Patent Application
20160336586
The present invention relates to negative electrode active materials for nonaqueous electrolyte secondary batteries and particularly relates to a negative electrode active material for nonaqueous electrolyte secondary batteries using a silicon-containing material as a negative electrode active material.
In order to increase the energy density of lithium secondary batteries, a silicon-containing material which stores lithium by an alloying reaction with lithium and which therefore has high volumetric specific capacity is promising as a candidate for a novel negative electrode active material instead of graphite materials in practical use.
However, silicon has a problem that charge/discharge cycle characteristics are reduced because the change in volume of an active material during the storage and release of lithium is large and therefore the active material is pulverized.
Patent Literature 1 discloses that a coating containing an oxoacid salt (lithium silicate or the like) is formed on the surface of silicon for the purpose of enhancing cycle characteristics of a battery using a silicon-containing material as a negative electrode active material.
Patent Literature 2 discloses the use of nano-sized silicon alloy particles.
Patent Literature 3 discloses particles in which insulating and conducting phases are uniformly dispersed in a phase made of silicon.
However, it is difficult for techniques disclosed in Patent Literatures 1 to 3 to cope with market requirements for the capacity and charge/discharge cycle characteristics of nonaqueous electrolyte secondary batteries. The further increase of capacity and the enhancement of cycle characteristics are required.
PTL 1: Japanese Published Unexamined Patent Application No. 2008-135382
PTL 2: Japanese Published Unexamined Patent Application No. 2011-32541
PTL 3: Japanese Published Unexamined Patent Application No. 2013-521620
However, in the case where only a coating preventing a reaction with an electrolyte solution is formed on the surface as described in Preceding Technical Literature 1, the coating on the surface of silicon is broken due to the expansion and contraction of silicon during charge and discharge in accordance with the progress of cycles and therefore sufficient cycle characteristics cannot be obtained.
The nano-sizing of particles of silicon as described in Preceding Technical Literature 2 is known as a method for suppressing the expansion and contraction of silicon. It is known that reducing the size of silicon reduces the absolute expansion of the particles and provides the effect of hardening the particles because of a nano-size effect. However, the use of nano-sized particles leads to an increase in surface area to increase the contact area with an electrolyte solution; hence, the degradation reaction of the electrolyte solution during charge and discharge is significant. Therefore, there is a problem in that cycle characteristics cannot be enhanced.
It has been proposed that an active metal phase containing silicon, an insulating phase, and a conducting phase are hybridized for the purpose of preventing a reaction with an electrolyte solution as described in Patent Literature 3. However, Patent Literature 3 does not sufficiently describe a hybridization state during hybridization or a hybridization technique. Therefore, the possibility that the active phase and the insulating phase are independently present is high. The insulating phase does not serve as a path for ions or electrons. Therefore, in order to make paths for ions and electrons, a state that internal silicon is sufficiently hybridized and has a bond is necessary. In the case where no paths for ions and electrons are formed, heterogeneous reactions occur in particles and some of the particles expand significantly; hence, the particles are broken and cycle characteristics are adversely affected. When the insulating phase and silicon are independently present, the effect of preventing the contact of silicon with an electrolyte solution by covering the surface of silicon with the insulating phase is not created. Therefore, there is a problem in that cycle characteristics cannot be enhanced.
Accordingly, it is an object of the present invention to achieve high capacity by containing silicon and to provide a negative electrode active material for nonaqueous electrolyte secondary batteries with excellent cycle characteristics.
A negative electrode active material for nonaqueous electrolyte secondary batteries contains at least silicon. At least one portion of the surface of each of primary particles containing silicon is covered with an inert phase made of a silicon compound with a silicon oxidation number higher than that of the silicon, a metal-silicon alloy, or metal.
Herein, the primary particles containing silicon may form secondary particles. The silicon compound with a silicon oxidation number higher than that of silicon is preferably Li2Si2O5, Li2SiO3, or Li4SiO4. Furthermore, the metal-silicon alloy is preferably FeSi. The metal is preferably Ti. Furthermore, the grain size of silicon is 500 Å or less.
