Patent Application
20210057727
The present disclosure relates to a negative electrode active material for a secondary battery, and a secondary battery.
It is known that silicon materials such as silicon (Si) and silicon oxide represented by SiOx can intercalate more ions such as lithium ions per unit volume than carbon materials such as graphite.
For example, Patent Literature 1 discloses a non-aqueous electrolyte secondary battery in which a mixture of SiOx and graphite is used as a negative electrode active material.
It is desired that charge/discharge cyclic characteristics be improved in secondary batteries in which silicon particles are used as a negative electrode active material.
Thus, an object of the present disclosure is to provide a negative electrode active material for a secondary battery that can prevent the deterioration in the charge/discharge cyclic characteristics of secondary batteries in which silicon particles are used as a negative electrode active material; and a secondary battery.
A negative electrode active material for a secondary battery according to one aspect of the present disclosure comprises: a silicate phase including Li, Si, and Mx, wherein Mx is an element other than an alkali metal, an alkaline earth metal, or Si; silicon particles dispersed in the silicate phase; and metal particles dispersed in the silicate phase and containing one or more metals selected from Fe, Cr, Ni, Mn, Cu, Mo, Zn, and Al or an alloy thereof as a main component, wherein, in the silicate phase, a Li content is 3 to 45 mol %, a Si content is 40 to 78 mol %, and an Mx content is 1 to 40 mol %, each based on the total amount of elements other than oxygen. When the silicate phase further includes an alkaline earth metal M, the M content is 1 to 10 mol %.
A secondary battery as an aspect of the present disclosure comprises: a negative electrode having the negative electrode active material for a secondary battery described above, a positive electrode, and an electrolyte.
According to one aspect of the present disclosure, deterioration in the charge/discharge cyclic characteristics can be prevented in secondary batteries in which silicon particles are used as a negative electrode active material.
For example, when silicon particles are used as a negative electrode active material for a lithium ion secondary battery, the following reactions occur upon charge/discharge of the secondary battery, for example.
Si+4Li++4e−->Li4Si Charge:
Li4Si->Si+4Li++4e− Discharge:
Usually, silicon particles have a large volume change due to the above charge/discharge reaction. Thus, when charge/discharge cycles are repeated, the particle structure is broken, resulting in the deterioration in the charge/discharge cyclic characteristics of the battery. The present inventors have thus been intensively studying to find that dispersion of silicon particles and predetermined metal particles in a silicate phase having a predetermined component can prevent a volume change of the silicon particles due to the charge/discharge reaction, to thereby prevent the breakage of the particle structure, thus conceiving a negative electrode active material of aspects described below.
A negative electrode active material for a secondary battery according to one aspect of the present disclosure comprises: a silicate phase including Li, Si, and Mx, wherein Mx is an element other than an alkali metal, an alkaline earth metal, or Si; silicon particles dispersed in the silicate phase; and metal particles dispersed in the silicate phase and containing one or more metals selected from Fe, Cr, Ni, Mn, Cu, Mo, Zn, and Al or an alloy thereof as a main component, wherein, in the silicate phase, a Li content is 3 to 45 mol %, a Si content is 40 to 78 mol %, and an Mx content is 1 to 40 mol %, each based on the total amount of elements other than oxygen. When the silicate phase further includes an alkaline earth metal M, the M content is 1 to 10 mol %. It is considered that a silicate phase having the specific components described above has a hardness sufficient to prevent the volume change of the silicon particles due to the charge/discharge reaction. Further, it is considered that dispersion of the metal particles described above in the silicate phase described above alleviates the volume change of the silicate phase or the silicon particles dispersed in the silicate phase due to the malleability of the metal particles. For these reasons, the volume change of the silicon particles due to the charge/discharge reaction is reduced and the breakage of the particle structure is prevented. It is thus considered that the deterioration in the charge/discharge cyclic characteristics of the battery is prevented. The silicate phase having the predetermined components described above exhibits a good ion conductivity to ions such as lithium ions. It is thus considered that, upon charge/discharge, ions such as lithium ions migrate relatively smoothly in the silicate phase to efficiently react with the silicon particles dispersed in the silicate phase.
The negative electrode active material for a secondary battery according to one aspect of the present disclosure is suitably used as a negative electrode active material for a lithium ion secondary battery, for example. Hereinafter, the negative electrode active material for a secondary battery according to one aspect of the present disclosure will be described with a lithium ion secondary battery taken as an example. The drawing referred to for the description of embodiments below is schematically illustrated, and the dimensions, the proportions, and the like of the components illustrated in the drawing may be different from those of actual products. Specific dimensions, proportions, and the like should be determined in consideration of the description below.
A lithium ion secondary battery as an exemplary embodiment comprises a negative electrode, a positive electrode, and an electrolyte. A separator is preferably disposed between the positive electrode and the negative electrode. In an exemplary structure of the lithium ion secondary battery, an exterior body houses an electrode assembly formed by winding the positive electrode and the negative electrode together with the separator therebetween, and the electrolyte. The electrode assembly is not limited to an electrode assembly having the wound structure, and an electrode assembly of another type may be applied, including an electrode assembly having a laminated structure formed by alternately laminating positive electrodes and negative electrodes with separators therebetween. The lithium ion secondary battery may be any form including a cylindrical shape, a rectangular shape, a coin shape, a button shape, and a laminated shape.
The positive electrode preferably includes a positive electrode current collector, such as a metal foil, and a positive electrode mixture layer formed on the current collector. Foil of a metal that is stable in the electric potential range of the positive electrode, such as aluminum, a film with such a metal disposed as an outer layer, and the like can be used for the positive electrode current collector. The positive electrode mixture layer preferably includes a positive electrode active material and additionally includes a conductive agent and a binder. The surface of the particles of the positive electrode active material may be coated with micro particles of an oxide such as aluminum oxide (Al2O3) or an inorganic compound such as a phosphoric acid compound or a boric acid compound.
