JP2004214054A - Negative electrode active material for lithium secondary battery, its manufacturing method, and lithium secondary battery - Google Patents

Negative electrode active material for lithium secondary battery, its manufacturing method, and lithium secondary battery Download PDF

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Publication number
JP2004214054A
JP2004214054A JP2003000446A JP2003000446A JP2004214054A JP 2004214054 A JP2004214054 A JP 2004214054A JP 2003000446 A JP2003000446 A JP 2003000446A JP 2003000446 A JP2003000446 A JP 2003000446A JP 2004214054 A JP2004214054 A JP 2004214054A
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Prior art keywords
negative electrode
active material
electrode active
lithium secondary
secondary battery
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JP2003000446A
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JP3827642B2 (en
Inventor
Kiin Chin
Keiko Matsubara
Teru Takakura
Toshiaki Tsuno
恵子 松原
揆允 沈
利章 津野
輝 高椋
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Samsung Sdi Co Ltd
三星エスディアイ株式会社
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Priority to JP2003000446A priority Critical patent/JP3827642B2/en
Priority claimed from US10/752,300 external-priority patent/US20040214085A1/en
Publication of JP2004214054A publication Critical patent/JP2004214054A/en
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134Electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1395Processes of manufacture of electrodes based on metals, Si or alloys

Abstract

The present invention provides a negative electrode active material which can completely suppress pulverization due to expansion and contraction of an alloy volume during charge and discharge and separation from a current collector, a method for producing the same, and a lithium secondary battery.
A plurality of voids having an average pore diameter in the range of 10 nm to 10 μm are formed inside the porous particles, and the average particle diameter of the aggregate is 1 μm. Provided is a negative electrode active material for a lithium secondary battery, which has a range of at least 100 μm or less.
[Selection diagram] None

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a negative electrode active material for a lithium secondary battery, a method for producing the same, and a lithium secondary battery.
[0002]
[Prior art]
Research on increasing the capacity of the negative electrode active material of lithium secondary batteries has been conducted before the battery system using the current negative electrode active material as carbon has been put into practical use, and even now, metal materials such as Si, Sn, and Al have been mainly used. Although it has been actively conducted, it has not yet been put to practical use. This mainly solves the problem that the metal such as Si, Sn, and Al alloys with lithium during charge / discharge causes volume expansion and contraction, which causes the metal to be pulverized and the cycle characteristics to be reduced. It is due to the inability to do so.
[0003]
Therefore, in order to solve this problem, an amorphous alloy such as that described in Patent Literature 1 below, or a Ni—Si alloy shown in Non Patent Literature 1 or Non Patent Literature 2 described below is used. A crystalline alloy comprising a metal that can be alloyed with lithium and a metal that cannot be alloyed with lithium has been studied.
[0004]
[Patent Document 1]
JP 2002-216746 A
[Non-patent document 1]
"The 42nd Battery Symposium Proceedings," The Institute of Electrical Engineers of Japan, Battery Technology Committee, November 21, 2001, p. 296-297
[Non-patent document 2]
"The 43rd Battery Symposium Proceedings," The Institute of Electrical Engineers of Japan, Battery Technology Committee, October 12, 2002, p. 326-327
[0005]
[Problems to be solved by the invention]
However, the above-mentioned crystalline alloy or amorphous alloy has a problem that the charge / discharge capacity per alloy mass is reduced due to the inclusion of a metal that does not alloy with lithium or an intermetallic compound having a low capacity even when alloyed. Was. In addition, when these alloys are used as powders, the particle size of the powders becomes relatively large, so that the volume of the alloys during charging / discharging becomes finer due to expansion and contraction, peeling from the current collector, and contact with conductive materials. However, there was a problem that the lack of the information cannot be completely suppressed.
[0006]
The present invention has been made in view of the above circumstances, and completely eliminates pulverization due to expansion and contraction of the active material volume during charge and discharge, peeling of the active material from the current collector, and lack of contact with the conductive material. An object is to provide a negative electrode active material that can be suppressed, a method for producing the same, and a lithium secondary battery.
[0007]
[Means for Solving the Problems]
In order to achieve the above object, the present invention employs the following configurations.
The negative electrode active material for a lithium secondary battery of the present invention is formed of an aggregate of porous particles made of Si, and a number of voids having an average pore diameter in a range of 10 nm to 10 μm are formed inside the porous particles, The average particle diameter of the aggregate is in a range of 1 μm or more and 100 μm or less.
[0008]
According to such a negative electrode active material for a lithium secondary battery, since a large number of voids are formed inside the porous particles, when Si constituting the porous particles alloys with lithium and expands in volume, the voids are formed. Is expanded while compressing the volume of the porous particles, so that the volume of the porous particles does not change much in appearance, thereby preventing the porous particles from being pulverized.
In particular, if the average particle diameter of the aggregate is in the range of 1 μm or more and 100 μm or less, the volume of the porous particles hardly changes apparently.
Further, since a large number of voids are formed inside the porous particles, when used as a negative electrode active material of a lithium secondary battery, the voids can be impregnated with a non-aqueous electrolyte, thereby increasing the lithium ion Can penetrate into the interior of the porous particles to efficiently diffuse lithium ions, thereby enabling high-rate charging and discharging.
[0009]
Further, the negative electrode active material for a lithium secondary battery of the present invention is the negative electrode active material for a lithium secondary battery described above, wherein the average pore diameter of the void is n, and the average particle diameter of the aggregate is N. At this time, the n / N ratio is in the range of 0.001 or more and 0.2 or less.
[0010]
According to such a negative electrode active material for a lithium secondary battery, the n / N ratio is in the range of 0.001 or more and 0.2 or less, and the pore size of the void is extremely small with respect to the particle size of the porous particles. The pulverization accompanying the volume change can be prevented without reducing the strength of the particles.
