pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 125 .mu.m or less.
Then, each of these hydrogen-absorbing alloys according to Examples 1-8 and Comparative Examples 1-3 was charged into the test sample vessel 33 (ambient temperature: 80.degree. C.) shown in FIG. 3. Thereafter, the first valve 37.sub.1 was closed, and both of the second valve 37.sub.2 and the third valve 37.sub.3 were opened. Under this condition, the vacuum pump 35 was actuated to exhaust the air in each of the pipe 32, the branched pipe 34 and the pressure accumulator 38. Then, after the second valve 37.sub.2 and the third valve 37.sub.3 are closed, the first valve 37.sub.1 was opened to supply hydrogen from the hydrogen gas cylinder 31 to each of the pipe 32, the branched pipe 34 and the pressure accumulator 38 thereby carrying out a hydrogen displacement of them. Subsequently, the first valve 37.sub.1 was closed and at the same time, the quantity of hydrogen introduced was calculated from the pressures of the system indicated by the manometer 36. Thereafter, the second valve 37.sub.2 was opened thereby feeding hydrogen to the test sample vessel 33, and the temperature thereof was monitored with the thermocouple 40. Then, the temperature of the test sample vessel 33 was kept constant by controlling the computer 41 and the temperature controller 42. At the same time, a change in pressure if any within the test sample vessel 33 was detected by means of the manometer 36 and recorded in the recorder 43.
The quantity of hydrogen (H/M) that was absorbed in each of the hydrogen-absorbing alloys during a time period of one hour after the introduction of a fixed amount of hydrogen into the test sample vessel 33 was measured by detecting the pressure change inside the test sample vessel 33, the results being shown as a hydrogen absorption rate (H/M.multidot.h.sup.-1) in the following Table 1.
TABLE 1______________________________________ Hydrogen absorption rate Hydrogen absorbing alloy (H/M .multidot. h.sup.-1)______________________________________Comparative Mg.sub.0.5 La.sub.0.5 Ni.sub.2 0.3Example 1Comparative Mg.sub.0.03 La.sub.0.02 Al.sub.0.95 Ni.sub.2 0.01Example 2Comparative Mg.sub.0.35 La.sub.0.3 Ce.sub.0.3 Ta.sub.0.05 Ni.sub.3 0.42Example 3Example 1 Mg.sub.4 La.sub.0.55 Al.sub.0.05 Ni.sub.3.02 1.15Example 2 Mg.sub.3 La.sub.0.6 Ag.sub.0.1 Ni.sub.3.4 1.08Example 3 Mg.sub.0.27 La.sub.0.6 Y.sub.0.03 V.sub.0.05 Mo.sub.0.05 Ni.sub.3.15 0.95Example 4 Mg.sub.0.34 Lm.sub.0.56 Nb.sub.0.03 Sn.sub.0.07 Ni.sub.3.38 1.05Example 5 Mg.sub.0.25 Lm.sub.0.65 Si.sub.0.02 Ga.sub.0.08 Ni.sub.3.21 1.06Example 6 Mg.sub.0.23 Lm.sub.0.76 V.sub.0.01 Ni.sub.3.6 1.05Example 7 Mg.sub.0.23 Lm.sub.0.76 V.sub.0.01 Ni.sub.3.8 0.92Example 8 Mg.sub.0.35 La.sub.0.3 Ce.sub.0.3 Ta.sub.0.05 Ni.sub.3 0.85______________________________________
As apparent from Table 1, the hydrogen-absorbing alloys according to Examples 1 to 8 which were manufactured by means of a casting method and represented by the general formula (1) indicated a higher hydrogen absorption rate at a temperature of 80.degree. C. as compared with the hydrogen-absorbing alloys according to Comparative Examples 1 to 3.
The reason for the low hydrogen absorption rate which was indicated by the hydrogen-absorbing alloy according to Comparative Example 1 can be attributed to the fact that the hydrogen-absorbing alloy according to Comparative Example 1 was La.sub.1-x Mg.sub.x Ni.sub.2 type alloy. On the other hand, although the hydrogen-absorbing alloy according to Comparative Example 3 had a composition which was similar to those of Example 8, the hydrogen-absorption rate thereof was lower as compared with those of Example 8, because the hydrogen-absorbing alloy according to Comparative Example 3 was manufactured by means of a melt-quenching method.
(Examples 9-15 and Comparative Example 4)
Each element was weighed so as to obtain the compositions shown in Table 2 shown below, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere, thereby preparing various kinds of hydrogen-absorbing alloy ingot. These alloy ingots were respectively pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 125 .mu.m or less.
Comparative Example 5
Each element was weighed so as to obtain the composition shown in Table 2 shown below, and the resultant composition was melted in an induction furnace filled with an argon gas atmosphere, thereby preparing an alloy ingot.
Then, the alloy ingot was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 890.degree. C. for 12 hours in an argon atmosphere and then pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 125 .mu.m or less.
The hydrogen absorption rate (H/M.multidot.h.sup.-1) at a temperature of 80.degree. C. of these hydrogen Examples 9-15 and Comparative Examples 4 and 5 was measured in the same manner as described above, the results being shown in the following Table 2.
TABLE 2______________________________________ Hydrogen absorption rate Hydrogen absorbing alloy (H/M .multidot. h.sup.-1)______________________________________Comparative Mg.sub.0.95 La.sub.0.05 (Ni.sub.0.98 Mn.sub.0.02).sub.2 0.06Example 4Comparative Mg.sub.0.35 Mm.sub.0.65 (Ni.sub.0.88 Cu.sub.0.1 Zn.sub.0.02).sub. 3.42 0.42Example 5Example 9 Mg.sub.0.25 La.sub.0.65 Ce.sub.0.1 (Ni.sub.0.9 Cr.sub.0.1).sub.3. 54 0.95Example 10 Mg.sub.0.3 Lm.sub.0.7 (Ni.sub.0.9 Cr.sub.0.05 Cu.sub.0.05).sub.3. 15 0.97Example 11 Mg.sub.0.28 Lm.sub.0.72 (Ni.sub.0.94 Cr.sub.0.05 Fe.sub.0.01).sub .3.32 0.91Example 12 Mg.sub.0.31 Lm.sub.0.69 (Ni.sub.0.76 Co.sub.0.2 Mn.sub.0.04).sub. 3.02 0.90Example 13 Mg.sub.0.35 Mm.sub.0.65 (Ni.sub.0.88 Cu.sub.0.1 Zn.sub.0.02).sub. 3.42 0.93Example 14 Mg.sub.0.24 La.sub.0.56 Pr.sub.0.2 (Ni.sub.0.85 Mn.sub.0.1 Fe.sub.0.05).sub.3.6 0.90Example 15 Mg.sub.0.24 La.sub.0.56 Pr.sub.0.2 (Ni.sub.0.85 Mn.sub.0.1 Fe.sub.0.05).sub.3.8 0.78______________________________________
As apparent from Table 2, the hydrogen-absorbing alloys according to Examples 9 to 15 which were manufactured by means of a casting method and represented by the general formula (2) indicated a higher hydrogen absorption rate at a temperature of 80.degree. C. as compared with the hydrogen-absorbing alloys according to Comparative Examples 4 and 5.
Although the hydrogen-absorbing alloy according to Comparative Example 5 had a composition which was similar to those of Example 13, the hydrogen-absorption rate thereof was lower as compared with those of Example 13, because the hydrogen-absorbing alloy according to Comparative Example 5 was manufactured by means of a melt-quenching method.
Examples 16-22 and Comparative Examples 6-8
Each element was weighed so as to obtain the compositions shown in Table 3 shown below, and the resultant compositions were sintered in an argon gas atmosphere and then heat-treated at a temperature close to the melting point thereof, thereby preparing various kinds of hydrogen-absorbing alloy ingot. These alloy ingots were respectively pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 75 .mu.m or less.
Comparative Example 9
Each element was weighed so as to obtain the composition shown in Table 3 shown below, and the resultant composition was melted in an induction furnace filled with an argon gas atmosphere, thereby preparing an alloy ingot.
Then, the alloy ingot was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 890.degree. C. for 12 hours in an argon atmosphere and then pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 75 .mu.m or less.
The hydrogen absorption rate (H/M.multidot.h.sup.-1) at a temperature of 80.degree. C. of these hydrogen Examples 16-22 and Comparative Examples 6 to 9 was measured in the same manner as described above, the results being shown in the following Table 3.
TABLE 3______________________________________ Hydrogen absorption rate Hydrogen absorbing alloy (H/M .multidot. h.sup.-1)______________________________________Comparative Mg.sub.0.67 La.sub.0.33 Ni.sub.3 0.5Example 6Comparative Mg.sub.0.02 La.sub.0.02 Si.sub.0.96 Ni.sub.2.6 Cu.sub.0.4 0.1Example 7Comparative Mg.sub.0.65 La.sub.0.25 Si.sub.0.1 Ni.sub.0.1 Cr.sub.2.9 0.1Example 8Comparative Mg.sub.0.4 Ce.sub.0.3 In.sub.0.2 P.sub.0.1 Ni.sub.1.9 Cu.sub.1.1 Zn.sub.0.3 0.3Example 9Example 16 Mg.sub.0.67 La.sub.0.23 Al.sub.0.1 Ni.sub.2.5 Co.sub.0.5 1.2Example 17 Mg.sub.0.57 Lm.sub.0.33 Ag.sub.0.2 Ni.sub.2.2 Mn.sub.0.8 1.1 (Lm; La: 84 at %, Ce: 10 at %, Pr: 1 at %, Nd: 5 at %)Example 18 Mg.sub.0.5 Sm.sub.0.3 Pb.sub.0.15 C.sub.0.05 Ni.sub.2.5 Cr.sub.0. 8 0.8Example 19 Mg.sub.0.4 Nd.sub.0.4 Ta.sub.0.1 Ge.sub.0.07 B.sub.0.03 Ni.sub.2. 3 Fe.sub.1.1 1.0Example 20 Mg.sub.0.4 Ce.sub.0.3 In.sub.0.2 P.sub.0.1 Ni.sub.1.9 Cu.sub.1.1 Zn.sub.0.3 0.9Example 21 Mg.sub.0.25 La.sub.0.63 Nd.sub.0.1 Al.sub.0.02 Ni.sub.3.5 Cr.sub.0.1 1.1Example 22 Mg.sub.0.25 La.sub.0.63 Nd.sub.0.1 Al.sub.0.02 Ni.sub.3.7 Cr.sub.0.1 0.8______________________________________
As apparent from Table 3, the hydrogen-absorbing alloys according to Examples 16 to 22 which were manufactured by means of a sintering method and represented by the general formula (3) indicated a higher hydrogen absorption rate at a temperature of 80.degree. C. as compared with the hydrogen-absorbing alloys according to Comparative Examples 6 to 9.
The reason for the low hydrogen absorption rate which was indicated by the hydrogen-absorbing alloy according to Comparative Example 6 can be attributed to the fact that the hydrogen-absorbing alloy according to Comparative Example 6 was La.sub.1-x Mg.sub.x Ni.sub.3 type alloy. On the other hand, although the hydrogen-absorbing alloy according to Comparative Example 9 had a composition which was similar to those of Example 20, the hydrogen-absorption rate thereof was lower as compared with those of Example 20, because the hydrogen-absorbing alloy according to Comparative Example 9 was manufactured by means of a melt-quenching method.
Examples 23-44 and Comparative Examples 10-13, 15, 17-18
Various kinds of mother alloys, i.e. an RNi.sub.5 -type alloy, an RNi.sub.3 -type alloy, an RNi.sub.2 -type alloy and an RNi-type alloy which are relatively high in melting point, and an MgNi.sub.2 -type alloy were prepared by making use of an induction furnace (an argon gas atmosphere). Then, each mother alloy was weighed to obtain a predetermined composition as shown in Tables 4 to 6 and then sintered in an argon atmosphere at high temperatures to obtain various alloy ingots, which were respectively pulverized to a particle diameter of 75 .mu.m or less.
Comparative Examples 14, 16 and 19
Each element was weighed so as to obtain the composition shown in the following Tables 4 to 6, and the resultant composition was melted in an induction furnace filled with an argon gas atmosphere, thereby preparing various kinds of alloy ingot.
Then, each alloy ingot was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 890.degree. C. for 12 hours in an argon atmosphere and then pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 75 .mu.m or less.
Electrodes were prepared according to the following procedures by making use of the hydrogen-absorbing alloy powders of Examples 23 to 44 and Comparative Examples 10 to 19. First of all, each hydrogen-absorbing alloy powder and electrolytic copper powder were mixed together at a ratio of 1:1. Then, 1 g of this mixture was press-molded for 5 minutes under a pressure of 10,000 kg by making use of a tablet molding machine (inner diameter: 10 mm) to produce a pellet. The resultant pellet was sandwiched between a pair of nickel meshes to form a composite, the periphery of which was then spot-welded. Thereafter, a nickel lead wire was further spot-welded thereby attaching it to the composite to produce an alloy electrode (a negative electrode).
Each of the negative electrodes thus obtained was immersed together with a sintered nickel electrode constituting a counter electrode in a 8N aqueous solution of potassium hydroxide whereby constituting a negative electrode capacity-controlled battery, and a charge/discharge cycle test was performed at a temperature of 250.degree. C. so as to measure the maximum discharge capacity and the cycle life (the number of cycle when the discharge capacity was lowered to 80% of the maximum discharge capacity). The charge/discharge conditions in this test were as follows. Namely, the secondary battery was subjected at first to a charging for 10 hours with a current of 100 mA per 1 g of the hydrogen-absorbing alloy, and, after 10 minute cessation, discharged with a current of 20 mA per 1 g of the hydrogen-absorbing alloy until the battery voltage (with respect to a mercury oxide electrode) was decreased down to -0.5V. This charge/discharge cycle was repeated. The results of this test are shown in the following Tables 4 to 6.
TABLE 4______________________________________ Maximum discharge capacity CycleHydrogen absorbing alloy (mAh/g) life______________________________________Comparative Mg.sub.0.5 La.sub.0.05 Ni.sub.2 45 10Example 10Comparative Mg.sub.0.67 La.sub.0.33 Ni.sub.3 100 15Example 11Comparative Mg.sub.0.5 La.sub.0.5 Ni.sub.3.5 150 20Example 12Comparative Mg.sub.0.03 La.sub.0.01 Ge.sub.0.96 Ni.sub.2 20 5Example 13Comparative Mg.sub.0.27 Mm.sub.0.53 Nb.sub.0.08 Sn.sub.0.12 Ni.sub.3.25 180 75Example 14 (Mm; La: 37.5 at %, Ce: 50.3 at %, Pr: 5.5 at %, Nd: 6.5 at %, Sm: 0.2 at %)Example 23 Mg.sub.0.33 La.sub.0.6 Al.sub.0.07 Ni.sub.3.02 360 295Example 24 Mg.sub.3 La.sub.0.5 Nd.sub.0.1 V.sub.0.07 Mo.sub.0.03 Ni.sub.3.4 365 320Example 25 Mg.sub.0.27 Mm.sub.0.53 Nb.sub.0.08 Sn.sub.0.12 Ni.sub.3.25 360 335 (Mm; La: 37.5 at %, Ce: 50.3 at %, Pr: 5.5 at %, Nd: 6.5 at %, Sm: 0.2 at %)Example 26 Mg.sub.0.4 La.sub.0.4 Ag.sub.0.2 Ni.sub.3.3 305 240Example 27 Mg.sub.0.25 La.sub.0.65 Ce.sub.0.1 Al.sub.0.02 Ni.sub.3.6 355 305Example 28 Mg.sub.0.25 La.sub.0.65 Ce.sub.0.1 Al.sub.0.02 Ni.sub.3.8 300 250______________________________________
TABLE 5______________________________________ Maximum discharge capacity CycleHydrogen absorbing alloy (mAh/g) life______________________________________Comparative Mg.sub.0.95 La.sub.0.05 (Ni.sub.0.98 Mn.sub.0.02).sub.2 20 20Example 15Comparative Mg.sub.0.35 Mm.sub.0.65 (Ni.sub.0.7 Cr.sub.0.1 Co.sub.0.2).sub.3.6 5 200 180Example 16Example 29 Mg.sub.0.4 La.sub.0.45 Ce.sub.0.15 (Ni.sub.0.9 Cr.sub.0.1).sub.3.5 4 320 280Example 30 Mg.sub.0.3 Lm.sub.0.7 (Ni.sub.0.9 Cr.sub.0.05 Cu.sub.0.05).sub.3.0 2 390 245Example 31 Mg.sub.0.27 Lm.sub.0.73 (Ni.sub.0.85 Cr.sub.0.1 Fe.sub.0.05).sub.3 .22 385 280Example 32 Mg.sub.0.35 Mm.sub.0.65 (Ni.sub.0.7 Cr.sub.0.1 Co.sub.0.2).sub.3.6 5 400 250Example 33 Mg.sub.0.5 Lm.sub.0.5 (Ni.sub.0.85 Cr.sub.0.05 Zn.sub.0.1).sub.3.1 5 270 300Example 34 Mg.sub.0.25 La.sub.0.55 Pr.sub.0.2 (Ni.sub.0.7 Co.sub.0.01 Cu.sub.0.1).sub.3.6 380 320Example 35 Mg.sub.0.25 La.sub.0.55 Pr.sub.0.2 (Ni.sub.0.7 Co.sub.0.2 Cu.sub.0.1).sub.3.8 320 280______________________________________
TABLE 6______________________________________ Maximum discharge capacity CycleHydrogen absorbing alloy (mAh/g) life______________________________________Comparative Mg.sub.0.5 La.sub.0.5 Ni.sub.2 45 10Example 10Comparative Mg.sub.0.67 La.sub.0.33 Ni.sub.3 100 15Example 11Comparative Mg.sub.0.5 La.sub.0.5 Ni.sub.3.5 150 20Example 12Comparative Mg.sub.0.02 La.sub.0.01 In.sub.0.97 Ni.sub.2.6 Cu.sub.0.4 20 10Example 17Comparative Mg.sub.0.7 La.sub.0.25 C.sub.0.05 Ni.sub.0.1 Fe.sub.2.9 50 15Example 18Comparative Mg.sub.0.4 Ce.sub.0.3 In.sub.0.2 P.sub.0.1 Ni.sub.1.9 Cu.sub.1.1 Zn.sub.0.03 100 75Example 19Example 36 Mg.sub.0.67 La.sub.0.23 Al.sub.0.1 Ni.sub.2.5 Co.sub.0.5 180 210Example 37 Mg.sub.0.57 Lm.sub.0.33 Ag.sub.0.01 Ni.sub.2.2 Mn.sub.0.8 195 200 (Lm; La: 84 at %, Ce: 10 at %, Pr: 1 at %, Nd: 5 at %)Example 38 Mg.sub.0.5 Sm.sub.0.3 Pb.sub.0.15 Co.sub.0.05 Ni.sub.2.5 Cr.sub.0. 8 250 150Example 39 Mg.sub.0.4 Nd.sub.0.4 Ta.sub.0.1 Ge.sub.0.07 B.sub.0.03 Ni.sub.2.3 Fe.sub.1.1 320 160Example 40 Mg.sub.0.4 Ce.sub.0.3 In.sub.0.2 P.sub.0.1 Ni.sub.1.9 Cu.sub.1.1 Zn.sub.0.03 330 170Example 41 Mg.sub.0.67 La.sub.0.23 Al.sub.0.1 Ni.sub.2.5 Cu.sub.1.2 175 110Example 42 Mg.sub.0.4 Gd.sub.0.3 Si.sub.0.25 B.sub.0.05 Ni.sub.1.9 Cr.sub.1.5 Fe.sub.0.03 295 120Example 43 Mg.sub.0.24 La.sub.0.74 Al.sub.0.02 Ni.sub.3.2 Co.sub.0.3 Cu.sub.0.1 365 320Example 44 Mg.sub.0.24 La.sub.0.74 Al.sub.0.02 Ni.sub.3.4 Co.sub.0.3 Cu.sub.0.1 320 250______________________________________
As apparent from Table 4, the nickel-hydrogen secondary batteries according to Examples 23 to 28 which were manufactured using a sintering method and a composition represented by the general formula (1) indicated more excellent properties in both maximum discharge capacity and charge/discharge cycle life as compared with the secondary batteries according to Comparative Examples 10 to 14. The reasons for poor performances in both discharge capacity and charge/discharge cycle life which were indicated by the secondary batteries according to Comparative Examples 10 to 12 can be attributed to the fact that the hydrogen-absorbing alloy constituting the negative electrode according to Comparative Examples 10 to 12 was either La.sub.1-x Mg.sub.x Ni.sub.2 type alloy or La.sub.1-x Mg.sub.x Ni.sub.3 type alloy. On the other hand, although the composition of the hydrogen-absorbing alloy contained in the negative electrode according to the secondary battery of Comparative Example 14 was similar to that of Example 25, both discharge capacity and charge/discharge cycle life were poor as compared with those of Example 25, because the hydrogen-absorbing alloy according to Comparative Example 14 was manufactured by means of a melt-quenching method.
