WO2014065417A1 - リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極及びリチウムイオン二次電池 - Google Patents
リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極及びリチウムイオン二次電池 Download PDFInfo
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- 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 a negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery.
- graphite is mainly used as a negative electrode material for lithium ion secondary batteries, and it is known that graphite has a theoretical capacity limit of 372 mAh / g in discharge capacity.
- a negative electrode using an element having a high theoretical capacity and capable of occluding and releasing lithium ions hereinafter also referred to as “specific element”.
- the element containing the specific element is also referred to as “specific element body”). Material development is active.
- silicon, tin, lead, aluminum and the like are well known.
- silicon oxide which is one of the specific element bodies, has advantages such as higher capacity, lower cost, and better workability than negative electrode materials composed of other specific elements. Research on negative electrode materials has been particularly active.
- silicon microcrystals or fine particles are dispersed in an inert and strong substance, for example, silicon dioxide, and carbon for imparting conductivity to at least a part of the surface is added.
- Japanese Patent No. 4171897 discloses a conductive powder in which a surface of a material capable of occluding and releasing lithium ions is coated with a graphite film.
- the graphite coating amount is 3 to 40% by weight, and the BET specific surface area is 2 to 30 m 2.
- a / g the graphite coating, according to the Raman spectrum, the negative electrode material for non-aqueous electrolyte secondary battery, wherein a Raman shift has a spectrum of graphite structure unique to around 1330 cm -1 and 1580 cm -1 It is disclosed. According to the technology of Japanese Patent No.
- lithium ions that can reach the characteristic level required by the market by controlling the physical properties of the graphite film covering the surface of the material capable of occluding and releasing lithium ions within a specific range. It is said that a negative electrode for a secondary battery is obtained.
- Japanese Patent Application Laid-Open No. 2011-90869 discloses a negative electrode material used for a negative electrode for a secondary battery using a nonaqueous electrolyte, and the negative electrode material is formed on the surface of silicon oxide particles represented by the general formula SiO x.
- a negative electrode material for a non-aqueous electrolyte secondary battery wherein the carbon film is coated with a carbon film, and the carbon film is subjected to a thermal plasma treatment. According to the technology of Japanese Patent Application Laid-Open No.
- silicon oxide which is one of the specific element bodies
- the initial charge / discharge efficiency is low, and the battery capacity of the positive electrode is excessive when applied to an actual battery.
- the feature of silicon oxide having a high capacity could not be fully utilized in an actual lithium ion secondary battery.
- a negative electrode material to be applied to lithium ion secondary batteries suitable for higher performance of mobile devices and the like in the future not only can a large amount of lithium ions be stored (that is, the charging capacity is high), but also storage. It is necessary to release more lithium ions.
- the present invention has been made in view of the above requirements, and provides a negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery excellent in initial discharge capacity and initial charge / discharge efficiency. The issue is to provide.
- a negative electrode material for a lithium ion secondary battery comprising carbon on a part or all of a surface of a silicon oxide, wherein the carbon is contained in an amount of 0.5 mass% or more and less than 5 mass%.
- ⁇ 3> The negative electrode material for a lithium ion secondary battery according to ⁇ 1> or ⁇ 2>, wherein a diffraction peak attributed to Si (111) is observed when powder X-ray diffraction (XRD) measurement is performed.
- ⁇ 4> a current collector, and a negative electrode material layer comprising the negative electrode material according to any one of ⁇ 1> to ⁇ 3> provided on the current collector, A negative electrode for a lithium ion secondary battery.
- a lithium ion secondary battery comprising a positive electrode, the negative electrode for a lithium ion secondary battery according to ⁇ 4>, and an electrolyte.
- a negative electrode material for a lithium ion secondary battery a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery that are excellent in initial discharge capacity and initial charge / discharge efficiency.
- FIG. 4 is an enlarged cross-sectional view of a part of the negative electrode material of FIGS. 1 to 3, and is a view for explaining one mode of the state of carbon 10 in the negative electrode material.
- FIG. 4 is an enlarged cross-sectional view of a part of the negative electrode material of FIGS. 1 to 3, and is a view for explaining another aspect of the state of carbon 10 in the negative electrode material.
- a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the amount of each component in the composition is the amount of each of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. It means the total amount.
- the negative electrode material for a lithium ion secondary battery of the present invention (sometimes abbreviated as “negative electrode material”) has carbon in part or all of the surface of the silicon oxide, and the carbon is 0.5 mass. % Or more and less than 5% by mass. With such a configuration, expansion and contraction associated with insertion and extraction of lithium ions can be mitigated, and a decrease in the capacity of silicon oxide per unit mass can be suppressed. Excellent charge / discharge efficiency.
- the silicon oxide according to the present invention may be an oxide containing a silicon element, and examples thereof include silicon monoxide (also referred to as silicon oxide), silicon dioxide, and silicon suboxide. These may be used alone or in combination of two or more.
- silicon oxides silicon oxide and silicon dioxide are generally represented as silicon monoxide (SiO) and silicon dioxide (SiO 2 ), respectively, but the surface state (for example, the presence of an oxide film), Depending on the state of formation of the compound, the measured value (or converted value) of the contained element may be represented by the composition formula SiOx (x is 0 ⁇ x ⁇ 2). In this case as well, the silicon oxide of the present invention is used.
- the value of x can be calculated, for example, by quantifying oxygen contained in silicon oxide by an inert gas melting-non-dispersive infrared absorption method.
- the chemical reaction includes silicon and silicon dioxide (in some cases, silicon oxide).
- silicon oxide according to the present invention is used.
- Silicon oxide can be obtained, for example, by a known sublimation method in which a gas of silicon monoxide generated by heating a mixture of silicon dioxide and metal silicon is cooled and precipitated. Moreover, it can obtain from a market as silicon oxide, silicon monoxide, Silicon Monooxide, etc.
- the silicon oxide preferably has a structure in which silicon crystallites are dispersed in the silicon oxide.
- the size of the silicon crystallite is preferably 8 nm or less, and more preferably 6 nm or less. When the crystallite size is 8 nm or less, silicon crystallites are difficult to localize in the silicon oxide, so that lithium ions are easily diffused in the silicon oxide, and a good discharge capacity is easily obtained.