Examples of the positive electrode active material include a lithium transition metal oxide, which contains a transition metal element such as Co, Mn, or Ni. Examples of the lithium transition metal oxide include LixCoO2, LixNiO2, LixMnO2, LixCoyNi1-yO2, LixCoyM1-yOz, LixNi1-yMyOz, LizMn2O4, LixMn2-yMyO4, LiMPO4, and Li2MPO4F (M; at least one of the group consisting of Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B, 0<x≤1.2, 0<y≤0.9, 2.0≤z≤2.3). These may be used singly or two or more thereof may be mixed and used.
Examples of the conductive agent include carbon materials such as carbon black, acetylene black. Ketjen black, and graphite. These may be used singly or in combinations of two more thereof.
Examples of the binder include fluoro resins, such as polytetrafluoroethylene (PTFE) and poly(vinylidene fluoride) (PVdF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins. These resins may be combined with carboxymethyl cellulose (CMC) or a salt thereof (e.g., CMC-Na, CMC-K, or CMC-NH which may be a partially neutralized salt), poly(ethylene oxide) (PEO), or the like. These may be used singly or in combinations of two ore thereof.
The negative electrode preferably includes a negative electrode current collector, such as a metal foil, and a negative electrode mixture layer formed on the current collector. Foil of a metal that is stable in the electric potential range of the negative electrode, such as copper, a film with such a metal disposed as an outer layer, and the like can be used for the negative electrode current collector. The negative electrode mixture layer preferably includes a negative electrode active material (negative electrode active material particles to be explained below) and additionally includes a binder. As the binder, fluoro resins, PAN, polyimide resins, acrylic resins, polyolefin resins, and the like can be used, as in the positive electrode. When a mixture slurry is prepared using an aqueous solvent, CMC or a salt thereof (e.g., CMC-Na, CMC-K, or CMC-NH4 which may be a partially neutralized salt), styrene-butadiene rubber (SBR), poly(acrylic acid) (PAA) or a salt thereof (e.g., PAA-Na or PAA-K which may be a partially neutralized salt), poly(vinyl alcohol) (PVA), or the like is preferably used.
The silicon particles 12 can intercalate more lithium ions than carbon materials such as graphite, and thus a larger capacity battery is achieved. On the surface of the silicon particles 12, SiO2 as a natural oxidized film may be formed. Increase in the amount of SiO2 as a natural oxidized film may lead to deterioration in the battery capacity, charge/discharge cyclic characteristics, or the like. Thus, the content of SiO2 as the natural oxidized film is preferably less than 10 mass % and more preferably less than 7 mass % based on the total mass of the base particle 13.
The content of the silicon particles 12 is preferably 20 mass % to 95 mass % and more preferably 35 mass % to 75 mass % based on the total mass of the base particle 13 (the total mass of the silicate phase 11, the silicon particles 12, and the metal particles 15) in view of a larger capacity, improvement in the charge/discharge cyclic characteristics, and the like. If the content of the silicon particles 12 is too low, the charge/discharge capacity decreases, for example, and also diffusion of lithium ions may be poor which deteriorates loading characteristics. If the content of the silicon particles 12 is too high, the effect of preventing deterioration in the charge/discharge cyclic characteristics may be reduced, for example.
The average particle size of the silicon particles 12 is, for example, 500 urn or less, preferably 200 nm or less, and more preferably 50 nm or less before the first charge. The average particle size is preferably 400 nm or less and more preferably 100 nm or less after charge/discharge. Fine silicon particles 12 exhibits a reduced volume change thereof upon charge/discharge and are thus likely to prevent breakage of the electrode structure. The average particle size of the silicon particles 12 is determined through observation of the cross section of the particles 10 of the negative electrode active material using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and specifically, is obtained by averaging the longest particle diameters of one hundred silicon particles 12.
The metal particles 15 are metal particles containing one or more metals selected from Fe, Cr, Ni, Mn, Cu, Mo, Zn, and Al or an alloy thereof as a main component (the component of which mass is the largest among the metals or alloy constituting the metal particles 15). It is considered that dispersion of the metal particles 15 in the silicate phase 11 alleviates the volume change of the base particle 13 (specifically, the silicon particles 12 or the silicate phase 11) due to the charge/discharge, to thereby prevent the breakage of the particle structure. The metal particles 15 are preferably metal particles containing as a main component, Fe, among the elements described above, in view of preventing the breakage of the particle structure and further preventing the deterioration in the charge/discharge cyclic characteristics. When the main component of the metal particles 15 is Fe, the content of Fe is preferably 50 mass % or more, more preferably 60 mass % or more, and particularly preferably 70 mass % or more based on the total mass of the metal particles 15. The metal particles containing Fe as a main component may be metal particles made of Fe, or an iron alloy containing Fe as a main component and containing Cr, Ni, Mn, Cu, Mo, Zn, Al, or the like (e.g., stainless steel).
The metal particles 15 may include two or more types of metal particles containing one or more metals selected from Fe, Cr, Ni, Mn, Cu, Mo, Zn, and Al or an alloy thereof as a main component, and may include, for example, two or more types of metal particles containing Fe as a main component, metal particles containing Cr as a main component, metal particles containing Ni as a main component, metal particles containing Mn as a main component, metal particles containing Cu as a main component, metal particles containing Mo as a main component, metal particles containing Zn as a main component, and metal particles containing Al as a main component.