As apparent from Table 5, the nickel-hydrogen secondary batteries according to Examples 29 to 35 which were manufactured using a sintering method and a composition represented by the general formula (2) indicated more excellent properties in both maximum discharge capacity and charge/discharge cycle life as compared with the secondary batteries according to Comparative Examples 15 and 16. Although the composition of the hydrogen-absorbing alloy contained in the negative electrode according to the secondary battery of Comparative Example 16 was similar to those of Example 32, both discharge capacity and charge/discharge cycle life were poor as compared with that of Example 32, because the hydrogen-absorbing alloy according to Comparative Example 16 was manufactured by means of a melt-quenching method.
As apparent from Table 6, the nickel-hydrogen secondary batteries according to Examples 36 to 44 which were manufactured using a sintering method and a composition represented by the general formula (3) indicated more excellent properties in both maximum discharge capacity and charge/discharge cycle life as compared with the secondary batteries according to Comparative Examples 10-12 and 17 to 19. Although the composition of the hydrogen-absorbing alloy contained in the negative electrode according to the secondary battery of Comparative Example 19 was similar to those of Example 40, both discharge capacity and charge/discharge cycle life were poor as compared with that of Example 40, because the hydrogen-absorbing alloy according to Comparative Example 19 was manufactured by means of a melt-quenching method.
Examples 45-55 and Comparative Examples 20-21
Each element was weighed so as to obtain the compositions shown in the following Table 7, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere, thereby obtaining 13 kinds of alloy ingot. Then, these ingots were subjected to a heat treatment in an argon atmosphere for 3 hours at a temperature of 950.degree. C. Subsequently, the alloy ingots were pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 150 .mu.m or less.
By the way, the misch metal (Lm) shown in Table 7 was composed of 84 at. % of La, 10 at. % of Ce, 1 at. % of Pr, 5 at. % of Nd and 0.2 at. % of Sm; while the misch metal (Mm) was composed of 27.5 at. % of La, 50.3 at. % of Ce, 5.5 at. % of Pr, 16.5 at. % of Nd and 0.2 at. % of Sm.
Each hydrogen absorbing alloy powder was then mixed with electrolytic copper powder at a ratio of 1:2 (weight ratio), and 1 g of the resultant mixture was pressed for 5 minutes with a pressure of 10 tons/cm.sup.2, thus obtaining 13 kinds of pellet each having a diameter of 12 mm. These pellets were sandwiched between Ni wire nettings, and the peripheral portion thereof was spot-welded and pressed. Subsequently, to this pressed body was connected Ni lead wires by means of spot-welding thereby preparing 13 kinds of hydrogen absorbing alloy electrode (a negative electrode).
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte) in a case, whereby assembling test cells (Examples 45-55, and Comparative Examples 20 to 21).
Comparative Example 22
A test cell was fabricated in the same manner as explained in Examples 45 to 55 except that the following hydrogen-absorbing alloy powder was employed in this example.
Namely, each element was weighed so as to obtain the composition shown in the following Table 7, and the resultant composition was melted in an induction furnace filled with an argon gas atmosphere, thereby preparing an alloy ingot.
Then, the alloy ingot was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 890.degree. C. for 12 hours in an argon atmosphere and then pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 150 .mu.m or less.
Then, the test cells according to Examples 45-55 and Comparative Examples 20-22 were subjected to a charge/discharge cycle test at a temperature of 25.degree. C. The charge/discharge conditions in this test were as follows. Namely, the secondary battery was subjected at first to a charging for 5 hours with a current of 100 mA per 1 g of the hydrogen-absorbing alloy, and, after 10 minute cessation, discharged with a current of 50 mA per 1 g of the hydrogen-absorbing alloy until the battery voltage (with respect to a mercury oxide electrode) was decreased down to -0.6V. This charge/discharge cycle was repeated so as to measure the maximum discharge capacity and the cycle life (the number of cycle when the discharge capacity was lowered to 80% of the maximum discharge capacity). The results of this test are shown in the following Table 7.
Furthermore, the hydrogen absorbing alloys of Examples 45-55 and Comparative Examples 20 to 22 were tested to measure, as a hydrogen absorption characteristic, a rechargeable hydrogen storage capacity (JIS H7003: Term for Hydrogen Absorbing Alloy) from the iso-thermal line of pressure-composition which was measured under a hydrogen pressure of less than 10 atm. at a temperature of 60.degree. C. by making use of Sieverts's method (JIS H7201). The results are shown in the following Table 7.
TABLE 7______________________________________ Compositions______________________________________Example 45 Mg.sub.0.31 La.sub.0.69 (Ni.sub.0.8 Co.sub.0.1 Al.sub.0.1).sub .3.2Example 46 Mg.sub.0.3 La.sub.0.5 Pr.sub.0.2 (Ni.sub.0.8 Mn.sub.0.15 Si.sub.0.05).sub.3.4Example 47 Mg.sub.0.27 La.sub.0.53 Nd.sub.0.2 (Ni.sub.0.8 Mn.sub.0.1 Co.sub.0.1).sub.3.05Example 48 Mg.sub.0.25 Lm.sub.0.75 (Ni.sub.0.85 Co.sub.0.1 Fe.sub.0.05).s ub.3.7Example 49 Mg.sub.0.24 Lm.sub.0.76 (Ni.sub.0.8 Mn.sub.0.15 Ga.sub.0.05).s ub.3.65Example 50 Mg.sub.0.34 Lm.sub.0.66 (Ni.sub.0.75 Co.sub.0.1 Mn.sub.0.1 Al.sub.0.05).sub.3.33Example 51 Mg.sub.0.25 Lm.sub.0.45 Pr.sub.0.3 (Ni.sub.0.68 Co.sub.0.2 Cu.sub.0.1 Zn.sub.0.02).sub.3.5Example 52 Mg.sub.0.28 Lm.sub.0.62 Nd.sub.0.1 (Ni.sub.0.84 Cu.sub.0.1 Sn.sub.0.05 B.sub.0.01).sub.3.3______________________________________ Discharge Rechargeable capacity hydrogen storage (mAh/g) Cycle life capacity (H/M)______________________________________Example 45 405 295 1.15Example 46 380 320 1.08Example 47 395 335 1.13Example 48 360 295 1.06Example 49 385 305 1.11Example 50 375 290 1.05Example 51 390 300 1.09Example 52 380 305 1.07______________________________________ Compositions______________________________________Example 53 Mg.sub.0.22 La.sub.0.78 (Ni.sub.0.74 Co.sub.0.1 Cu.sub.0.1 Mn.sub.0.05 Al.sub.0.01).sub.3.6Example 54 Mg.sub.0.22 La.sub.0.78 (Ni.sub.0.74 Co.sub.0.1 Cu.sub.0.1 Mn.sub.0.05 Al.sub.0.01).sub.3.8Example 55 Mg.sub.0.35 Mm.sub.0.65 (Ni.sub.0.75 Mn.sub.0.2 Al.sub.0.05).s ub.3.01Comparative Mg.sub.0.6 La.sub.0.4 Ni.sub.4.8 Al.sub.0.3Example 20Comparative Mg.sub.0.1 La.sub.0.8 Ce.sub.0.1 Ni.sub.1.1 Sn.sub.0.9Example 21Comparative Mg.sub.0.35 Mm.sub.0.65 (Ni.sub.0.75 Mn.sub.0.2 Al.sub.0.05).s ub.3.01Example 22______________________________________ Discharge Rechargeable capacity hydrogen storage (mAh/g) Cycle life capacity (H/M)______________________________________Example 53 365 300 1.02Example 54 330 260 0.95Example 55 300 250 0.81Comparative 50 150 0.15Example 20Comparative 60 100 0.20Example 21Comparative 180 120 0.43Example 22______________________________________
As apparent from Table 7, the hydrogen-absorbing alloys according to Examples 45 to 55 which were manufactured by means of a casting method and represented by the general formula (4) indicated a higher rechargeable hydrogen storage capacity as compared with the hydrogen-absorbing alloys according to Comparative Examples 20 to 22.
Further, the secondary batteries comprising a negative electrode containing any one of the hydrogen-absorbing alloys of Examples 45 to 55 indicated more excellent properties in both maximum discharge capacity and charge/discharge cycle life as compared with the secondary batteries comprising a negative electrode containing any one of the hydrogen-absorbing alloys of Comparative Examples 20 to 22.
Examples 56-65 and Comparative Examples 23-24
Each element was weighed so as to obtain the compositions shown in the Table 8, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere and then cast into a water-cooled copper mold, each melt cast in this manner being allowed to solidify to obtain various kinds of alloy ingot. Then, these ingots were subjected to a heat treatment in an argon atmosphere for 3 hours at a temperature of 950.degree. C. Subsequently, the alloy ingots were pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 150 .mu.m or less.
By the way, the misch metal (Lm) shown in Table 8 was composed of 90 at. % of La, 1 at. % of Ce, 6 at. % of Pr, 3 at. % of Nd; while the misch metal (Mm) was composed of 34 at. % of La, 50.8 at. % of Ce, 8 at. % of Pr, 7 at. % of Nd and 0.2 at. % of Sm.
Each hydrogen absorbing alloy powder was then mixed with electrolytic copper powder at a ratio of 1:3 (weight ratio), and 1 g of the resultant mixture was pressed for 8 minutes with a pressure of 8 tons/cm.sup.2, thus obtaining 12 kinds of pellet each having a diameter of 10 mm. These pellets were sandwiched between Ni wire nettings, and the peripheral portion thereof was spot-welded and pressed. Subsequently, to this pressed body was connected Ni lead wires by means of spot-welding thereby preparing 12 kinds of hydrogen absorbing alloy electrode (a negative electrode).
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 6N-KOH (electrolyte) in a case, whereby assembling test cells (Examples 56-65, and Comparative Examples 23-24).
Comparative Example 25
A test cell was fabricated in the same manner as explained in Examples 56 to 65 except that the following hydrogen-absorbing alloy powder was employed in this example.
Namely, each element was weighed so as to obtain the composition shown in the following Table 8, and the resultant composition was melted in an induction furnace filled with an argon gas atmosphere, thereby preparing an alloy ingot.
Then, the alloy ingot was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 890.degree. C. for 12 hours in an argon atmosphere and then pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 150 .mu.m or less.
Then, the test cells according to Examples 56-65 and Comparative Examples 23-25 were subjected to a charge/discharge cycle test at a temperature of 25.degree. C. The charge/discharge conditions in this test were as follows. Namely, the secondary battery was subjected at first to a charging for 3 hours with a current of 200 mA per 1 g of the hydrogen-absorbing alloy, and, after 10 minute cessation, discharged with a current of 100 mA per 1 g of the hydrogen-absorbing alloy until the battery voltage (with respect to a mercury oxide electrode) was decreased down to -0.55V. This charge/discharge cycle was repeated so as to measure the maximum discharge capacity and the cycle life (the number of cycle when the discharge capacity was lowered to 80% of the maximum discharge capacity). The results of this test are shown in the following Table 8.
Furthermore, the hydrogen absorbing alloys of Examples 56-65 and Comparative Examples 23 to 25 were tested to measure, as a hydrogen absorption characteristic, a rechargeable hydrogen storage capacity (JIS H7003: Term for Hydrogen Absorbing Alloy) from the isothermal line of pressure-composition which was measured under a hydrogen pressure of less than 10 atm. at a temperature of 45.degree. C. by making use of Sieverts's method (JIS H7201). The results are shown in the following Table 8.
TABLE 8______________________________________ Compositions______________________________________Example 56 La.sub.0.71 Mg.sub.0.28 Zr.sub.0.01 (Ni.sub.0.8 Co.sub.0.1 Mn.sub.0.08 Al.sub.0.02).sub.3.33Example 57 La.sub.0.57 Pr.sub.0.17 Mg.sub.0.25 Ti.sub.0.01 (Ni.sub.0.92 Co.sub.0.05 Mn.sub.0.02 Al.sub.0.01).sub.3.54Example 58 Lm.sub.0.75 Mg.sub.0.24 Hf.sub.0.01 (Ni.sub.0.72 Cu.sub.0.15 Mn.sub.0.05 Al.sub.0.01 Si.sub.0.01).sub.3.52Example 59 Lm.sub.0.69 Mg.sub.0.3 Ca.sub.0.01 (Ni.sub.0.84 Co.sub.0.1 Fe.sub.0.05 Al.sub.0.01).sub.3.12Example 60 Lm.sub.0.5 Mm.sub.0.24 Mg.sub.0.24 Zr.sub.0.02 (Ni.sub.0.84 Cu.sub.0.1 Mn.sub.0.05 Ga.sub.0.01).sub.3.6Example 61 Lm.sub.0.5 Mm.sub.0.24 Mg.sub.0.24 Zr.sub.0.02 (Ni.sub.0.84 Cu.sub.0.1 Mn.sub.0.05 Ga.sub.0.01).sub.3.8Example 62 Lm.sub.0.5 Mm.sub.0.25 Mg.sub.0.24 Ca.sub.0.01 (Ni.sub.0.65 Co.sub.0.25 Mn.sub.0.05 Zn.sub.0.05).sub.3.47Example 63 Lm.sub.0.58 Mg.sub.0.32 Zr.sub.0.1 (Ni.sub.0.68 Co.sub.0.1 Cu.sub.0.1 Mn.sub.0.1 Sn.sub.0.02).sub.3.23Example 64 Lm.sub.0.68 Mg.sub.0.27 Ca.sub.0.05 (Ni.sub.0.8 Cu.sub.0.1 Mn.sub.0.08 B.sub.0.01).sub.3.39Example 65 Mg.sub.0.6 Mg.sub.0.35 Zr.sub.0.05 (Ni.sub.0.89 Co.sub.0.01 Mn.sub.0.05 Cu.sub.0.05).sub.3.08Comparative La.sub.0.3 Mg.sub.0.7 (Ni.sub.0.1 Co.sub.0.6 Al.sub.0.3).sub.3.25Example 23Comparative La.sub.0.05 Mg.sub.0.3 Ca.sub.0.65 (Ni.sub.0.5 Mn.sub.0.5).sub.3. 58Example 24Comparative Mm.sub.0.6 Mg.sub.0.35 Zr.sub.0.05 (Ni.sub.0.89 Co.sub.0.01 Mn.sub.0.05 Cu.sub.0.05).sub.3.08Example 25______________________________________ Discharge Rechargeable capacity hydrogen storage (mAh/g) Cycle life capacity (H/M)______________________________________Example 56 365 350 0.98Example 57 370 330 1.00Example 58 360 345 0.97Example 59 355 340 0.97Example 60 345 360 0.95Example 61 315 290 0.85Example 62 350 360 0.96Example 63 340 375 0.94Example 64 370 350 1.01Example 65 305 300 0.83Comparative 40 25 0.14Example 23Comparative 160 12 0.75Example 24Comparative 220 120 0.78Example 25______________________________________
As apparent from Table 8, the hydrogen-absorbing alloys according to Examples 56 to 65 which were manufactured by means of a casting method and represented by the general formula (5) indicated a higher rechargeable hydrogen storage capacity as compared with the hydrogen-absorbing alloys according to Comparative Examples 23 to 25.