- the size of the silicon crystallite is preferably 2 nm or more, and more preferably 3 nm or more. When the crystallite size is 2 nm or more, the reaction between lithium ions and silicon oxide is controlled, and good charge / discharge efficiency is easily obtained.
- a structure in which silicon crystallites are dispersed in silicon oxide can be produced, for example, by heat-treating silicon oxide in a temperature range of 700 ° C. to 1300 ° C. in an inert atmosphere and disproportionating. Moreover, it can produce by adjusting the heating temperature in the heat processing for providing the below-mentioned carbon to a silicon oxide. In addition, there exists a tendency for the size of a silicon crystallite to become large, so that the heating temperature at the time of heat processing becomes high, and heating time becomes long.
- the silicon oxide is preferably pulverized and classified when a lump of about several cm square is prepared. Specifically, it is preferable to firstly perform primary pulverization and classification to a size that can be charged into a fine pulverizer, and then secondary pulverize this with a fine pulverizer.
- the average particle diameter of the silicon oxide particles obtained by the secondary pulverization is preferably 0.1 ⁇ m to 20 ⁇ m, preferably 0.5 ⁇ m to 10 ⁇ m, in accordance with the final desired negative electrode material size. More preferred.
- the average particle diameter is a volume cumulative 50% particle diameter (D50%) of the particle size distribution.
- D50% volume cumulative 50% particle diameter
- the negative electrode material of the present invention has carbon in part or all of the surface of the silicon oxide, and the carbon is contained in the whole negative electrode material in an amount of 0.5% by mass or more and less than 5.0% by mass. With such a configuration, the initial discharge capacity and the initial charge / discharge efficiency are improved.
- carbon is preferably contained in an amount of 0.5% by mass or more and 4.5% by mass or less, and more preferably 0.5% by mass or more and 4.0% by mass or less.
- the carbon content (mass basis) in the whole negative electrode material can be determined by high-frequency firing-infrared analysis.
- a carbon-sulfur simultaneous analyzer manufactured by LECO Japan LLC, CSLS600
- LECO Japan LLC, CSLS600 carbon-sulfur simultaneous analyzer
- the negative electrode material of the present invention has carbon in part or all of the surface of the silicon oxide.
- 1 to 4 are schematic cross-sectional views showing examples of the configuration of the negative electrode material of the present invention.
- carbon 10 covers the entire surface of silicon oxide 20.
- the carbon 10 covers the entire surface of the silicon oxide 20 but does not cover it uniformly.
- carbon 10 is partially present on the surface of silicon oxide 20, and the surface of silicon oxide 20 is partially exposed.
- carbon 10 particles having a particle diameter smaller than that of the silicon oxide 20 are present on the surface of the silicon oxide 20.
- FIG. 5 it is a modification of FIG. 4, and the particle shape of the carbon 10 is scaly.
- the shape of the silicon oxide 20 is schematically represented as a sphere (a circle as a cross-sectional shape). (A shape with corners) or the like may be used.
- FIGS. 1 to 3 are enlarged cross-sectional views of a part of the negative electrode material of FIGS. 1 to 3.
- FIG. 6A illustrates one embodiment of the shape of carbon 10 in the negative electrode material
- FIG. 6B illustrates carbon in the negative electrode material. Another aspect of the ten shapes will be described.
- the carbon 10 may be entirely composed of carbon as shown in FIG. 6A, or the carbon 10 may be composed of fine particles 12 as shown in FIG. 6B.
- the outline shape of the fine particles 12 remains in the carbon 10, but the fine particles 12 may be bonded to each other.
- the carbon 10 may be entirely composed of carbon, but a void may be included in a part of the carbon 10.
- carbon 10 is a particle, as shown in FIG. 4, the carbon 10 particle may be partially present on the surface of silicon oxide 20, and the surface of silicon oxide 20 may be partially exposed. 6B, carbon 10 particles may be present on the entire surface of the silicon oxide 20.
- the carbon is preferably low crystalline.
- Low crystallinity means 0.5 or more in the following R value.
- the carbon is in the profiles obtained by laser Raman spectroscopy of the excitation wavelength 532 nm, the intensity of the peak appearing in the vicinity of 1360 cm -1 Id, the intensity of the peak appearing in the vicinity of 1580 cm -1 and Ig, the intensity of the two peaks
- the ratio Id / Ig (also expressed as D / G) is an R value
- the R value is preferably 0.5 or more and 1.5 or less, more preferably 0.7 or more and 1.3 or less. 0.8 or more and 1.2 or less is more preferable.
- the R value is 0.5 or more, a high discharge capacity tends to be obtained, and when it is 1.5 or less, an increase in irreversible capacity tends to be suppressed.
- the peak appearing near 1360 cm -1 generally a peak identified as corresponding to the amorphous structure of the carbon, for example, refers to peaks observed at 1300cm -1 ⁇ 1400cm -1.
- the peak appearing near 1580 cm -1 generally a peak identified as corresponding to the graphite crystal structure, for example, refers to peaks observed at 1530cm -1 ⁇ 1630cm -1.
- the R value was measured using a Raman spectrum measuring apparatus (for example, NSR-1000 type manufactured by JASCO Corporation, excitation wavelength 532 nm), and 1050 cm ⁇ 1 to 1750 cm ⁇ with respect to the measurement range (830 cm ⁇ 1 to 1940 cm ⁇ 1 ). 1 can be obtained as a baseline.
- a method to provide carbon to the surface of a silicon oxide Methods, such as a wet mixing method, a dry-type mixing method, a chemical vapor deposition method, are mentioned.
- the wet mixing method or the dry mixing method is preferable from the viewpoint that the reaction system can be uniformly controlled and the shape of the negative electrode material can be maintained.
- the wet mixing method for example, silicon oxide and a solution in which a carbon source is dissolved in a solvent are mixed, the carbon source solution is adhered to the silicon oxide surface, and the solvent is removed as necessary. Thereafter, the carbon source can be carbonized by heat treatment under an inert atmosphere to impart carbon to the surface of the silicon oxide.
- a carbon source when it does not melt
- silicon oxide and a carbon source are mixed with each other to form a mixture, and the carbon source is carbonized by heat-treating the mixture in an inert atmosphere. Carbon can be imparted to the surface.
- you may perform the process for example, mechanochemical process
- a chemical vapor deposition method a known method can be applied. For example, carbon can be imparted to the surface of the silicon oxide by heat-treating the silicon oxide in an atmosphere containing a gas obtained by vaporizing a carbon source. .
