WO2014136368A1 - 珪素含有粒子、非水電解質二次電池の負極材、および、非水電解質二次電池 - Google Patents
珪素含有粒子、非水電解質二次電池の負極材、および、非水電解質二次電池 Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to silicon-containing particles, a negative electrode material for a non-aqueous electrolyte secondary battery using the same, and a non-aqueous electrolyte secondary battery.
- silicon shows a theoretical capacity of 4200 mAh / g, which is far higher than the theoretical capacity of 372 mAh / g of carbon materials currently in practical use, it is the most promising material for battery miniaturization and high capacity.
- Patent Document 1 discloses a lithium ion secondary battery using single crystal silicon as a support for a negative electrode active material.
- Patent Document 2 discloses a lithium ion secondary battery using a lithium alloy composed of Li x Si (where x is 0 to 5) of single crystal silicon, polycrystalline silicon and amorphous silicon, In particular, Li x Si using amorphous silicon is preferable, and pulverized crystalline silicon coated with amorphous silicon obtained by plasma decomposition of monosilane is exemplified.
- the proportion of silicon in the negative electrode material is 30% by mass and a small amount of silicon is used. It did not show stability and was not put to practical use.
- Patent Documents 3 to 5 disclose a method in which an amorphous silicon thin film is deposited on an electrode current collector by vapor deposition and used as a negative electrode. In this method of directly vapor-growing silicon on the current collector, a method is also disclosed in which the growth direction is controlled to suppress deterioration of cycle characteristics due to volume expansion (see Patent Document 6). Although this method achieves improved cycle characteristics, it is expensive because the electrode production rate is limited, it is difficult to increase the thickness of the silicon thin film, and copper as the negative electrode current collector is not contained in silicon. There was a problem of spreading.
- Patent Documents 7 to 9 a method of suppressing the volume expansion by limiting the battery capacity utilization rate of silicon while using silicon-containing particles (see Patent Documents 7 to 9), the grain boundary of the polycrystalline particles is used as a buffer band for volume change.
- a method of rapidly cooling a silicon melt to which alumina is added see Patent Document 10
- a method of using polycrystalline particles made of ⁇ , ⁇ -FeSi 2 mixed phase polycrystal see Patent Document 11
- Patent Document 12 a single crystal A high-temperature plastic working method of silicon ingot
- metal silicon and silicon alloys having various crystal structures have been proposed in order to use silicon as an active material, but none of them exhibits cycle stability comparable to that of graphite, and is also cost-effective. However, it has not yet been proposed a production method capable of mass synthesis at low cost.
- the present invention has been made in view of the above problems, and when used as a negative electrode active material for a non-aqueous electrolyte secondary battery, has a higher capacity than graphite and has excellent cycle characteristics. It aims at providing the silicon-containing particle
- the crystal particle diameter determined by the Scherrer method (Scherrer method) from the full width at half maximum of the diffraction line belonging to) is 300 nm or less, and the true density is higher than 2.320 g / cm 3 and lower than 3.500 g / cm 3.
- a silicon-containing particle is provided.
- the battery capacity per unit weight of the active material is 900-3000 mAh / g, Provides a negative electrode for a non-aqueous electrolyte secondary battery with high electronic conductivity, relatively small volume expansion, and high cycle characteristics, although it decreases compared to the theoretical battery capacity per unit weight of active material (4200 mAh / g) Even when mixed with a graphite-based negative electrode material, good cycle characteristics can be obtained.
- the powder particle diameter of the silicon-containing particles is a volume average value D 50 according to a laser diffraction scattering type particle size distribution measuring method (that is, the particle diameter when the cumulative volume is 50% or
- the median diameter is preferably 1 ⁇ m or more and 20 ⁇ m or less.
- the particle diameter of the silicon-containing particles, the volume mean D 50, With 20 ⁇ m or less, with the risk that causes the silicon-containing particles are short-circuited through a negative electrode membrane can be minimized, Since the formation of the electrode does not become difficult, and the possibility of peeling from the current collector in contact with the negative electrode can be sufficiently reduced, the formation of the electrode is facilitated.
- the value of the volume mean value D 50 of the particle diameter divided by the crystal grain size of the silicon-containing particles is 1 or more and 5000 or less.
- the volume average D 50 particle size of the silicon-containing particles, the relationship between the crystal grain size of the silicon-containing particles is not more as described above, relaxation effect of volumetric expansion due to fine particles of silicon-containing particles are obtained.
- the silicon-containing particles are selected from boron, aluminum, phosphorus, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, germanium, tin, antimony, indium, tantalum, tungsten, and gallium. It is preferable to contain one or two or more elements. Since the volume resistivity can be lowered if it contains one or two or more elements selected from such an element group, the negative electrode of a non-aqueous electrolyte secondary battery excellent in electron conductivity can be obtained. Can be formed.
- the silicon-containing particles described above can be used as a negative electrode material for a nonaqueous electrolyte secondary battery as a negative electrode active material for a nonaqueous electrolyte secondary battery.
- a high-capacity and long-life non-aqueous electrolyte secondary battery can be obtained. It can be provided at low cost.
- the negative electrode material of the nonaqueous electrolyte secondary battery may further include graphite as a conductive agent.
- the electrical conductivity of the negative electrode material of a nonaqueous electrolyte secondary battery can be maintained by further including graphite as a conductive agent.
- the nonaqueous electrolyte secondary battery is a negative electrode molded body made of the negative electrode material of the nonaqueous electrolyte secondary battery described above, a positive electrode molded body, the negative electrode molded body, and a separator that separates the positive electrode molded body.
- the nonaqueous electrolyte is preferably included.