Further, the secondary batteries comprising a negative electrode containing any one of the hydrogen-absorbing alloys of Examples 56 to 65 indicated more excellent properties in both maximum discharge capacity and charge/discharge cycle life as compared with the secondary batteries comprising a negative electrode containing any one of the hydrogen-absorbing alloys of Comparative Examples 23 to 25.
Examples 66-68 and Comparative Example 26
Each element was weighed so as to obtain the compositions shown in the Table 9, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere and then cast into a water-cooled copper mold, each melt cast in this manner being allowed to solidify to obtain four kinds of alloy ingot. Then, these ingots were subjected to a heat treatment in an argon atmosphere for 3 hours at a temperature of 950.degree. C. Subsequently, the alloy ingots were pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 150 .mu.m or less.
By the way, the misch metal (Lm) shown in Table 9 was the same as explained with reference to Table 8.
Each hydrogen absorbing alloy powder was then treated in the same manner as in the cases of Examples 56-65, thereby preparing a hydrogen absorbing alloy electrode (a negative electrode).
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 6N-KOH (electrolyte) in a case, whereby assembling test cells (Examples 66-68, and Comparative Example 26).
Then, the test cells according to Examples 66-68 and Comparative Example 26 were subjected to a charge/discharge cycle test at a temperature of 25.degree. C. to measure the maximum discharge capacity and the cycle life (the number of cycle when the discharge capacity was lowered to 80% of the maximum discharge capacity). The results of this test are shown in the following Table 9. By the way, the conditions for this charge/discharge cycle test was the same as in the cases of Examples 56-65.
Furthermore, the hydrogen absorbing alloys of Examples 66-68 and Comparative Example 26 were tested to measure, as a hydrogen absorption characteristic, a rechargeable hydrogen storage capacity (JIS H7003: Term for Hydrogen Absorbing Alloy) from the iso-thermal line of pressure-composition which was measured under a hydrogen pressure of less than 10 atm. at a temperature of 45.degree. C. by making use of Sieverts's method (JIS H7201). The results are shown in the following Table 9.
TABLE 9__________________________________________________________________________ Recharge- able hydrogen Discharge storage capacity Cycle capacityCompositions (mAh/g) life (H/M)__________________________________________________________________________Example 66 Mg.sub.0.3 Lm.sub.0.65 Ca.sub.0.05 (Ni.sub.0.9 Fe.sub.0.05 Al.sub.0. 05).sub.3.12 360 350 1.00Example 67 Mg.sub.0.3 Lm.sub.0.6 Ca.sub.0.1 (Ni.sub.0.9 Fe.sub.0.05 Al.sub.0.05 ).sub.3.12 355 335 0.99Example 68 Mg.sub.0.3 Lm.sub.0.5 Ca.sub.0.2 (Ni.sub.0.9 Fe.sub.0.05 Al.sub.0.05 ).sub.3.12 345 290 0.98Comparative Mg.sub.0.3 Lm.sub.0.35 Ca.sub.0.35 (Ni.sub.0.9 Fe.sub.0.05 Al.sub.0. 05).sub.3.12 300 50 0.92Example 26__________________________________________________________________________
As apparent from Table 9, the hydrogen-absorbing alloys according to Examples 66-68 where the Ca content is 0.3 or less indicated a higher rechargeable hydrogen storage capacity as compared with the hydrogen-absorbing alloy according to Comparative Example 26 where the Ca content is more than 0.3.
Further, the secondary batteries according to Examples 66-68 indicated more excellent properties in both maximum discharge capacity and charge/discharge cycle life as compared with the secondary battery according to Comparative Example 26.
Examples 69-78
Each element was weighed so as to obtain the compositions shown in the following Table 10, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere, thereby obtaining 10 kinds of alloy ingot. Then, these ingots were subjected to a heat treatment in an argon atmosphere for 5 hours at a temperature ranging from 950.degree. C. to 1,000.degree. C. By the way, the misch metal (Lm) shown in Table 10 was composed of 92 at. % of La, 4 at. % of Ce, 1 at. % of Pr and 3 at. % of Nd.
Subsequently, the alloy ingots were pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 100 .mu.m or less.
Each hydrogen absorbing alloy powder was then mixed with electrolytic copper powder at a ratio of 1:2 (weight ratio), and 1 g of the resultant mixture was pressed for 5 minutes with a pressure of 10 tons/cm.sup.2, thus obtaining 10 kinds of pellet each having a diameter of 12 mm. These pellets were sandwiched between Ni wire nettings, and the peripheral portion thereof was spot-welded and pressed. Subsequently, to this pressed body was connected Ni lead wires by means of spot-welding thereby preparing 10 kinds of hydrogen absorbing alloy electrode (a negative electrode).
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte) in a case, whereby assembling test cells.
Then, the test cells according to Examples 69-78 were subjected to a charge/discharge cycle test at a temperature of 20.degree. C. The charge/discharge conditions in this test were as follows. Namely, the secondary battery was subjected at first to a charging for 2.5 hours with a current of 200 mA per 1 g of the hydrogen-absorbing alloy, and, after 10 minute cessation, discharged with a current of 100 mA per 1 g of the hydrogen-absorbing alloy until the battery voltage (with respect to a mercury oxide electrode) was decreased down to -0.7V. This charge/discharge cycle was repeated so as to measure the maximum discharge capacity and the cycle life (the number of cycle when the discharge capacity was lowered to 80% of the maximum discharge capacity). The results of this test are shown in the following Table 11.
Furthermore, the hydrogen absorbing alloys of Examples 69-78 were tested to measure hydrogen absorption characteristics. That is, the isothermal line of pressure-composition was measured under a hydrogen pressure of less than 10 atm. at a temperature of 50.degree. C. by making use of Sieverts's method (JIS H7201). Then, a plateau slope at the moment of hydrogen desorption (JIS H7003: Term for Hydrogen Absorbing Alloy) was calculated from the iso-thermal line of pressure-composition. In this case, the hydrogen pressures, which can be determined by extending the straight lines of the plateau region to a portion of hydrogen absorption quantity exhibiting (H/M)=0 and to another portion of hydrogen absorption quantity exhibiting (H/M)=1, were defined as P.sub.0 and P.sub.1, respectively, and the plateau slope was determined from the ratio between P.sub.0 and P.sub.1. Further, a ratio between the hydrogen absorption pressure (PA) and the hydrogen desorption pressure (PD) at the center of the plateau region was calculated from the isothermal line of pressure-composition. Hysteresis (JIS H7003: Term for Hydrogen Absorbing Alloy) was determined from the ratio between PA and PD. The results of these tests are shown in the following Table 11.
TABLE 10______________________________________ Compositions______________________________________Example 69 La.sub.0.7 Mg.sub.0.3 (Ni.sub.0.85 Co.sub.0.15).sub.3.2Example 70 La.sub.0.71 Mg.sub.0.29 (Ni.sub.0.77 Co.sub.0.2 Mn.sub.0.03).s ub.3.45Example 71 Lm.sub.0.75 Mg.sub.0.25 (Ni.sub.0.82 Co.sub.0.13 Cu.sub.0.05). sub.3.28Example 72 La.sub.0.63 Zr.sub.0.1 Mg.sub.0.27 (Ni.sub.0.85 Co.sub.0.1 Cr.sub.0.03 Al.sub.0.02).sub.3.67Example 73 La.sub.0.71 Mg.sub.0.29 (Ni.sub.0.97 Mn.sub.0.03).sub.3.45Example 74 La.sub.0.71 Mg.sub.0.29 (Ni.sub.0.77 Mn.sub.0.23).sub.3.45Example 75 La.sub.0.70 Mg.sub.0.30 (Ni.sub.0.50 Co.sub.0.50).sub.3.2Example 76 La.sub.0.70 Mg.sub.0.30 (Ni.sub.0.40 Co.sub.0.60).sub.3.2Example 77 La.sub.0.70 Mg.sub.0.30 (Ni.sub.0.65 Co.sub.0.15 Mn.sub.0.20). sub.3.2Example 78 La.sub.0.70 Mg.sub.0.30 (Ni.sub.0.55 Co.sub.0.15 Mn.sub.0.30). sub.3.2______________________________________
TABLE 11______________________________________ Discharge Plateau Hysteresis capacity Cycle Slope (P.sub.1 /P.sub.0) (P.sub.a /P.sub.d) (mAh/g) life______________________________________Example 69 3.45 2.6 405 354Example 70 3.65 3.4 390 376Example 71 2.95 2.9 386 380Example 72 3.25 2.8 380 400Example 73 5.93 3.6 350 330Example 74 7.20 3.7 355 325Example 75 3.10 3.2 400 360Example 76 3.90 3.6 360 320Example 77 3.50 3.3 410 355Example 78 3.95 3.7 360 320______________________________________
As apparent from Tables 10 and 11, the hydrogen-absorbing alloys according to Examples 69 to 78 indicated a lower plateau slope and a lower hysteresis, thus suggesting an excellent property of these alloy.
Further, the secondary batteries comprising a negative electrode containing any one of these hydrogen-absorbing alloys according to Examples 69 to 78 indicated more excellent properties in both discharge capacity and charge/discharge cycle life. In particular, the secondary batteries comprising a hydrogen-absorbing alloy containing Co according to Example 69 indicated a longer cycle life, a smaller plateau slope and a smaller hysteresis as compared with the secondary batteries of Examples 73 and 74 where a negative electrode containing Co-free alloy was employed. Further, the secondary batteries according to Example 75 where the negative electrode contained the alloy having a Co content of 0.5 indicated a longer cycle life, and a smaller plateau slope and a smaller hysteresis of the alloy as compared with the secondary batteries of Example 76 where the negative electrode contained the alloy having a Co content of more than 0.5. Furthermore, the secondary batteries according to Example 77 where the negative electrode contained the alloy having a Mn content of 0.2 indicated a longer cycle life, and a smaller plateau slope and a smaller hysteresis of the alloy as compared with the secondary batteries of Example 78 where the negative electrode contained the alloy having a Mn content of more than 0.2.
Examples 79-93
Each element was weighed so as to obtain the compositions shown in the following Table 12, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere, thereby obtaining 15 kinds of alloy ingot. Then, these ingots were subjected to a heat treatment in an argon atmosphere for 5 hours at a temperature ranging from 950.degree. C. to 1,000.degree. C. By the way, the misch metal (Lm) shown in Table 12 was composed of 92 at. % of La, 4 at. % of Ce, 1 at. % of Pr and 3 at. % of Nd; while the misch metal (Mm) shown in Table 12 was composed of 37.5 at. % of La, 45.3 at. % of Ce, 5.5 at. % of Pr, 11.5 at. % of Nd and 0.2 at. % of Sm.
Subsequently, the alloy ingots were pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 100 .mu.m or less. Each hydrogen absorbing alloy powder was then mixed with electrolytic copper powder at a ratio of 1:2 (weight ratio), and lg of the resultant mixture was pressed for 5 minutes with a pressure of 10 tons/cm.sup.2, thus obtaining 15 kinds of pellet each having a diameter of 12 mm. These pellets were sandwiched between Ni wire nettings, and the peripheral portion thereof was spot-welded and pressed. Subsequently, to this pressed body was connected Ni lead wires by means of spot-welding thereby preparing 15 kinds of hydrogen absorbing alloy electrode (a negative electrode).
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte) in a case, whereby assembling test cells.
Then, the test cells according to Examples 79-93 were subjected to a charge/discharge cycle test at a temperature of 20 .degree. C. The charge/discharge conditions in this test were as follows. Namely, the secondary battery was subjected at first to a charging for 2.5 hours with a current of 200 mA per 1 g of the hydrogen-absorbing alloy, and, after 10 minute cessation, discharged with a current of 100 mA per 1 g of the hydrogen-absorbing alloy until the battery voltage (with respect to a mercury oxide electrode) was decreased down to -0.7V. This charge/discharge cycle was repeated so as to measure the maximum discharge capacity and the cycle life (the number of cycle when the discharge capacity was lowered to 80% of the maximum discharge capacity). The results of this test are shown in the following Table 12.
TABLE 12__________________________________________________________________________Compositions Discharge capacity (mAh/g) Cycle life__________________________________________________________________________Example 79 La.sub.0.47 Lm.sub.0.23 Mg.sub.0.3 (Ni.sub.0.82 Co.sub.0.13 Al.sub.0.03 Si.sub.0.02).sub.3.15 410 380Example 80 La.sub.0.73 Mg.sub.0.27 (Ni.sub.0.77 Co.sub.0.2 Mn.sub.0.03).sub.3.5 380 340Exmaple 81 Lm.sub.0.75 Mg.sub.0.25 (Ni.sub.0.85 Co.sub.0.1 Cu.sub.0.05).sub.3.2 378 320Example 82 La.sub.0.63 Nd.sub.0.1 Mg.sub.0.27 (Ni.sub.0.85 Co.sub.0.1 Cr.sub.0. 03 Fe.sub.0.02).sub.3.7Example 83 La.sub.0.64 Ce.sub.0.05 Mg.sub.0.31 (Ni.sub.0.67 CO.sub.0.25 Nb.sub.0.05 B.sub.0.03).sub.3.4 385 355Example 84 La.sub.0.68 Pr.sub.0.1 Mg.sub.0.22 (Ni.sub.0.85 Co.sub.0.1 Sn.sub.0. 05).sub.3.6 380 330Example 85 Lm.sub.0.7 Mg.sub.0.3 (Ni.sub.0.75 Co.sub.0.2 Ga.sub.0.03 P.sub.0.02 ).sub.3.65 390 370Example 86 Lm.sub.0.73 Mg.sub.0.27 (Ni.sub.0.85 Co.sub.0.1 Mn.sub.0.04 B.sub.0.01).sub.3.42 395 325Example 87 Lm.sub.0.6 Mm.sub.0.16 Mg.sub.0.24 (Ni.sub.0.8 Co.sub.0.15 Si.sub.0. 05).sub.3.65 380 305Example 88 Lm.sub.0.76 Mg.sub.0.24 (Ni.sub.0.75 Co.sub.0.1 V.sub.0.1 Mn.sub.0.0 5).sub.3.33 375 290Example 89 (La.sub.0.1 Nd.sub.0.9).sub.0.73 Mg.sub.0.27 (Ni.sub.0.77 Co.sub.0.2 Mn.sub.0.03).sub.3.5 360 280Example 90 Pr.sub.0.73 Mg.sub.0.27 (Ni.sub.0.77 Co.sub.0.2 Mn.sub.0.03).sub.3.5 355 275Example 91 (La.sub.0.9 Nd.sub.0.1).sub.0.73 Mg.sub.0.27 (Ni.sub.0.77 Co.sub.0.2 Mn.sub.0.03).sub.3.5 405 375Example 92 Lm.sub.0.67 mg.sub.0.3 Ca.sub.0.03 (Ni.sub.0.7 Co.sub.0.2 Fe.sub.0.0 5 Al.sub.0.05).sub.3.12 380 300Example 93 La.sub.0.68 Pr.sub.0.1 Mg.sub.0.22 (Ni.sub.0.85 Co.sub.0.1 Sn.sub.0. 05).sub.3.8 330 250__________________________________________________________________________
As apparent from Table 12, the hydrogen-absorbing alloys according to Examples 79 to 93 indicated a high discharge capacity and a long cycle life.
Further, the secondary battery according to Example 91 where the negative electrode contained the alloy containing La in the rare earth component and also containing a rare earth component other than La at a ratio of less than 0.9 was found more excellent in both discharge capacity and cycle life as compared with any of the secondary batteries according to Examples 89, 90 and 80; i.e. the secondary battery of Example 89 where the negative electrode contained the alloy containing La at a ratio 0.1 in the rare earth component; the secondary battery of Example 90 where the negative electrode contained the alloy not containing La at all in the rare earth component; and the secondary battery of Example 80 where the negative electrode contained the alloy wherein the rare earth was entirely occupied by La.
Examples 94-108
Each element was weighed so as to obtain the compositions shown in the following Table 13, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere and then subjected to a heat treatment in an argon gas atmosphere for 5 hours at a temperature of 950.degree. C., thereby obtaining 15 kinds of alloy ingot. By the way, the misch metal (Lm) shown in Table 13 was composed of 92 at. % of La, 1 at. % of Ce, 5 at. % of Pr, 2 at. % of Nd; while the misch metal (Mm) was composed of 34 at. % of La, 50.4 at. % of Ce, 9 at. % of Pr, 6 at. % of Nd and 0.6 at. % of Sm.
Subsequently, the alloy ingots were pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 80 .mu.m or less. Each hydrogen absorbing alloy powder was then mixed with electrolytic copper powder at a ratio of 1:3 (weight ratio), and 1 g of the resultant mixture was pressed for 8 minutes with a pressure of 8 tons/cm.sup.2, thus obtaining 15 kinds of pellet each having a diameter of 10 mm. These pellets were sandwiched between Ni wire nettings, and the peripheral portion thereof was spot-welded and pressed. Subsequently, to this pressed body was connected Ni lead wires by means of spot-welding thereby preparing 15 kinds of hydrogen absorbing alloy electrode (a negative electrode).
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte) in a case, whereby assembling test cells.