- the carbon source is not particularly limited, and may be any compound that can leave carbon by heat treatment.
- phenol resin styrene Polymers such as resins, polyvinyl alcohol, polyvinyl chloride, polyvinyl acetate, and polybutyral; thermal decomposition of ethylene heavy end pitch, coal-based pitch, petroleum pitch, coal tar pitch, asphalt decomposition pitch, polyvinyl chloride, etc.
- pitches such as naphthalene pitch produced by polymerizing generated PVC pitch, naphthalene and the like in the presence of a super strong acid; polysaccharides such as starch and cellulose; and the like.
- These carbon sources may be used alone or in combination of two or more.
- carbon source When carbon is imparted by chemical vapor deposition, it is preferable to use a gaseous or easily gasifiable compound among aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, and the like as the carbon source.
- gases include methane, ethane, propane, toluene, benzene, xylene, styrene, naphthalene, cresol, anthracene, and derivatives thereof.
- These carbon sources may be used alone or in combination of two or more.
- the heat treatment temperature for carbonizing the carbon source is not particularly limited as long as the carbon source is carbonized, and is preferably 700 ° C. or higher, more preferably 800 ° C. or higher, and 900 ° C. or higher. More preferably it is. Further, from the viewpoint of making carbon low crystalline and generating the silicon crystallites in a desired size, it is preferably 1300 ° C. or lower, more preferably 1200 ° C. or lower, and more preferably 1100 ° C. or lower. More preferably.
- the heat treatment time is appropriately selected depending on the type of carbon source used and the amount of the carbon source used, and is preferably 1 hour to 10 hours, and more preferably 2 hours to 7 hours.
- the heat treatment apparatus is not particularly limited as long as it is a reaction apparatus having a heating mechanism, and examples thereof include a heating apparatus capable of processing by a continuous method, a batch method, or the like. Specifically, a fluidized bed reaction furnace, a rotary furnace, a vertical moving bed reaction furnace, a tunnel furnace, a batch furnace or the like can be appropriately selected according to the purpose.
- the heat-treated product obtained by the heat treatment is preferably crushed because individual particles may be aggregated. Moreover, when adjustment to a desired average particle diameter is required, you may further grind
- carbonaceous materials such as amorphous carbon such as soft carbon and hard carbon; graphite;
- the method using is mentioned.
- the negative electrode material having a shape in which carbon 10 is present as particles on the surface of silicon oxide 20 as shown in FIGS. 4 and 5 can also be produced.
- the wet mixing method or the dry mixing method can be applied.
- the fine particles of the carbonaceous material and the organic compound (compound capable of leaving carbon by heat treatment) as a binder are mixed to form a mixture, and this mixture and silicon oxide are further mixed. By doing so, the mixture is made to adhere to the surface of the silicon oxide, and then it is heat-treated.
- the organic compound is not particularly limited as long as it is a compound that can leave carbon by heat treatment.
- the heat treatment conditions for applying the wet mixing method may be the heat treatment conditions for carbonizing the carbon source.
- the carbonaceous fine particles and silicon oxide are mixed together to form a mixture, and mechanical energy is applied to the mixture (for example, mechanochemical treatment). Produced. Even when the dry mixing method is applied, it is preferable to perform heat treatment in order to generate silicon crystallites in the silicon oxide.
- the heat treatment conditions for applying the dry mixing method may be the heat treatment conditions for carbonizing the carbon source.
- the volume-based average particle diameter of the negative electrode material of the present invention is preferably 0.1 ⁇ m to 20 ⁇ m, and more preferably 0.5 ⁇ m to 10 ⁇ m.
- the average particle size is 20 ⁇ m or less, the distribution of the negative electrode material in the negative electrode is made uniform, and further, the expansion and contraction during charge / discharge are made uniform, and the deterioration of cycle characteristics tends to be suppressed. Further, when the average particle diameter is 0.1 ⁇ m or more, the negative electrode density tends to increase and the capacity tends to be increased.
- the specific surface area of the negative electrode material of the present invention is preferably 0.1m 2 / g ⁇ 15m 2 / g, more preferably 0.5m 2 / g ⁇ 10m 2 / g, 1.0m 2 / More preferably, it is g to 7 m 2 / g.
- the specific surface area is 15 m 2 / g or less, an increase in the first irreversible capacity of the obtained lithium ion secondary battery tends to be suppressed. Furthermore, when producing a negative electrode, the increase in the amount of binder used tends to be suppressed.
- the specific surface area is 0.1 m 2 / g or more, the contact area with the electrolytic solution increases, and the charge / discharge efficiency tends to increase.
- a known method such as the BET method (nitrogen gas adsorption method) can be employed.
- the negative electrode material of the present invention preferably contains carbon in an amount of 0.5% by mass or more and less than 5.0% by mass, and the silicon crystallite size is preferably 2 nm or more and 8 nm or less. More preferably, it is contained in an amount of not less than mass% and not more than 4.5 mass%, and the silicon crystallite size is not less than 3 nm and not more than 6 nm.
- the negative electrode material may be used in combination with a carbon-based negative electrode material conventionally known as an active material for a negative electrode of a lithium ion secondary battery, if necessary.
- a carbon-based negative electrode material conventionally known as an active material for a negative electrode of a lithium ion secondary battery, if necessary.
- Conventionally known carbon-based negative electrode materials include natural graphite such as flaky natural graphite, spherical natural graphite obtained by spheroidizing flaky natural graphite, artificial graphite, amorphous carbon, and the like. Further, these carbon-based negative electrode materials may further have carbon on a part or all of the surface thereof. These carbon-based negative electrode materials may be used alone or in combination with the negative electrode material of the present invention.
- the ratio of the negative electrode material of the present invention (denoted as SiO—C) to the carbon-based negative electrode material (denoted as C) (SiO— C: C) can be appropriately adjusted according to the purpose.
- the ratio is 0.5: 99.5 to 15:85, more preferably 1:99 to 10:90.
- the negative electrode for a lithium ion secondary battery of the present invention (hereinafter sometimes abbreviated as “negative electrode”) is a negative electrode material comprising a current collector and the negative electrode material for a lithium ion secondary battery provided on the current collector. And a layer.
- the negative electrode for a lithium ion secondary battery of the present invention is conventionally known as the negative electrode material for a lithium ion secondary battery, a solvent such as an organic binder, a solvent or water, and if necessary, a thickener, a conductive aid.