[0011]
Further, the negative electrode active material for a lithium secondary battery according to the present invention is the negative electrode active material for a lithium secondary battery described above, wherein the porosity of the voids per volume of the porous particles is 0.1% or more and 50% or more. It is characterized by the following range.
[0012]
According to such a negative electrode active material for a lithium secondary battery, since the void porosity is in the range of 0.1% or more and 50% or less, the volume expansion of Si accompanying alloying with lithium can be sufficiently absorbed by the voids. Since the appearance of the porous particles hardly changes and the strength of the porous particles does not decrease, pulverization can be prevented.
[0013]
Further, the negative electrode active material for a lithium secondary battery of the present invention is the negative electrode active material for a lithium secondary battery described above, wherein a part of the structure of the porous particles is an amorphous phase, and the rest is crystalline. It is characterized by being a hue.
[0014]
According to such a negative electrode active material for a lithium secondary battery, since a part of the structure of the porous particles is an amorphous phase, the cycle characteristics of a battery using the negative electrode active material can be improved.
[0015]
Further, the negative electrode active material for a lithium secondary battery of the present invention is the negative electrode active material for a lithium secondary battery described above, wherein the porous particles include Sn, Al, Pb, In, Ni, Co, Ag, An alloy melt containing at least one or more elements M and Si of Mn, Cu, Ge, Cr, Ti, and Fe is quenched to form a quenched alloy, and the element M contained in the quenched alloy is acid or alkaline. It is characterized by being formed by elution and removal.
[0016]
According to such a negative electrode active material for a lithium secondary battery, the porous particles are obtained by eluting and removing the element M from a quenched alloy composed of Si and the element M, and the element M is removed in the quenched alloy. Since the portion formed becomes a void, it has an extremely fine void.
[0017]
The negative electrode active material for a lithium secondary battery of the present invention is the negative electrode active material for a lithium secondary battery described above, wherein the content of the element M in the molten alloy is 0.01% by mass or more and 70% by mass or less. It is characterized by being within the range.
[0018]
According to such a negative electrode active material for a lithium secondary battery, since the content of the element M in the molten alloy is in the above range, the average pore diameter of voids and the porosity of voids can be in the above ranges.
[0019]
Next, a lithium secondary battery of the present invention is characterized by comprising the negative electrode active material for a lithium secondary battery described in any one of the above.
[0020]
According to such a lithium secondary battery, the negative electrode active material is provided, and there is no fear that the negative electrode active material is pulverized or falls off the current collector, the contact with the conductive material is maintained, and the charge and discharge are performed. The capacity can be improved and the cycle characteristics can be improved.
[0021]
Further, the method for producing a negative electrode active material for a lithium secondary battery according to the present invention includes the method of producing at least one of Sn, Al, Pb, In, Ni, Co, Ag, Mn, Cu, Ge, Cr, Ti, and Fe. A quenched alloy is formed by quenching the molten alloy containing the elements M and Si, and the element M contained in the quenched alloy is eluted and removed with an acid or alkali in which the element M is soluble, thereby comprising Si. It is characterized by obtaining an aggregate of porous particles.
[0022]
According to such a method for producing a negative electrode active material for a lithium secondary battery, the element M is eluted and removed from the quenched alloy composed of Si and the element M, so that the porous body made of Si having a portion where the element M is removed as a void is formed. Particles can be formed. Since the formed voids have an extremely small average pore size and are evenly distributed throughout the porous particles, when the Si is alloyed with lithium and expands in volume, the voids are compressed. It becomes possible to expand, and the porous particle whose volume does not change much in appearance can be obtained.
In addition, by removing the element M from the quenched alloy, most of the structure of the porous particles can be made only of Si that easily alloys with lithium, and a negative electrode active material having a high energy density per weight can be obtained. .
Furthermore, by quenching the molten alloy, at least a part of the structure of the obtained quenched alloy can be made to be an amorphous phase that is easily alloyed with lithium, thereby improving cycle characteristics.
Furthermore, by rapidly cooling the molten alloy, a crystalline phase composed of fine crystal grains may be formed in the structure of the obtained rapidly cooled alloy. In this case, only the element M contained in the crystalline phase is formed. Can be easily eluted and removed. The voids obtained by eluting and removing the element M from the crystalline phase and the amorphous phase having small crystal grains have a smaller average pore size than the case where the element M is removed from the crystalline phase including large crystal grains. , And are evenly distributed throughout the particle. If the average pore diameter of the voids is large and non-uniformly present throughout the particles, it becomes difficult to uniformly disperse the influence of Si when the volume expands due to charging, and the strength of the particles is also reduced. It is not preferable because it causes deterioration.
[0023]
The method for producing a negative electrode active material for a lithium secondary battery according to the present invention is the method for producing a negative electrode active material for a lithium secondary battery described above, wherein the alloy melt is subjected to a gas atomization method, a water atomization method, a roll quenching method. Quenching by any one of the methods described above.
[0024]
According to such a method for producing a negative electrode active material for a lithium secondary battery, a quenched alloy can be easily obtained by employing any of the quenching methods described above.
[0025]
Further, the method for producing a negative electrode active material for a lithium secondary battery according to the present invention is the method for producing a negative electrode active material for a lithium secondary battery described above, wherein the quenching rate of the molten alloy is 100 K / sec or more. It is characterized by.
[0026]
According to the method for producing a negative electrode active material for a lithium secondary battery, by setting the quenching rate of the molten alloy to 100 K / sec or more, it is possible to easily obtain a quenched alloy in which at least a part of the structure is a crystalline phase. it can.
Further, by setting the quenching speed of the molten alloy to the above range, a crystalline phase may be formed in the structure, and in this case, the crystal grains constituting the crystalline phase can be reduced.
[0027]
Further, the method for producing a negative electrode active material for a lithium secondary battery of the present invention is the method for producing a negative electrode active material for a lithium secondary battery described above, wherein the quenched alloy is an acid or After the element M is eluted by being immersed in an alkali solution, the element M in the quenched alloy is eluted and removed by washing and drying.