Then, the test cells according to Examples 94-108 were subjected to a charge/discharge cycle test at a temperature of 25.degree. C. The charge/discharge conditions in this test were as follows. Namely, the secondary battery was subjected at first to a charging for 4.5 hours with a current of 100 mA per 1 g of the hydrogen-absorbing alloy, and, after 10 minute cessation, discharged with a current of 100 mA per 1 g of the hydrogen-absorbing alloy until the battery voltage (with respect to a mercury oxide electrode) was decreased down to -0.7V. This charge/discharge cycle was repeated so as to measure the maximum discharge capacity and the cycle life (the number of cycle when the discharge capacity was lowered to 80% of the maximum discharge capacity). The results of this test are shown in the following Table 13.
TABLE 13__________________________________________________________________________ Discharge capacity CycleCompositions (mAh/g) life__________________________________________________________________________Example 94 Lm.sub.0.71 Mg.sub.0.28 Zr.sub.0.01 (Ni.sub.0.8 Co.sub.0.11 Mn.sub.0.08 Al.sub.0.01).sub.3.3 360 385Example 95 Lm.sub.0.54 Pr.sub.0.17 Mg.sub.0.28 Ti.sub.0.01 (Ni.sub.0.92 Co.sub.0.05 Cu.sub.0.02 Al.sub.0.01).sub.3.42 365 370Example 96 Lm.sub.0.71 Mg.sub.0.28 Hf.sub.0.01 (Ni.sub.0.72 Co.sub.0.15 Mn.sub.0.05 Al.sub.0.01 Si.sub.0.01).sub.3.38 360 365Example 97 Lm.sub.0.7 Mg.sub.0.3 Ca.sub.0.01 (Ni.sub.0.79 Co.sub.0.15 Fe.sub.0. 05 Al.sub.0.01).sub.3.12 355 350Example 98 Lm.sub.0.5 Mm.sub.0.24 Mg.sub.0.24 Zr.sub.0.02 (Ni.sub.0.74 Co.sub.0.2 Mn.sub.0.05 Ga.sub.0.01).sub.3.6 345 370Example 99 Lm.sub.0.5 Mm.sub.0.24 Mg.sub.0.24 Zr.sub.0.02 (Ni.sub.0.74 Co.sub.0.2 Mn.sub.0.05 Ga.sub.0.01).sub.3.8 315 300Example 100 Lm.sub.0.5 Mm.sub.0.25 Mg.sub.0.24 Ca.sub.0.01 (Ni.sub.0.75 Co.sub.0.15 Mn.sub.0.05 Zn.sub.0.05).sub.3.52 350 360Example 101 Lm.sub.0.67 Mg.sub.0.32 Zr.sub.0.01 (Ni.sub.0.78 Co.sub.0.1 Cu.sub.0.1 Sn.sub.0.02).sub.3.23 340 375Example 102 Lm.sub.0.54 Nd.sub.0.17 Mg.sub.0.27 Ca.sub.0.02 (Ni.sub.0.81 Co.sub.0.1 Cu.sub.0.08 B.sub.0.01).sub.3.39 370 350Example 103 Lm.sub.0.63 Mg.sub.0.32 Zr.sub.0.05 (Ni.sub.0.89 Co.sub.0.01 Cu.sub.0.05 Mn.sub.0.05).sub.3.08 360 360Example 104 La.sub.0.63 Y.sub.0.05 Mg.sub.0.3 Zr.sub.0.02 (Ni.sub.0.77 Co.sub.0. 1 Cu.sub.0.1 Al.sub.0.03).sub.3.05 365 365Example 105 La.sub.0.63 Ce.sub.0.05 Mg.sub.0.3 Zr.sub.0.02 (Ni.sub.0.79 Co.sub.0.1 Cu.sub.0.1 Si.sub.0.01).sub.3.05 360 370Example 106 Lm.sub.0.63 Y.sub.0.05 Mg.sub.0.3 Zr.sub.0.02 (Ni.sub.0.77 Co.sub.0. 1 Cu.sub.0.1 Al.sub.0.03).sub.3.05 360 375Example 107 La.sub.0.38 Mm.sub.0.25 Y.sub.0.05 Mg.sub.0.3 Zr.sub.0.02 (Ni.sub.0. 77 Co.sub.0.1 Cu.sub.0.1 Al.sub.0.03).sub.3.05 355 380Example 108 Mm.sub.0.6 Mg.sub.0.35 Zr.sub.0.05 (Ni.sub.0.89 Co.sub.0.01 Mn.sub.0.07 Cu.sub.0.03).sub.3.08 305 290__________________________________________________________________________
As apparent from Table 13, the hydrogen-absorbing alloys according to Examples 94 to 108 indicated a high discharge capacity and a long cycle life.
Examples 109-117
(Evaluation of electrode)
Each element was weighed so as to obtain the compositions shown in the following Table 14, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere, thereby obtaining 9 kinds of alloy ingot. Then, all of the alloy ingots excluding the ingot of Example 117 were heat-treated in an argon atmosphere at a temperature of 1,000.degree. C. for 5 hours.
Subsequently, the alloy ingots thus obtained were pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 75 .mu.m or less. Each hydrogen absorbing alloy powder was then mixed with electrolytic copper powder at a ratio of 1:3 (weight ratio), and 1 g of the resultant mixture was pressed for 5 minutes with a pressure of 10 tons/cm.sup.2, thus obtaining 9 kinds of pellet each having a diameter of 10 mm. These pellets were sandwiched between Ni wire nettings, and the peripheral portion thereof was spot-welded and pressed. Subsequently, to this pressed body was connected Ni lead wires by means of spot-welding thereby preparing 9 kinds of hydrogen absorbing alloy electrode (a negative electrode).
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte) in a case, whereby assembling test cells.
Comparative Example 27
A test cell was assembled in the same manner as in the cases of Examples 109 to 117 except that a hydrogen-absorbing alloy powder to be explained below was employed.
Each element was weighed so as to obtain the composition shown in the following Table 14, and the resultant composition was melted in an induction furnace filled with an argon gas atmosphere, thereby preparing an alloy ingot.
Then, the alloy ingot was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 890.degree. C. for 12 hours in an argon atmosphere and then pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 75 .mu.m or less.
Then, the test cells according to Examples 109-117 and Comparative Example 27 were subjected to a charge/discharge cycle test at a temperature of 25.degree. C. The charge/discharge conditions in this test were as follows. Namely, the secondary battery was subjected at first to a charging for 5 hours with a current of 100 mA per 1 g of the hydrogen-absorbing alloy, and, after 10 minute cessation, discharged with a current of 50 mA per 1 g of the hydrogen-absorbing alloy until the battery voltage (with respect to a mercury oxide electrode) was decreased down to -0.6V. This charge/discharge cycle was repeated so as to measure the maximum discharge capacity and the cycle life (the number of cycle when the discharge capacity was lowered to 80% of the maximum discharge capacity). The results of this test are shown in the following Table 14.
(Vickers hardness)
The hydrogen-absorbing alloys obtained in Examples 109-117 and Comparative Example 27 were respectively sliced to a strip having a thickness of 8 mm by making use of a micro-cutter, and then mirror-finished by making use of a diamond paste having a particle diameter of 0.25 .mu.m, whereby preparing an evaluation sample. Then, the Vickers hardness of each sample was measured using a micro-Vickers hardness meter (AKASHI Co., Ltd.) under the conditions wherein a load of 25 gf was applied for 15 seconds. The results of the measurement are shown in the following Table 14.
TABLE 14__________________________________________________________________________ Discharge Vickers capacity Cycle Compositions hardness (mAh/g) life__________________________________________________________________________Example 109 Mg.sub.0.32 (La.sub.0.7 Pr.sub.0.3).sub.0.68 Ni.sub.3.04 520 370 315Example 110 Mg.sub.0.23 (La.sub.0.9 Sm.sub.0.1).sub.0.77 Ni.sub.3.58 473 365 305Example 111 Mg.sub.0.24 (La.sub.0.9 Gd.sub.0.1).sub.0.76 Ni.sub.3.52 452 362 320Example 112 Mg.sub.0.28 (La.sub.0.78 Y.sub.0.01 Pr.sub.0.21).sub.0.72 Ni.sub.3. 32 503 365 325Example 113 Mg.sub.0.24 (La.sub.0.88 Ce.sub.0.12).sub.0.76 Ni.sub.3.6 605 345 310Example 114 Mg.sub.0.2 (La.sub.0.64 Pr.sub.0.36).sub.0.8 Ni.sub.3.8 545 375 320Example 115 Mg.sub.0.25 (La.sub.0.7 Ce.sub.0.1 Pr.sub.0.2).sub.0.75 Ni.sub.3.52 570 360 325Example 116 Mg.sub.0.33 (La.sub.0.5 Ce.sub.0.5).sub.0.67 Ni.sub.3.02 655 295 275Example 117 Mg.sub.0.35 (La.sub.0.54 Ce.sub.0.2 Nd.sub.0.26).sub.0.65 Ni.sub.3. 01 715 285 205Comparative Mg.sub.0.33 (La.sub.0.5 Ce.sub.0.5).sub.0.67 Ni.sub.3.23 755 200 120Example 27__________________________________________________________________________
As apparent from Table 14, the secondary batteries according to Examples 109 to 117 comprising alloys which were manufactured by means of a casting method and represented by the general formula (8) indicated a larger discharge capacity and a longer cycle life as compared with the secondary battery according to Comparative Example 27. It is also apparent that the secondary battery of Examples 109 to 116 which comprised a negative electrode containing a hydrogen-absorbing alloy having a Vickers hardness of less than 700 Hv was more excellent in the discharge capacity and the cycle life as compared with the secondary battery of Example 117 which comprised a negative electrode containing a hydrogen-absorbing alloy having a Vickers hardness of 700 Hv or more.
Examples 118-126
(Evaluation of electrode)
Each element was weighed so as to obtain the compositions shown in the following Table 15, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere, thereby obtaining 9 kinds of alloy ingot. Then, all of the alloy ingots excluding the ingot of Example 126 were heat-treated in an argon atmosphere at a temperature of 1,000.degree. C. for 5 hours.
Subsequently, the alloy ingots thus obtained were pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 75 .mu.m or less. Each hydrogen absorbing alloy powder was then mixed with electrolytic copper powder at a ratio of 1:3 (weight ratio), and 1 g of the resultant mixture was pressed for 5 minutes with a pressure of 10 tons/cm.sup.2, thus obtaining 9 kinds of pellet each having a diameter of 10 mm. These pellets were sandwiched between Ni wire nettings, and the peripheral portion thereof was spot-welded and pressed. Subsequently, to this pressed body was connected Ni lead wires by means of spot-welding thereby preparing 9 kinds of hydrogen absorbing alloy electrode (a negative electrode).
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte) in a case, whereby assembling test cells.
Comparative Example 28
A test cell was assembled in the same manner as in the cases of Examples 118 to 126 except that a hydrogen-absorbing alloy powder to be explained below was employed.
Each element was weighed so as to obtain the composition shown in the following Table 15, and the resultant composition was melted in an induction furnace filled with an argon gas atmosphere, thereby preparing an alloy ingot.
Then, the alloy ingot was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 890.degree. C. for 12 hours in an argon atmosphere and then pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 75 .mu.m or less.
Then, the test cells according to Examples 118 to 126 and Comparative Example 28 were subjected to a charge/discharge cycle test at a temperature of 25.degree. C. The charge/discharge conditions in this test were as follows. Namely, the secondary battery was subjected at first to a charging for 5 hours with a current of 100 mA per 1 g of the hydrogen-absorbing alloy, and, after 10 minute cessation, discharged with a current of 50 mA per 1 g of the hydrogen-absorbing alloy until the battery voltage (with respect to a mercury oxide electrode) was decreased down to -0.6V. This charge/discharge cycle was repeated so as to measure the maximum discharge capacity and the cycle life (the number of cycle when the discharge capacity was lowered to 80% of the maximum discharge capacity). The results of this test are shown in the following Table 15.
(Vickers hardness)
The hydrogen-absorbing alloys obtained in Examples 118 to 126 and Comparative Example 28 were tested to measure the Vickers hardness thereof in the same manner as explained with reference to Examples 109 to 117. The results of the measurement are shown in the following Table 15.
TABLE 15______________________________________ Compositions______________________________________Example 118 Mg.sub.0.32 (La.sub.0.7 Pr.sub.0.3).sub.0.68 (Ni.sub.0.9 Co.sub.0. 1).sub.3.04Example 119 Mg.sub.0.23 (La.sub.0.9 Sm.sub.0.1).sub.0.77 (Ni.sub.0.7 Co.sub.0. 2 Fe.sub.0.05 Al.sub.0.05).sub.3.12Example 120 Mg.sub.0.21 (La.sub.0.9 Gd.sub.0.1).sub.0.79 (Ni.sub.0.48 Co.sub.0.5 B.sub.0.02).sub.3.55Example 121 Mg.sub.0.28 (La.sub.0.88 Y.sub.0.01 Pr.sub.0.11).sub.0.72 (Ni.sub.0.79 Co.sub.0.15 Fe.sub.0.05 Al.sub.0.01).sub.3.32Example 122 Mg.sub.0.24 (La.sub.0.9 Ce.sub.0.1).sub.0.76 (Ni.sub.0.74 Cu.sub.0.2 Mn.sub.0.05 Ga.sub.0.01).sub.3.6Example 123 Mg.sub.0.21 (La.sub.0.64 Pr.sub.0.36).sub.0.79 (Ni.sub.0.68 Co.sub.0.1 Cu.sub.0.1 Mn.sub.0.1 Sn.sub.0.02).sub.3.8Example 124 Mg.sub.0.25 (La.sub.0.64 Ce.sub.0.1 Pr.sub.0.26).sub.0.75 (Ni.sub.0.75 Co.sub.0.15 Mn.sub.0.02 Zn.sub.0.05).sub.3.52Example 125 Mg.sub.0.33 (La.sub.0.5 Ce.sub.0.5).sub.0.67 (Ni.sub.0.78 Co.sub.0.1 Cu.sub.0.1 Si.sub.0.02).sub.3.02Example 126 Mg.sub.0.35 (La.sub.0.54 Ce.sub.0.2 Nd.sub.0.26).sub.0.65 (Ni.sub.0.51 Co.sub.0.1 Fe.sub.0.3 B.sub.0.01).sub.3.01Comparative Mg.sub.0.33 (La.sub.0.5 Ce.sub.0.5).sub.0.67 (Ni.sub.0.78 Co.sub.0.1 Cu.sub.0.1 Si.sub.0.02).sub.3.23Example 28______________________________________ Vickers Discharge capacity hardness (mAh/g) Cycle life______________________________________Example 118 480 390 305Example 119 483 380 307Example 120 412 402 299Example 121 553 385 325Example 122 545 375 310Example 123 645 335 300Example 124 570 380 330Example 125 605 305 285Example 126 720 285 200Comparative 750 220 130Example 28______________________________________
As apparent from Table 15, the secondary batteries according to Examples 118 to 126 comprising alloys which were manufactured by means of a casting method and represented by the general formula (9) indicated a larger discharge capacity and a longer cycle life as compared with the secondary battery according to Comparative Example 28. It is also apparent that the secondary battery of Examples 118 to 125 which comprised a negative electrode containing a hydrogen-absorbing alloy having a Vickers hardness of less than 700 Hv was more excellent in the discharge capacity and the cycle life as compared with the secondary battery of Example 126 which comprised a negative electrode containing a hydrogen-absorbing alloy having a Vickers hardness of 700 Hv or more.
Examples 127-140 and Comparative Examples 29-31
Each element was weighed, taking the yield into consideration, so as to ultimately obtain the compositions shown in the Table 16, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere thereby manufacturing alloy ingots. Each alloy ingot was then heat-treated in an argon atmosphere at a temperature of 1,000.degree. C. for 5 hours, thereby preparing the hydrogen-absorbing alloy ingots each having a composition shown in the following Table 16.
Then, these hydrogen absorbing alloy ingots were pulverized and sieved to prepare the alloy powders having a particle diameter of 75 .mu.m or less.
Then, a hydrogen-absorbing alloy electrode was manufactured through the procedures as illustrated below.
150 .mu.L (5% by weight) of aqueous solution of PVA (polyvinyl alcohol)was added to 600 mg of each alloy powder and sufficiently kneaded to obtain a paste. The paste was then stuffed into a foamed metal substrate having a size of 2 cm.times.2 cm and provided with a terminal and then sufficiently dried in air atmosphere and in vacuum. The resultant composite body was pressed with a pressure of 2 tons/cm.sup.2, thus obtaining the hydrogen absorbing alloy electrode (a negative electrode).
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte), and a charge/discharge test was performed at temperatures of 25.degree. C. and 50.degree. C.
The charge/discharge conditions in this test were as follows. Namely, in each temperature (25.degree. C. and 50.degree. C.), the secondary battery was subjected at first to a charging for 5 hours with a current of 100 mA per 1 g of the hydrogen-absorbing alloy, and, after 10 minute cessation, discharged with a current of 50 mA per 1 g of the hydrogen-absorbing alloy until the battery voltage (with respect to a mercury oxide reference electrode) was decreased down to -0.6V, which was followed by a 10 minute cessation.
Then, a discharge capacity maintenance rate (%) at a temperature of 50.degree. C. was calculated from the discharge capacities at temperatures of 25.degree. C. and 50.degree. C. according to the following formula (i), the results being shown in the following Table 17.
Maintenance rate (%)={C(50.degree. C.)/C(25.degree. C.)}.times.100(i)
wherein C(50.degree. C.) is a discharge capacity at the 50th cycle in the charge/discharge test at a temperature of 50.degree. C.; and C(25.degree. C.) is a discharge capacity at the 50th cycle in the charge/discharge test at a temperature of 25.degree. C.