- Preparing a coating liquid in which the carbon-based negative electrode material is mixed applying (applying) this coating liquid to the current collector, drying the solvent or water, and then forming the negative electrode layer by pressure molding Is obtained.
- this coating liquid is kneaded with an organic binder, a solvent, and the like, and formed into a sheet shape, a pellet shape, or the like.
- the organic binder is not particularly limited.
- styrene-butadiene copolymer methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylonitrile, hydroxyethyl (meth) (Meth) acrylic copolymer obtained by copolymerizing ethylenically unsaturated carboxylic acid ester such as acrylate and ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid And polymer compounds such as polyvinylidene fluoride, polyethylene oxide, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, polyimide, and polyamideimide.
- “(Meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto. The same applies to other similar expressions such as “(meth) acrylic cop
- organic binders may be dispersed or dissolved in water or dissolved in an organic solvent such as N-methyl-2-pyrrolidone (NMP) depending on the respective physical properties.
- NMP N-methyl-2-pyrrolidone
- an organic binder whose main skeleton is polyacrylonitrile, polyimide or polyamideimide is preferable because of its excellent adhesion, and as described later, the heat treatment temperature during the preparation of the negative electrode is low, and the flexibility of the electrode is excellent. Therefore, an organic binder whose main skeleton is polyacrylonitrile is more preferable.
- organic binder having polyacrylonitrile as a main skeleton for example, a product obtained by adding acrylic acid for imparting adhesiveness and a linear ether group for imparting flexibility to a polyacrylonitrile skeleton (manufactured by Hitachi Chemical Co., Ltd.) LSR7 (trade name) or the like can be used.
- the content ratio of the organic binder in the negative electrode material layer of the lithium ion secondary battery negative electrode material is preferably 0.1% by mass to 20% by mass, and preferably 0.2% by mass to 20% by mass. More preferably, it is 0.3 to 15% by mass. Adhesiveness is good when the content ratio of the organic binder is 0.1% by mass or more, and the negative electrode tends to be prevented from being destroyed by expansion and contraction during charge and discharge. On the other hand, it is in the tendency which can suppress that electrode resistance becomes large because it is 20 mass% or less.
- a thickener for adjusting the viscosity carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, polyacrylic acid (salt), oxidized starch, phosphorylated starch, casein, and the like are the organic binders described above. May be used together.
- the solvent used for mixing the organic binder is not particularly limited, and N-methylpyrrolidone, dimethylacetamide, dimethylformamide, ⁇ -butyrolactone and the like are used.
- a conductive support agent to the said coating liquid.
- the conductive assistant include carbon black, acetylene black, oxides showing conductivity, and nitrides showing conductivity. These conductive assistants may be used alone or in combination of two or more.
- the content of the conductive additive is preferably 0.1% by mass to 20% by mass in the negative electrode material layer (100% by mass).
- the material of the current collector is not particularly limited, and examples thereof include aluminum, copper, nickel, titanium, stainless steel, porous metal (foamed metal), and carbon paper.
- the shape of the current collector is not particularly limited, and examples thereof include a foil shape, a perforated foil shape, and a mesh shape.
- the method for applying (applying) the coating liquid to the current collector is not particularly limited.
- a metal mask printing method, an electrostatic coating method, a dip coating method, a spray coating method, a roll coating method, a doctor blade method examples include a gravure coating method and a screen printing method.
- a pressure treatment with a flat plate press, a calender roll or the like, if necessary.
- the integration of the coating liquid and the current collector formed into a sheet shape, a pellet shape, or the like can be performed by, for example, integration by a roll, integration by a press, or integration by a combination thereof.
- the negative electrode material layer formed on the current collector or the negative electrode material layer integrated with the current collector is preferably heat-treated according to the organic binder used.
- heat treatment is preferably performed at 100 ° C. to 180 ° C., and when using an organic binder having polyimide or polyamideimide as the main skeleton, 150 ° C. It is preferable to perform the heat treatment at a temperature of from °C to 450 °C. This heat treatment increases the strength by removing the solvent and curing the organic binder, thereby improving the adhesion between the negative electrode material and the adhesion between the negative electrode material and the current collector.
- these heat treatments are preferably performed in an inert atmosphere such as helium, argon, nitrogen, or a vacuum atmosphere in order to prevent oxidation of the current collector during the treatment.
- the negative electrode is preferably pressed (pressurized) before the heat treatment.
- the electrode density can be adjusted by applying pressure treatment. It
- the negative electrode for a lithium ion secondary battery of the present invention it is preferable that the electrode density of 1.4g / cm 3 ⁇ 1.9g / cm 3, a 1.5g / cm 3 ⁇ 1.85g / cm 3 Is more preferable, and is more preferably 1.6 g / cm 3 to 1.8 g / cm 3 .
- the volume capacity of the negative electrode tends to be improved, and the adhesion between the negative electrode material and the adhesion between the negative electrode material and the current collector tend to be improved.
- the lithium ion secondary battery of the present invention includes a positive electrode, the negative electrode, and an electrolyte.
- the negative electrode can be a lithium ion secondary battery by disposing a positive electrode opposite to each other with a separator interposed therebetween and injecting an electrolytic solution containing an electrolyte.
- the positive electrode can be obtained by forming a positive electrode layer on the current collector surface in the same manner as the negative electrode.
- the current collector in the positive electrode the same current collector as described in the negative electrode can be used.
- the material used for the positive electrode of the lithium ion secondary battery of the present invention may be any compound that can be doped or intercalated with lithium ions.
- lithium cobaltate (LiCoO 2 ) nickel Examples include lithium acid lithium (LiNiO 2 ) and lithium manganate (LiMnO 2 ).
- a positive electrode is prepared by mixing the positive electrode material described above, an organic binder such as polyvinylidene fluoride, and a solvent such as N-methyl-2-pyrrolidone or ⁇ -butyrolactone, and applying this positive electrode
- the liquid can be applied (applied) to at least one surface of a current collector such as an aluminum foil, and then the solvent can be removed by drying, followed by pressure treatment as necessary.
- the conductive assistant include carbon black, acetylene black, oxides showing conductivity, and nitrides showing conductivity. These conductive assistants may be used alone or in combination of two or more.
- the electrolyte used in the lithium ion secondary battery of the present invention is not particularly limited, and a known one can be used.