- the nonaqueous electrolyte secondary battery includes the negative electrode molded body made of the negative electrode material of the nonaqueous electrolyte secondary battery described above, whereby a nonaqueous electrolyte secondary battery having a high capacity and a long life can be obtained.
- the non-aqueous electrolyte preferably contains lithium ions.
- the negative electrode molded body made of the negative electrode material of the nonaqueous electrolyte secondary battery described above can be suitably used for a lithium ion secondary battery in which the nonaqueous electrolyte contains lithium ions.
- the silicon-containing particles of the present invention for the negative electrode active material of a non-aqueous electrolyte secondary battery, a high-capacity and long-life non-aqueous electrolyte secondary battery can be provided.
- the present inventors have disclosed a silicon-based active material in which the battery capacity per unit mass of the active material exceeds the theoretical capacity of 372 mAh / g of the carbon material while maintaining cycle stability, and an inexpensive manufacturing method thereof.
- the value is 300 nm or less.
- X-ray diffractometer D8 ADVANCE manufactured by BRUKER AXS can be used.
- X-ray source uses Cu K ⁇ ray and Ni filter, output 40kv / 40mA, slit width 0.3 °, step width 0.0164 °, measurement up to 10-90 ° with counting time of 1 second per step To do.
- the data processing after the measurement is performed by removing the K ⁇ 2 line at an intensity ratio of 0.5 and performing smoothing processing.
- the silicon-containing particles of the present invention are selected by analyzing by the Scherrer method (Scherrer method) from the full width at half maximum of the 28.4 ° diffraction line attributed to Si (111), and calculating the crystal particle diameter.
- the silicon-containing particles of the present invention are preferably 300 nm or less, more preferably 200 nm or less.
- the silicon-containing particles of the present invention have a true density value of more than 2.320 g / cm 3 and less than 3.500 g / cm 3 as measured by a dry densimeter.
- the measurement conditions of a dry-type density meter are as follows, for example.
- As a dry densitometer Accupic II 1340 manufactured by Shimadzu Corporation can be used.
- the purge gas used was helium gas, and the measurement was performed after repeating 200 purges in a sample holder set at a temperature of 23 ° C.
- the true density of the silicon-containing particles described above can also be achieved, for example, by adding an element different from silicon.
- elements to be added in terms of vapor pressure and effect, boron, aluminum, phosphorus, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, germanium, tin, antimony, indium, tantalum, It is particularly preferable to use one or more elements selected from tungsten and gallium.
- the addition amount of such an element is added as necessary, and may be approximately 50% by mass or less, preferably 0.001 to 30% by mass, and more preferably 0.01 to 10% by mass. More preferred. When the content is 0.01% by mass or more, the volume resistivity is surely lowered. On the other hand, when the content is 10% by mass or less, segregation of the additive element hardly occurs, and an increase in volume expansion can be further prevented.
- the silicon-containing particles for the negative electrode active material of the non-aqueous electrolyte secondary battery of the present invention have a particle diameter of a volume average value D 50 measured by a laser diffraction scattering type particle size distribution measurement method (particles when the cumulative volume is 50%).
- D 50 or median diameter is preferably 1 ⁇ m or more and 20 ⁇ m or less.
- the value obtained by dividing the volume average value D 50 by the crystal particle diameter is 1 It is preferably 5000 or less, more preferably 3 or more and 1000 or less, and particularly preferably 50 or more and 500 or less.
- the silicon-containing particles as described above have an amorphous grain boundary and a crystal grain boundary, and the particle collapse in the charge / discharge cycle is reduced by the stress relaxation effect of the amorphous grain boundary and the crystal grain boundary. Therefore, by using such silicon-containing particles for the negative electrode material of the non-aqueous electrolyte secondary battery, the negative electrode material of the non-aqueous electrolyte secondary battery can withstand the stress of volume expansion change due to charge and discharge, A non-aqueous electrolyte secondary battery using such silicon-containing particles as a negative electrode material exhibits high capacity and long life battery characteristics.
- the method for producing silicon-containing particles for a negative electrode active material for a non-aqueous electrolyte secondary battery of the present invention and the obtained silicon-containing particles for a negative electrode active material for a non-aqueous electrolyte secondary battery are used as a negative electrode active material.
- Examples of the negative electrode material, the negative electrode, and the nonaqueous electrolyte secondary battery used will be described in detail, but the present invention is not limited thereto.
- silicon can be deposited by vapor deposition on a vapor deposition substrate under reduced pressure, and silicon, boron, aluminum, phosphorus, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic It is also preferable to deposit a silicon alloy by vapor deposition using one or more elements selected from germanium, tin, antimony, indium, tantalum, tungsten, and gallium as raw materials.
- silicon used as a raw material is classified into single-crystal silicon, polycrystalline silicon, amorphous silicon depending on crystallinity, or chemical grade silicon called metal silicon due to difference in purity, metallurgical grade silicon, Any of these may be used. It is particularly preferable to use an inexpensive one.
- the silicon deposition method is achieved by vacuum deposition or sputtering, but an efficient vacuum deposition method with a high deposition rate is preferable.
- Various vacuum vapor deposition methods are selected depending on the vapor deposition material and the vapor deposition substrate, and examples include resistance heating, electron beam heating, induction heating, and laser heating methods.
- An electron beam heating method with higher thermal efficiency is advantageous.
- it is a silicon-containing alloy deposited by a vapor deposition method such as a vacuum deposition method, it is possible to arbitrarily control the crystal particle diameter from an amorphous state to a polycrystalline state regardless of the metal species to be added, This is a useful method.