The metal or alloy constituting the metal particles 15 may be alloyed with at least one of Si (silicon particles 12) and silicate (silicate phase 11). It is possible to alloy the metal particles 15 with at least one of Si and silicate by means of heat treatment in the process of manufacturing the particles 10 of the negative electrode active material. Such alloying reinforces the adhesion between the metal particles 15 and the silicate phase 11, for example, to thereby facilitate prevention of the breakage of the particles due to rapid charge/discharge. The fact that the metal or alloy constituting the metal particles 15 is alloyed with at least one of Si and silicate can be confirmed using energy dispersive X-ray spectroscopy (EDS).
The content of the metal particles 15 is preferably 0.01 mass % to 20 mass % and more preferably 9 mass % to 15 mass % based on the total mas of the base particle 13 (the total mass of the silicate phase 11, the silicon particles 12, and the metal particles 15) in view of preventing the deterioration in the charge/discharge cyclic characteristics and the like.
The average particle size of the metal particles 15 is preferably 100 nm or less and more preferably in the range of 15 to 80 nm. As long as the particle size of the metal particles 15 is within this range, a uniform dispersion state of the metal particles 15 in the silicate phase 11 is likely to be formed, and the deterioration in the charge/discharge cyclic characteristics may be further prevented. The average particle size of the metal particles 15 is measured through observation of the cross section of the particles 10 of the negative electrode active material using a SEM or TEM, as in the case of the silicon particles 12, and is specifically determined by averaging the longest particle diameters of one hundred metal particles 15.
The silicate phase 11 includes Li, Si, and Mx, wherein Mx is an element other than an alkali metal, an alkaline earth metal, or Si. In the silicate phase 11, the Li content is 3 to 45 mol %, the Si content is 40 to 78 mol %, and the Mx content is 1 to 40 mol %, each based on the total amount of elements other than oxygen. When the silicate phase 11 further includes an alkaline earth metal M, the M content is 1 to 10 mol %. M is an element for an optional component MO, which may be included in the silicate phase 11, and M is an alkaline earth metal. Thus, it is considered that the silicate phase 11, having the specific components in the predetermined amount, as stated hereinabove, has a hardness sufficient to prevent the volume change of the silicon particles 12 and also has a high ion conductivity. Mx is any one of M1, M2, M3, and M4, and M1, M2, M3, and M4 are elements for M12O3, M2O2, M32O5, and M4O, respectively. Thus, it can be considered that the silicate phase 11 has a structure in which Li2O, SiO2, and for example, oxides including M1O2, M2O3, M3O5, and M4O3, are bonded to each other.
In view of for example, securely preventing the deterioration in the charge/discharge cyclic characteristics, in the silicate phase 11, the Li content is preferably 5 to 23 mol %, the Si content is preferably 45 to 78 mol %, and the content of M1, M2, M3, and M4 is preferably 2 to 35 mol %, each based on the total amount of elements other than oxygen.
It is preferable that the silicate phase 11 include M1 as a result of, for example, adding M1O2 and sintering the resultant to produce the silicate phase 11. Specifically, it is preferable that the silicate phase 11 include any one element of Zr, Ge, and Ti as a result of adding as M1O2 at least any one of ZrO2, GeO2, and TiO2 and sintering the resultant. Through sintering the oxide, the hardness or the ion conductivity of the silicate phase 11 may increase to thereby securely prevent the deterioration in the charge/discharge cyclic characteristics or obtain a larger capacity battery.
It is preferable that the silicate phase 11 include M2 as a result of for example, adding M22O3 and sintering the resultant to produce the silicate phase 11. Specifically, it is preferable that the silicate phase 11 include any one element of Al, B, Bi, Y, La, and Sb as a result of adding as M22O3 at least any one of Al2O3, B2O3, Bi2O3, Y2O3, La2O3, and Sb2O3, and sintering the resultant. Through sintering the oxide, the hardness or the ion conductivity of the silicate phase 11 may increase to thereby securely prevent the deterioration in the charge/discharge cyclic characteristics or obtain a larger capacity battery.
It is preferable that the silicate phase 11 include M3 as a result of, for example, adding M32O5 and sintering the resultant to produce the silicate phase 11. Specifically, it is preferable that the silicate phase 11 include any one element of Nb, La, Ta, P, and V as a result of adding as M32O5 at least any one of Nb2O5, La2O5, Ta2O5, P2O5, and V2O5, and sintering the resultant. Through sintering the oxide, the hardness or the ion conductivity of the silicate phase 11 may increase to thereby securely prevent the deterioration in the charge/discharge cyclic characteristics or obtain a larger capacity battery.
It is preferable that the silicate phase 11 include M4 as a result of for example, adding M4O3 and sintering the resultant to produce the silicate phase 11. Specifically, it is preferable that the silicate phase 11 include W as a result of adding WO3 as M4O3 and sintering the resultant. Through sintering the oxide, the hardness or the ion conductivity of the silicate phase 11 may increase to thereby securely prevent the deterioration in the charge/discharge cyclic characteristics or obtain a larger capacity battery.
The silicate phase 11 may include an alkaline earth metal M as a result of, for example, adding MO (alkaline earth metal) and sintering the resultant. When the silicate phase 11 includes M, the M content in the silicate phase 11 is 1 to 10 mol % and preferably 1 to 5 mol % based on the total amount of elements other than oxygen. If the M content in the silicate phase 11 is more than 10 mol %, the ion conductivity may decrease to thereby fail to sufficiently prevent the deterioration in the charge/discharge cyclic characteristics.
When the silicate phase 11 includes an alkaline eth metal M, M includes at least any one of Be, Mg, Ca, Sr, Ba, Ra, Pb, and Cu. In this case, the silicate phase 11 can be produced through, for example, adding as MO at least any one of BeO, MgO, CaO, SrO, BaO, RaO, PbO, and CuO, and sintering the resultant. When the content of the oxide is less than the given value, the hardness or the ion conductivity of the silicate phase 11 may increase to thereby securely prevent the deterioration in the charge/discharge cyclic characteristics or obtain a larger capacity battery.