TABLE 16__________________________________________________________________________Compositions of hydrogen absorbing alloy__________________________________________________________________________Example 127 MgO.sub.0.34 (La.sub.0.72 Ce.sub.0.15 Pr.sub.0.03 Nd.sub.0.10).sub.0 .65 Ca.sub.0.01 (Ni.sub.0.79 Fe.sub.0.01 Al.sub.0.02).sub.3.32Example 128 MgO.sub.0.23 (La.sub.0.92 Ce.sub.0.02 Pr.sub.0.03 Nd.sub.0.03).sub.0 .74 Ti.sub.0.02 Zr.sub.0.01 (Ni.sub.0.77 Sn.sub.0.2 Cu.sub.0.02 Si.sub.0.01).sub.3.55Example 129 MgO.sub.0.29 (La.sub.0.89 Ce.sub.0.07 Nd.sub..sub.0.04).sub.0.69 Zr.sub.0.02 (Ni.sub.0.74 Mn.sub.0.24 B.sub.0.01 Zn.sub.0.01).sub.3.0 3Example 130 MgO.sub.0.32 (La.sub.0.86 Ce.sub.0.05 Pr.sub.0.01 Nd.sub.0.07).sub.0 .63 Hf.sub..sub.0.05 (Ni.sub.0.9 Co.sub.0.1).sub.3.19Example 131 MgO.sub.0.33 (La.sub.0.86 Ce.sub.0.10 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.66 Hf.sub..sub.0.01 (Ni.sub.0.64 Co.sub.0.21 Mn.sub.0.1 Al.sub.0.05).sub.3.32Example 132 MgO.sub.0.25 (La.sub.0.82 Ce.sub.0.14 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.72 Ca.sub.0.02 Zr.sub.0.01 (Ni.sub.0.84 Mn.sub.0. 1 Cu.sub.0.03 Si.sub.0.02 B.sub.0.01).sub.3.53Example 133 MgO.sub.0.34 (La.sub.0.792 Ce.sub.0.168 Pr.sub.0.02 Nd.sub.0.02).sub .0.63 Hf.sub.0.02 (Ni.sub.0.93 Fe.sub.0.02 Ga.sub.0.04 Cu.sub.0.01). sub.3.3Example 134 MgO.sub.0.17 (La.sub.0.738 Ce.sub.0.162 Pr.sub.0.05 Nd.sub.0.05).sub .0.78 Zr.sub.0.01 Ca.sub.0.04 (Ni.sub.0.75 Mn.sub.0.18 Al.sub.0.05 Fe.sub.0.01 Sn.sub.0.01).sub.3.56Example 135 MgO.sub.0.38 (La.sub.0.75 Ce.sub.0.14 Pr.sub.0.05 Nd.sub.0.02 Sm.sub.0.04).sub.0.55 Ti.sub.0.04 Zr.sub.0.03 (Ni.sub.0.83 Al.sub.0. 13 Zn.sub.0.01 B.sub.0.01 Fe.sub.0.02).sub.3.66Example 136 MgO.sub.0.22 (La.sub.0.83 Ce.sub.0.10 Pr.sub.0.01 Nd.sub.0.04 Sm.sub.0.02).sub.0.67 Hf.sub.0.07 Ca.sub.0.04 (Ni.sub.0.74 Sn.sub.0. 22 Cu.sub.0.02 Si.sub.0.01 B.sub.0.01).sub.3.75Example 137 MgO.sub.0.16 (La.sub.0.74 Ce.sub.0.13 Pr.sub.0.08 Nd.sub.0.03 Sm.sub.0.02).sub.0.80 Ca.sub.0.01 Ti.sub.0.03 (Ni.sub.0.49 Mn.sub.0. 39 Al.sub.0.06 Sn.sub.0.06).sub.3.69Example 138 MgO.sub.0.34 (La.sub.0.72 Ce.sub.0.15 Pr.sub.0.03 Nd.sub.0.10).sub.0 .65 Ca.sub.0.01 (Ni.sub.0.79 Fe.sub.0.01 Al.sub.0.2).sub.3.32Example 139 MgO.sub.0.47 (La.sub.0.84 Ce.sub.0.04 Pr.sub.0.08 Nd.sub.0.02 Sm.sub.0.02).sub.0.52 Hf.sub.0.01 (Ni.sub.0.78 Mn.sub.0.19 Al.sub.0. 03).sub.3.87Example 140 MgO.sub.0.28 (La.sub.0.74 Ce.sub.0.19 Pr.sub.0.03 Nd.sub.0.03 Sm.sub.0.01).sub.0.68 Ca.sub.0.03 Zr.sub.0.01 (Ni.sub.0.88 Sn.sub.0. 08 Cu.sub.0.01 Si.sub.0.02 B.sub.0.01).sub.3.92Comparative MgO.sub.0.65 (La.sub.0.36 Ce.sub.0.52 Pr.sub.0.03 Nd.sub.0.08 Sm.sub.0.01).sub.0.27 Ca.sub.0.08 (Ni.sub.0.68 Mn.sub.0.2 Al.sub.0.0 8 Fe.sub.0.02 Ga.sub.0.02).sub.4.6Example 29Comparative MgO.sub.0.53 (La.sub.0.22 Ce.sub.0.67 Pr.sub.0.02 Nd.sub.0.09).sub.0 .27 Ti.sub.0.01 (Ni.sub.0.57 Ga.sub.0.34 Zn.sub.0.02 Si.sub.0.07).su b.4.2Example 30Comparative MgO.sub.0.2 (La.sub.0.08 Ce.sub.0.77 Pr.sub.0.04 Nd.sub.0.08 Sm.sub.0.03).sub.0.2 Zr.sub.0.2 Ti.sub.0.4 (Ni.sub.0.65 Fe.sub.0.2 Ga.sub.0.15 Cu.sub.0.1).sub.2.8Example 31__________________________________________________________________________
TABLE 17______________________________________ Discharge capacity maintenance rate (%) at 50.degree. C.______________________________________Example 127 83Example 128 86Example 129 87Example 130 86Example 131 87Example 132 85Example 133 85Example 134 83Example 135 82Example 136 82Example 137 84Example 138 83Example 139 80Example 140 82Comparative 77Example 29Comparative 74Example 30Comparative 67Example 31______________________________________
As apparent from Tables 16 and 17, the secondary batteries of Examples 127 to 140 each comprising a negative electrode containing a hydrogen-absorbing alloy where Ce content in the R2 was less than 20% by weight were capable of more effectively suppressing the deterioration of discharge capacity at high temperatures as compared with the secondary batteries of Comparative Examples 29 to 31 comprising a negative electrode containing a hydrogen-absorbing alloy where Ce content in the R2 was more than 20% by weight.
Examples 141-150 and Comparative Examples 32-35
Each element was weighed, taking the yield into consideration, so as to ultimately obtain the compositions shown in the Table 18, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere thereby manufacturing alloy ingots. Then, each alloy ingot was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 89.degree. C. for 12 hours in an argon atmosphere.
Then, these hydrogen absorbing alloy flakes were pulverized and sieved to prepare the alloy powders having a particle diameter of 75 .mu.m or less. Then, a hydrogen-absorbing alloy electrode (a negative electrode) was manufactured in the same manner as illustrated with reference to the aforementioned Examples 127 to 140.
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte), and a charge/discharge test was performed at temperatures of 25.degree. C. and 50.degree. C. The charge/discharge conditions in this test were the same as illustrated with reference to the aforementioned Examples 127 to 140.
Then, a discharge capacity maintenance rate (%) at a temperature of 50.degree. C. was calculated from the discharge capacities at temperatures of 25.degree. C. and 50.degree. C. according to the aforementioned formula (i), the results being shown in the following Table 19.
TABLE 18__________________________________________________________________________Compositions of hydrogen absorbing alloy__________________________________________________________________________Example 141 Mg.sub.0.30 (Y.sub.0.01 La.sub.0.91 Ce.sub.0.05 Pr.sub.0.02 Sm.sub.0.01).sub.0.69 Ca.sub.0.01 (Ni.sub.0.77 Mn.sub.0.02 Co.sub.0. 15 Al.sub.0.05 B.sub.0.01).sub.3.05Example 142 Mg.sub.0.19 (La.sub.0.83 Ce.sub.0.11 Pr.sub.0.04 Nd.sub.0.01 Sm.sub.0.01).sub.0.79 Ti.sub.0.01 Hf.sub.0.01 (Ni.sub.0.84 Fe.sub.0. 01 Sn.sub.0.05 Cu.sub.0.10).sub.3.53Example 143 Mg.sub.0.30 (La.sub.0.89 Ce.sub.0.08 Pr.sub.0.02 Eu.sub.0.01).sub.0. 69 Zr.sub.0.01 (Ni.sub.0.88 Co.sub.0.10 Ga.sub.0.01 Si.sub.0.01).sub .3.30Example 144 Mg.sub.0.15 (La.sub.0.92 Ce.sub.0.03 Pr.sub.0.04 Gd.sub.0.01).sub.0. 60 Ca.sub.0.07 Ti.sub.0.05 Zr.sub.0.08 Hf.sub.0.05 (Ni.sub.0.82 Fe.sub.0.01 Zn.sub.0.01 Cu.sub.0.15 B.sub.0.01).sub.3.10Example 145 Mg.sub.0.12 (La.sub.0.76 Ce.sub.0.17 Pr.sub.0.05 Tb.sub.0.01 Lu.sub.0.01).sub.0.87 Zr.sub.0.01 (Ni.sub.0.82 Co.sub.0.15 Mn.sub.0. 01 Al.sub.0.01 B.sub.0.01).sub.3.57Example 146 Mg.sub.0.38 (La.sub.0.72 Ce.sub.0.19 Pr.sub.0.08 Dy.sub.0.01).sub.0. 60 Ca.sub.0.01 Hf.sub.0.01 (Ni.sub.0.65 Fe.sub.0.10 Co.sub.0.10 Al.sub.0.05 Cu.sub.0.1).sub.3.01Example 147 Mg.sub.0.36 (La.sub.0.78 Ce.sub.0.15 Pr.sub.0.07).sub.0.62 Ti.sub.0. 01 Hf.sub.0.01 (Ni.sub.0.78 Mn.sub.0.05 Fe.sub.0.10 Al.sub.0.05 Zn.sub.0.01 Si.sub.0.01).sub.3.65Example 148 Mg.sub.0.12 (La.sub.0.74 Ce.sub.0.15 Pr.sub.0.07 Nd.sub.0.03 Ho.sub.0.01).sub.0.73 Zr.sub.0.05 Ca.sub.0.05 Hf.sub.0.05 (Ni.sub.0. 45 Mn.sub.0.15 Co.sub.0.20 Al.sub.0.10 Cu.sub.0.10).sub.3.78Example 149 Mg.sub.0.46 (La.sub.0.87 Ce.sub.0.02 Pr.sub.0.08 Nd.sub.0.02 Er.sub.0.01).sub.0.53 Zr.sub.0.01 (Ni.sub.0.82 Fe.sub.0.01 Co.sub.0. 10 Ga.sub.0.01 Sn.sub.0.05 B.sub.0.01).sub.3.12Example 150 Mg.sub.0.05 (Ld.sub.0.88 Ce.sub.0.02 Pr.sub.0.08 Tm.sub.0.01 Yb.sub.0.01).sub.0.94 Ti.sub.0.01 (Ni.sub.0.60 Mn.sub.0.05 Co.sub.0. 10 Al.sub.0.05 Zn.sub.0.10 Cu.sub.0.10).sub.3.90Comparative Mg.sub.0.05 (Y.sub.0.01 La.sub.0.50 Ce.sub.0.45 Pr.sub.0.02 Nd.sub.0.02).sub.0.55 Ca.sub.0.40 (Ni.sub.0.20 Mn.sub.0.20 Al.sub.0. 30 Zn.sub.0.20 Si.sub.0.10).sub.2.80Example 32Comparative Mg.sub.0.25 (La.sub.0.66 Ce.sub.0.27 Pr.sub.0.02 Sm.sub.0.01 Dy.sub.0.01 Ho.sub.0.01 Yb.sub.0.01).sub.0.65 Ti.sub.0.10 (Ni.sub.0. 79 M.sub.0.21).sub.4.05Example 33 (M; Mn.sub.0.05 Al.sub.0.05 Sn.sub.0.10 B.sub.0.01)Comparative Mg.sub.0.29 (La.sub.0.15 Ce.sub.0.75 Pr.sub.0.04 Nd.sub.0.03 Sm.sub.0.01 Gd.sub.0.01 Er.sub.0.01).sub.0.70 Hf.sub.0.01 (Ni.sub.0. 54 Fe.sub.0.10 Co.sub.0.15 Cu.sub.0.20 B.sub.0.01).sub.3.21Example 34Comparative Mg.sub.0.60 (La.sub.0.50 Ce.sub.0.35 Pr.sub.0.07 Nd.sub.0.03 Sm.sub.0.02 Eu.sub.0.01 Tb.sub.0.01 Tm.sub.0.01).sub.0.39 Hf.sub.0.0 1 (Ni.sub.0.69 M.sub.0.21 Co.sub.0.10).sub.3.50Example 35 (M; Fe.sub.0.10 Ga.sub.0.01 Cu.sub.0.10)__________________________________________________________________________
TABLE 19______________________________________ Discharge capacity maintenance rate (%) at 50.degree. C.______________________________________Example 141 87Example 142 84Example 143 86Example 144 81Example 145 85Example 146 82Example 147 83Example 148 84Example 149 82Example 150 79Comparative 42Example 32Comparative 38Example 33Comparative 43Example 34Comparative 34Example 35______________________________________
As apparent from Tables 18 and 19, the secondary batteries of Examples 141 to 150 each comprising a negative electrode containing a hydrogen-absorbing alloy where Ce content in the R2 was less than 20% by weight were capable of more effectively suppressing the deterioration of discharge capacity at high temperatures as compared with the secondary batteries of Comparative Examples 32 to 35 comprising a negative electrode containing a hydrogen-absorbing alloy where Ce content in the R2 was more than 20% by weight.
The hydrogen-absorbing alloys included in the negative electrode of the second batteries according to Examples 141 to 150 were manufactured by means of a melt-quenching method. While the hydrogen-absorbing alloys included in the negative electrode of the second batteries according to previous Examples 127 to 140 were manufactured by means of a casting method, so that the cooling rate of the alloy was relatively slow as compared with that in Examples 141 to 150.
As apparent from Tables 16 to 19, the secondary batteries of Examples 141 to 150 exhibited respectively a discharge capacity which was comparable to the secondary batteries of Examples 127 to 140. The reason for enabling the secondary batteries according to Examples 141 to 150 to exhibit a high discharge capacity maintenance rate at a temperature of 50.degree. C. even if the hydrogen-absorbing alloy was manufactured through a quench solidification such as a melt-quenching method using a roll may be attributed to the fact that since the compositions thereof contained less than 20% by weight of Ce in its R2 component, it was possible to obtain a hydrogen-absorbing alloy which was minimal in plane defect even though the alloy was manufactured by means of a melt-quenching method.
Examples 151-163 and Comparative Examples 36-40
Each element was weighed, taking the yield into consideration, so as to ultimately obtain the compositions shown in the Table 20, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere thereby manufacturing alloy ingots. Each alloy ingot was then heat-treated in an argon atmosphere at a temperature of 1,000.degree. C. for 5 hours, thereby preparing the hydrogen-absorbing alloy ingots each having a composition shown in the following Table 20.
Then, these hydrogen absorbing alloy ingots were pulverized and sieved to prepare the alloy powders having a particle diameter of 75 .mu.m or less.
Then, a hydrogen-absorbing alloy electrode was manufactured through the same procedures as illustrated with reference to the aforementioned Examples 127 to 140.
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte), and a charge/discharge test was performed at temperatures of 25.degree. C. and 50.degree. C. The charge/discharge conditions in this test were the same as illustrated with reference to the aforementioned Examples 127 to 140.
Then, a discharge capacity maintenance rate (%) at a temperature of 50.degree. C. was calculated from the discharge capacities at temperatures of 25.degree. C. and 50.degree. C. according to the aforementioned formula (i), the results being shown in the following Table 21. By the way, Table 21 also shows the acceptable Ce content "m" (weight %) which was calculated from the aforementioned formula (I): m=125y+20, as well as the Ce content (weight %) which was actually included in the R3 of the hydrogen-absorbing alloy.