According to the present invention, at least one portion of the surface of each of primary particles containing silicon is provided with an inert phase made of a silicon compound with a silicon oxidation number higher than that of silicon, a metal-silicon alloy, or metal and therefore good initial charge/discharge characteristics and charge/discharge cycle characteristics can be enhanced.
The present invention is further described in detail with reference to examples. The present invention is not limited to the examples below. Appropriate modifications can be made without departing from the spirit of the present invention.
[Preparation of Negative Electrode Active Material]
First, a silicon ingot produced by a metallurgical process was crushed, whereby granular silicon with a particle size of 1 mm was prepared. Thereafter, 5 kg of the granular silicon with a particle size of 1 mm and stainless steel balls (20 mm, 30 mm) were charged into a 200 L stainless steel vessel. Next, the stainless steel vessel was subjected to a first mechanical milling treatment in a rotary bail mill so as to have a specific surface area of 10 m/g to 100 m/g as determined by a BET method.
Thereafter, 50 g of a mixture of the silicon subjected to the first mechanical milling treatment and a Li2SiO3 powder (the mixing ratio of Si to Li2SiO3 was 70:30 on a mol basis) and stainless steel bails (20 mm) were charged into a 500 ml stainless steel vessel and a second mechanical milling treatment was performed for 50 hours in a planetary bail mill. These powders were heat-treated at 600° C. for 4 hours in a 196 MPa inert atmosphere under high-pressure conditions. Thereafter, a sintered product was pulverized and classified in a jet mill such that the median diameter D50 was about 5μm, whereby a negative electrode active material a1 was obtained.
Lc=Kλ/(βcosθ)
K: Scherrer constant (=0.9400)
λ: Wavelength of X-ray beam (=1.54056 Å)
β: Full width at half maximum of peak (radian)
θ: Bragg angle of X-ray diffraction line
Since an active phase of the negative electrode active material a1 is 100 nm or less, it is clear that the active phase is obviously a polycrystal composed of a plurality of grains. When primary particles of silicon are polycrystalline, the grain size is the size of grains contained in the primary particles.
The size of grains forming the active phase is preferably 10 Å to 500 Å and more preferably 150 Å or less. When the grain size is within this range, negative electrode active material particles 33 have increased mechanical strength and are unlikely to be cracked; hence, cycle characteristics are enhanced. When the grain size is too small, the number of electrons not involved in bonds such as dangling bonds increases, which may possibly lead to an increase in irreversible capacity.
A product obtained by esterifying benzophenone tetracarboxylate dianhydride with 2 equivalents of ethanol and m-phenylenediamine were dissolved in N-methyl-2-pyrrolidone such that the molar ratio of the product to m-phenylenediamine was 1:1, whereby a binder precursor solution was obtained.
The negative electrode active material a1; a graphite powder, serving as a negative electrode conductive agent, having an average particle size of 3 μm and a BET specific surface area of 12.5 m2/g; and the binder precursor solution were mixed together such that the mass ratio of the negative electrode active material powder to the negative electrode conductive agent powder to a negative electrode active material layer binder was 75:10:15, whereby negative electrode mix slurry was prepared.
Incidentally, for the negative electrode active material layer binder, the mass of a binder obtained by the removal of N-methyl-2-pyrrolidone from the binder precursor solution by drying, a polymerization reaction, and an imidization reaction was used.
The negative electrode mix slurry prepared as described above was applied to a surface of a negative electrode current collector, made of a copper alloy, having a thickness of 18 μm, a surface roughness of 0.25 μm, and an average peak distance S of 0.85 μm at 25° C. in air, followed by drying at 120° C. in air and then rolling at 25° C. in air. Thereafter, a rectangle with a length of 50 mm and a width of 20 mm was cut out, followed by heat treatment at 300° C. for 10 hours under an argon atmosphere, whereby a mix layer was formed on a surface of the current collector. The amount of a negative electrode active material layer on the negative electrode current collector was 3.0 mg/cm2, and the thickness of the mix layer was 28 μm.