- a non-aqueous lithium ion secondary battery can be manufactured by using a solution obtained by dissolving an electrolyte in an organic solvent as the electrolytic solution.
- Examples include LiC (CF 3 SO 2 ) 3 and LiCl, LiI.
- the organic solvent only needs to dissolve the electrolyte, and examples thereof include propylene carbonate, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, vinyl carbonate, ⁇ -butyrolactone, 1,2-dimethoxyethane, and 2-methyltetrahydrofuran.
- separator various known separators can be used. Specific examples include a paper separator, a polypropylene separator, a polyethylene separator, a glass fiber separator, and the like.
- a method for manufacturing a lithium ion secondary battery for example, first, two electrodes of a positive electrode and a negative electrode are wound through a separator. The obtained spiral wound group is inserted into a battery can, and a tab terminal previously welded to a negative electrode current collector is welded to the bottom of the battery can. Inject the electrolyte into the obtained battery can, weld the tab terminal that was previously welded to the positive electrode current collector to the battery lid, and place the lid on the top of the battery can via the insulating gasket A battery is obtained by caulking and sealing the part where the lid and the battery can are in contact.
- the form of the lithium ion secondary battery of the present invention is not particularly limited, and examples include lithium ion secondary batteries such as paper batteries, button batteries, coin batteries, stacked batteries, cylindrical batteries, and prismatic batteries. .
- the above-described negative electrode material for a lithium ion secondary battery according to the present invention has been described as being used for a lithium ion secondary battery. However, it can be applied to any electrochemical device that uses a charge / discharge mechanism to insert and desorb lithium ions. It is.
- Example 1 Preparation of negative electrode material
- silicon oxide bulk silicon oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd., 10 mm to 30 mm square) was roughly pulverized with a mortar to obtain silicon oxide particles.
- the silicon oxide particles are further pulverized by a vibration mill (small vibration mill NB-0, manufactured by Nisto Kagaku Co., Ltd.) and then sized with a 300M (300 mesh) test sieve to obtain fine particles having an average particle diameter of 5 ⁇ m Got.
- vibration mill small vibration mill NB-0, manufactured by Nisto Kagaku Co., Ltd.
- the obtained heat-treated product was crushed with a mortar and sieved with a 300M (300 mesh) test sieve to obtain a negative electrode material.
- the carbon content of the negative electrode material was measured by high-frequency firing-infrared analysis.
- the high-frequency firing-infrared analysis method is an analysis method in which a sample is heated and burned with an oxygen stream in a high-frequency furnace, carbon and sulfur in the sample are converted into CO 2 and SO 2 , respectively, and quantified by an infrared absorption method.
- the measuring apparatus and measurement conditions are as follows. Apparatus: Simultaneous carbon sulfur analyzer (manufactured by LECO Japan LLC, CSLS600) ⁇ Frequency: 18MHz ⁇ High frequency output: 1600W Sample weight: about 0.05g ⁇ Analysis time: Automatic mode is used in the instrument setting mode. Standard sample: Leco 501-224 (C: 3.03% ⁇ 0.04, S: 0.055% ⁇ 0.002) -Number of measurements: 2 times (the value of carbon content in Table 2 is the average value of the two measurements)
- the wave number of the obtained spectrum is the wave number of each peak obtained by measuring the reference material indene (Wako Pure Chemical Industries, Ltd., Wako first grade) under the same conditions as above, and the theoretical wave number of each peak of indene. Correction was performed using a calibration curve obtained from the difference. Among the profile obtained after the correction, 1360 cm -1 to the intensity of the peak appearing in the vicinity of Id, and Ig the intensity of a peak appearing near 1580 cm -1, at both peak intensity ratio Id / Ig of (D / G) It calculated
- the negative electrode material was analyzed using a powder X-ray diffractometer (MultiFlex (2 kW), manufactured by Rigaku Corporation).
- the measurement conditions were as follows.
- the obtained profile was subjected to background (BG) removal and peak separation with the following settings using the structural analysis software (JADE6, manufactured by Rigaku Corporation) attached to the above apparatus.
- the addition amount of the binder was adjusted so that it might become 10 mass% with respect to the total mass of a slurry.
- This slurry is applied to the glossy surface of the electrolytic copper foil so that the coating amount is 10 mg / cm 2, and after preliminary drying at 90 ° C. for 2 hours, the density is 1.65 g / cm 3 with a roll press. Adjusted. Thereafter, a curing treatment was performed by drying at 120 ° C. for 4 hours in a vacuum atmosphere to obtain a negative electrode.
- the electrode obtained above was used as the negative electrode, metallic lithium as the counter electrode, and ethylene carbonate / ethyl methyl carbonate (3: 7 volume ratio) and vinyl carbonate (VC) (1.0% by mass) containing 1M LiPF 6 as the electrolyte.
- a 2016-type coin cell was prepared using a mixed liquid, a polyethylene microporous film having a thickness of 25 ⁇ m as a separator, and a copper plate having a thickness of 250 ⁇ m as a spacer.
- Examples 2 to 6, Comparative Examples 2 and 3 In the production of the negative electrode material of Example 1, a negative electrode material was produced in the same manner as in Example 1 except that the mixing ratio of silicon oxide and coal-based pitch was changed as shown in the following table, and the same evaluation was performed. went.
- Example 1 A negative electrode material was produced in the same manner as in Example 1 except that the pitch was not mixed and only silicon oxide was heat-treated in the production of the negative electrode material of Example 1, and the same evaluation was performed.
- the evaluation results of the above examples and comparative examples are shown in Table 2 below.
- the negative electrode materials for lithium ion secondary batteries shown in Examples 1 to 6 were compared with Comparative Example 1 without carbon coating and Comparative Examples 2 and 3 with a carbon coating amount of 5% by mass or more. It can be seen that the material has a high initial discharge capacity and excellent initial charge / discharge efficiency. When only artificial graphite was used as the negative electrode material, the initial charge capacity was 378 mAh / g, and the initial discharge capacity was 355 Ah / g. In consideration of the result of using only this artificial graphite, this example contains 5% by mass of the negative electrode material of the present invention and 95% by mass of artificial graphite as the negative electrode material. It can be seen that even when the amount of the negative electrode material is blended, the initial charge capacity and discharge capacity are remarkably improved.