- the melt quenching method is particularly advantageous in the case of using a metal having a low melting point or a composition having a eutectic point with silicon.
- the raw material is charged into a carbon crucible and melted by high-frequency induction heating, and the inside of the melting apparatus is performed in an inert gas atmosphere in order to suppress the formation of oxides.
- the silicon-containing particles for the negative electrode active material for a non-aqueous electrolyte secondary battery of the present invention can be produced to a desired crystal particle diameter by a melt quench method or a vacuum deposition method, and depending on the metal species to be added, The melt quenching method or the vacuum evaporation method can be used properly.
- the silicon mass or silicon alloy mass produced as described above is pulverized and classified by a known method shown below in order to obtain a predetermined particle diameter.
- a pulverizer to be used for example, a ball mill, a media agitating mill, or a roller compression machine that moves a pulverizing medium such as a ball or a bead and pulverizes a material to be crushed using an impact force, a frictional force, or a compressive force due to the kinetic energy.
- a hammer mill, a pin mill, a disk mill, a colloid mill using a shearing force, a high-pressure wet opposed collision type disperser “Ultimizer”, or the like can be used.
- the pulverization can be used for both wet and dry processes.
- dry classification In order to adjust the particle size distribution, dry classification, wet classification or sieving classification is performed after pulverization.
- dry classification an air stream is mainly used, and dispersion, separation (separation of fine particles and coarse particles), collection (separation of solid and gas), and discharge are performed sequentially or simultaneously.
- Pre-treatment adjustment of moisture, dispersibility, humidity, etc.
- Pre-treatment adjustment of moisture, dispersibility, humidity, etc.
- pulverization and classification are performed at a time, and a desired particle size distribution can be obtained.
- the silicon-containing particles for the negative electrode active material for a non-aqueous electrolyte secondary battery which have been pulverized in advance to a predetermined particle size, are used at a temperature of 200 to 1200 ° C. (preferably 600 to 1000 ° C.) under normal pressure or reduced pressure.
- negative electrode active materials for non-aqueous electrolyte secondary batteries by performing aging treatment by performing heat treatment in an active gas atmosphere, or applying thermal chemical vapor deposition treatment by introducing hydrocarbon compound gas and / or vapor A carbon film may be formed on the surface of the silicon-containing particles to further improve the conductivity.
- the silicon-containing particles for the negative electrode active material for a non-aqueous electrolyte secondary battery previously ground to a predetermined particle size are coated with a metal oxide such as aluminum oxide, titanium oxide, zinc oxide, zirconium oxide or a mixture thereof. May be.
- the required value is 300 nm or less, and the true density is higher than 2.320 g / cm 3 and lower than 3.500 g / cm 3 .
- it has a high battery capacity of 900 to 3000 mAh / g, high coulomb efficiency, and excellent cycle characteristics even when mixed with graphite material.
- the compounding amount of the silicon-containing particles in the negative electrode material of the present invention can be 3 to 97% by mass with respect to the whole negative electrode material.
- the blending amount of the binder in the negative electrode material is preferably 1 to 20% by mass (more preferably 3 to 10% by mass) with respect to the whole negative electrode material.
- the conductivity is improved by diluting with an active material such as graphite.
- an active material such as graphite.
- the effect of mitigating the volume expansion can be obtained.
- the battery capacity of the negative electrode material is reduced depending on the dilution ratio, but it is possible to increase the capacity compared to the conventional graphite material, and the cycle characteristics are improved as compared with the case of the silicon-containing particles alone. .
- the type of graphite material is not particularly limited, and specifically, natural graphite, artificial graphite, various coke powders, mesophase carbon, vapor-grown carbon fiber, pitch-based carbon fiber, PAN-based carbon fiber, various resins Graphite such as a fired body can be used.
- the amount added is 2 to 96% by mass with respect to the whole negative electrode material, and even if it is 60 to 95% by mass, the capacity is higher than that of the conventional graphite material.
- the negative electrode material for a nonaqueous electrolyte secondary battery of the present invention obtained as described above can be used as a negative electrode as follows, for example. That is, a negative electrode material composed of the negative electrode active material, a graphite material, a binder, and other additives is kneaded with a solvent suitable for dissolving and dispersing the binder such as N-methylpyrrolidone or water. To form a paste mixture, and the mixture is applied to the current collector in a sheet form.
- any material that is usually used as a negative electrode current collector such as a copper foil or a nickel foil, can be used without any particular limitation on thickness and surface treatment.
- molds a mixture into a sheet form is not specifically limited, A well-known method can be used.
- a negative electrode including such a negative electrode material for a non-aqueous electrolyte secondary battery is used for the negative electrode active material for a non-aqueous electrolyte secondary battery of the present invention in which the volume change during charge / discharge is significantly smaller than that of conventional silicon-containing particles. It is mainly composed of a negative electrode active material composed of silicon-containing particles, and the change in film thickness before and after charging does not exceed 3 times (particularly 2.5 times).
- the non-aqueous electrolyte secondary battery is characterized in that the negative electrode molded body is used, and other positive electrodes (molded bodies), separators, electrolytes, non-aqueous electrolyte materials, and battery shapes are particularly limited. Not.
- examples of the positive electrode active material include oxides or sulfides capable of inserting and extracting lithium ions, and any one or more of these are used.
- a lithium composite oxide mainly composed of Li p MetO 2 is desirable.
- Met is preferably at least one of cobalt, nickel, iron, and manganese, and p is usually a value in the range of 0.05 ⁇ p ⁇ 1.10.