The content of each element included in the silicate phase 11 can be determined in the following manner, for example.
First, a sample of the silicate phase 11 is thoroughly dissolved in a hot acid solution (mixed acid of hydrofluoric acid, nitric acid, and sulfuric acid), and carbon that is the insoluble residue is removed by filtration. The filtrate obtained is analyzed by inductively coupled plasma atomic emission spectroscopy (ICP-AES) to determine the spectral intensity of each metal element. A calibration curve is prepared using commercially available standard solutions of metal elements, and the content of each metal element included in the silicate phase 11 is calculated on the calibration curve. The contents of silicon and boron are determined in the same manner as above, except that the sample is melted with sodium carbonate, followed by filtration.
The content of each metal oxide in the silicate phase 11 can be estimated, for example, from the content of each metal element determined as above. For example, when the metal element is Al, the amount of Al2O3 calculated on the supposition that all Al forms Al2O3 is taken as the amount of the Al oxide assumed. When the metal element is Ca, the amount of CaO calculated on the supposition that all Ca forms CaO is taken as the amount of the Ca oxide assumed.
The content of the silicate phase 11 is preferably 5 mass % to 80 mass % and more preferably 25 mass % to 65 mass % based on the total mass of the base particle 13 (the total mass of the silicate phase 11, the silicon particles 12, and the metal particles 15) in view of the improvement in the charge/discharge cyclic characteristics and the like.
The average particle size of the particles 10 of the negative electrode active material is preferably 1 to 15 μm, and more preferably 4 to 10 μm in view of for example, larger capacity and improvement in the cyclic characteristics. The average particle size of the particles 10 of the negative electrode active material herein means a diameter (a volume average particle size) at an integrated volume of 50% in the particle size distribution analyzed according to the laser diffraction/scattering method (using, for example, “LA-750” manufactured by HORIBA, Ltd.). If the average particle size of the particles 10 of the negative electrode active material is too small, the surface area thereof is larger, and therefore the amount thereof reacting with an electrode is likely to be larger, resulting in decrease in the capacity. On the other hand, if the average particle size of the particles 10 of the negative electrode active material is too large, the change in the volume due to charge/discharge may be larger, sometimes resulting in reduction in the effect of preventing decrease in the charge/discharge cyclic characteristics. It is preferable to form a conductive layer 14 on the surface of the particles 10 (base particle 13) of the negative electrode active material. However, the thickness of the conductive layer 14 is so small that it has substantially no influence on the average particle size of the particles 10 of the negative electrode active material (the particle size of the particle 10 of the negative electrode active material≈the particle size of the base particle 13).
The particles 10 of the negative electrode active material may be used alone as a negative electrode active material in the negative electrode mixture layer, or may be combined with another active material. For example, a carbon material such as graphite is preferable as the other active material. When a carbon material is combined therewith, the mass ratio of the particles 10 of the negative electrode active material and the carbon material is preferably 1:99 to 30:70 in view of for example, a larger capacity and improvement in the charge/discharge cyclic characteristics.
The base particles 13 are produced through, for example, the following steps 1 to 4. The following steps are each preferably conducted in an inert atmosphere, although step 1 can be conducted in atmospheric air.
(1) Predetermined amounts of a Li material, a Si material, a material including at least any one of an M1 material, an M material, an M3 material, and an M4 material, and an M material are mixed, and the mixture is heated and melted. The melt is made into flakes through metal rolls to produce silicate. Then, the silicate flakes are heat-treated for crystallization in atmospheric air at a temperature of the glass transition point or more and the melting point or less. Alternately, the silicate flakes may be used without undergoing crystallization. The mixture obtained by mixing the predetermined amounts of the materials may be fired at a temperature equal to or less than the crystal melting point without undergoing melting, to thereby produce silicate through a solid-phase reaction. Examples of the Li material include lithium oxide, lithium carbonate, and lithium hydroxide. Examples of the Si material include silicon oxide. Examples of the M1 material, the M2 material, the M3 material, and the M4 material include an oxide, a hydroxide, and a carbonate compound of an element other than an alkali metal, an alkaline earth metal, or Si. Examples of the M material include an oxide, a hydroxide, and a carbonate compound of an alkaline earth metal. It is preferable to avoid contamination with an alkali metal other than lithium as much as possible, because the existence of an alkali metal other than lithium, such as sodium and potassium, in the silicate decreases the ion conductivity. However, when the silicate is contaminated with any alkali metal other than lithium as an inevitable impurity, the content thereof is preferably less than 3 mol %.
(2) A silicate powder obtained by grinding the silicate described above to the average particle size of approximately several micrometers to several tens of micrometers, a Si powder having an average particle size of approximately several micrometers to several tens of micrometers, and the metal particles mentioned above are mixed in a predetermined mass ratio to produce a mixture.
(3) Then, the mixture is ground for atomization in a ball mill. Alternatively, the material powders may each be atomized and then mixed to produce a mixture. The time duration for the grinding treatment is desirably a duration such that the crystallite size of the ground powder becomes 25 nm or less, the crystallite size of the ground powder being calculated by Scherrer equation from the half width of the diffraction peak of the Si (111) plane in the XRD pattern obtained by XRD measurement on the ground powder. The specific conditions and the like for the measurement of the crystallite size are as follows.