Abstract
Description
そこで、理論容量が高く、リチウムイオンを吸蔵及び放出可能な元素(以下、「特定元素」ともいう。また、該特定元素を含んでなるものを、「特定元素体」ともいう)を用いた負極材料の開発が活発化している。
特許第3952180号公報の技術によれば、珪素微結晶又は微粒子を不活性で強固な物質、例えば、二酸化珪素に分散し、更に、この表面の少なくとも一部に導電性を賦与するための炭素を融着させることによって、表面の導電性はもちろん、リチウムの吸蔵及び放出に伴う体積変化に対して安定な構造となり、結果として、長期安定性及び初期効率が改善されるとされている。
特許第4171897号公報の技術によれば、リチウムイオンを吸蔵及び放出し得る材料の表面に被覆する黒鉛皮膜の物性を特定範囲に制御することで、市場の要求する特性レベルに到達し得るリチウムイオン二次電池の負極が得られるとされている。
特開2011-90869号公報の技術によれば、酸化珪素の欠点である電極の膨張と、ガス発生による電池の膨張を解決し、サイクル特性に優れた非水電解質二次電池負極用として有効な負極材料が得られるとされている。
本発明は、上記要求に鑑みなされたものであり、初期の放電容量及び初期の充放電効率に優れるリチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極、並びにリチウムイオン二次電池を提供することを課題とする。
前記集電体上に設けられる、前記<1>~<3>のいずれか1項に記載の負極材料を含む負極材層と、
を有するリチウムイオン二次電池用負極。
更に、本明細書において組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合には、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
本発明のリチウムイオン二次電池用負極材料(「負極材料」と略称する場合がある)は、珪素酸化物の表面の一部又は全部に炭素を有してなり、前記炭素が0.5質量%以上5質量%未満で含まれる。このような構成とすることにより、リチウムイオンの吸蔵及び放出に伴う膨張収縮を緩和することができるとともに、単位質量あたりの珪素酸化物の容量低下を抑えることができるため、初期の放電容量及び初期の充放電効率に優れる。
本発明に係る珪素酸化物としては、珪素元素を含む酸化物であればよく、例えば、一酸化珪素(酸化珪素ともいう)、二酸化珪素及び亜酸化珪素が挙げられる。これらは単一種で使用してもよく、複数種を組み合わせて使用してもよい。
珪素酸化物の中で、酸化珪素及び二酸化珪素は、一般的には、それぞれ一酸化珪素(SiO)及び二酸化珪素(SiO2)として表されるが、表面状態(例えば、酸化皮膜の存在)、化合物の生成状況によって、含まれる元素の実測値(又は換算値)として組成式SiOx(xは0<x≦2)で表される場合があり、この場合も本発明の珪素酸化物とする。なお、xの値は、例えば、不活性ガス融解-非分散型赤外線吸収法にて珪素酸化物中に含まれる酸素を定量することにより算出することができる。また、本発明の負極材料の製造工程中に、珪素酸化物の不均化反応(2SiO→Si+SiO2)を伴う場合は、化学反応上、珪素及び二酸化珪素(場合によって酸化珪素)を含む状態で表される場合があり、この場合も本発明に係る珪素酸化物とする。
なお、酸化珪素は、例えば、二酸化珪素と金属珪素との混合物を加熱して生成した一酸化珪素の気体を冷却及び析出させる公知の昇華法にて得ることができる。また、酸化珪素、一酸化珪素、Silicon Monoxide等として市場から入手することができる。
また、珪素の結晶子のサイズは2nm以上であることが好ましく、より好ましくは、3nm以上である。結晶子サイズが2nm以上の場合には、リチウムイオンと珪素酸化物との反応が制御され、良好な充放電効率が得られやすい。
また、炭素10が粒子の場合、図4に示すように炭素10の粒子は珪素酸化物20の表面に部分的に存在し、一部で珪素酸化物20の表面が露出していてもよいし、図6(B)に示すように炭素10の粒子が珪素酸化物20の表面全体に存在していてもよい。
前記炭素は、励起波長532nmのレーザーラマン分光測定により求めたプロファイルの中で、1360cm-1付近に現れるピークの強度をId、1580cm-1付近に現れるピークの強度をIgとし、その両ピークの強度比Id/Ig(D/Gとも表記する)をR値とした際、そのR値が0.5以上1.5以下あることが好ましく、0.7以上1.3以下であることがより好ましく、0.8以上1.2以下であることがより好ましい。
R値が、0.5以上であると高い放電容量が得られる傾向があり、1.5以下であると不可逆容量の増大を抑制できる傾向がある。
なお、R値はラマンスペクトル測定装置(例えば、日本分光(株)製NSR-1000型、励起波長532nm)を用い、測定範囲(830cm-1~1940cm-1)に対して1050cm-1~1750cm-1をベースラインとして求めることができる。
湿式混合法の場合は、例えば、珪素酸化物と、炭素源を溶媒に溶解させた溶液と、を混合し、炭素源の溶液を珪素酸化物表面に付着させ、必要に応じて溶媒を除去し、その後、不活性雰囲気下で熱処理することにより炭素源を炭素化させて炭素を珪素酸化物の表面に付与することができる。なお、炭素源が溶媒に溶解しない等の場合は、炭素源を分散媒中に分散させた分散液とすることもできる。
乾式混合法の場合は、例えば、珪素酸化物と炭素源とを固体同士で混合して混合物とし、この混合物を不活性雰囲気下で熱処理することにより炭素源を炭素化させて、珪素酸化物の表面に炭素を付与することができる。なお、珪素酸化物と炭素源とを混合する際、力学的エネルギーを加える処理(例えば、メカノケミカル処理)を施してもよい。
化学蒸着法の場合は、公知の方法が適用でき、例えば、炭素源を気化させたガスを含む雰囲気中で珪素酸化物を熱処理することで、珪素酸化物の表面に炭素を付与することができる。
従来知られている炭素系負極材料としては、鱗片状天然黒鉛、鱗片状天然黒鉛を球形化した球状天然黒鉛等の天然黒鉛類、人造黒鉛、非晶質炭素などが挙げられる。また、これらの炭素系負極材料は、その表面の一部又は全部に更に炭素を有していてもよい。これら炭素系負極材料の単独種又は複合種を、上記本発明の負極材料に混合して使用してもよい。
本発明のリチウムイオン二次電池用負極(以下「負極」と略称する場合がある)は、集電体と、前記集電体上に設けられた前記リチウムイオン二次電池用負極材料含む負極材層と、を有する。例えば、本発明のリチウムイオン二次電池用負極は、前記リチウムイオン二次電池用負極材料、有機結着剤、溶剤又は水等の溶媒、及び必要により増粘剤、導電助剤、従来知られている炭素系負極材料等を混合した塗布液を調製し、この塗布液を集電体に付与(塗布)した後、溶剤又は水を乾燥し、加圧成形して負極材層を形成することにより得られる。一般に、有機結着剤及び溶媒等と混練して、シート状、ペレット状等の形状に成形される。