TABLE 20__________________________________________________________________________Compositions of hydrogen absorbing alloy__________________________________________________________________________Example 151 Mg.sub.0.31 (La.sub.0.87 Ce.sub.0.09 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.78 Co.sub.0.1 Mn.sub.0.1 Sn.sub.0.02).sub.3.12Example 152 Mg.sub.0.31 (La.sub.0.81 Ce.sub.0.15 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.78 Co.sub.0.1 Mn.sub.0.1 Sn.sub.0.02).sub.3.12Example 153 Mg.sub.0.31 (La.sub.0.69 Ce.sub.0.27 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.78 Co.sub.0.1 Mn.sub.0.1 Sn.sub.0.02).sub.3.12Comparative Mg.sub.0.31 (La.sub.0.61 Ce.sub.0.35 Pr.sub.0.02 Nd.sub.0.10 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.78 Co.sub.0.1 Mn.sub.0.1 Sn.sub.0.02).sub.3.12Example 36Example 154 Mg.sub.0.31 (La.sub.0.87 Ce.sub.0.09 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.65 Co.sub.0.2 Mn.sub.0.1 Al.sub.0.05).sub.3.05Example 155 Mg.sub.0.31 (La.sub.0.74 Ce.sub.0.22 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.65 Ce.sub.0.2 Mn.sub.0.1 Al.sub.0.05).sub.3.05Example 156 Mg.sub.0.31 (La.sub.0.56 Ce.sub.0.40 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.65 Co.sub.0.2 Mn.sub.0.1 Al.sub.0.05).sub.3.05Comparative Mg.sub.0.31 (La.sub.0.49 Ce.sub.0.47 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.65 Co.sub.0.2 Mn.sub.0.1 Al.sub.0.05).sub.3.05Example 37Example 157 Mg.sub.0.31 (La.sub.0.81 Ce.sub.0.15 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.51 Co.sub.0.37 Al.sub.0. 05 Cu.sub.0.07).sub.3.08Example 158 Mg.sub.0.31 (La.sub.0.57 Ce.sub.0.39 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.51 Co.sub.0.37 Al.sub.0. 05 Cu.sub.0.07).sub.3.08Example 159 Mg.sub.0.31 (La.sub.0.33 Ce.sub.0.63 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.51 Co.sub.0.37 Al.sub.0. 05 Cu.sub.0.07).sub.3.08Comparative Mg.sub.0.31 (La.sub.0.24 Ce.sub.0.72 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.51 Co.sub.0.37 Al.sub.0. 05 Cu.sub.0.07).sub.3.08Example 38Example 160 Mg.sub.0.31 (La.sub.0.61 Ce.sub.0.35 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.67 Ti.sub.0.02 (Ni.sub.0.65 Co.sub.0.2 Mn.sub.0.1 Al.sub.0.05).sub.3.05Example 161 Mg.sub.0.28 (La.sub.0.45 Ce.sub.0.5 Pr.sub.0.02 Nd.sub.0.03).sub.0.6 9 Zr.sub.0.03 (Ni.sub.0.63 Co.sub.0.3 Ga.sub.0.03 Zn.sub.0.04).sub.3 .42Example 162 Mg.sub.0.33 (La.sub.0.76 Ce.sub.0.19 Pr.sub.0.02 Sm.sub.0.03).sub.0. 62 Hf.sub.0.05 (Ni.sub.0.81 Co.sub.0.12 Al.sub.0.02 Cu.sub.0.01 Si.sub.0.04).sub.3.22Example 163 Mg.sub.0.27 (La.sub.0.66 Ce.sub.0.30 Pr.sub.0.02 Nd.sub.0.01 Sm.sub.0.01).sub.0.62 Ce.sub.0.01 (Ni.sub.0.79 Co.sub.0.16 Al.sub.0. 02 Fe.sub.0.02 B.sub.0.01).sub.3.35Comparative Mg.sub.0.5 (La.sub.0.3 Ce.sub.0.65 Pr.sub.0.02 Nd.sub.0.03).sub.0.43 Ca.sub.0.05 Ti.sub.0.02 (Ni.sub.0.74 Co.sub.0.23 Mn.sub.0.02 Al.sub.0.01).sub.3.35Example 39Comparative Mg.sub.0.34 (La.sub.0.5 Ce.sub.0.41 Pr.sub.0.03 Nd.sub.0.03 Sm.sub.0.03).sub.0.63 Ca.sub.0.03 (Ni.sub.0.83 Co.sub.0.11 Fe.sub.0. 03 Si.sub.0.02 B.sub.0.01).sub.3.21Example 40__________________________________________________________________________
TABLE 21______________________________________Acceptable Ce content Discharge capacityCe content (wt %) in the R3 maintenance rate"m" (wt %) of the alloy (%) at 50.degree. C.______________________________________Example 151 32.5 9 87Example 152 32.5 15 87Example 153 32.5 27 86Comparative 32.5 35 68Example 36Example 154 45 9 86Example 155 45 22 87Example 156 45 40 85Comparative 45 47 65Example 37Example 157 66.25 15 85Example 158 66.25 39 83Example 159 66.25 63 84Comparative 66.25 72 69Example 38Example 160 45 35 88Example 161 57.5 50 83Example 162 35 19 84Example 163 40 30 84Comparative 48.75 65 68Example 39Comparative 33.75 41 75Example 40______________________________________
As apparent from Tables 20 and 21, the secondary batteries of Examples 151 to 153 each comprising a negative electrode containing a hydrogen-absorbing alloy where Ce content in the R3 was less than the value (m % by weight) calculated from the formula (I) were capable of more effectively suppressing the deterioration of discharge capacity at a high temperature environment as compared with the secondary battery of Comparative Example 36 comprising a negative electrode containing a hydrogen-absorbing alloy where Ce content in the R3 was more than m % by weight.
Further, from the comparison in property between the secondary batteries of Examples 154 to 156 and the secondary battery of Comparative Example 37, as well as from the comparison in property between the second batteries of Examples 157 to 159 and the secondary battery of Comparative Example 38, it is apparent that when Co content is altered likewise, the similar tendency as illustrated above would be recognized. Moreover, as seen from Examples 160 to 163, even when the atomic ratio of each element or the kind of the element is changed, it is possible to suppress the deterioration of discharge capacity at high temperatures as far as the Ce content in the R3 is less than m % by weight.
Examples 164-175 and Comparative Examples 41-47
Each element was weighed, taking the yield into consideration, so as to ultimately obtain the compositions shown in the Table 22, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere thereby manufacturing alloy ingots. Then, each alloy ingot was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 890.degree. C. for 12 hours in an argon atmosphere.
Then, these hydrogen absorbing alloy flakes were pulverized and sieved to prepare the alloy powders having a particle diameter of 75 .mu.m or less.
Then, a hydrogen-absorbing alloy electrode was manufactured through the same procedures as illustrated with reference to the aforementioned Examples 127 to 140.
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte), and a charge/discharge test was performed at temperatures of 25.degree. C. and 50.degree. C. The charge/discharge conditions in this test were the same as illustrated with reference to the aforementioned Examples 127 to 140.
Then, a discharge capacity maintenance rate (%) at a temperature of 50.degree. C. was calculated from the discharge capacities at temperatures of 25.degree. C. and 50.degree. C. according to the aforementioned formula (i), the results being shown in the following Table 23.
TABLE 22__________________________________________________________________________Compositions of hydrogen absorbing alloy__________________________________________________________________________Example 164 Mg.sub.0.29 (La.sub.0.89 Ce.sub.0.05 Pr.sub.0.03 Nd.sub.0.02 Sm.sub.0.01).sub.0.70 Hf.sub.0.01 (Ni.sub.0.86 Co.sub.0.08 Al.sub.0. 05 Cu.sub.0.01).sub.3.28Example 165 Mg.sub.0.29 (La.sub.0.84 Ce.sub.0.10 Pr.sub.0.03 Nd.sub.0.02 Sm.sub.0.01).sub.0.70 Hf.sub.0.01 (Bi.sub.0.86 Co.sub.0.08 Al.sub.0. 05 Cu.sub.0.01).sub.3.28Example 166 Mg.sub.0.29 (La.sub.0.67 Ce.sub.0.27 Pr.sub.0.03 Nd.sub.0.02 Sm.sub.0.01).sub.0.70 Hf.sub.0.01 (Ni.sub.0.86 Co.sub.0.08 Al.sub.0. 05 Cu.sub.0.01).sub.3.28Comparative Mg.sub.0.29 (La.sub.0.59 Ce.sub.0.235 Pr.sub.0.03 Nd.sub.0.02 Sm.sub.0.01).sub.0.70 Hf.sub.0.01 (Ni.sub.0.86 Co.sub.0.08 Al.sub.0. 05 Cu.sub.0.01).sub.3.28Example 41Example 167 Mg.sub.0.29 (La.sub.0.87 Ce.sub.0.07 Pr.sub.0.03 Nd.sub.0.02 Sm.sub.0.01).sub.0.70 Hf.sub.0.01 (Ni.sub.0.73 Fe.sub.0.01 Co.sub.0. 25 B.sub.0.01).sub.3.32Example 168 Mg.sub.0.29 (La.sub.0.73 Ce.sub.0.21 Pr.sub.0.03 Nd.sub.0.02 Sm.sub.0.01).sub.0.07 Hf.sub.0.01 (Ni.sub.0.73 Fe.sub.0.01 Co.sub.0. 25 B.sub.0.01).sub.3.32Example 169 Mg.sub.0.29 (La.sub.0.49 Ce.sub.0.45 Pr.sub.0.03 Nd.sub.0.02 Sm.sub.0.01).sub.0.07 Hf.sub.0.01 (Ni.sub.0.73 Fe.sub.0.01 Co.sub.0. 25 B.sub.0.01).sub.3.32Comparative Mg.sub.0.29 (La.sub.0.39 Ce.sub.0.55 Pr.sub.0.03 Nd.sub.0.02 Sm.sub.0.01).sub.0.07 Hf.sub.0.01 (Ni.sub.0.73 Fe.sub.0.01 Co.sub.0. 25 B.sub.0.01).sub.3.32Example 42Example 170 Mg.sub.0.29 (La.sub.0.76 Ce.sub.0.18 Pr.sub.0.03 Nd.sub.0.02 Sm.sub.0.01).sub.0.70 Hf.sub.0.01 (Ni.sub.0.59 Co.sub.0.38 Sn.sub.0. 01 Cu.sub.0.01 Si.sub.0.01).sub.3.31Example 171 Mg.sub.0.29 (La.sub.0.54 Ce.sub.0.40 Pr.sub.0.03 Nd.sub.0.02 Sm.sub.0.01).sub.0.70 Hf.sub.0.01 (Ni.sub.0.59 Co.sub.0.38 Sn.sub.0. 01 Cu.sub.0.01 Si.sub.0.10).sub.3.31Example 172 Mg.sub.0.29 (La.sub.0.33 Ce.sub.0.61 Pr.sub.0.02 Nd.sub.0.02 Sm.sub.0.01).sub.0.70 Hf.sub.0.01 (Ni.sub.0.59 Co.sub.0.38 Sn.sub.0. 01 Cu.sub.0.01 Si.sub.0.01).sub.3.31Comparative Mg.sub.0.29 (La.sub.0.23 Ce.sub.0.71 Pr.sub.0.03 Nd.sub.0.02 Sm.sub.0.01).sub.0.70 Hf.sub.0.01 (Ni.sub.0.59 Co.sub.0.38 Sn.sub.0. 01 Cu.sub.0.01 Si.sub.0.01).sub.3.31Example 43Example 173 Mg.sub.0.32 (Y.sub.0.01 La.sub.0.65 Ce.sub.0.30 Pr.sub.0.02 Sm.sub.0.01 Er.sub.0.01).sub.0.67 Zr.sub.0.01 (Ni.sub.0.79 Mn.sub.0. 01 Fe.sub.0.01 Co.sub.0.18 Zn.sub.0.01).sub.3.05Example 174 Mg.sub.0.23 (La.sub.0.88 Ce.sub.0.05 Pr.sub.0.02 Eu.sub.0.01 Dy.sub.0.01 Ho.sub.0.01 Yb.sub.0.01 Lu.sub.0.01).sub.0.76 Ti.sub.0.0 1 (Ni.sub.0.84 Co.sub.0.10 Al.sub.0.05 Ga.sub.0.01).sub.3.43Example 175 Mg.sub.0.28 (La.sub.0.82 Ce.sub.0.12 Pr.sub.0.03 Gd.sub.0.01 Tb.sub.0.01 Tm.sub.0.01).sub.0.70 Ca.sub.0.01 Hf.sub.0.01 (Ni.sub.0. 87 Co.sub.0.09 Al.sub.0.02 Cu.sub.0.01 B.sub.0.01).sub.3.10Comparative Mg.sub.0.60 (La.sub.0.33 Ce.sub.0.62 Pr.sub.0.02 Tb.sub.0.01 Dy.sub.0.01 Er.sub.0.01).sub.0.39 Ti.sub.0.01 (Ni.sub.0.67 Mn.sub.0. 01 Co.sub.0.30 Zn.sub.0.01 Si.sub.0.01).sub.3.50Example 44Comparative Mg.sub.0.05 (La.sub.0.52 Ce.sub.0.41 Pr.sub.0.04 Nd.sub.0.01 Sm.sub.0.01 Lu.sub.0.01).sub.0.93 Ca.sub.0.01 Zr.sub.0.01 (Ni.sub.0. 60 Co.sub.0.13 Al.sub.0.07 Sn.sub.0.10 B.sub.0.10).sub.2.83Example 45Comparative Mg.sub.0.25 (La.sub.0.54 Ce.sub.0.39 Pr.sub.0.03 Eu.sub.0.01 Tb.sub.0.01 Ho.sub.0.01 Tm.sub.0.01).sub.0.73 Tu.sub.0.01 (Ni.sub.0. 37 M.sub.0.53 Co.sub.0.10).sub.3.30Example 46 (M; Mn.sub.0.15 Fe.sub.0.12 Al.sub.0.05 Ga.sub.0.10 Cu.sub.0.11)Comparative Mg.sub.0.31 (La.sub.0.55 Ce.sub.0.38 Pr.sub.0.03 Nd.sub.0.01 Gd.sub.0.01 Ho.sub.0.01 Yb.sub.0.01).sub.0.29 Ca.sub.0.20 Zr.sub.0.1 0 Hf.sub.0.10 (Ni.sub.0.82 M.sub.0.07 Co.sub.0.11).sub.3.32Example 47 (M; Al.sub.0.05 Si.sub.0.01 B.sub.0.01)__________________________________________________________________________
TABLE 23______________________________________ Acceptable Ce content Discharge capacity Ce content (wt %) in the R3 maintenance rate "m" (wt %) of the alloy (%) at 50.degree. C.______________________________________Example 164 30 5 87Example 165 30 10 88Example 166 30 27 86Comparative 30 35 45Example 41Example 167 51.25 7 88Example 168 51.25 21 85Example 169 51.25 45 83Comparative 51.25 55 39Example 42Example 170 67.5 18 83Example 171 67.5 40 84Example 172 67.5 81 80Comparative 67.5 71 47Example 43Example 173 42.5 30 85Example 174 32.5 5 86Example 175 31.3 12 83Comparative 57.5 62 43Example 44Comparative 36.25 41 32Example 45Comparative 32.5 39 38Example 46Comparative 33.75 38 46Example 47______________________________________
As apparent from Tables 22 and 23, the secondary batteries of Examples 164 to 166 each comprising a negative electrode containing a hydrogen-absorbing alloy where Ce content in the R3 was less than the value (m % by weight) calculated from the formula (I) were capable of more effectively suppressing the deterioration of discharge capacity at a high temperature environment as compared with the secondary battery of Comparative Example 41 comprising a negative electrode containing a hydrogen-absorbing alloy where Ce content in the R3 was more than m % by weight.
Further, from the comparison in property between the second batteries of Examples 167 to 169 and the secondary battery of Comparative Example 42, as well as from the comparison in property between the second batteries of Examples 170 to 172 and the secondary battery of Comparative Example 43, it is apparent that when Co content is altered likewise, the similar tendency as illustrated above would be recognized. Moreover, as seen from Examples 173 to 175, even when the atomic ratio of each element or the kind of the element is changed, it is possible to suppress the deterioration of discharge capacity at high temperatures as far as the Ce content in the R3 is less than m % by weight.
The hydrogen-absorbing alloys included in the negative electrode of the secondary batteries according to Examples 164 to 175 were manufactured by means of a melt-quenching method. While the hydrogen-absorbing alloys included in the negative electrode of the secondary batteries according to previous Examples 151 to 163 were manufactured by means of a casting method, so that the cooling rate of the alloy was relatively slow as compared with that in Examples 164 to 175.
As apparent from Tables 20 to 23, the secondary batteries of Examples 164 to 175 exhibited respectively a discharge capacity which was comparable to the secondary batteries of Examples 151 to 163. The reason for enabling the secondary batteries according to Examples 164 to 175 to exhibit a high discharge capacity maintenance rate at a temperature of 50.degree. C. even if the hydrogen-absorbing alloy was manufactured through a quench solidification such as a melt-quenching method using a roll may be attributed to the fact that since the Ce content in the R3 component was confined to the range defined by the aforementioned formula (I), it was possible to obtain a hydrogen-absorbing alloy which was minimal in plane defect even though the alloy was manufactured by means of a melt-quenching method.
Examples 176-195 and Comparative Examples 48-49
Each element was weighed so as to obtain the compositions shown in the following Table 24, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere and then cast into a water-cooled copper mold, each melt cast in this manner being allowed to solidify to obtain various kinds of alloy ingot. Then, these ingots were subjected to a heat treatment in an argon atmosphere for 8 hours at a temperature of 900.degree. C. Subsequently, the alloy ingots were pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 150 .mu.m or less.
By the way, the misch metal (Lm) shown in Table 24 was composed of 90 wt. % of La, 2 wt. % of Ce, 5 wt. % of Pr and 3 wt. % of Nd; while the misch metal (Mm) was composed of 35 wt. % of La, 50.3 wt. % of Ce, 5.5 wt. % of Pr, 9 wt. % of Nd and 0.2 wt. % of Sm.
Comparative Examples 50 to 52
Each element was weighed so as to obtain the composition shown in the following Table 24, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere, thereby preparing alloy ingots.
Then, each alloy ingots was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 900.degree. C. for 8 hours in an argon atmosphere and then pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 150 .mu.m or less.
The hydrogen-absorbing alloys obtained in Examples 176-195 and Comparative Examples 48-52 were measured with respect to the following properties (1) and (2).
(1) Each principal phase of the hydrogen-absorbing alloy was subjected to a component analysis using an EDX analyzer (Energy Dispersive X-ray Spectrometer) of transmission electron microscope and setting the diameter of the beam to 4 nm, the values of "a" and "z" in each resultant composition of the principal phase being shown in the following Table 25.
(2) In each hydrogen-absorbing alloy, the (100) plane of the principal phase having a composition represented by the aforementioned general formula (12) where the values of "a" and "z" therein are indicated in Table 25 was photographed (magnification: .times.20,000) in ten visual fields, each visual field being dislocated from others, by using a transmission electron microscope. Then, the number of plane defect per 100 nm was counted in optional ten regions in each visual field, the resultants being shown in the following Table 24.