Measurement system: In-plane multipurpose X-ray diffraction system Ultima IV (manufactured by Rigaku Corporation)
Analytical software: one-stop full-function powder X-ray diffraction analysis software PDXL (manufactured by Rigaku Corporation)
Measurement conditions: 20 to 90°, using a diffraction peak of Si(111) plane (2=28 to 29°), 5000 counts or more at the top of the peak
Anticathode: Cu-Kα
Tube current/voltage: 40 mA/40 kV
Counting time: 1.0 s
Divergence slit: ⅔°
Vertical divergence limiting slit: 10 mm
S Scattering slit: ⅔°
Light receiving slit: 0.3 mm
Sample spinning: 60 rpm
(4) The ground mixture is heat-treated at, for example, 600 to 1000° C. In this heat treatment, pressure may be applied to the mixture, as in hot press, to produce a sintered compact of the mixture. The Si powder and the silicate powder may be mixed and heat-treated without using a bell mill to produce base particles 13.
The silicate produced in step (1) is for forming the silicate phase 11 described above and has high hardness. Thus, the silicate powder having a high hardness is brought into contact with the Si powder in step (3), and the Si powder is therefore easily atomized. Thus, the time required for reaching the prescribed atomization level can be shortened.
The conductive material for forming the conductive layer 14 is preferably electrochemically stable, and is preferably at least one selected from the group consisting of a carbon material, a metal, and a metal compound. As the carbon material, carbon black, acetylene black, Ketjen black, graphite, and a mixture of two or more thereof can be used, as in the conductive material for the positive electrode mixture layer. As the metal, copper, nickel, and an alloy thereof that is stable in the electric potential range of the negative electrode can be used. Examples of the metal compounds include a copper compound and a nickel compound (a metal or metal compound layer can be formed on the surface of the base particle 13 by, for example, nonelectrolytic plating). Among these, the carbon material is particularly preferably used.
Examples of the method for coating the surface of the base particle 13 with the carbon material include a CVD method involving using acetylene, methane, or the like, and a method in which the base particles 13 are mixed and heat-treated with coal pitch, petroleum pitch, a phenol resin, or the like. Alternatively, carbon black, Ketjen black, or the like may be adhered to the surface of the base particles 13 with a binder.
Preferably, almost the whole area of the surface of the base particle 13 is covered with the conductive layer 14. The thickness of the conductive layer 14 is preferably 1 to 200 nm and more preferably 5 to 100 nm in view of ensuring the conductivity and the diffusibility of lithium ions into the base particles 13. If the thickness of the conductive layer 14 is too small, the conductivity decreases, and it is also difficult to uniformly cover the base particles 13. On the other hand, if the thickness of the conductive layer 14 is too large, there is a tendency for the diffusion of the lithium ions into the base particles 13 to be inhibited, which decreases the capacity. The thickness of the conductive layer 14 can be measured through observation of the cross section of the particle using SEM, TEM, or the like.
The electrolyte includes a solvent and an electrolyte salt dissolved in the solvent. The electrolyte is not limited to a liquid electrolyte and may be a solid electrolyte using a gel polymer or the like. As the solvent, it is possible to use a non-aqueous solvent comprising, for example, esters, ethers, nitriles such as acetonitrile, amides such as dimethylformamide, and mixed solvents of two or more thereof or an aqueous solvent. The non-aqueous solvent may contain a halogen-substituted product formed by replacing at least one hydrogen atom of any of the above solvents with a halogen atom such as fluorine.
Examples of the esters include cyclic carbonate esters, such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate, chain carbonate esters, such as dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate, ethyl propyl carbonate, and methyl isopropyl carbonate, cyclic carboxylate esters such as γ-butyrolactone (GBL) and γ-valerolactone (GVL), and chain carboxylate esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP), ethyl propionate, and γ-butyrolactone.
Examples of the ethers include cyclic ethers such as 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4-dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineole, and crown ethers, and chain ethers such as, 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, o-dimethoxybenzene, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, 1,1-dimethoxymethane, 1,1-diethoxyethane, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
Examples of the halogen-substituted product preferable for use include a fluorinated cyclic carbonate ester such as fluoroethylene carbonate (FEC), a fluorinated chain carbonate ester, and a fluorinated chain carboxylate ester such as methyl fluoropropionate (FMP).
As the electrolyte salt, a lithium salt or the like is used. Examples of the lithium salt include LiBF4, LiCOl4, LiPF6, LiAsF6, LiSbF6, LiACl4, LiSCN, LiCF3SO3, LiCF3CO2, Li(P(C2O4)F4), LiPF6-x(CnF2n+1)x(1<x<6, n is 1 or 2), LiB10Cl10, LiCl, LiBr, LiI, chloroborane lithium, lithium lower aliphatic carboxylate, borates such as Li2B4O7 and Li(B(C2O4)F2), and imide salts such as LiN(SO2CF3)2, LiN(ClF2l+1SO2)(CmF2m+1SO2) (wherein l and m are integers of 0 or more). These lithium salts may be used singly, or two or more thereof may be mixed and used. Among these, LiPF6 is preferably used in view of ionic conductivity, electrochemical stability, and other properties. The concentration of the lithium salt is preferably 0.8 to 1.8 mol per 1 L of the non-aqueous solvent.
An ion-permeable and insulating porous sheet is used as the separator. Specific examples of the porous sheet include a microporous thin film, woven fabric, and nonwoven fabric. Suitable examples of the material for the separator include olefin resins such as polyethylene and polypropylene, and cellulose. The separator may be a laminate including a cellulose fiber layer and a layer of fibers of a thermoplastic resin such as an olefin resin.
Hereinafter, the present disclosure will be described in more detail by way of Examples, but the present disclosure is not limited thereby.