A nickel plate serving as a negative electrode current-collecting tab was connected to an end portion of a working electrode prepared as described above, whereby a negative electrode plate was obtained.
Commercially available metallic Li was used as an active material for a counter electrode. Metallic Li was cut to a length of 80 mm and a width of 50 mm and was used as a counter electrode. A nickel plate serving as a current-collecting tab was connected to an end portion of the counter electrode.
Under an argon atmosphere, 1 mole per liter of lithium hexafluorophosphate was dissolved in a solvent prepared by mixing ethylene carbonate and methyl ethyl carbonate at a volume ratio of 3:7, whereby a nonaqueous electrolyte solution was prepared.
The single positive electrode; the single negative electrode; and two separators composed of a microporous membrane, made of polyethylene, having a thickness of 20 μm, a length of 100 mm, a width of 55 mm, a piercing strength of 340 g, and a porosity of 45% were used. The positive electrode and the negative electrode were arranged to face each other with the separators therebetween and were spirally wound around a columnar winding core such that a positive electrode tab and a negative electrode tab were located on the outermost periphery, whereby a spiral electrode assembly was prepared, followed by obtaining a cylindrical electrode assembly.
The cylindrical electrode assembly and the electrolyte solution prepared as described above were provided in an enclosure made of an aluminium laminate at 25° C. and 1 atm under an argon atmosphere, followed by sealing the laminate, whereby Battery A1 was prepared.
First, a silicon ingot produced by a metallurgical process was crushed, whereby granular silicon with a particle size of 1 mm was prepared. Thereafter, 5 kg of the granular silicon with a particle size of 1 mm and stainless steel bails (20 mm, 30 mm) were charged into a 200 L stainless steel vessel. Next, the stainless steel vessel was subjected to a first mechanical milling treatment in a rotary ball mill so as to have a specific surface area of 10 m/g to 100 m/g as determined by a BET method,
Thereafter, 5 kg of a mixture of the silicon subjected to the first mechanical milling treatment and a Li2SiO3 powder (the mixing ratio of Si to Li2SiO3 was 70:30 on a mol basis) and stainless steel bails (20 mm, 30 mart) were charged into a 200 L stainless steel vessel and a second mechanical milling treatment was performed for 50 hours in a planetary ball mill. These powders were heat-treated at 800° C. for 4 hours in a 196 MPa inert atmosphere under high-pressure conditions. Thereafter, a sintered product was pulverized and classified in a jet mill such that the median diameter D50 was about 5 μm, whereby a negative electrode active material a2 was obtained.
Battery A2 was prepared in substantially the same manner as that described in Example 1 except that, the negative electrode active material a2 was used instead of the negative electrode active material a1 in the preparation of the negative electrode of Battery A1.
First, a silicon ingot produced by a metallurgical process was crushed, whereby granular silicon with a particle size of 1 mm was prepared. Thereafter, the granular silicon was pulverized and classified in a jet mill such that, the median diameter D50 was about 10 μm.
Thereafter, 50 g of a mixture of a silicon powder pulverized in the jet mill and a Li2SiO3 powder (the mixing ratio of Si to Li2SiO3 was 84:16 on a mol basis) and stainless steel balls (12 mm) were charged into a 500 mi stainless steel vessel and a mechanical milling treatment was performed for 30 hours in a planetary ball mill. These powders were heat-treated at 600° C. for 10 hours in an inert atmosphere under atmospheric pressure conditions, whereby a negative electrode active material a3 was obtained.
Battery A3 was prepared in substantially the same manner as that described in Example 1 except that the negative electrode active material a3 was used instead of the negative electrode active material a1 in the preparation of the negative electrode of Battery A1.