- Specific examples of such lithium composite oxides include LiCoO 2 , LiNiO 2 , LiFeO 2 , Li q Ni r Co 1-r O 2 having a layer structure (where q and r are the charge / discharge states of the battery) Usually, 0 ⁇ q ⁇ 1, 0.7 ⁇ r ⁇ 1), spinel-structured LiMn 2 O 4 and orthorhombic LiMnO 2 are mentioned.
- LiMet s Mn 1-s O 4 (0 ⁇ s ⁇ 1) is also used as a substituted spinel manganese compound for high voltage applications, where Met is titanium, chromium, iron, cobalt, nickel, copper and zinc. Etc.
- the lithium composite oxide is obtained by, for example, grinding lithium carbonate, nitrate, oxide or hydroxide, and transition metal carbonate, nitrate, oxide or hydroxide according to a desired composition. It can be prepared by mixing and baking at a temperature in the range of 600 to 1000 ° C. in an oxygen atmosphere.
- organic materials can also be used as the positive electrode active material.
- Illustrative examples include polyacetylene, polypyrrole, polyparaphenylene, polyaniline, polythiophene, polyacene, polysulfide compounds and the like.
- the above positive electrode active material is kneaded with the conductive agent and binder used in the negative electrode mixture and applied to the current collector, and can be formed into a positive electrode molded body by a known method.
- the separator used between the positive electrode and the negative electrode is not particularly limited as long as it is stable with respect to the electrolytic solution and has excellent liquid retention, but in general, polyolefins such as polyethylene and polypropylene, and copolymers thereof. Examples thereof include a porous sheet such as a polymer and an aramid resin, or a nonwoven fabric. These may be used as a single layer or multiple layers, and ceramics such as metal oxide may be laminated on the surface. Moreover, porous glass, ceramics, etc. are also used.
- the solvent for the non-aqueous electrolyte secondary battery used in the present invention is not particularly limited as long as it can be used as a non-aqueous electrolyte.
- aprotic high dielectric constant solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, ⁇ -butyrolactone, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, dipropyl carbonate, diethyl ether, tetrahydrofuran, 1,2, -Aprotic low viscosity such as acetate esters or propionate esters such as dimethoxyethane, 1,2-diethoxyethane, 1,3-dioxolane, sulfolane, methylsulfolane, acetonitrile, propionitrile, anisole, methyl acetate A solvent is mentioned.
- ionic liquids using imidazolium, ammonium, and pyridinium type cations can be used.
- the counter anion is not particularly limited, and examples thereof include BF 4 ⁇ , PF 6 ⁇ , (CF 3 SO 2 ) 2 N ⁇ and the like.
- the ionic liquid can be used by mixing with the non-aqueous electrolyte solvent described above.
- silicone gel silicone polyether gel, acrylic gel, silicone acrylic gel, acrylonitrile gel, poly (vinylidene fluoride), etc.
- silicone gel silicone polyether gel
- acrylic gel silicone acrylic gel
- acrylonitrile gel poly (vinylidene fluoride), etc.
- polymer material silicone gel, silicone polyether gel, acrylic gel, silicone acrylic gel, acrylonitrile gel, poly (vinylidene fluoride), etc.
- These may be polymerized in advance or may be polymerized after injection. These can be used alone or as a mixture.
- Light metal salts include alkali metal salts such as lithium salts, sodium salts, or potassium salts, alkaline earth metal salts such as magnesium salts or calcium salts, or aluminum salts. Selected.
- the concentration of the electrolyte salt in the non-aqueous electrolyte is preferably 0.5 to 2.0 mol / L from the viewpoint of electrical conductivity.
- the conductivity of the electrolyte at 25 ° C. is preferably 0.01 S / cm or more, and is adjusted according to the type or concentration of the electrolyte salt.
- various additives may be added to the nonaqueous electrolytic solution as necessary.
- vinylene carbonate methyl vinylene carbonate, ethyl vinylene carbonate, 4-vinylethylene carbonate for the purpose of improving cycle life
- biphenyl alkylbiphenyl, cyclohexylbenzene, t-butylbenzene, diphenyl ether for the purpose of preventing overcharge
- Benzofuran and the like various carbonate compounds for the purpose of deoxidation and dehydration, various carboxylic acid anhydrides, various nitrogen-containing compounds and sulfur-containing compounds.
- the shape of the non-aqueous electrolyte secondary battery is arbitrary and is not particularly limited.
- a coin type battery in which an electrode punched into a coin shape and a separator are stacked, and a square type or cylindrical type battery in which an electrode sheet and a separator are wound in a spiral shape are included.
- volume resistivity was measured with a four-probe type volume resistivity meter (MCP-PD51 manufactured by Mitsubishi Chemical Corporation), and the value at a load of 12 kN was shown. Further, the cumulative volume 50% diameter D 50 was measured by a wet method using a laser diffraction type particle size distribution analyzer (MT3300EX II manufactured by Nikkiso Co., Ltd.). Elemental analysis was performed by an absolute calibration curve method using ICPAES (Agilent Technology Agilent 730).
- Example 1-5 A multi-point copper crucible with a carbon hearth liner with a thickness of 5 mm is placed inside a vacuum chamber with an exhaust system consisting of an oil diffusion pump, mechanical booster pump and oil rotary vacuum pump, and metal silicon mass and additive elements are introduced. The pressure inside the chamber was reduced. The ultimate pressure after 2 hours was 2 ⁇ 10 ⁇ 4 Pa.
- Ge is used as an additive element
- Al is used as an additive element
- Co is used as an additive element
- Example 4 as an additive element.
- Ti was used, and in Example 5, Co and Ge were used as additive elements.