Lithium oxide, silicon dioxide, calcium oxide, boron oxide, and aluminum oxide were mixed in a molar ratio of Li2O/SiO2/CaO/B2O3/Al2O3=22/72/1/2/3. The resulting mixture was melted in an inert atmosphere at 1500° C. for 5 hours, and the melt was passed through metal rollers to obtain flakes. The flakes were heat-treated for crystallization at 750° C. for 5 hours to produce silicate including Li, Si, Ca, B, and Al.
The silicate was ground to an average particle size of 10 μm to obtain a silicate powder. Then, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder were weighed in a mass ratio of 42:58, an Fe powder (10 μm ground product) was added thereto such that the content thereof reached 0.01 mass %, and the mixture was placed in a pot (made of SUS, volume: 500 mL) of a planetary ball mill (P-5, manufactured by FRITSCH). Twenty four SUS balls (diameter: 20 mm) were placed in the pot, and a lid was put thereon, followed by grinding treatment at 200 rpm for 25 hours. Then, the resulting powder was taken out in an inert atmosphere, and heat-treated in conditions of a temperature of 600° C. for 4 hours in an inert atmosphere. The heat-treated powder (hereinafter, referred to as base particles) was ground and passed through a 40-μm mesh, and the resulting powder was mixed with coal pitch (MCP 250, manufactured by JFE Chemical Corporation). The mixture was heat-treated in conditions of a temperature of 800° C. for 5 hours in an inert atmosphere to coat the surface of each base particle with carbon, thereby forming a conductive layer. The amount of the carbon coating was 5 mass % based on the total mass of the particle composed of the base particle and the conductive layer. The resultant was then conditioned using an Elbow-Jet classifier so as to have an average particle size of 5 μm, thereby obtaining a negative electrode active material.
As the result of the observation with a SEM on the cross sections of the particles of the negative electrode active material, the average particle size of the Si particles dispersed in the silicate phase was less than 100 nm, and the average particle size of the Fe powder dispersed in the silicate phase was 100 nm. The content of each element in the silicate phase was calculated through ICP emission spectral analysis. It is necessary for Si particles to be distinguished from the Si element in the silicate phase so that the content of Si element in the silicate phase is calculated so as not to include Si particles. Specifically, it was calculated in the following manner. First, the amount of Si included in the whole of the negative electrode active material was determined through ICP emission spectral analysis. Then, Si particles dispersed in the lithium silicate phase were heated for crystallization in a vacuumed atmosphere at 930° C. for 10 hours, and the resulting powder was subjected to XRD analysis. The Si content was calculated from the integrated value of Si peaks in the XRD analysis. From the measurement results, the amount of Si element in the lithium silicate phase was determined by arithmetic operation. The contents of Li, Si, Ca, B, and Al elements in the silicate phase were 34.6 mol %, 56.7 mol % 0.8 mol %, 3.1 mol %, and 4.7 mol % respectively. The content of the Fe powder dispersed in the silicate phase is 0.01 mass % based on the mass of the base particle as described above.
Next, the above-described negative electrode active material and polyacrylonitrile (PAN) were mixed in a mass ratio of 95:5, and N-methyl-2-pyrolidone (NMP) was added thereto. The resulting mixture was then stirred using a mixer (THINKY MIXER Awatori-Rentaroh, manufactured by THINKY CORPORATION) to prepare a negative electrode mixture slurry. Then, the slurry was applied to one side of a copper foil so that the mass of the negative electrode mixture layer was 25 g per m2. The coating was dried at 105° C. in atmospheric air, and then rolled to produce a negative electrode. The packing density of the negative electrode mixture layer was 1.50 g/cm3.
Ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed in a volume ratio of 3:7. LiPF6 was added to the mixed solvent to a concentration of 1.0 mol/L to thereby prepare a non-aqueous electrolyte solution.
In an inert atmosphere, the negative electrode described above and a lithium metal foil, each having a Ni tab attached thereto, were disposed opposite to each other with a polyethylene separator interposed therebetween to thereby form an electrode assembly. The electrode assembly was then housed in a battery exterior body made of an aluminum-laminated film, and the non-aqueous electrolyte solution was injected to the battery exterior body. The battery exterior body was sealed to thereby prepare a non-aqueous electrolyte secondary battery.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder of Example 1 were weighed in a mass ratio of 42:58, and an Fe powder (10 μm ground product) was added thereto such that the content thereof reached 0.1 mass %. The content of each element in the silicate phase was the same as in Example 1. Additionally, the content of the Fe powder dispersed in the silicate phase is 0.1 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder of Example 1 were weighed in amass ratio of 42:58, and an Fe powder (10 μm ground product) was added thereto such that the content thereof reached 1 mass %. The content of each element in the silicate phase was the same as in Example 1. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder of Example 1 were weighed in a mass ratio of 42:58 and an Fe powder (10 μm ground product) was added thereto such that the content thereof reached 9 mass %. The content of each element in the silicate phase was the same as in Example 1. The content of the Fe powder dispersed in the silicate phase is 9 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder of Example 1 were weighed in a mass ratio of 42:58 and an Fe powder (10 μm ground product) was added thereto such that the content thereof reached 20 mass %. The content of each element in the silicate phase was the same as in Example 1. Additionally, the content of the Fe powder dispersed in the silicate phase is 20 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder of Example 1 were weighed in a mass ratio of 42:58, and a Cr powder (10 μm ground product) was added thereto such that the content thereof reached 0.1 mass %. The content of each element in the silicate phase was the same as in Example 1. Additionally, the content of the Cr powder dispersed in the silicate phase is 0.1 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder of Example 1 were weighed in a mass ratio of 42:58, and a Ni powder (10 μm ground product) was added thereto such that the content thereof reached 0.1 mass %. The content of each element in the silicate phase was the same as in Example 1. Additionally, the content of the Ni powder dispersed in the silicate phase is 0.1 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder of Example 1 were weighed in a mass ratio of 42:58, and a Zn powder (10 μm ground product) was added thereto such that the content thereof reached 0.1 mass %. The content of each element in the silicate phase was the same as in Example 1. Additionally, the content of the Zn powder dispersed in the silicate phase is 0.1 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder of Example 1 were weighed in a mass ratio of 42:58, and an Al powder (10 μm ground product) was added thereto such that the content thereof reached 0.1 mass %. The content of each element in the silicate phase was the same as in Example 1. Additionally, the content of the Al powder dispersed in the silicate phase is 0.1 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, B, and Al was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, boron oxide, and aluminum oxide were mixed in a molar ratio of Li2O/SiO2/B2O3/Al2O3=22/58/10/10.