First, a silicon ingot produced by a metallurgical process was crushed, whereby granular silicon with a particle size of 1 mm was prepared. Thereafter, the granular silicon was pulverized and classified in a jet mill such that the median diameter D50 was about 10 μm.
Thereafter, 50 g of a mixture of a silicon powder pulverized in the jet mill and a Li4SiO4 powder (the mixing ratio of Si to Li4SiO4 was 75:25 on a mol basis) and stainless steel balls (12 mm) were charged into a 500 ml stainless steel vessel and a mechanical milling treatment was performed for 100 hours in a planetary bail mill. These powders were heat-treated at 300 ° C. for 10 hours in an inert, atmosphere under atmospheric pressure conditions, whereby a negative electrode active material a4 was obtained.
First, a silicon ingot produced by a metallurgical process was crushed, whereby granular silicon with a particle size of 1 mm was prepared. Thereafter, the granular silicon was pulverized and classified in a jet mill such that the median diameter D50 was about 10 μm.
Thereafter, 50 g of a mixture of a silicon powder pulverized in the jet mill and a Li2SiO3 powder (the mixing ratio of Si to Li2SiO3 was 50:50 on a mol basis) and stainless steel balls (12 mm) were charged into a 500 ml stainless steel vessel and a mechanical milling treatment was performed for 100 hours in a planetary bail mill. These powders were heat-treated at 600° C. for 10 hours in an inert atmosphere under atmospheric pressure conditions, whereby a negative electrode active material a5 was obtained.
Battery A5 was prepared in substantially the same manner as that described in Example 1 except that the negative electrode active material a5 was used instead of the negative electrode active material a1 in the preparation of the negative electrode of Battery A1.
First, a silicon ingot produced by a metallurgical process was crushed, whereby granular silicon with a particle size of 1 mm was prepared. Thereafter, the granular silicon was pulverized and classified in a jet mill such that the median diameter D50 was about 10 μm.
Thereafter, 50 g of a mixture of a silicon powder pulverized in the jet mill, a Li2SiO3 powder, and a Ti powder (the mixing ratio of Si to Li2SiO3 to Ti was 77:15:8 on a mol basis) and stainless steel balls (12 mm) were charged into a 500 ml stainless steel vessel and a mechanical milling treatment was performed for 30 hours in a planetary ball mill. These powders were heat-treated at 600° C. for 10 hours in an inert atmosphere under atmospheric pressure conditions, whereby a negative electrode active material a6 was obtained.
Battery A6 was prepared in substantially the same manner as that described in Example 1 except that the negative electrode active material a6 was used instead of the negative electrode active material a1 in the preparation of the negative electrode of Battery A1.
First, a silicon ingot produced by a metallurgical process was crushed, whereby granular silicon with a particle size of 1 mm was prepared. Thereafter, the granular silicon was pulverized and classified in a jet mill such that the median diameter D50 was about 10 μm.
Thereafter, 50 g of a mixture of a silicon powder pulverized in the jet mill and a Li2SiO3 powder (the mixing ratio of Si to Li2SiO3 was 70:30 on a mol basis) and stainless steel balls (12 mm) were charged into a 500 ml stainless steel vessel and a mechanical milling treatment was performed for 30 hours in a planetary ball mill. These powders were heat-treated at 600° C. for 10 hours in an inert atmosphere under atmospheric pressure conditions, whereby a negative electrode active material a7 was obtained.
Battery A7 was prepared in substantially the same manner as that described in Example 1 except that the negative electrode active material a7 was used instead of the negative electrode active material a1 in the preparation of the negative electrode of Battery A1.
As a comparison to the inventive powder a1, a negative electrode active material b1 was obtained in such a manner that a silicon ingot was crushed, followed by pulverization and classification in a jet mill such that the median diameter D50 was about 5 μm. Battery B1 was prepared in substantially the same manner as that described in Example 1 except that the negative electrode active material b1 was used.