[0028]
According to the method for producing a negative electrode active material for a lithium secondary battery, the quenched alloy is immersed in a solution of an acid or an alkali in which the element M is soluble to elute the element M. Can be done.
[0029]
The method for producing a negative electrode active material for a lithium secondary battery according to the present invention is the method for producing a negative electrode active material for a lithium secondary battery described above, wherein the content of the element M in the molten alloy is 0.01 mass. % To 70% by mass or less.
[0030]
According to the method for producing a negative electrode active material for a lithium secondary battery, since the content of the element M in the quenched molten metal is in the above range, the element M is too small, the number of voids is reduced, or the element M is excessive. Therefore, there is no possibility that the average pore diameter of the voids becomes excessively large.
[0031]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
The negative electrode active material for a lithium secondary battery of the present invention is an aggregate of porous particles made of Si, in which a number of voids having an average pore size of 10 nm or more and 10 μm or less are formed inside the porous particles. And the average particle size of the aggregate of porous particles is in the range of 1 μm or more and 100 μm or less.
[0032]
This negative electrode active material is provided for a negative electrode of a lithium secondary battery. When the lithium secondary battery is charged, lithium moves from the positive electrode to the negative electrode. At this time, lithium is alloyed with Si constituting the porous particles in the negative electrode. The volume expansion of Si occurs with this alloying. At the time of discharge, lithium is desorbed from Si and moves to the positive electrode side. With this desorption, the expanded Si contracts to its original volume. As described above, the expansion and contraction of Si occurs with the repetition of charging and discharging.
[0033]
According to this negative electrode active material, since a large number of voids are formed inside the porous particles, when Si constituting the porous particles is alloyed with lithium to expand the volume, the void volume is reduced. Since it expands, the size of the porous particles hardly changes in appearance, thereby preventing the porous particles from being pulverized.
[0034]
In addition, the porous particles constituting the negative electrode active material of the present embodiment include at least one of Sn, Al, Pb, In, Ni, Co, Ag, Mn, Cu, Ge, Cr, Ti, and Fe. The molten alloy containing the elements M and Si is quenched to form a quenched alloy, and the element M contained in the quenched alloy is formed by elution and removal with an acid or alkali. That is, the porous particles of the present embodiment are obtained by eluting and removing the element M from the quenched alloy containing Si and the element M, and the portion of the quenched alloy from which the element M has been removed becomes voids. It has fine voids.
[0035]
FIG. 1 is a schematic sectional view showing an example of the porous particles.
As shown in FIG. 1, a large number of voids 2 are formed inside the porous particles 1 of this example. The cross-sectional shape of each void 2 is relatively uniform.
FIG. 2 is a schematic sectional view showing another example of the porous particles.
As shown in FIG. 2, a large number of voids 12 are formed inside the porous particles 11 of this other example. The cross-sectional shapes of the voids 12 are irregular and non-uniform.
[0036]
In the porous particles 1 and 11 shown in FIGS. 1 and 2, a part of the structure is an amorphous phase of Si, and the rest is composed of a crystalline phase of Si. In some cases, these porous particles 1 and 11 may be entirely composed of a crystalline phase of Si. As will be described later, such a difference in the structure is mainly caused by a difference in the crystal structure of the quenched alloy formed in advance in the production of the negative electrode active material.
If a part of the structure of the porous particles 1 and 11 contains an amorphous phase, the cycle characteristics of the negative electrode active material can be improved.
[0037]
The average particle diameter of the porous particles 1 and 11 is preferably 1 μm or more and 100 μm or less. If the average particle size is less than 1 μm, the proportion of the voids 2 and 12 in the porous particles 1 and 11 is relatively increased, and the strength of the porous particles 1 and 11 is undesirably reduced. On the other hand, if the average particle size exceeds 100 μm, the volume change of the porous particles 1 and 11 themselves becomes large, and the pulverization proceeds, which is not preferable.
[0038]
The voids 2,..., 12... In the porous particles 1, 11 have an average pore diameter of 10 nm or more and 10 μm or less.
In particular, the voids 2 included in the porous particles 1 shown in FIG. 1 have an average pore diameter of 10 nm or more and 0.5 μm or less. The voids 12 contained in the porous particles 11 in FIG. 2 have an average pore diameter in a range of 200 nm or more and 2 μm or less, and have a larger pore diameter than the void 2 shown in FIG.
[0039]
If the average pore size of the voids 2 ..., 12 ... is less than 10 nm, the volume of the voids 2 ..., 12 ... becomes extremely small, and when Si is alloyed with lithium and volume-expanded, this expansion cannot be absorbed. Since the size of the porous particles 1 and 11 changes in appearance, there is a possibility that the porous particles 1 and 11 may be cracked and pulverized, which is not preferable. If the average pore size of the voids 2,..., 12 exceeds 10 μm, the void volume increases and the strength of the porous particles themselves decreases, which is not preferable.
[0040]
When the average pore diameter of the voids 2 and 12 is n and the average particle diameter of the porous particles 1 and 11 is N, the n / N ratio is preferably in the range of 0.001 to 0.2. When the n / N ratio is in this range, the relative pore size of the voids 2 and 12 with respect to the particle size of the porous particles 1 and 11 becomes extremely small, and the pulverization accompanying the volume change can be performed without reducing the strength of the porous particles. Can be prevented.
If the n / N ratio is less than 0.001, the relative pore diameters of the voids 2 and 12 become too small, so that the volume expansion accompanying the alloying of lithium and Si cannot be absorbed. On the other hand, if the n / N ratio exceeds 0.2, the strength of the porous particles 1 and 11 decreases, and the pulverization proceeds, which is not preferable.
[0041]
Further, the porosity of the voids 2, 12 per volume of the porous particles 1, 11 is preferably in the range of 0.1% or more and 50% or less. When the void porosity is within this range, the volume expansion of Si caused by alloying with lithium can be sufficiently absorbed by the void, and the volume of the porous particles hardly changes in appearance, and Since the strength of the porous particles does not decrease, pulverization can be prevented.