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder described above were weighed in a mass ratio of 42:58, an Fe powder (10 μm ground product) was added thereto such that the content thereof reached 0.1 mass %, and the grinding treatment time was 19 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, B, and Al contents were found to be 31.0 mol %, 40.8 mol %, 14.1 mol %, and 14.1 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 0.1 mass % based on the of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, B, and Al was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, boron oxide, and aluminum oxide were mixed in a molar ratio of Li2O/SiO2/B2O3/Al2O3=22/48/15/15.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder described above were weighed in a mass ratio of 42:58, an Fe powder (10 μm ground product) was added thereto such that the content thereof reached 1 mass %, and the grinding treatment time was 18 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, B, and A contents were found to be 28.9 mol %, 31.6 mol %, 19.7 mot %, and 19.7 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, Ca, Mg, B, and Al was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, calcium oxide, magnesium oxide, boron oxide, and aluminum oxide were mixed in a molar ratio of Li2O/SiO2/CaO/MgO/B2O3/Al2O3=22/67/1/5/2/3.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 26 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, Ca, Mg, B, and Al contents were 34.6 mol %, 52.8 mol %, 0.8 mol %, 3.9 mol %, 3.1 mol %, and 4.7 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, Ca, B, Al, and Zr was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, calcium oxide, boron oxide, aluminum oxide, and zirconium oxide were mixed in a molar ratio of Li2O/SiO2/CaO/B2O3/Al2O3/ZrO2=22/67/1/2/3/5.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 20 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, Ca, B, Al, and Zr contents were 34.6 mol %, 52.8 mol %, 0.8 mol % 3.1 mol %, 4.7 mol %, and 3.9 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, Ca, B, Al, and Nb was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, calcium oxide, boron oxide, aluminum oxide, and niobium oxide were mixed in a molar ratio of Li2O/SiO2/CaO/B2O3/Al2O3/Nb2O5=22/67/1/2/3/5.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 21 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, Ca, B, Al, and Nb contents were 33.3 mol %, 50.8 mol %, 0.8 mol %, 3.0 mol %, 4.5 mol %, and 7.6 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, Ca, B, Al, and Ta was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, calcium oxide, boron oxide, aluminum oxide, and tantalum oxide were mixed in a molar ratio of Li2O/SiO2/CaO/B2O3/Al2O3/Ta2O5=22/67/1/2/3/5.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 20 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, Ca, B, Al, and Ta contents were 33.3 mol %, 50.8 mol %, 0.8 mol % 3.0 mol %, 4.5 mol %, and 7.6 mol % respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, Ca, B, Al, and La was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, calcium oxide, boron oxide, aluminum oxide, and lanthanum oxide were mixed in a molar ratio of Li2O/SiO2/CaO/B2O3/Al2O3/La2O5=22/67/1/2/3/5.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 20 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, Ca, B, Al, and La contents were 33.3 mol %, 50.8 mol %, 0.8 mol %, 3.0 mol %, 4.5 mol %, and 7.6 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, Ca, B, Al, and V was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, calcium oxide, boron oxide, aluminum oxide, and vanadium oxide were mixed in a molar ratio of Li2O/SiO2/CaO/Bi2O3/Al2O3/V2O5=22/67/1/2/3/5.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 19 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, Ca, B, Al, and V contents were 33.3 mol %, 50.8 mol %, 0.8 mol %, 3.0 mol %, 4.5 mol %, and 7.6 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, Ca, B, Al, and Y was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, calcium oxide, boron oxide, aluminum oxide, and yttrium oxide were mixed in a molar ratio of Li2O/SiO2/CaO/B2O3/Al2O3/Y2O3=22/67/1/2/3/5.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 18 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, Ca, B, Al, and Y contents were 33.3 mol %, 50.8 mol %, 0.8 mol %, 3.0 mol %, 4.5 mol %, and 7.6 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, Ca, B, Al, and Ti was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, calcium oxide, boron oxide, aluminum oxide, and titanium oxide were mixed in a molar ratio of Li2O/SiO2/CaO/B2O3/Al2O3/TiO2=22/67/1/2/3/5.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 32 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, Ca, B, Al, and Ti contents were 34.6 mol %, 52.8 mol %, 0.8 mol %, 3.1 mol %, 4.7 mol %, and 3.9 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, Ca, B, Al, and P was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, calcium oxide, boron oxide, aluminum oxide, and phosphorus pentaoxide were mixed in a molar ratio of Li2O/SiO2/CaO/B2O3/Al2O3/P2O5=22/67/1/2/3/5.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 40 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, Ca, B, Al, and P contents were 33.3 mol %, 50.8 mol %, 0.8 mol %, 3.0 mol %, 4.5 mol %, and 7.6 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, Ca, B, Al, and W was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, calcium oxide, boron oxide, aluminum oxide, and tungsten oxide were mixed in a molar ratio of Li2SiO2/CaO/B2O3/Al2O3/WO3=22/67/1/2/3/5.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 35 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, Ca, B, Al, and W contents were 34.6 mol %, 52.8 mol %, 0.8 mol %, 3.1 mol %, 4.7 mol %, and 3.9 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, Ca, Mg, B, Al, Zr, Ti, P, and W was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, calcium oxide, magnesium oxide, boron oxide, aluminum oxide, zirconium oxide, titanium oxide, phosphorus pentaoxide, and tungsten oxide were mixed in a molar ratio of Li2O/SiO2/CaO/MgO/B2O3/Al2O3/ZrO3/TiO2/P2O5/WO3=22/55/2/3/5/5/1/1/5/1.