有機結着剤の含有比率が0.1質量%以上であることで密着性が良好で、充放電時の膨張及び収縮によって負極が破壊されることが抑制される傾向にある。一方、20質量%以下であることで、電極抵抗が大きくなることを抑制できる傾向にある。
有機結着剤の混合に使用する溶剤としては、特に制限はなく、N-メチルピロリドン、ジメチルアセトアミド、ジメチルホルムアミド、γ-ブチロラクトン等が用いられる。
また、シート状、ペレット状等の形状に成形された塗布液と集電体との一体化は、例えば、ロールによる一体化、プレスによる一体化及びこれらの組み合わせによる一体化により行うことができる。
この熱処理により溶媒の除去、有機結着剤の硬化による高強度化が進み、負極材料間の密着性及び負極材料と集電体との間の密着性を向上させることができる。なお、これらの熱処理は、処理中の集電体の酸化を防ぐため、ヘリウム、アルゴン、窒素等の不活性雰囲気又は真空雰囲気で行うことが好ましい。
本発明のリチウムイオン二次電池は、正極と、前記負極と、電解質と、を備える。
前記負極は、例えば、セパレータを介して正極を対向して配置し、電解質を含む電解液を注入することにより、リチウムイオン二次電池とすることができる。
なお、正極塗布液には導電助剤を添加してもよい。前記導電助剤としては、例えば、カーボンブラック、アセチレンブラック、導電性を示す酸化物及び導電性を示す窒化物が挙げられる。これらの導電助剤は1種単独で又は2種類以上を組み合わせて使用してもよい。
(負極材料の作製)
珪素酸化物として、塊状の酸化珪素((株)高純度化学研究所製、10mm~30mm角)を乳鉢により粗粉砕し珪素酸化物粒子を得た。この珪素酸化物粒子を振動ミル(小型振動ミルNB-0、日陶科学(株)製)によって更に粉砕した後、300M(300メッシュ)の試験篩で整粒し、平均粒子径が5μmの微粒子を得た。
測定試料(5mg)を界面活性剤(エソミンT/15、ライオン(株)製)0.01質量%水溶液中に入れ、振動攪拌機で分散した。得られた分散液をレーザー回折式粒度分布測定装置(SALD3000J、(株)島津製作所製)の試料水槽に入れ、超音波をかけながらポンプで循環させ、レーザー回折式で測定した。測定条件は下記の通りとした。得られた粒度分布の体積累積50%粒径(D50%)を平均粒子径とした。以下、実施例において、平均粒子径の測定は同様にして行った。
・光源:赤色半導体レーザー(690nm)
・吸光度:0.10~0.15
・屈折率:2.00-0.20i
負極材料の炭素含有率を高周波焼成-赤外分析法にて測定した。高周波焼成-赤外分析法は、高周波炉にて酸素気流で試料を加熱燃焼させ、試料中の炭素及び硫黄をそれぞれCO2及びSO2に変換し、赤外線吸収法によって定量する分析方法である。測定装置及び測定条件等は下記の通りである。
・装置:炭素硫黄同時分析装置(LECOジャパン合同会社製、CSLS600)
・周波数:18MHz
・高周波出力:1600W
・試料質量:約0.05g
・分析時間:装置の設定モードで自動モードを使用
・助燃材:Fe+W/Sn
・標準試料:Leco501-024(C:3.03%±0.04、S:0.055%±0.002)
・測定回数:2回(表2中の炭素含有率の値は2回の測定値の平均値である)
ラマンスペクトル測定装置(日本分光(株)製NSR-1000型)を用い、得られたスペクトルは下記範囲をベースラインとし、負極材料の分析を行った。測定条件は、下記の通りとした。
・レーザー波長:532nm
・照射強度:1.5mW(レーザーパワーモニターでの測定値)
・照射時間:60秒
・照射面積:4μm2
・測定範囲:830cm-1~1940cm-1
・ベースライン:1050cm-1~1750cm-1
補正後に得られたプロファイルの中で、1360cm-1付近に現れるピークの強度をId、1580cm-1付近に現れるピークの強度をIgとし、その両ピークの強度比Id/Ig(D/G)をR値として求めた。
高速比表面積/細孔分布測定装置ASAP2020(MICRO MERITICS製)を用い、液体窒素温度(77K)での窒素吸着を5点法で測定しBET法(相対圧範囲:0.05~0.2)より算出した。
粉末X線回折測定装置(MultiFlex(2kW)、(株)リガク製)を用いて負極材料の分析を行った。珪素の結晶子サイズは、2θ=28.4°付近に存在するSi(111)の結晶面に帰属されるピークの半値幅から、Scherrerの式を用いて算出した。測定条件は下記の通りとした。
・測定範囲:2θ=10°~40°
・サンプリングステップ幅:0.02°
・スキャンスピード:1°/分
・管電流:40mA
・管電圧:40kV
・発散スリット:1°
・散乱スリット:1°
・受光スリット:0.3mm
・Kα1/Kα2強度比:2.0
・BG点からのBGカーブ上下(σ):0.0
・Si(111)に帰属するピーク:28.4°±0.3°
・SiO2に帰属するピーク:21°±0.3°
・プロファイル形状関数:Pseudo-Voigt
・バックグラウンド固定
D=Kλ/B cosθ
B=(Bobs 2-b2)1/2
D:結晶子サイズ(nm)
K:Scherrer定数(0.94)
λ:線源波長(0.154056nm)
θ:測定半値幅ピーク角度
Bobs:半値幅(構造解析ソフトから得られた測定値)
b:標準珪素(Si)の測定半値幅
上記手法で作製した負極材料の粉末3.75質量%、炭素系負極材料として人造黒鉛(日立化成(株)製)71.25質量%(作製した負極材料:人造黒鉛=5:95(質量比))に、導電助剤としてアセチレンブラック(電気化学工業(株)製)の粉末15質量%、バインダとしてLSR-7(日立化成(株)製)を添加し、その後混練し均一なスラリーを作製した。なお、バインダの添加量は、スラリーの総質量に対して10質量%となるように調整した。このスラリーを、電解銅箔の光沢面に塗布量が10mg/cm2となるように塗布し、90℃で2時間の予備乾燥させた後、ロールプレスで密度1.65g/cm3になるように調整した。その後、真空雰囲気下で、120℃で4時間乾燥させることによって硬化処理を行い、負極を得た。
上記で得られた電極を負極とし、対極として金属リチウム、電解液として1MのLiPF6を含むエチレンカーボネート/エチルメチルカーボネート(3:7体積比)とビニルカーボネート(VC)(1.0質量%)の混合液、セパレータとして厚さ25μmのポリエチレン製微孔膜、スペーサーとして厚さ250μmの銅板を用いて2016型コインセルを作製した。
<初回放電容量、充放電効率>