- the deposition was continued for 2 hours at an output of 10 kW and an output density of 1.2 kW / cm 2 .
- the temperature of the vapor deposition substrate made of stainless steel was controlled at 600 ° C.
- the chamber was opened to obtain a deposited silicon mass.
- the produced deposited silicon lump was pulverized and classified using a roll crusher mill and a jet mill to obtain silicon-containing particles.
- the obtained silicon-containing particles were heat-treated for 3 hours in a rotary kiln having an alumina core tube maintained at 400 ° C. under an Ar stream.
- Comparative Example 1-4 silicon for solar cells (manufactured by REC), silicon for semiconductors (manufactured by REC), and silicon for chemicals (manufactured by SIMCOA) were pulverized and classified using a roll crusher mill and a jet mill. Silicon-containing particles were obtained. In Comparative Example 4, silicon-containing particles were obtained in the same manner as Example 1. However, Mn, Co, and Ge were used as additive elements.
- Table 1 summarizes the silicon-containing particle composition, cumulative volume 50% diameter D 50 , crystal particle diameter, true density, and volume resistivity at 12 kN load of Example 1-5 and Comparative Example 1-4.
- the silicon-containing particles of Example 1-5 had a crystal grain size of 300 nm or less and a true density of 2.320 to 3.500 g / cm 3 .
- This slurry was applied to a copper foil having a thickness of 12 ⁇ m using a 150 ⁇ m doctor blade, and after preliminary drying, the electrode was pressure-formed by a roller press at 60 ° C., dried at 160 ° C. for 2 hours, and then 2 cm 2 . Punched into a negative electrode molded body.
- the obtained molded negative electrode was prepared using a lithium foil as a counter electrode, and lithium bis (trifluoromethanesulfonyl) imide as a nonaqueous electrolyte in a 1/1 (volume ratio) mixture of ethylene carbonate and diethyl carbonate at a concentration of 1 mol / L.
- lithium ion secondary batteries for evaluation each using a 30 ⁇ m thick polyethylene microporous film as a separator were prepared using the non-aqueous electrolyte solution dissolved in (1). Then, the produced lithium ion secondary battery was aged overnight at room temperature, two of them were disassembled, the thickness of the negative electrode was measured, and the electrode density based on the initial weight in the electrolyte solution swollen state was calculated. Note that the amount of increase in lithium due to the electrolyte and charging was not included.
- a molded negative electrode produced from the negative electrode active materials of Example 1-5 and Comparative Example 1-4 was prepared.
- a positive electrode molded body was prepared using a single layer sheet (trade name: PIOCELL C-100, manufactured by Pionics Corporation) using LiCoO 2 as a positive electrode material and a positive electrode active material and an aluminum foil as a current collector.
- non-aqueous electrolyte a non-aqueous electrolyte solution in which lithium hexafluorophosphate was dissolved in a 1/1 (volume ratio) mixture of ethylene carbonate and diethyl carbonate at a concentration of 1 mol / L was used, and a polyethylene having a thickness of 30 ⁇ m was used as the separator.