If the porosity is less than 0.1%, it is not preferable because volume expansion accompanying the alloying of lithium and Si cannot be absorbed. On the other hand, if the porosity exceeds 50%, the strength of the porous particles 1 and 11 is reduced, and pulverization proceeds, which is not preferable.
[0042]
Next, the lithium secondary battery of the present embodiment includes at least a negative electrode including the above-described negative electrode active material, a positive electrode, and an electrolyte.
[0043]
As the negative electrode of the lithium secondary battery, for example, a negative electrode active material formed of an aggregate of porous particles is solidified and formed into a sheet by using a binder for binding the porous particles to each other.
Further, the pellets are not limited to those solidified and formed into the above-mentioned sheet shape, and may be pellets solidified and formed into a column shape, a disk shape, a plate shape or a column shape.
[0044]
The binder may be either organic or inorganic, but may be any material that disperses or dissolves in the solvent together with the porous particles and further binds the porous particles by removing the solvent. . Alternatively, the porous particles may be mixed with the porous particles and solidified by pressure molding or the like to bind the porous particles together. As such a binder, for example, a vinyl resin, a cellulose resin, a phenol resin, a thermoplastic resin, a thermosetting resin, and the like can be used. For example, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, styrene butadiene rubber, and the like can be used. Resin can be exemplified.
Further, in the negative electrode according to the present invention, in addition to the negative electrode active material and the binder, carbon black, graphite powder, metal powder, or the like may be added as a conductive auxiliary.
[0045]
Next, as the positive electrode, for example, LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , LiFeO 2 , V 2 O 5 , TiS, MoS, etc., and those containing a positive electrode active material capable of inserting and extracting lithium, such as organic disulfide compounds and organic polysulfide compounds.
Further, in addition to the positive electrode active material, a binder such as polyvinylidene fluoride or a conductive auxiliary material such as carbon black may be added to the positive electrode.
Specific examples of the positive electrode and the negative electrode include those obtained by applying the positive electrode or the negative electrode to a current collector made of a metal foil or a metal net and forming the same into a sheet.
[0046]
Furthermore, examples of the electrolyte include an organic electrolyte obtained by dissolving a lithium salt in an aprotic solvent.
Examples of aprotic solvents include propylene carbonate, ethylene carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, dioxolan, 4-methyldioxolan, N, N-dimethylformamide, dimethylacetamide, dimethylacetate Sulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl butyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate , Diethylene glycol, dimethyl Aprotic solvents such as ether, or a mixed solvent obtained by mixing two or more of these solvents, and in particular, any one of propylene carbonate (PC), ethylene carbonate (EC), and butylene carbonate (BC) And preferably one of dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), and diethyl carbonate (DEC).
[0047]
As the lithium salt, LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y11 SO 2 ) (Where x and y are natural numbers), LiCl, LiI, etc., and a mixture of one or more lithium salts. 6 , LiBF 4 Those containing any one of the above are preferred.
In addition, other known organic electrolytes for lithium secondary batteries can also be used.
[0048]
Further, as another example of the electrolyte, a so-called polymer electrolyte such as a mixture of any of the above-described lithium salts in a polymer such as PEO or PVA, or a polymer obtained by impregnating an organic electrolyte with a polymer having a high swelling property is used. May be used.
Furthermore, the lithium secondary battery of the present invention is not limited to the positive electrode, the negative electrode, and the electrolyte, and may include other members and the like as necessary, and may include, for example, a separator that separates the positive electrode and the negative electrode. .
[0049]
According to such a lithium secondary battery, the negative electrode active material is provided, and there is no fear that the negative electrode active material is pulverized or falls off the current collector, the contact with the conductive material is maintained, and the charge and discharge are performed. The capacity can be improved and the cycle characteristics can be improved.
In addition, since a large number of voids are formed inside the porous particles, when used as a negative electrode active material of a lithium secondary battery, the voids can be impregnated with a non-aqueous electrolyte, thereby increasing lithium ion Can penetrate into the interior of the porous particles to efficiently diffuse lithium ions, thereby enabling high-rate charging and discharging.
[0050]
Next, a method for producing the negative electrode active material for a lithium secondary battery of the present invention will be described.
The method for producing a negative electrode active material for a lithium secondary battery generally includes a step of producing a quenched alloy containing Si and an element M, and a step of eluting the obtained quenched alloy. Hereinafter, each step will be described in order.
[0051]
First, in the step of manufacturing a quenched alloy, a molten alloy containing Si and the element M is quenched to form a quenched alloy. The alloy melt contains at least one element M of Sn, Al, Pb, In, Ni, Co, Ag, Mn, Cu, Ge, Cr, Ti, and Fe, and Si. Can be obtained by simultaneously melting a simple substance or an alloy thereof by, for example, a high frequency induction heating method.
The content of the element M in the molten alloy is preferably in the range of 0.01% by mass to 70% by mass. When the content of the element M in the molten alloy is in the above range, there is no possibility that the amount of the element M is too small to reduce the number of voids, or that the element M becomes excessive and the average pore diameter of the voids becomes excessively large.
[0052]
As a method of rapidly cooling the molten alloy, for example, a gas atomizing method, a water atomizing method, a roll quenching method, or the like can be used. A powder quenched alloy is obtained by the gas atomizing method and the water atomizing method, and a thin strip quenched alloy is obtained by the roll quenching method. The strip-shaped quenched alloy is further pulverized into a powder. The average particle size of the powdered quenched alloy thus obtained is the average particle size of the aggregate of porous particles to be finally obtained. Therefore, when obtaining a quenched alloy powder, it is necessary to adjust the average particle size to a range of 1 μm or more and 100 μm or less.