(3) A rechargeable hydrogen storage capacity (JIS H7003: Term for Hydrogen Absorbing Alloy), i.e. one of the hydrogen-absorption properties, was determined on each hydrogen-absorbing alloy powder by making use of the iso-thermal line of pressure-composition which was measured under a hydrogen pressure of less than 10 atm. at a temperature of 60.degree. C. by means of Sieverts's method (JIS H7201), the results being shown in the following Table 25.
Further, a magnified picture (20,000 times) of the (100) plane of crystal grain constituting the principal phase of the hydrogen-absorbing alloy according to Example 177 was taken by making use of a transmission electron microscope, the microscopic picture thus obtained is shown in FIG. 4.
Furthermore, various kinds of hydrogen absorbing alloy electrode (a negative electrode) were manufactured from the hydrogen-absorbing alloy powders obtained in Examples 176-195 and Comparative Examples 48-52 by making use of the following method. Namely, each hydrogen absorbing alloy powder was mixed with electrolytic copper powder at a ratio of 1:3 (weight ratio), and 1 g of the resultant mixture was pressed for 5 minutes with a pressure of 10 tons/cm.sup.2, thus obtaining various kinds of pellet each having a diameter of 10 mm. These pellets were respectively sandwiched between Ni wire nets, and the peripheral portion thereof was spot-welded and pressed. Subsequently, to this pressed body was connected Ni lead wires by means of spot-welding thereby preparing the hydrogen absorbing alloy electrodes (a negative electrode).
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte) in a case thereby to perform a charge/discharge cycle test at a temperature of 20.degree. C. The charge/discharge conditions in this test were as follows. Namely, the secondary battery was subjected at first to a charging for 5 hours with a current of 100 mA per 1 g of the hydrogen-absorbing alloy, and, after 10 minute cessation, discharged with a current of 100 mA per 1 g of the hydrogen-absorbing alloy until the battery voltage (with respect to a mercury oxide electrode) was decreased down to -0.7V. This charge/discharge cycle was repeated so as to measure the maximum discharge capacity and the cycle life (the number of cycle when the discharge capacity was lowered to 70% of the maximum discharge capacity). The results of this test are shown in the following Table 25.
TABLE 24__________________________________________________________________________ Number of plane defect per Compositions 100 nm__________________________________________________________________________Example 176 La.sub.0.75 Mg.sub.0.25 (Ni.sub.0.86 Cu.sub.0.08 Co.sub.0.05 Al.sub.0.01).sub.3.5 0 to 3Example 177 La.sub.0.5 Pr.sub.0.22 Mg.sub.0.28 (Ni.sub.0.85 Cr.sub.0.05 Fe.sub.0.03 Si.sub.0.01).sub.3.2 0 to 4Example 178 La.sub.0.48 Nd.sub.0.22 Mg.sub.0.3 (Ni.sub.0.85 Cu.sub.0.1 Mn.sub.0.03 V.sub.0.02).sub.3.1 0 to 6Example 179 Lm.sub.0.67 Mg.sub.0.33 (Ni.sub.0.8 Cu.sub.0.1 Cr.sub.0.05 Al.sub.0.03 Nb.sub.0.02).sub.3.02 0 to 10Example 180 Lm.sub.0.78 Mg.sub.0.22 (Ni.sub.0.84 Co.sub.0.1 Fe.sub.0.05 S.sub.0.01).sub.3.65 0 to 3Example 181 La.sub.0.7 Ce.sub.0.1 Mg.sub.0.2 (Ni.sub.0.78 Mn.sub.0.05 Co.sub.0. 15 Zn.sub.0.02).sub.3.8 0 to 7Example 182 La.sub.0.7 Y.sub.0.05 Mg.sub.0.25 (Ni.sub.0.8 Co.sub.0.1 Cu.sub.0.0 8 Sn.sub.0.02).sub.3.52 0 to 3Example 183 Lm.sub.0.66 Mg.sub.0.34 (Ni.sub.0.75 Co.sub.0.13 Mn.sub.0.1 Mo.sub.0.01 P.sub.0.01).sub.3.21 1 to 20Example 184 Lm.sub.0.74 Mg.sub.0.26 (Ni.sub.0.85 Co.sub.0.13 W.sub.0.01 B.sub.0.01).sub.3.45 0 to 5Example 185 Lm.sub.0.6 Mm.sub.0.16 Mg.sub.0.24 (Ni.sub.0.8 Co.sub.0.1 Mn.sub.0. 05 Ga.sub.0.05).sub.3.55 0 to 2Example 186 Lm.sub.0.5 Mm.sub.0.2 Mg.sub.0.3 (Ni.sub.0.75 Co.sub.0.14 Mn.sub.0. 1 Ta.sub.0.01).sub.3.33 0 to 8Example 187 Lm.sub.0.65 Mg.sub.0.3 Ca.sub.0.05 (Ni.sub.0.89 Co.sub.0.05 Cr.sub.0.05 S.sub.0.01).sub.3.12 1 to 18Example 188 Lm.sub.0.73 Mg.sub.0.25 Zr.sub.0.02 (Ni.sub.0.8 Co.sub.0.1 Cu.sub.0.05 Cr.sub.0.05).sub.3.53 0 to 3Example 189 Lm.sub.0.71 Mg.sub.0.28 Hf.sub.0.01 (Ni.sub.0.8 Cu.sub.0.1 Mn.sub.0.05 Al.sub.0.05).sub.3.28 0 to 4Example 190 Lm.sub.0.67 Mg.sub.0.25 Zr.sub.0.08 (Ni.sub.0.08 (Ni.sub.0.8 Cr.sub.0.14 Fe.sub.0.05 Mo.sub.0.01).sub.3.53 0 to 2Example 191 Lm.sub.0.72 Mg.sub.0.24 Ti.sub.0.04 (Ni.sub.0.83 Co.sub.0.13 Si.sub.0.02 Nb.sub.0.02).sub.3.6 0 to 5Example 192 Lm.sub.0.76 Mg.sub.0.23 Zr.sub.0.01 (Ni.sub.0.84 Co.sub.0.13 V.sub.0.02 P.sub.0.01).sub.3.65 0 to 3Example 193 Lm.sub.0.6 Mm.sub.0.14 Mg.sub.0.24 Zr.sub.0.02 (Ni.sub.0.39 Cu.sub.0.1 B.sub.0.01).sub.3.58 0 to 4Example 194 Lm.sub.0.6 Mm.sub.0.14 Mg.sub.0.25 Ti.sub.0.01 (Ni.sub.0.85 Cu.sub.0.1 Zn.sub.0.05).sub.3.53 0 to 4Example 195 Lm.sub.0.7 Mg.sub.0.31 Zr.sub.0.01 (Ni.sub.0.87 Co.sub.0.10 Ga.sub.0.02 Ta.sub.0.01).sub.3.13 0 to 7Comparative La.sub.0.3 Mg.sub.0.7 Ni.sub.3.12 30 to 50Example 48Comparative La.sub.0.5 Mg.sub.0.5 (Ni.sub.0.8 Cu.sub.0.15 Zn.sub.0.05).sub.2.12 30 to 85Example 49Comparative La.sub.0.7 Y.sub.0.3 (Ni.sub.0.76 Cu.sub.0.2 Al.sub.0.04).sub.3.5 25 to 65Example 50Comparative Mm.sub.0.68 Mg.sub.0.32 (Ni.sub.0.74 Co.sub.0.1 Mn.sub.0.1 Al.sub.0.05 Fe.sub.0.01).sub.3.05 40 to 70Example 51Comparative Mm.sub.0.72 Mg.sub.0.28 (Ni.sub.0.77 Co.sub.0.01 Mn.sub.0.1 Al.sub.0.03).sub.3.6 30 to 60Example 52__________________________________________________________________________
TABLE 25__________________________________________________________________________ Rechargeable "a" in the "Z" in the hydrogen storage Discharge capacity Cycle principal principal capacity (H/M) (mAh/g) life phase phase__________________________________________________________________________Example 176 1.05 400 380 0.25 3.51Example 177 0.98 380 350 0.29 3.21Example 178 0.97 365 250 0.31 3.19Example 179 0.93 350 210 0.32 3.13Example 180 0.99 385 370 0.24 3.52Example 181 0.95 350 290 0.21 3.71Example 182 0.98 370 355 0.24 3.53Example 183 0.90 345 200 0.28 3.25Example 184 0.94 365 365 0.26 3.42Example 185 1.02 385 335 0.24 3.55Example 186 0.93 355 280 0.27 3.26Example 187 0.95 365 220 0.29 3.25Example 188 0.94 375 360 0.25 3.50Example 189 1.03 380 330 0.29 3.19Example 190 0.96 365 340 0.26 3.46Example 191 0.95 360 320 0.23 3.55Example 192 0.98 370 350 0.22 3.65Example 193 0.96 355 330 0.25 3.52Example 194 0.95 365 340 0.24 3.51Example 195 0.91 350 285 0.29 3.21Comparative 0.14 50 220 0.55 3.01Example 48Comparative 0.56 240 20 0.45 2.01Example 49Comparative 0.45 200 40 -- --Example 50Comparative 0.42 150 290 0.37 3.6Example 51Comparative 0.40 140 270 0.35 3.9Example 52__________________________________________________________________________
As apparent from Tables 24 and 25, the hydrogen-absorbing alloys of Examples 176 to 195 comprising, as a principal phase, a crystal phase represented by the aforementioned general formula (12) where the values of "a" and "z" therein meet the formula (II), a plane defect in the principal phase being not more than 20 in number per 100 nm, were found more excellent in rechargeable hydrogen storage capacity (H/M) as compared with the hydrogen-absorbing alloys of Comparative Examples 48 to 52. Furthermore, the secondary batteries of Examples 176 to 195 which comprised a negative electrode containing a hydrogen-absorbing alloy where a crystal phase having such a specific composition was contained as a principal phase, and the plane defect in the principal phase thereof was limited within the aforementioned range were found more excellent in both discharge capacity and cycle life as compared with the secondary batteries of Comparative Examples 48 to 52.
Examples 196-215 and Comparative Examples 53-54
Each element was weighed so as to obtain the compositions shown in the following Table 26, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere and then cast into a water-cooled copper mold, each melt cast in this manner being allowed to solidify to obtain various kinds of alloy ingot. Then, these ingots were subjected to a heat treatment in an argon atmosphere for 12 hours at a temperature of 890.degree. C. Subsequently, the alloy ingots were pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 125 .mu.m or less.
By the way, the misch metal (Lm) shown in Table 26 was composed of 94 wt. % of La, 2 wt. % of Ce, 2 wt. % of Pr and 2 wt. % of Nd; while the misch metal (Mm) was composed of 35 wt. % of La, 50.3 wt. % of Ce, 5.5 wt. % of Pr, 9 wt. % of Nd and 0.2 wt. % of Sm.
Comparative Examples 55 to 57
Each element was weighed so as to obtain the composition shown in the following Table 26, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere, thereby preparing alloy ingots.
Then, each alloy ingots was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 890.degree. C. for 12 hours in an argon atmosphere and then pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 125 .mu.m or less.
The hydrogen-absorbing alloys obtained in Examples 196-215 and Comparative Examples 53-57 were measured with respect to the following properties (1) to (3).
(1) Each principal phase of the hydrogen-absorbing alloy was subjected to a component analysis using an EDX analyzer (Energy Dispersive X-ray Spectrometer) of transmission electron microscope and setting the diameter of the beam to 4 nm, the values of "a" and "z" in each resultant composition of the principal phase being shown in the following Table 26.
(2) Each of the hydrogen-absorbing alloy was photographed (magnification: .times.30,000) at different ten crystal grains through a transmission electron microscope. Then, the number of plane defect per 100 nm was counted in optional ten regions in each crystal grain, and an average number of plane defect per 100 nm determined from the ten crystal grains was calculated. Further, the area ratio of crystal grains where the average number of plane defect was 20 or less per 100 nm was calculated, the results were shown in the following Table 27.
(3) A rechargeable hydrogen storage capacity (JIS H7003: Term for Hydrogen Absorbing Alloy), i.e. one of the hydrogen-absorption properties, was determined on each hydrogen-absorbing alloy powder by making use of the iso-thermal line of pressure-composition which was measured under a hydrogen pressure of less than 10 atm. at a temperature of 60.degree. C. by means of Sieverts's method (JIS H7201), the result being shown in the following Table 27.
Furthermore, various kinds of hydrogen absorbing alloy electrode (a negative electrode) were manufactured from the hydrogen-absorbing alloy powders obtained in Examples 196-215 and Comparative Examples 53-57 by following the same procedures as explained with reference to Examples 176-195.
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte) in a case thereby to perform a charge/discharge cycle test at a temperature of 20.degree. C. The charge/discharge conditions in this test were as follows. Namely, the secondary battery was subjected at first to a charging for 5 hours with a current of 100 mA per 1 g of the hydrogen-absorbing alloy, and, after 10 minute cessation, discharged with a current of 150 mA per 1 g of the hydrogen-absorbing alloy until the battery voltage (with respect to a mercury oxide electrode) was decreased down to -0.7V. This charge/discharge cycle was repeated so as to measure the maximum discharge capacity and the cycle life (the number of cycle when the discharge capacity was lowered to 70% of the maximum discharge capacity). The results of this test are shown in the following Table 27.
TABLE 26______________________________________ Composition______________________________________Example 196 La.sub.0.74 Mh.sub.0.26 (Ni.sub.0.86 Cu.sub.0.08 Cr.sub.0.05 Al.sub.0.01).sub.3.4Example 197 La.sub.0.5 Pr.sub.0.22 Mg.sub.0.28 (Ni.sub.0.85 Co.sub.0.05 Fe.sub.0.03 Si.sub.0.01)3.25Example 198 La.sub.0.58 Nd.sub.0.12 Mg.sub.0.3 (Ni.sub.0.85 Cu.sub.0.1 Mn.sub.0.03 Nb.sub.0.02).sub.3.1Example 199 Lm.sub.0.67 Mg.sub.0.33 (Ni.sub.0.8 Co.sub.0.1 Cr.sub.0.05 Al.sub.0.03 V.sub.0.02).sub.3.02Example 200 Lm.sub.0.77 Mg.sub.0.23 (Ni.sub.0.84 Cr.sub.0.1 Fe.sub.0.05 S.sub.0.01).sub.3.6Example 201 La.sub.0.7 Ce.sub.0.1 Mg.sub.0.2 (Ni.sub.0.78 Mn.sub.0.05 Co.sub.0.09 Cu.sub.0.06 Zn.sub.0.2).sub.3.78Example 202 La.sub.0.7 Y.sub.0.05 Mg.sub.0.25 (Ni.sub.0.8 Co.sub.0.1 Cu.sub.0.08 Mo.sub.0.01 P.sub.0.01).sub.3.52Example 203 Lm.sub.0.66 Mg.sub.0.34 (Ni.sub.0.75 Co.sub.0.13 Mn.sub.0.1 Sn.sub.0.02).sub.3.21Example 204 Lm.sub.0.74 Mg.sub.0.26 (Ni.sub.0.8 Co.sub.0.1 Mn.sub.0.05 Ga.sub.0.05).sub.3.4Example 205 Lm.sub.0.6 Mm.sub.0.16 Mg.sub.0.24 (Ni.sub.0.85 Co.sub.0.13 W.sub.0.01 B.sub.0.01).sub.3.6Example 206 Lm.sub.0.56 Mm.sub.0.14 Mg.sub.0.3 (Ni.sub.0.75 Co.sub.0.14 Mn.sub.0.1 Ta.sub.0.01).sub.3.13Example 207 Lm.sub.0.67 Mg.sub.0.30 Ca.sub.0.03 (Ni.sub.0.89 Co.sub.0.05 Cu.sub.0.05 S.sub.0.01).sub.3.25Example 208 Lm.sub.0.73 Mg.sub.0.25 Hf.sub.0.02 (Ni.sub.0.8 Co.sub.0.1 Cu.sub.0.05 Al.sub.0.05).sub.3.53Example 209 Lm.sub.0.71 Mg.sub.0.28 Zr.sub.0.01 (Ni.sub.0.8 Cu.sub.0.1 Mn.sub.0.05 Cr.sub.0.05).sub.3.28Example 210 Lm.sub.0.7 Mg.sub.0.25 Zr.sub.0.05 (Ni.sub.0.8 Co.sub.0.1 Cr.sub.0.04 Fe.sub.0.05 Mo.sub.0.01).sub.3.53Example 211 Lm.sub.0.72 Mg.sub.0.24 Ti.sub.0.04 (Ni.sub.0.84 Co.sub.0.13 V.sub.0.02 P.sub.0.01).sub.3.6Example 212 Lm.sub.0.72 Mg.sub.0.27 Zr.sub.0.01 (Ni.sub.0.83 Co.sub.0.13 Si.sub.0.02 Nb.sub.0.02).sub.3.4Example 213 Lm.sub.0.6 Mm.sub.0.14 Mg.sub.0.24 Zr.sub.0.02 (Ni.sub.0.89 Cu.sub.0.1 B.sub.0.01).sub.3.62Example 214 Lm.sub.0.6 Mm.sub.0.14 Mg.sub.0.25 Ti.sub.0.1 (Ni.sub.0.87 Co.sub.0.1 Ga.sub.0.02 Ta.sub.0.01).sub.3.53Example 215 Lm.sub.0.68 Mg.sub.0.31 Zr.sub.0.01 (Ni.sub.0.85 Cu.sub.0.1 Zn.sub.0.05).sub.3.13Comparative La.sub.0.5 Mg.sub.0.5 Ni.sub.3.12Example 53Comparative La.sub.0.7 Er.sub.0.3 (Ni.sub.0.8 Co.sub.0.15 Al.sub.0.05).sub.3 .13Example 54Comparative La.sub.0.4 Mg.sub.0.6 (Ni.sub.0.8 Cu.sub.0.15 Mn.sub.0.05).sub.2 .35Example 55Comparative Mm.sub.0.67 Mg.sub.0.33 (Ni.sub.0.74 Co.sub.0.1 Mn.sub.0.1 Al.sub.0.06).sub.3.03Example 56Comparative Mm.sub.0.73 Mg.sub.0.27 (Ni.sub.0.73 Co.sub.0.1 Mn.sub.0.1 Al.sub.0.06 Fe.sub.0.01)3.55Example 57______________________________________ "a" in the "Z" in the principal phase principal phase______________________________________Example 196 0.26 3.43Example 197 0.28 3.28Example 198 0.31 3.10Example 199 0.32 3.06Example 200 0.24 3.55Example 201 0.21 3.75Example 202 0.25 3.50Example 203 0.29 3.25Example 204 0.26 3.55Example 205 0.25 3.51Example 206 0.30 3.12Example 207 0.29 3.18Example 208 0.25 3.51Example 209 0.28 3.30Example 210 0.25 3.48Example 211 0.24 3.53Example 212 0.26 3.47Example 213 0.23 3.60Example 214 0.25 3.51Example 215 0.30 3.18Comparative 0.58 3.10Example 53Comparative -- --Example 54Comparative 0.46 2.02Example 55Comparative 0.39 3.60Example 56Comparative 0.37 3.90Example 57______________________________________
TABLE 27__________________________________________________________________________ Rate of crystal RechargeableNumber of plane grain meeting hydrogen storage Dischargedefect (f) f .ltoreq. 20 capacity capacity Cycle(number/100 nm) (vol %) (H/M) (mAh/g) life__________________________________________________________________________Example 196 0 to 3 97 1.03 390 360Example 197 0 to 4 95 1.00 380 340Example 198 0 to 6 90 0.98 380 280Example 199 0 to 20 83 0.98 360 220Example 200 0 to 3 95 1.00 370 350Example 201 0 to 7 90 0.95 350 285Example 202 0 to 3 96 1.00 375 345Example 203 1 to 19 82 0.95 365 220Example 204 0 to 3 96 0.98 370 350Example 205 0 to 4 94 0.92 355 330Example 206 0 to 8 88 0.91 350 280Example 207 0 to 6 90 0.94 360 285Example 208 0 to 2 95 0.96 365 350Example 209 0 to 4 92 0.99 370 335Example 210 0 to 3 94 0.95 365 340Example 211 0 to 5 91 0.93 355 320Example 212 0 to 4 93 0.96 365 330Example 213 0 to 3 94 0.98 370 345Example 214 0 to 4 93 1.00 370 335Example 215 0 to 7 85 0.97 360 285Comparative 30 to 60 40 0.25 100 180Example 53Comparative 25 to 70 30 0.48 220 35Example 54Comparative 30 to 85 50 0.61 260 20Example 55Comparative 25 to 70 35 0.41 140 240Example 56Comparative 30 to 60 40 0.42 150 250Example 57__________________________________________________________________________
As apparent from Tables 26 and 27, the hydrogen-absorbing alloys of Examples 196 to 215 comprising, as a principal phase, a crystal phase represented by the aforementioned general formula (13) where the values of "a" and "z" therein meet the formula (II), and having more than 70% by volume of the crystal phase where the plane defect in crystal grain is not more than 20 in number per 100 nm were found more excellent in rechargeable hydrogen storage capacity (H/M) as compared with the hydrogen-absorbing alloys of Comparative Examples 53 to 57. Furthermore, the secondary batteries of Examples 196 to 215 which comprised a negative electrode containing a hydrogen-absorbing alloy where a crystal phase having such a specific composition was contained as a principal phase and the ratio of crystal phase where the plane defect in the crystal grain thereof was within the aforementioned range were found more excellent in both discharge capacity and cycle life as compared with the secondary batteries of Comparative Examples 53 to 57.