- a coin-type lithium ion secondary battery using the manufactured microporous film was produced.
- Table 2 shows the values (capacity maintenance rate) obtained by dividing the discharge capacity after 100 cycles and 300 cycles by the initial discharge capacity after 300 cycles.
- Example 1-5 formed a negative electrode material having a higher charge capacity than the charge capacity per weight of graphite (372 mAh / g). Further, the volume expansion coefficient is lower than that of Comparative Example 1-3, and the capacity retention rate of the cycle is negative electrode material using silicon alone (Comparative Example 1-3), and the true density is 3.500 g / cm 3. It can be seen that it is superior to a negative electrode material (Comparative Example 4) using a silicon alloy exceeding the above.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
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Abstract
Description
また、特許文献2では、単結晶珪素、多結晶珪素及び非晶質珪素のLixSi(但し、xは0~5)からなるリチウム合金を使用したリチウムイオン二次電池を開示しており、特に非晶質珪素を用いたLixSiが好ましく、モノシランをプラズマ分解した非晶質珪素で被覆した結晶性珪素の粉砕物が例示されている。
しかしながら、この場合においては、その実施例にあるように負極材に占める珪素の割合が30質量%と珪素を少量使用しているにもかかわらず、黒鉛系の様に数千回レベルでのサイクル安定性を示さず、実用に供されることがなかった。
この集電体に直接珪素を気相成長させる方法において、成長方向を制御することで体積膨張によるサイクル特性の低下を抑制する方法も開示されている(特許文献6参照)。この方法によればサイクル特性の改良が達成されるものの、電極の生産速度が限られるためコストが高く、また珪素薄膜の厚膜化が困難であり、更に負極集電体である銅が珪素中に拡散するという問題があった。
このように、珪素含有粒子の粒子径を、体積平均値D50で、1μm以上とすることで、嵩密度が低下することに起因して、単位体積あたりの充放電容量が低下する危険性を低くすることができる。
また、珪素含有粒子の粒子径を、体積平均値D50で、20μm以下とすることで、珪素含有粒子が負極膜を貫通してショートする原因となるおそれを最小限に抑えることができるとともに、電極の形成が難しくなることもなく、負極と接している集電体からの剥離の可能性を十分に低くすることができるので、電極の形成が容易になる。
珪素含有粒子の粒子径の体積平均値D50と、珪素含有粒子の結晶粒子径との関係が上記のようであれば、珪素含有粒子の微粒子化による体積膨張の緩和効果が得られる。
このような元素グループから選択される一種又は二種以上の元素を含有するものであれば、体積抵抗率を低くすることができるので、電子伝導性に優れた非水電解質二次電池の負極を形成することができる。
このように、上述した珪素含有粒子を、非水電解質二次電池の負極活物質として、非水電解質二次電池の負極材に用いることで、高容量で長寿命な非水電解質二次電池を安価で提供できる。
このように、黒鉛を導電剤としてさらに含むことで、非水電解質二次電池の負極材の導電性を保持することができる。
このように、非水電解質二次電池が、上述した非水電解質二次電池の負極材からなる負極成型体を具備することで、高容量で長寿命の非水電解質二次電池が得られる。
上述した非水電解質二次電池の負極材からなる負極成型体は、非水電解質がリチウムイオンを含んでいるリチウムイオン二次電池に、好適に用いることができる。
前述のように、珪素を活物質として利用するために、種々の結晶構造を持つ金属珪素や珪素合金が従来提案されているが、いずれも黒鉛並みのサイクル安定性を示すことはなく、また、安価に大量合成が可能な製造方法を提案できていなかった。
その結果、非水電解質二次電池用負極活物質用の珪素含有粒子として、結晶粒径がX線回折パターンの分析において2θ=28.4°付近のSi(111)に帰属される回折線の半値全幅よりシェラー法(Scherrer法)で求められる値が300nm以下であり、真密度が2.320g/cm3より高く3.500g/cm3未満である珪素含有粒子を用いることで、900~3000mAh/gという高い電池容量を示すとともに、クーロン効率が高く、黒鉛材料との混合使用においてもサイクル安定性に優れていることを見出し、本発明をなすに至った。
このような珪素含有粒子であれば、非水電解質を用いる二次電池用の負極活物質に用いた場合、充放電時の体積変化が抑制されて結晶粒界での応力が緩和されるため、珪素の高い初期効率と電池容量が維持される。
また、一般的に体積膨張の少ない黒鉛系材料との混合使用に於いても珪素粒子のみが大きく体積膨張を起こさないことから、黒鉛材料と珪素粒子の分離が小さく、サイクル特性に優れた非水電解質二次電池が得られる。
X線回折装置としては、BRUKER AXS社製のD8 ADVANCEを使用できる。X線源はCu Kα線、Niフィルターを使用して、出力40kv/40mA、スリット幅0.3°、ステップ幅0.0164°、1ステップあたり1秒の計数時間にて10-90°まで測定する。測定後のデータ処理は強度比0.5にてKα2線を除去して、スムージング処理を行ったもので比較する。この測定によって、10-60°の範囲を詳細に観察すると、ダイヤモンド構造のSi(111)に帰属される28.4°の回折線、Si(220)に帰属される47.2°の回折線、Si(311)に帰属される56.0°の回折線の3本のシグナルが強度大で鋭いシグナルとして観測される。
なお、乾式密度計の測定条件は、例えば、以下のとおりである。
乾式密度計としては株式会社島津製作所製のアキュピックII1340を使用することができる。使用するパージガスはヘリウムガスとし、温度23℃に設定したサンプルホルダー内にて、200回のパージを繰り返した後、測定を行った。
添加する元素としては、蒸気圧と効果の点において、ホウ素、アルミニウム、リン、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、ヒ素、ゲルマニウム、スズ、アンチモン、インジウム、タンタル、タングステン、ガリウムから選択される一種又は二種以上の元素とすることが特に好ましい。