[0053]
The quenched alloy obtained from the molten alloy is a quenched alloy in which the entire structure is an amorphous phase, or a quenched alloy in which a part is an amorphous phase and the remainder is a crystalline phase composed of fine crystal grains, or a structure. It becomes a quenched alloy which is a crystalline phase composed entirely of fine crystal grains.
The amorphous phase mainly includes an alloy phase of Si and the element M. On the other hand, when a crystalline phase exists, one or more phases of an alloy phase containing the element M and Si, a single phase of Si, and a single phase of the element M are included. Therefore, the quenched alloy includes an alloy phase of Si and element M as an amorphous phase, an alloy phase of element M and Si as a crystalline phase, a single phase of Si as a crystalline phase, and an element M as a crystalline phase. One or more of the following single phases: Si and the element M form an alloy phase at a constant ratio. However, if the amount of Si contained in the molten alloy is excessive, a single Si phase in addition to the alloy phase is easily formed, and if the element M is excessive, the alloy phase is excessive. In addition, a phase composed of the element M is easily formed. The crystalline phase is composed of fine crystal grains having an average particle size of several to several tens nm. Such fine crystal grains can be obtained only by rapidly cooling the molten alloy.
[0054]
In addition, it is preferable that the rapid cooling speed at the time of rapid cooling is 100 K / sec or more. If the quenching rate is less than 100 K / sec, the crystal grains contained in the crystalline phase may be enlarged, and voids having a large average pore diameter may be formed in the subsequent elution step, which is not preferable.
[0055]
Next, in the step of eluting the quenched alloy, the element M contained in the quenched alloy is eluted and removed with an acid or alkali in which the element M is soluble.
Specifically, the powdered quenched alloy is immersed in a solution of an acid or an alkali in which the element M is soluble to elute the element M, followed by washing and drying. When eluting, it is preferable to perform stirring for about 1 to 5 hours while heating at 30 to 60 ° C.
The acid used to elute the element M depends on the type of the element M, but hydrochloric acid or sulfuric acid is preferred. The alkali used to elute the element M depends on the type of the element M, but is preferably sodium hydroxide or potassium hydroxide. Preferably, these acids or alkalis do not corrode Si.
[0056]
By eluting the element M from the quenched alloy, porous particles made of Si having a portion where the element M is removed as a void can be obtained.
As described above, the quenched alloy includes a metal phase of Si and an element M as an amorphous phase, an alloy phase as a crystalline phase, a single phase of Si as a crystalline phase, and an element M as a crystalline phase. Any one or more of the single phases may be included.
When the element M is eluted and removed from the quenched alloy having such a structure, the alloy phase becomes a Si single phase, and the entire element M single phase is removed. In this way, the quenched alloy powder after elution contains one or both of the Si single phase as the amorphous phase and the Si single phase as the crystalline phase.
[0057]
The Si single phase formed by removing the element M from the amorphous alloy phase has voids 2 having a substantially uniform cross-sectional shape and a uniform hole diameter as shown in FIG. . On the other hand, when all of the element M single phase is removed from the crystalline phase, voids 12 having uneven cross-sectional shapes and irregular pore diameters as shown in FIG. 2 are obtained. . The voids 2 and 12 thus obtained have an average pore diameter of 10 nm or more and 10 μm or less.
[0058]
According to the method for producing a negative electrode active material for a lithium secondary battery of the present embodiment, the element M is eluted and removed from the quenched alloy composed of Si and the element M, so that the part where the element M has been removed has a void. Porous particles can be formed. Since the formed voids have an extremely small average pore size and are evenly distributed throughout the porous particles, when the Si is alloyed with lithium and expands in volume, the voids are compressed. It is possible to expand the porous particles and to obtain porous particles whose size does not change much in appearance.
In addition, by removing the element M from the quenched alloy, most of the structure of the porous particles can be made only of Si that easily alloys with lithium, and a negative electrode active material having a high energy density per weight can be obtained. .
Furthermore, by quenching the molten alloy, at least a part of the structure of the obtained quenched alloy can be made into an amorphous phase, and thereby the cycle characteristics can be improved.
Furthermore, by rapidly cooling the molten alloy, a crystalline phase composed of fine crystal grains may be formed in the structure of the obtained rapidly cooled alloy. In this case, the element M phase contained in the crystalline phase may be formed. Alone can be easily eluted and removed.
[0059]
【Example】
[Production of negative electrode active material]
(Example 1)
50 parts by weight of massive Si having a size of about 5 mm square and 50 parts by weight of Ni powder were prepared, mixed, and then melted in a Ar atmosphere by a high-frequency heating method to obtain a molten alloy. 80kg / cm of this alloy melt 2 By quenching by a gas atomizing method using helium gas at a pressure of, a powder of a quenched alloy having an average particle size of 9 μm was obtained. The rapid cooling rate at this time is 1 × 10 5 K / sec. When X-ray diffraction was performed on the obtained powder, NiSi 2 The existence of an alloy phase having a mixture of a crystalline phase and an amorphous phase having the following composition was confirmed.
Next, the obtained quenched alloy powder was placed in dilute nitric acid, stirred at 50 ° C. for 1 hour, filtered while sufficiently washing, and dried in a drying oven at 100 ° C. for 2 hours. Thus, the negative electrode active material of Example 1 was manufactured.
[0060]
(Example 2)
A negative electrode active material of Example 2 was manufactured in the same manner as in Example 1 except that 80 parts by weight of Si and 20 parts by weight of Ni were used.
The quenched alloy powder at this time includes a single phase of Si as a crystalline phase and NiSi of a crystalline phase and an amorphous phase. 2 Alloy phases of different compositions were observed.
Si single phase and NiSi in the structure of quenched alloy powder 2 It is considered that the reason why the alloy phase was detected was that a part of Si could not be alloyed with Ni because the amount of Si was larger than the amount of Ni, and a part of this Si was precipitated as a Si single phase.