Into a 20 L stainless steel vessel, 5 kg of granular silicon, mainly containing silicon, having a particle size of 1 mm and stainless steel balls (10 mm, 5 mm) were charged. Next, the stainless steel vessel was set to a mechanical milling machine and was treated for 50 hours.
Thereafter, 500 g of a mixture of silicon subjected to a first mechanical milling treatment and a Li2SiO3 powder (the mixing ratio of Si to Li2SiO3 was 70:30 on a mol basis) and stainless steel balls (10 mm, 5 mm) were charged into a 20 L stainless steel vessel and a mechanical milling treatment was performed for 50 hours in a planetary ball mill.
These powders were heat-treated at 600° C. for 4 hours in a 196 MPa inert atmosphere under high-pressure conditions. Thereafter, a sintered product was pulverized and classified in a let mill such that the median diameter D50 was about 5 μm, whereby a negative electrode active material b2 was obtained.
Battery B2 was prepared in substantially the same manner as that described in Example 1 except that the negative electrode active material b2 was used.
It is known that the energy generated by a mechanical milling treatment using a rotary ball mill depends on the size of a vessel and the mass of each ball. Furthermore, it is known that, a planetary ball mill can generate higher energy as compared to the rotary ball mill. In the above comparative example, the energy used to hybridize the active phases 1 made of silicon and the inert phases 2 made of Li2SiO3 is lower than that used in each example. This probably yields a state that no silicon is covered with an inert phase and no secondary particles are formed.
Batteries A1 to A5 of the above examples and batteries B1 and B2 of the above comparative examples were evaluated for charge/discharge characteristics under charge/discharge cycle conditions below.
After constant-current charge was performed at a current of 0.01 I·t for 10 hours, constant-current charge was performed at a current of 0.05 I·t until the potential of a working electrode reached 0 V.
Constant-current discharge was performed at a current of 0.05 I·t until the voltage of each battery reached 2.0 V.
Constant-current charge was performed at a current of 1 I·t until the battery voltage reached 0 V.
Next, the cycle life was determined by a calculation method below.
The cycle life was determined as the tenth-cycle capacity retention (the value obtained by dividing the tenth-cycle discharge capacity by the first-cycle discharge capacity was defined as the tenth-cycle capacity retention). Results are shown in Table 1 below.
As is clear from the results shown in Table 1, batteries A1 to A6 of Examples 1 to 6 have enhanced cycle characteristics as compared to Battery B1 of Comparative Example 1 that lacks secondary particles and that is not covered with an inert phase made of a silicon compound with a silicon oxidation number higher than that of silicon, a metal-silicon alloy, or metal.
It is clear that batteries A1 to A6 of Examples 1 to 6 have enhanced cycle characteristics as compared to Battery B2 of Comparative Example 2 that simply mixes Li2SiO3 and that lacks secondary particles.
Preparation conditions for hybridizing an active phase and an inert phase, the crystallite size of an active phase that is determined from results of X-ray diffraction, and the cycle life are shown in Table 2 below.
As is clear from results shown in Table 2, Battery A1 of Example 1 and Battery A7 of Example 7 have enhanced cycle characteristics as compared to Battery B1 of Comparative Example 1 that has a large crystallite size. Furthermore, Battery A1 of Example 1 that has a small crystallite size has enhanced cycle characteristics as compared to and Battery A7 of Example 7 that has a large crystallite size.
From the above, it is clear that excellent cycle characteristics are exhibited due to secondary particles composed of a plurality of aggregated primary particles containing silicon and the fact that the surface of each of the secondary particles is covered with an inert phase made of a silicon compound with a silicon oxidation number higher than that of silicon, a metal-silicon alloy, or metal.
The present invention is applicable to, for example, power supplies for driving mobile data terminals such as mobile phones, notebook personal computers, and PDAs and particularly applications requiring high energy density.
1 Active phases
2 Inert phases
| Number | Date | Country | Kind |
|---|---|---|---|
| 2014-012962 | Jan 2014 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2015/000273 | 1/22/2015 | WO | 00 |