このような元素の添加量は必要に応じて添加され、概ね50質量%以下であれば良いが、好ましくは0.001~30質量%であり、さらに0.01~10質量%であることがより好ましい。0.01質量%以上であれば体積抵抗率が確実に低下し、一方、10質量%以下であれば添加元素の偏析が生じにくく、より体積膨張の増加を防止できる。
D50を1μm以上とすることによって、嵩密度が低下し、単位体積あたりの充放電容量が低下する危険性を極力低くすることができる。
また、D50を20μm以下とすることによって、負極膜を貫通してショートする原因となるおそれを最小限に抑えることができるとともに、電極の形成が難しくなることもなく、集電体からの剥離の可能性を十分に低いものとすることができる。
特に、真空蒸着法のような気相蒸着法によって析出した珪素含有合金であれば、添加する金属種に寄らず結晶粒子径をアモルファス状態から多結晶状態に任意に制御することが可能であり、有用な方法である。
そして粉砕は、湿式、乾式共に用いることができる。
乾式分級は、主として気流を用い、分散、分離(細粒子と粗粒子の分離)、捕集(固体と気体の分離)、排出のプロセスが逐次もしくは同時に行われる。粒子相互間の干渉、粒子の形状、気流の流れの乱れ、速度分布、静電気の影響などで分級効率を低下させないように、分級をする前に前処理(水分、分散性、湿度などの調整)を行うか、使用される気流の水分や酸素濃度を調整して行うことができる。
また、乾式で分級機が一体となっているタイプでは、一度に粉砕、分級が行われ、所望の粒度分布とすることが可能となる。
この導電剤の添加量・配合量を上記範囲とすることによって、負極材の導電性が乏しくなって、初期抵抗が高くなることを確実に抑制することができる。
このような非水電解質二次電池用負極材を含む負極は、充放電での体積変化が従来の珪素含有粒子に比べて大幅に小さい本発明の非水電解質二次電池用負極活物質用の珪素含有粒子からなる負極活物質から主に構成されており、充電前後の膜厚変化が3倍(特には2.5倍)を超えないものとなっている。
この場合、非水電解質二次電池は、上記負極成型体を用いる点に特徴を有し、その他の正極(成型体)、セパレーター、電解液、非水電解質などの材料及び電池形状などは特に限定されない。
具体的には、TiS2、MoS2、NbS2、ZrS2、VS2あるいはV2O5、MoO3及びMg(V3O8)2等のリチウムを含有しない金属硫化物もしくは酸化物、又はリチウム及びリチウムを含有するリチウム複合酸化物が挙げられ、また、NbSe2等の複合金属、オリビン酸鉄も挙げられる。中でも、エネルギー密度を高くするには、LipMetO2を主体とするリチウム複合酸化物が望ましい。なお、Metは、コバルト、ニッケル、鉄及びマンガンのうちの少なくとも1種が良く、pは、通常、0.05≦p≦1.10の範囲内の値である。このようなリチウム複合酸化物の具体例としては、層構造を持つLiCoO2、LiNiO2、LiFeO2、LiqNirCo1-rO2(但し、q及びrの値は電池の充放電状態によって異なり、通常、0<q<1、0.7<r≦1)、スピネル構造のLiMn2O4及び斜方晶LiMnO2が挙げられる。更に高電圧対応型として置換スピネルマンガン化合物としてLiMetsMn1-sO4(0<s<1)も使用されており、この場合のMetはチタン、クロム、鉄、コバルト、ニッケル、銅及び亜鉛等が挙げられる。
一般にエチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、γ-ブチロラクトン等の非プロトン性高誘電率溶媒や、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、メチルプロピルカーボネート、ジプロピルカーボネート、ジエチルエーテル、テトラヒドロフラン、1,2-ジメトキシエタン、1,2-ジエトキシエタン、1,3-ジオキソラン、スルホラン、メチルスルホラン、アセトニトリル、プロピオニトリル、アニソール、メチルアセテート等の酢酸エステル類あるいはプロピオン酸エステル類等の非プロトン性低粘度溶媒が挙げられる。これらの非プロトン性高誘電率溶媒と非プロトン性低粘度溶媒を適当な混合比で併用することが望ましい。
更には、イミダゾリウム、アンモニウム、及びピリジニウム型のカチオンを用いたイオン液体を使用することができる。対アニオンは特に限定されるものではないが、BF4 -、PF6 -、(CF3SO2)2N-等が挙げられる。イオン液体は前述の非水電解液溶媒と混合して使用することが可能である。
軽金属塩にはリチウム塩、ナトリウム塩、あるいはカリウム塩等のアルカリ金属塩、又はマグネシウム塩あるいはカルシウム塩等のアルカリ土類金属塩、又はアルミニウム塩などがあり、目的に応じて1種又は複数種が選択される。例えば、リチウム塩であれば、LiBF4、LiClO4、LiPF6、LiAsF6、CF3SO3Li、(CF3SO2)2NLi、C4F9SO3Li、CF3CO2Li、(CF3CO2)2NLi、C6F5SO3Li、C8F17SO3Li、(C2F5SO2)2NLi、(C4F9SO2)(CF3SO2)NLi、(FSO2C6F4)(CF3SO2)NLi、((CF3)2CHOSO2)2NLi、(CF3SO2)3CLi、(3,5-(CF3)2C6F3)4BLi、LiCF3、LiAlCl4あるいはC4BO8Liが挙げられ、これらのうちのいずれか1種又は2種以上が混合して用いられる。
例えば、サイクル寿命の向上を目的としたビニレンカーボネート、メチルビニレンカーボネート、エチルビニレンカーボネート、4-ビニルエチレンカーボネート等や、過充電防止を目的としたビフェニル、アルキルビフェニル、シクロヘキシルベンゼン、t-ブチルベンゼン、ジフェニルエーテル、ベンゾフラン等や、脱酸や脱水を目的とした各種カーボネート化合物、各種カルボン酸無水物、各種含窒素及び含硫黄化合物が挙げられる。
なお、下記の例において体積抵抗率は四探針式体積抵抗率計(三菱化学株式会社製MCP-PD51)により測定し、12kN荷重時の値を示した。また、累積体積50%径D50はレーザー光回折式粒度分布測定機(日機装株式会社製MT3300EX II)により湿式法にて測定した。元素分析はICPAES(アジレント・テクノロジー製Agilent730)を用いて絶対検量線法による分析を行った。
油拡散ポンプ、メカニカルブースターポンプおよび油回転真空ポンプからなる排気装置を有した真空チャンバー内部に、厚さ5mmのカーボン製ハースライナーを有する多点銅坩堝を設置し、金属珪素塊及び添加元素を投入してチャンバー内を減圧とした。2時間後の到達圧力は2×10-4Paであった。
なお、実施例1においては、添加元素としてGeを使い、実施例2においては、添加元素としてAlを使い、実施例3においては、添加元素としてCoを使い、実施例4においては、添加元素としてTiを使い、実施例5においては、添加元素としてCo、Geを使った。
次に、チャンバーに設置した偏向型電子銃によって徐々に出力を上げながら溶解を完結した後、出力10kW、出力密度1.2kW/cm2にて蒸着を2時間継続した。蒸着中、ステンレスからなる蒸着基板の温度を600℃に制御した。チャンバーを開放して蒸着珪素塊を得た。
比較例1、2および3はそれぞれ太陽電池用シリコン(REC社製)、半導体用シリコン(REC社製)、ケミカル用シリコン(SIMCOA社製)をロールクラッシャーミルおよびジェットミルを用いて粉砕・分級し、珪素含有粒子を得た。
また、比較例4は、実施例1と同様にして珪素含有粒子を得た。ただし、添加元素として、Mn、Co、Geを使った。
実施例1-5、比較例1-4の珪素含有粒子について、負極活物質としての有用性を確認するため、電池特性の評価を行った。