[0061]
(Example 3)
70 parts by weight of massive Si having a size of about 5 mm square and 30 parts by weight of Al powder were prepared, mixed, and melted by a high frequency heating method in an argon atmosphere to obtain a molten alloy. 80kg / cm of this alloy melt 2 By quenching by a gas atomization method using helium gas having a pressure of, a powder of a quenched alloy having an average particle size of 10 µm was obtained. When the obtained powder was subjected to X-ray diffraction, the existence of an Al single phase and a Si single phase as crystalline phases was confirmed.
Next, the obtained quenched alloy powder was placed in an aqueous hydrochloric acid solution, stirred at 50 ° C. for 4 hours, then filtered while sufficiently washing, and dried in a drying oven at 100 ° C. for 2 hours. Thus, the negative electrode active material of Example 3 was manufactured.
[0062]
(Example 4)
A negative electrode active material of Example 4 was produced in the same manner as in Example 3 except that sulfuric acid was used instead of hydrochloric acid.
[0063]
(Comparative Example 1)
50 parts by weight of massive Si having a size of about 5 mm square and 50 parts by weight of Ni powder were prepared, mixed, and then melted by a high frequency heating method in an argon atmosphere to obtain a molten alloy. 80kg / cm of this alloy melt 2 By quenching by a gas atomizing method using helium gas at a pressure of, a powder of a quenched alloy having an average particle size of 9 μm was obtained. This powder was used as a negative electrode active material of Comparative Example 1. When X-ray diffraction was performed on the obtained powder, NiSi 2 The existence of an alloy phase having a mixture of a crystalline phase and an amorphous phase having the following composition was confirmed.
[0064]
(Comparative Example 2)
50 parts by weight of bulk Si having a size of about 5 mm square and 50 parts by weight of Ni powder are prepared, mixed, solidified and formed into pellets, put into an electric furnace, and placed in an electric furnace at 1600 in an argon atmosphere. C. and melted naturally to obtain an ingot. This ingot was pulverized to obtain a powder having an average particle diameter of 20 μm.
Next, the obtained powder was placed in dilute nitric acid, stirred at 50 ° C. for 1 hour, filtered while sufficiently washing, and dried in a drying oven at 100 ° C. for 2 hours. Thus, the negative electrode active material of Comparative Example 2 was manufactured.
[0065]
(Comparative Example 3)
The Si powder having an average particle size of 1 μm was used as the negative electrode active material of Comparative Example 3.
[0066]
(Manufacture of lithium secondary batteries)
70 parts by weight of each of the negative electrode active materials of Examples 1 to 4 and Comparative Examples 1 to 3, 20 parts by weight of graphite powder having an average particle diameter of 2 μm as a conductive material, and 10 parts by weight of polyvinylidene fluoride were mixed. After adding methylpyrrolidone and stirring, a slurry was prepared. Next, this slurry was applied on a copper foil having a thickness of 14 μm, dried, and then rolled to form a negative electrode having a thickness of 80 μm. The prepared negative electrode was punched into a circle having a diameter of 13 mm. Metal lithium was stacked on the negative electrode as a counter electrode with a porous polypropylene separator interposed therebetween, and a mixed solvent of EC: DMC: DEC = 3: 3: 1 by volume ratio. LiPF 6 Was added at a concentration of 1 mol / L to thereby produce a coin-type lithium secondary battery.
The obtained lithium secondary battery was repeatedly charged and discharged at a current density of 0.2 C for 30 cycles at a battery voltage of 0 V to 1.5 V.
[0067]
(Physical Properties of Negative Electrode Active Materials of Examples 1 to 4)
Observation of the negative electrode active material of Example 1 with an electron microscope revealed that porous particles having voids having a substantially uniform cross-sectional shape as shown in FIG. 1 were obtained. The average pore size of the voids was on the order of 200-500 nm. Further, when the porous particles were subjected to elemental analysis using an energy dispersive X-ray analyzer, Ni was not observed on either the surface or the cross section of the porous particles.
Therefore, it was found that Ni was eluted and removed by the above-mentioned elution with hydrochloric acid, and thereafter, a uniform void was formed.
[0068]
Next, when the negative electrode active material of Example 2 was observed with an electron microscope, it was found that porous particles having irregular cross-sectional shapes and having voids of non-uniform pore diameter were obtained as shown in FIG. did. The average pore diameter of the void was about 200 nm to 2 μm, which was larger than the void of Example 1. Further, when the porous particles were subjected to elemental analysis using an energy dispersive X-ray analyzer, Ni was not observed on either the surface or the cross section of the porous particles.
The irregular shape of the voids was caused by the fact that the quenched alloy powder was formed by a plurality of structures having different compositions, and the Si single phase and the NiSi 2 From the alloy phase, NiSi 2 It is considered that Ni contained only in the alloy phase was eluted and removed.
[0069]
Next, when the negative electrode active material of Example 3 was observed with an electron microscope, it was found that porous particles having a non-uniform cross-sectional shape and having voids having a non-uniform pore size were obtained as shown in FIG. did. The average pore diameter of the void was about 300 nm to 2 μm, which was larger than the void of Example 1. Further, when the porous particles were subjected to elemental analysis using an energy dispersive X-ray analyzer, no Al was observed on any of the surface and the cross section of the porous particles.
The irregular shape of the voids is considered to be because only the Al single phase was eluted and removed from the Si single phase and the Al single phase contained in the quenched alloy powder.
[0070]
Next, as in Example 3, the negative electrode active material of Example 4 had voids of irregular cross-sectional shapes and non-uniform pore diameters. The average pore diameter of the voids was the same as in Example 3. As a result of elemental analysis, Al was not detected, and it was found that Al could be removed even by treatment with sulfuric acid.
[0071]
(Characteristics of lithium secondary battery)
Table 1 shows the capacity retention ratio of the discharge capacity at the 30th cycle to the discharge capacity at the 1st cycle.
[0072]
[Table 1]
[0073]
It can be seen that the lithium secondary batteries of Examples 1 to 4 had good capacity retention rates of 83 to 95%. On the other hand, it is understood that Comparative Examples 1 to 3 have a low capacity retention ratio of 20 to 45%.