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 23 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li Si, Ca, Mg, B, Al, Zr, Ti, P, and W contents were found to be 32.1 mol %, 40.1 mol %, 1.5 mol %, 2.2 mol %, 7.3 mol %, 7.3 mol %, 0.7 mol %, 0.7 mol %, 7.3 mol %, and 3.9 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, B, and Al was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, boron oxide, and aluminum oxide were mixed in a molar ratio of Li2O/SiO2/B2O3/Al2O3=15/65/10/10.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 17 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, B, and Al contents were found to be 22.2 mol %, 48.1 mol %, 14.8 mol %, and 14.8 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, B, and Al was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, boron oxide, and aluminum oxide were mixed in a molar ratio of Li2O/SiO2O3/Al2O3=8/72/10/10.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 16 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, B, and Al contents were found to be 12.5 mol %, 56.3 mol %, 15.6 mol %, and 15.6 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, B, and Al was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, boron oxide, and aluminum oxide were mixed in a molar ratio of Li2O/SiO2/B2O3/Al2O3=377/10/10.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 15 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, B, and Al contents were found to be 4.9 mol %, 62.6 mol %, 16.3 mol %, and 16.3 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, and B was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, and boron oxide were mixed in a molar ratio of Li2O/SiO2/B2O3=33/47/20.
A negative electrode active material was produced in the same manner as in Example 11, except that the silicate powder produced was used and the grinding treatment time was 35 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li Si, and B contents were found to be 43.1 mol %, 30.7 mol % and 26.1 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as in Example 11. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder of Example 1 were weighed in a mass ratio of 42:58, and an Fe powder (10 μm ground product) was added thereto such that the content thereof reached 0.005 mass %. The content of each element in the silicate phase was the same as in Example 1. The content of the Fe powder dispersed in the silicate phase is 0.005 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder of Example 1 were weighed in a mass ratio of 42:58, and an Fe powder (10 μm ground product) was added thereto such that the content thereof reached 25 mass %. The content of each element in the silicate phase was the same as in Example 1. The content of the Fe powder dispersed in the silicate phase is 25 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li and Si was produced under the same conditions as in Example 1, except that lithium oxide and silicon dioxide were mixed in a molar ratio of Li2O/SiO2=50/50.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder described above were weighed in a mass ratio of 42:58, an Fe powder (10 μm ground product) was added thereto such that the content thereof reached 1 mass %, and the grinding treatment time was 50 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li and Si contents were found to be 66.7 mol % and 33.3 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A silicate including Li, Si, and Ca was produced under the same conditions as in Example 1, except that lithium oxide, silicon dioxide, and calcium oxide were mixed in a molar ratio of Li2O/SiO2/CaO=33/47/20.
A negative electrode active material was produced in the same manner as in Example 1, except that, in an inert atmosphere, a Si powder (3N, 10 μm ground product) and the silicate powder described above were weighed in a mass ratio of 42:58, an Fe powder (10 μm ground product) was added thereto such that the content thereof reached 1 mass %, and the grinding treatment time was 40 hours. As a result of the measurement of the contents of elements in the silicate phase through ICP emission spectral analysis, the Li, Si, and Ca contents were found to be 49.6 mol %, 35.3 mol %, and 15.0 mol %, respectively. The content of the Fe powder dispersed in the silicate phase is 1 mass % based on the mass of the base particle as described above. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that this negative electrode active material was used.
A charge/discharge cyclic test was carried out on each of the batteries according to Examples and Comparative Examples in the following manner.
Charge A constant current charging was carried out at a current of 1 It (800 mA) to a voltage of 4.2 V, and then a constant voltage charging was carried out at a constant voltage of 4.2 V to a current of 1/20 It (40 mA).
Discharge
A constant current discharging was carried out at a current of 1 It (800 mA) to a voltage of 2.75 V.
Quiescent Period
The quiescent period between the charge and discharge described above was 10 minutes.
Charge/Discharge Cycles
The cycle consisting of the charge and the discharge described above was carried out 100 times.
The characteristics of the silicate phase and the capacity retention of the battery of each of Examples and Comparative Examples calculated by the equation below are shown in Tables 1 and 2. Note that the capacity retention of Example 3 is taken as the reference (100), and the capacity retentions of the batteries of other Examples and Comparative Examples are indicated as relative values with respect to the reference. Additionally, the first charge capacity of Example 3 is taken as the reference (100), and the first charge capacities of the batteries of other Examples and Comparative Examples are indicated as relative values with respect to the reference. The results are shown in Table 2.
capacity retention (%)=(discharge capacity at 100th cycle/discharge capacity at first cycle)×100
As shown in Table 2, the batteries of Examples 1 to 28 resulted a higher capacity retention and further prevention of deterioration in the charge/discharge cyclic characteristics than those of Comparative Examples 1 and 2. Particularly, the batteries of Examples 1 to 26, in which the content of the metal particles dispersed in the silicate phase is 0.01 mass % to 20 mass % based on the mass of the base particle, resulted a higher capacity retention and further prevention of deterioration in the charge/discharge cyclic characteristics than those of Examples 27 and 28.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-013998 | Jan 2018 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2019/001662 | 1/21/2019 | WO | 00 |