負極活物質として実施例1-5および比較例1-4の珪素含有粒子を15質量%と、導電剤として人造黒鉛(平均粒子径D50=10μm)を79.5質量%と、CMC(カルボキシメチルセルロース)粉を1.5質量%混合した。これにアセチレンブラックの水分散物(固形分17.5%)を固形分換算で2.5質量%とSBR(スチレン-ブタジエンラバー)の水分散物(固形分40%)を固形分換算で1.5質量%を加え、イオン交換水で希釈してスラリーとした。
そして作製したリチウムイオン二次電池を一晩室温でエージングし、この内2個を解体して、負極の厚み測定を行い、電解液膨潤状態での初期重量に基づく電極密度を算出した。なお、電解液及び充電によるリチウム増加量は含まないものとした。
得られた負極成型体のサイクル特性を評価するために、実施例1-5、比較例1-4の負極活物質から作製した負極成型体を準備した。正極材料としてLiCoO2を正極活物質、集電体としてアルミ箔を用いた単層シート(パイオニクス(株)製、商品名;ピオクセル C-100)を用いて、正極成型体を作製した。非水電解質には六フッ化リン酸リチウムをエチレンカーボネートとジエチルカーボネートの1/1(体積比)混合液に1mol/Lの濃度で溶解した非水電解質溶液を用い、セパレーターに厚さ30μmのポリエチレン製微多孔質フィルムを用いたコイン型リチウムイオン二次電池を作製した。
Claims (8)
- 非水電解質二次電池の負極活物質に使われる珪素含有粒子であって、
X線回折パターンの分析において2θ=28.4°付近のSi(111)に帰属される回折線の半値全幅よりシェラー法(Scherrer法)で求められる結晶粒子径が300nm以下であり、
真密度が2.320g/cm3より高く3.500g/cm3未満であることを特徴とする珪素含有粒子。 - 粒子径の体積平均値D50が1μm以上、20μm以下であることを特徴とする請求項1に記載の珪素含有粒子。
- 粒子径の体積平均値D50を前記結晶粒子径で割った値が1以上、5000以下であることを特徴とする請求項1に記載の珪素含有粒子。
- 前記珪素含有粒子は、ホウ素、アルミニウム、リン、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、ヒ素、ゲルマニウム、スズ、アンチモン、インジウム、タンタル、タングステン、ガリウムから選択される一種又は二種以上の元素を含有することを特徴とする請求項1乃至請求項3のいずれか一項に記載の珪素含有粒子。
- 請求項1乃至請求項4のいずれか一項に記載の珪素含有粒子を、非水電解質二次電池の負極活物質として含むことを特徴とする非水電解質二次電池の負極材。
- 黒鉛を、導電剤としてさらに含むことを特徴とする請求項5に記載の非水電解質二次電池の負極材。
- 請求項5又は請求項6に記載の非水電解質二次電池用負極材からなる負極成型体と、
正極成型体と、
前記負極成型体と、前記正極成型体とを分離するセパレーターと、
非水電解質と、
を具備するものであることを特徴とする非水電解質二次電池。 - 前記非水電解質がリチウムイオンを含むものであることを特徴とする請求項7記載の非水電解質二次電池。
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KR1020157023901A KR102107481B1 (ko) | 2013-03-05 | 2014-01-07 | 규소 함유 입자, 비수전해질 이차 전지의 부극재, 및 비수전해질 이차 전지 |
US14/769,146 US20150380726A1 (en) | 2013-03-05 | 2014-01-07 | Silicon-containing particle, negative-electrode material for use in non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
EP14760542.2A EP2966712B1 (en) | 2013-03-05 | 2014-01-07 | Silicon-containing particle, negative electrode material for use in non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
US15/642,901 US9837658B2 (en) | 2013-03-05 | 2017-07-06 | Silicon-containing particle, negative-electrode material for use in non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
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US9472804B2 (en) * | 2014-11-18 | 2016-10-18 | StoreDot Ltd. | Anodes comprising germanium for lithium-ion devices |
JP6460960B2 (ja) | 2015-11-18 | 2019-01-30 | 信越化学工業株式会社 | 負極活物質、混合負極活物質材料、非水電解質二次電池用負極、リチウムイオン二次電池、負極活物質の製造方法、及びリチウムイオン二次電池の製造方法 |
US11387442B2 (en) * | 2017-08-24 | 2022-07-12 | Nec Corporation | Negative electrode for lithium ion secondary battery and lithium ion secondary battery comprising the same |
WO2019053983A1 (ja) * | 2017-09-14 | 2019-03-21 | 株式会社豊田自動織機 | Al含有シリコン材料を含む負極活物質 |
JP6859930B2 (ja) * | 2017-09-14 | 2021-04-14 | 株式会社豊田自動織機 | Al含有シリコン材料 |
KR20200027786A (ko) * | 2018-09-05 | 2020-03-13 | 주식회사 엘지화학 | 음극 및 이를 포함하는 이차전지 |
CN112753113B (zh) * | 2018-09-26 | 2024-05-10 | 松下知识产权经营株式会社 | 非水电解质二次电池用负极以及非水电解质二次电池 |
KR102590416B1 (ko) * | 2018-10-24 | 2023-10-18 | 주식회사 엘지에너지솔루션 | 입경이 상이한 흑연 및 실리콘계 소재를 포함하는 음극 및 이를 포함하는 리튬 이차전지 |
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US20170301913A1 (en) | 2017-10-19 |
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EP2966712A1 (en) | 2016-01-13 |
US9837658B2 (en) | 2017-12-05 |
JP6006662B2 (ja) | 2016-10-12 |
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