[0074]
In the negative electrode active material of Comparative Example 1, no Ni elution treatment was performed, so that voids were not formed in the particles constituting the powder of the negative electrode active material, and therefore the volume change of the negative electrode active material increased due to repeated charging and discharging. It is considered that the pulverization of the negative electrode active material progressed and the capacity retention ratio decreased.
[0075]
In addition, in the negative electrode active material of Comparative Example 2, the alloy melt was allowed to cool naturally without quenching the alloy melt, so that the crystal grains in the structure of the alloy after cooling were enlarged, and the pore size of the voids was accordingly increased. Was. For this reason, it is considered that the strength of the particles constituting the powder of the negative electrode active material decreased, and the repetition of charge and discharge promoted the pulverization of the negative electrode active material, resulting in a lower capacity retention rate.
[0076]
Further, since the negative electrode active material of Comparative Example 3 is a mere Si powder, the volume change of the negative electrode active material increases due to repetition of charge and discharge, as in Comparative Example 1, and the fineness of the negative electrode active material proceeds, resulting in a low capacity retention rate. It seems to have become.
[0077]
As described above, the negative electrode active materials of Examples 1 to 4 obtained by the formation of the quenched alloy by the gas atomizing method and the subsequent elution removal treatment have improved cycle characteristics as compared with Comparative Examples 1 to 3. However, in the negative electrode active materials of Examples 1 to 4, the state of the structure of the quenched alloy before elution and removal greatly affects the shape of voids and final battery characteristics.
In other words, when the crystalline phase in the structure is refined by rapid solidification, uniform and fine voids are formed when the element M to be removed and Si are alloyed, and the volume change in charge and discharge is flexibly absorbed. be able to. When the size of the voids is large, the strength of the particles is reduced, so that the size is slightly reduced.
In addition, the porous particles facilitate the impregnation of the electrolytic solution, which facilitates diffusion of lithium ions and contributes to improvement of battery characteristics.
[0078]
【The invention's effect】
As described above in detail, according to the negative electrode active material for a lithium secondary battery of the present invention, since a large number of voids are formed inside the porous particles, Si constituting the porous particles is lithium. When the alloy is alloyed with and expands in volume, the void expands while compressing the volume of the void, so that the volume of the porous particles does not change much in appearance, thereby preventing the porous particles from being pulverized.
In particular, if the average particle diameter of the aggregate is in the range of 1 μm or more and 100 μm or less, the volume of the porous particles hardly changes apparently.
Further, since a large number of voids are formed inside the porous particles, when used as a negative electrode active material of a lithium secondary battery, the voids can be impregnated with a non-aqueous electrolyte, thereby increasing the lithium ion Can penetrate into the interior of the porous particles to efficiently diffuse lithium ions, thereby enabling high-rate charging and discharging.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of porous particles constituting a negative electrode active material for a lithium secondary battery according to an embodiment of the present invention.
FIG. 2 is a schematic cross-sectional view showing another example of porous particles constituting a negative electrode active material for a lithium secondary battery according to an embodiment of the present invention.
[Explanation of symbols]
1, 11: porous particles, 2, 12: void

Claims (12)

  1. It is composed of an aggregate of porous particles made of Si, and a number of voids having an average pore size in a range of 10 nm or more and 10 μm or less are formed inside the porous particles, and the average particle size of the aggregate is 1 μm or more and 100 μm or less A negative electrode active material for a lithium secondary battery, wherein the negative electrode active material has a range.
  2. The n / N ratio is in a range of 0.001 or more and 0.2 or less, where n is an average pore diameter of the void and N is an average particle diameter of the aggregate. Negative electrode active material for lithium secondary batteries.
  3. 3. The negative electrode active material for a lithium secondary battery according to claim 1, wherein a porosity of the voids per volume of the porous particles is in a range of 0.1% or more and 50% or less. 4.
  4. 4. The negative electrode active material for a lithium secondary battery according to claim 1, wherein a part of the structure of the porous particles is an amorphous phase, and the remaining part is a crystalline phase. 5. .
  5. The porous particles are formed by quenching a molten alloy containing at least one element M and Si of Sn, Al, Pb, In, Ni, Co, Ag, Mn, Cu, Ge, Cr, Ti, and Fe. 5. The quenched alloy as claimed in claim 1, wherein said element M contained in said quenched alloy is formed by elution and removal with an acid or an alkali. Negative electrode active material for lithium secondary batteries.
  6. The negative electrode active material for a lithium secondary battery according to claim 5, wherein the content of the element M in the molten alloy is in a range of 0.01% by mass to 70% by mass.
  7. A lithium secondary battery comprising the negative electrode active material for a lithium secondary battery according to claim 1.
  8. A quenched alloy is formed by quenching a molten alloy containing at least one element M and Si of at least one of Sn, Al, Pb, In, Ni, Co, Ag, Mn, Cu, Ge, Cr, Ti, and Fe. A lithium secondary battery characterized by obtaining an aggregate of porous particles made of Si by eluting and removing the element M contained in the quenched alloy with an acid or alkali in which the element M is soluble. Of producing a negative electrode active material for use.
  9. The method for producing a negative electrode active material for a lithium secondary battery according to claim 8, wherein the molten alloy is quenched by any one of a gas atomization method, a water atomization method, and a roll quenching method.
  10. The method for producing a negative electrode active material for a lithium secondary battery according to claim 8 or 9, wherein the quenching rate of the molten alloy is 100 K / sec or more.
  11. The quenched alloy is immersed in an acid or alkali solution in which the element M is soluble to elute the element M, and then washed and dried to elute and remove the element M in the quenched alloy. The method for producing a negative electrode active material for a lithium secondary battery according to claim 8, wherein:
  12. The method for producing a negative electrode active material for a lithium secondary battery according to claim 8, wherein the content of the element M in the molten alloy is in a range of 0.01% by mass to 70% by mass.