Examples 216-235 and Comparative Examples 58-59
Each element was weighed so as to obtain the compositions shown in the following Table 28, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere and then cast into a water-cooled copper mold, each melt cast in this manner being allowed to solidify to obtain various kinds of alloy ingot. Then, these ingots were subjected to a heat treatment in an argon atmosphere for 12 hours at a temperature of 890.degree. C. Subsequently, the alloy ingots were pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 100 .mu.m or less.
By the way, the misch metal (Lm) shown in Table 28 was composed of 85 wt. % of La, 3 wt. % of Ce, 10 wt. % of Pr and 2 wt. % of Nd; while the misch metal (Mm) was composed of 38 wt. % of La, 50.3 wt. % of Ce, 5.5 wt. % of Pr, 6 wt. % of Nd and 0.2 wt. % of Sm.
Comparative Examples 60 to 63
Each element was weighed so as to obtain the composition shown in the following Table 28, and the resultant compositions were melted in an induction furnace filled with an argon gas atmosphere, thereby preparing alloy ingots.
Then, each alloy ingots was melted and the resultant melt was dropped in an argon gas atmosphere on the surface of a copper roll rotating at a peripheral velocity of 5 m/sec to quench the melt, thereby obtaining a thin hydrogen-absorbing alloy flake. Subsequently, the thin alloy flake was heat-treated at a temperature of 890.degree. C. for 12 hours in an argon atmosphere and then pulverized to prepare hydrogen absorbing alloy powder having a particle diameter of 100 .mu.m or less.
The hydrogen-absorbing alloys obtained in Examples 216-235 and Comparative Examples 58-63 were measured with respect to the following properties (1) and (2).
(1) The analysis of each hydrogen-absorbing alloy was performed by taking the pictures of the secondary electronic image and the back scattered electronic image thereof by making use of a scanning electron microscope (SEM), and then by performing the component analysis of each phase by making use of an EDX analyzer (Energy Dispersive X-ray Spectrometer) of scanning electron microscope, thus determining the values of "a" and "z" in composition of the principal phase, the area ratios of a crystal phase having a CaCu.sub.5 type crystal structure, and of a crystal phase having a MgCu.sub.2 type crystal structure. The results thus measured are shown in the following Table 29.
(2) A rechargeable hydrogen storage capacity (JIS H7003: Term for Hydrogen Absorbing Alloy), i.e. one of the hydrogen-absorption properties, was determined on each hydrogen-absorbing alloy powder by making use of the isothermal line of pressure-composition which was measured under a hydrogen pressure of less than 10 atm. at a temperature of 60.degree. C. by means of Sieverts's method (JIS H7201), the results being shown in the following Table 30.
Furthermore, various kinds of hydrogen absorbing alloy electrode (a negative electrode) were manufactured from the hydrogen-absorbing alloy powders obtained in Examples 216-235 and Comparative Examples 58-63 by following the same procedures as explained with reference to Examples 176-195.
Each of the negative electrodes thus obtained was dipped together with a counter electrode (sintered nickel electrode) into an aqueous solution of 8N-KOH (electrolyte) in a case thereby to perform a charge/discharge cycle test at a temperature of 20.degree. C. The charge/discharge conditions in this test were as follows. Namely, the secondary battery was subjected at first to a charging for 5 hours with a current of 100 mA per 1 g of the hydrogen-absorbing alloy, and, after 10 minute cessation, discharged with a current of 200 mA per 1 g of the hydrogen-absorbing alloy until the battery voltage (with respect to a mercury oxide electrode) was decreased down to -0.7V. This charge/discharge cycle was repeated so as to measure the maximum discharge capacity and the cycle life (the number of cycle when the discharge capacity was lowered to 70% of the maximum discharge capacity). The results of this test are shown in the following Table 30.
TABLE 28______________________________________ Compositions______________________________________Example 216 La.sub.0.75 Mg.sub.0.25 (Ni.sub.0.86 Cu.sub.0.08 Co.sub.0.05 Cr.sub.0.01).sub.3.52Example 217 La.sub.0.60 Pr.sub.0.12 Mg.sub.0.28 (Ni.sub.0.85 Cr.sub.0.05 Fe.sub.0.03 Si.sub.0.01).sub.3.22Example 218 La.sub.0.58 Nd.sub.0.12 Mg.sub.0.3 (Ni.sub.0.85 Cu.sub.0.1 Mn.sub.0.03 V.sub.0.20).sub.3.08Example 219 Lm.sub.0.68 Mg.sub.0.32 (Ni.sub.0.8 Cu.sub.0.1 Cr.sub.0.06 Al.sub.0.02 Nb.sub.0.02).sub.3.05Example 220 Lm.sub.0.76 Mg.sub.0.24 (Ni.sub.0.84 Co.sub.0.10 Fe.sub.0.05 S.sub.0.01).sub.3.55Example 221 La.sub.0.7 Ce.sub.0.1 Mg.sub.0.2 (Ni.sub.0.78 Cr.sub.0.05 Co.sub.0.15 Zn.sub.0.02).sub.3.8Example 222 Lm.sub.0.7 Y.sub.0.05 Mg.sub.0.25 (Ni.sub.0.8 Co.sub.0.1 Cu.sub.0.08 Sn.sub.0.20).sub.3.5Example 223 Lm.sub.0.66 Mg.sub.0.34 (Ni.sub.0.85 Co.sub.0.13 W.sub.0.0.1 B.sub.0.01).sub.3.21Example 224 Lm.sub.0.73 Mg.sub.0.27 (Ni.sub.0.75 Co.sub.0.13 Mn.sub.0.1 Mo.sub.0.01 P.sub.0.01).sub.3.4Example 225 Lm.sub.0.7 Mm.sub.0.06 Mg.sub.0.24 (Ni.sub.0.8 Co.sub.0.1 Mn.sub.0.05 Ga.sub.0.05).sub.3.6Example 226 Lm.sub.0.6 Mm.sub.0.16 Mg.sub.0.3 (Ni.sub.0.75 Co.sub.0.14 Mn.sub.0.1 Ta.sub.0.01).sub.3.4Example 227 Lm.sub.0.66 Mg.sub.0.3 Ca.sub.0.04 (Ni.sub.0.89 Co.sub.0.05 Cr.sub.0.04 Si.sub.0.02).sub.3.12Example 228 Lm.sub.0.72 Mg.sub.0.25 Zr.sub.0.03 (Ni.sub.0.8 Co.sub.0.1 Cu.sub.0.05 Cr.sub.0.05).sub.3.5Example 229 Lm.sub.0.7 Mg.sub.0.28 Hf.sub.0.02 (Ni.sub.0.8 Cu.sub.0.13 Mn.sub.0.05 Al.sub.0.20).sub.3.32Example 230 Lm.sub.0.67 Mg.sub.0.25 Zr.sub.0.08 (Ni.sub.0.84 Co.sub.0.13 V.sub.0.02 P.sub.0.01).sub.3.53Example 231 Lm.sub.0.74 Mg.sub.0.24 Ti.sub.0.02 (Ni.sub.0.83 Co.sub.0.14 S.sub.0.01 Nb.sub.0.02).sub.3.6Example 232 Lm.sub.0.76 Mg.sub.0.23 Zr.sub.0.01 (Ni.sub.0.8 Cr.sub.0.14 Fe.sub.0.05 Mo.sub.0.01).sub.3.65Example 233 Lm.sub.0.06 Mm.sub.0.14 Mg.sub.0.24 Zr.sub.0.02 (Ni.sub.0.89 Cu.sub.0.06 Cr.sub.0.04 B.sub.0.01).sub.3.58Example 234 Lm.sub.0.6 Mm.sub.0.14 Mg.sub.0.25 Ti.sub.0.01 (Ni.sub.0.8 Co.sub.0.1 Cr.sub.0.06 Zn.sub.0.04).sub.3.53Example 235 Lm.sub.0.68 Mg.sub.0.31 Zr.sub.0.01 (Ni.sub.0.87 Cu.sub.0.1 Ga.sub.0.02 Ta.sub.0.10).sub.3.33Comparative La.sub.0.4 Mg.sub.0.6 Ni.sub.3.5Example 58Comparative La.sub.0.7 Dy.sub.0.3 (Ni.sub.0.74 Co.sub.0.25 Mn.sub.0.01).sub.3 .2Example 59Comparative Lm.sub.0.5 Mg.sub.0.5 (Ni.sub.0.8 Cu.sub.0.1 Co.sub.0.15).sub.2.1 2Example 60Comparative Mm.sub.0.67 Mg.sub.0.33 (Ni.sub.0.74 Co.sub.0.1 Mn.sub.0.1 Al.sub.0.04 Fe.sub.0.02).sub.3.23Example 61Comparative Mm.sub.0.72 Mg.sub.0.28 (Ni.sub.0.74 Co.sub.0.01 Mn.sub.0.1 Al.sub.0.06).sub.3.55Example 62Comparative Lm.sub.0.6 (Mg.sub.0.4 Ti.sub.0.1 (Ni.sub.0.85 Fe.sub.0.1 Al.sub.0.05).sub.3Example 63______________________________________
TABLE 29______________________________________"a" in the "Z" in the Ratio of CaCu.sub.5 Ratio of MgCu.sub.2principal principal type phase type phasephase phase (vol %) (vol %)______________________________________Example 216 0.25 3.50 3 1Example 217 0.28 3.30 4 2Example 218 0.30 3.21 3 4Example 219 0.26 3.55 2 5Example 220 0.25 3.51 4 1Example 221 0.21 3.75 8 0Example 222 0.24 3.55 2 0.5Example 223 0.28 3.27 3 5Example 224 0.27 3.31 4 1Example 225 0.24 3.57 6 0.5Example 226 0.29 3.25 5 3Example 227 0.30 3.13 2 4Example 228 0.24 3.60 3 1Example 229 0.28 3.26 3 2Example 230 0.24 3.53 2 3Example 231 0.23 3.62 3 2Example 232 0.23 3.64 5 0.5Example 233 0.25 3.52 4 0.5Example 234 0.26 3.48 3 0.5Example 235 0.28 3.29 3 4Comparative 0.42 3.51 25 25Example 58Comparative -- -- 5 3Example 59Comparative 0.51 2.01 3 65Example 60Comparative 0.39 3.52 25 30Example 61Comparative 0.35 3.72 35 10Example 62Comparative 0.33 3.25 15 18Example 63______________________________________
TABLE 30______________________________________ Rechargeable Discharge hydrogen storage capacity Cycle capacity (H/M) (mAh/g) life______________________________________Example 216 1.02 385 350Example 217 1.01 380 330Example 218 0.98 360 300Example 219 0.95 355 280Example 220 1.00 370 320Example 221 0.90 345 250Example 222 0.96 365 340Example 223 0.92 350 290Example 224 0.95 360 330Example 225 0.97 365 335Example 226 0.96 360 340Example 227 0.98 365 310Example 228 1.00 370 330Example 229 1.02 375 320Example 230 1.00 370 310Example 231 0.98 365 320Example 232 0.96 360 315Example 233 0.97 365 320Example 234 0.99 370 330Example 235 0.95 355 300Comparative 0.12 40 250Example 58Comparative 0.5 240 25Example 59Comparative 0.69 280 15Example 60Comparative 0.41 160 200Example 61Conparative 0.39 130 220Example 62Comparative 0.52 220 180Example 63______________________________________
As apparent from Tables 28 and 30, the hydrogen-absorbing alloys of Examples 216 to 235 comprising, as a principal phase, a crystal phase represented by the aforementioned general formula (14) where the values of "a" and "z" therein meet the formula (II), and further comprising not more than 20% by volume of a crystal phase having a CaCu.sub.5 type crystal structure and not more than 10% by volume of a crystal phase having a MgCu.sub.2 type crystal were found more excellent in rechargeable hydrogen storage capacity (H/M) as compared with the hydrogen-absorbing alloys of Comparative Examples 58 to 63. Furthermore, the secondary batteries of Examples 216 to 235 which comprised a negative electrode containing a hydrogen-absorbing alloy having such specific crystal phases in such a specific ratio were found more excellent in both discharge capacity and cycle life as compared with the secondary batteries of Comparative Examples 58 to 63.
As explained above, it is possible according to this invention to provide a hydrogen-absorbing alloy which is capable of further improving the hydrogen desorption property as compared with the conventional Mg-based hydrogen-absorbing alloy, while ensuring a high hydrogen absorption capacity. Therefore, it is possible according to the hydrogen-absorbing alloy of this invention to further expand the field of application to which other kinds of hydrogen-absorbing alloys have been applied. For example, the hydrogen-absorbing alloys according to this invention can be applied to the storage and transport of hydrogen, the storage and transport of heat, the conversion of heat energy to mechanical energy, the separation and purification of hydrogen, the separation of hydrogen isotope, a battery employing hydrogen as an active material, a catalyst in synthetic chemistry, a temperature sensor, etc. Furthermore, it is also possible according to the hydrogen-absorbing alloy of this invention to further develop a new field of application utilizing a hydrogen-absorbing alloy.
Additionally, it possible according to the secondary battery of this invention to realize a high capacity and a long charge/discharge cycle life, thus exhibiting prominent effects.
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.

Number	Date	Country
9-160276	Jun 1997	JPX
9-253872	Sep 1997	JPX
9-344436	Nov 1997	JPX
10-002994	Jan 1998	JPX
10-065349	Mar 1998	JPX

Number	Name	Date
5242656	Zhang et al.	Sep 1993
5354576	Zhang et al.	Oct 1994
5616432	Ovshinsky et al.	Apr 1997

Number	Date	Country
62-271349	Nov 1987	JPX
62-271348	Nov 1987	JPX
7-56803	Jun 1995	JPX
10-1731	Jan 1998	JPX
WO 9636083	Nov 1995	WOX
WO 9534918	Dec 1995	WOX
WO 9703213	Jan 1997	WOX

Hydrogen-absorbing alloy

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