上記で得られた電池を、25℃に保持した恒温槽に入れ、0.43mA(0.32mA/cm2)で0Vになるまで定電流充電を行った後、0Vの定電圧で電流が0.043mAに相当する値に減衰するまで更に充電し、初回充電容量を測定した。充電後、30分間の休止を入れたのちに放電を行った。放電は0.43mA(0.32mA/cm2)で1.5Vになるまで行い、初回放電容量を測定した。このとき、容量は用いた負極材料の質量(作製した負極材料と人造黒鉛とを混合した総質量)当たりに換算した。初回放電容量を初回充電容量で割った値を初期の充放電効率(%)として算出した。
実施例1の負極材料の作製において、珪素酸化物と石炭系ピッチとの混合割合を、下記表のように変更した以外は、実施例1と同様にして負極材料を作製し、同様の評価を行った。
実施例1の負極材料の作製において、ピッチを混合せず、珪素酸化物のみを熱処理するように変更した以外は、実施例1と同様にして負極材料を作製し、同様の評価を行った。以上の実施例及び比較例の評価結果を下記表2に示す。
なお、負極材料として人造黒鉛のみを用いた場合の初回の充電容量は378mAh/gであり、初回の放電容量は355Ah/gであった。この人造黒鉛のみを用いた場合の結果を踏まえると、本実施例では、負極材料として本発明の負極材料を5質量%含有し、人造黒鉛を95質量%含むものであるが、このような本発明の負極材料の配合量であっても、初回の充電容量及び放電容量が格段に向上していることが分かる。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (5)
- 珪素酸化物の表面の一部又は全部に炭素を有してなり、前記炭素が0.5質量%以上5質量%未満で含まれるリチウムイオン二次電池用負極材料。
- 前記炭素が、低結晶性炭素である請求項1に記載のリチウムイオン二次電池用負極材料。
- 粉末X線回折(XRD)測定を行ったとき、Si(111)に帰属される回折ピークが観察される請求項1又は請求項2に記載のリチウムイオン二次電池用負極材料。
- 集電体と
前記集電体上に設けられる、請求項1~請求項3のいずれか1項に記載の負極材料を含む負極材層と、
を有するリチウムイオン二次電池用負極。 - 正極と、請求項4に記載のリチウムイオン二次電池用負極と、電解質と、を備えるリチウムイオン二次電池。
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WO2016194288A1 (ja) * | 2015-06-02 | 2016-12-08 | 信越化学工業株式会社 | 非水電解質二次電池用負極活物質、非水電解質二次電池用負極、及び非水電解質二次電池、並びに負極活物質粒子の製造方法 |
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US10535872B2 (en) | 2015-06-02 | 2020-01-14 | Shin-Etsu Chemical Co., Ltd. | Negative electrode active material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of producing negative electrode active material particles |
WO2017022455A1 (ja) * | 2015-07-31 | 2017-02-09 | 信越化学工業株式会社 | リチウムイオン二次電池用負極材、その製造方法及びリチウムイオン二次電池 |
JPWO2017022455A1 (ja) * | 2015-07-31 | 2017-12-28 | 信越化学工業株式会社 | リチウムイオン二次電池用負極材、その製造方法及びリチウムイオン二次電池 |
CN107925074A (zh) * | 2015-07-31 | 2018-04-17 | 信越化学工业株式会社 | 锂离子二次电池用负极材料、其制造方法和锂离子二次电池 |
EP3331068A4 (en) * | 2015-07-31 | 2019-03-27 | Shin-Etsu Chemical Co., Ltd. | NEGATIVE LITHIUM-ION RECHARGEABLE BATTERY ELECTRODE, MANUFACTURING METHOD THEREOF, AND LITHIUM-ION RECHARGEABLE BATTERY |
CN107925074B (zh) * | 2015-07-31 | 2022-03-01 | 信越化学工业株式会社 | 锂离子二次电池用负极材料、其制造方法和锂离子二次电池 |
JP2017103202A (ja) * | 2015-11-19 | 2017-06-08 | パナソニックIpマネジメント株式会社 | リチウムイオン二次電池 |
JP2019145291A (ja) * | 2018-02-20 | 2019-08-29 | Tdk株式会社 | リチウムイオン二次電池用負極およびリチウムイオン二次電池 |
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CN104737337A (zh) | 2015-06-24 |
US10693130B2 (en) | 2020-06-23 |
TWI624984B (zh) | 2018-05-21 |
CA2889207A1 (en) | 2014-05-01 |
US20150263339A1 (en) | 2015-09-17 |
EP2913871B1 (en) | 2018-06-13 |
JP6256346B2 (ja) | 2018-01-10 |
US11251421B2 (en) | 2022-02-15 |
KR20200102539A (ko) | 2020-08-31 |
KR20150073995A (ko) | 2015-07-01 |
EP2913871A4 (en) | 2016-06-08 |
CN110010880A (zh) | 2019-07-12 |
KR102332760B1 (ko) | 2021-12-01 |
EP2913871A1 (en) | 2015-09-02 |
CN110021735A (zh) | 2019-07-16 |
TW201424097A (zh) | 2014-06-16 |
KR102281034B1 (ko) | 2021-07-22 |
US20200280053A1 (en) | 2020-09-03 |
JPWO2014065417A1 (ja) | 2016-09-08 |
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