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US8039151B2 (en) 2005-07-07 2011-10-18 Kabushiki Kaisha Toshiba Negative electrode active material, nonaqueous electrolyte battery, battery pack and vehicle
US20110294012A1 (en) * 2010-05-28 2011-12-01 Takashi Nakabayashi Anode for lithium-ion rechargeable battery and lithium-ion rechargeable battery including same
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US9853292B2 (en) 2009-05-11 2017-12-26 Nexeon Limited Electrode composition for a secondary battery cell
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US9647263B2 (en) 2010-09-03 2017-05-09 Nexeon Limited Electroactive material
JP2014123575A (en) * 2010-09-03 2014-07-03 Nexeon Ltd Porous electroactive material
JP2012084521A (en) * 2010-09-17 2012-04-26 Furukawa Electric Co Ltd:The Porous silicon particle and manufacturing method thereof and lithium ion secondary battery anode and lithium ion secondary battery
JP2012082126A (en) * 2010-09-17 2012-04-26 Furukawa Electric Co Ltd:The Complex porous silicon particle and method for manufacturing the same
JP2012084522A (en) * 2010-09-17 2012-04-26 Furukawa Electric Co Ltd:The Lithium ion secondary battery anode, lithium ion secondary battery, and lithium ion secondary battery anode manufacturing method
JP2012082125A (en) * 2010-09-17 2012-04-26 Furukawa Electric Co Ltd:The Porous silicon particle and method for manufacturing the same
CN102485945A (en) * 2010-12-01 2012-06-06 鸿富锦精密工业(深圳)有限公司 Porous silicon material and preparation method thereof
US8911901B2 (en) 2011-02-28 2014-12-16 Hitachi, Ltd. Negative electrode for non-aqueous secondary battery and non-aqueous secondary battery
JP2012178287A (en) * 2011-02-28 2012-09-13 Hitachi Ltd Negative electrode for non-aqueous secondary battery and non-aqueous secondary battery
US10077506B2 (en) 2011-06-24 2018-09-18 Nexeon Limited Structured particles
JP2014525651A (en) * 2011-08-19 2014-09-29 ウィリアム・マーシュ・ライス・ユニバーシティ Anode battery material and manufacturing method thereof
JP2017152385A (en) * 2011-08-19 2017-08-31 ウィリアム・マーシュ・ライス・ユニバーシティ Anode battery materials and methods of making the same
JP2015508934A (en) * 2012-01-30 2015-03-23 ネクソン リミテッドNexeon Limited Si / C electroactive material composition
US10388948B2 (en) 2012-01-30 2019-08-20 Nexeon Limited Composition of SI/C electro active material
US10103379B2 (en) 2012-02-28 2018-10-16 Nexeon Limited Structured silicon particles
WO2013146658A1 (en) * 2012-03-26 2013-10-03 古河電気工業株式会社 Negative electrode material for lithium ion secondary batteries, method for producing same, negative electrode for lithium ion secondary batteries using same, and lithium ion secondary battery
JPWO2013146658A1 (en) * 2012-03-26 2015-12-14 古河電気工業株式会社 Negative electrode material for lithium ion secondary battery, method for producing the same, negative electrode for lithium ion secondary battery and lithium ion secondary battery using the same
JP2013203626A (en) * 2012-03-29 2013-10-07 Furukawa Electric Co Ltd:The Porous silicon particle and method for producing the same
US10090513B2 (en) 2012-06-01 2018-10-02 Nexeon Limited Method of forming silicon
JP2014534633A (en) * 2012-09-17 2014-12-18 インテル コーポレイション Energy storage device, method of manufacturing the same, and mobile electronic device including the same
US10008716B2 (en) 2012-11-02 2018-06-26 Nexeon Limited Device and method of forming a device
JP2016513346A (en) * 2013-02-14 2016-05-12 シャイレシュ ウプレティ Silicon composite or tin composite particles
JP2016539065A (en) * 2013-10-07 2016-12-15 スプリングパワー インターナショナル インコーポレイテッド Mass production method of silicon nanowire and / or nanobelt, and lithium battery and anode using silicon nanowire and / or nanobelt
US10153484B2 (en) 2013-10-31 2018-12-11 Lg Chem, Ltd. Anode active material and method of preparing the same
CN104756290A (en) * 2013-10-31 2015-07-01 株式会社Lg化学 Negative electrode active material and method for preparing same
JP2016504722A (en) * 2013-10-31 2016-02-12 エルジー・ケム・リミテッド Negative electrode active material and method for producing the same
US10396355B2 (en) 2014-04-09 2019-08-27 Nexeon Ltd. Negative electrode active material for secondary battery and method for manufacturing same
CN106537656A (en) * 2014-08-18 2017-03-22 奈克松有限公司 Electroactive materials for metal-ion batteries
WO2016027079A1 (en) * 2014-08-18 2016-02-25 Nexeon Limited Electroactive materials for metal-ion batteries
JP2017536645A (en) * 2014-10-02 2017-12-07 エルジー・ケム・リミテッド Negative electrode active material for lithium secondary battery, method for producing the same, and lithium secondary battery including the same
CN107112519A (en) * 2014-10-02 2017-08-29 株式会社Lg 化学 Cathode active material, its preparation method and the lithium secondary battery for including the material
US10476072B2 (en) 2014-12-12 2019-11-12 Nexeon Limited Electrodes for metal-ion batteries
CN106159246A (en) * 2015-03-31 2016-11-23 中国科学院金属研究所 A kind of siliceous porous amorphous alloy lithium ion battery negative material and preparation method thereof
WO2016208480A1 (en) * 2015-06-26 2016-12-29 松本油脂製薬株式会社 Slurry composition for nonaqueous electrolyte secondary battery negative electrodes and use of same
JP2017065938A (en) * 2015-09-28 2017-04-06 株式会社豊田自動織機 Method for producing silicon material

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