WO2013077325A1 - 非水電解質系2次電池用負極材料およびその製造方法 - Google Patents
非水電解質系2次電池用負極材料およびその製造方法 Download PDFInfo
- Publication number
- WO2013077325A1 WO2013077325A1 PCT/JP2012/080082 JP2012080082W WO2013077325A1 WO 2013077325 A1 WO2013077325 A1 WO 2013077325A1 JP 2012080082 W JP2012080082 W JP 2012080082W WO 2013077325 A1 WO2013077325 A1 WO 2013077325A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- negative electrode
- secondary battery
- carbon
- electrode material
- electrolyte secondary
- Prior art date
Links
Images
Classifications
-
- 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
- H01M4/58—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M4/58—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells
Definitions
- the present invention relates to a negative electrode material for a nonaqueous electrolyte secondary battery such as a lithium ion secondary battery, and more particularly to a negative electrode material from which a nonaqueous electrolyte secondary battery having high-rate discharge characteristics can be obtained.
- a lithium ion secondary battery which is a non-aqueous electrolyte secondary battery using a carbon material that functions as a host that reversibly occludes and releases lithium ions as the negative electrode and an organic solvent solution of lithium salt as the electrolyte, is a self-discharge.
- a small secondary battery with a small amount of electromotive force and high energy density its use is rapidly expanding mainly for power supplies for portable devices and electric vehicles.
- the theoretical capacity of a negative electrode made of metallic lithium is very high at about 3800 mAh / g, whereas in the negative electrode made of carbon material, the theoretical capacity of LiC 6 composition which is an intercalation compound in which lithium ions are densely stored between graphite layers 372 mAh / g is considered to be the limit capacity, and the capacity is an order of magnitude lower than that of metallic lithium.
- the capacity is an order of magnitude lower than that of metallic lithium.
- dendritic precipitation during charging which is unavoidable with metallic lithium negative electrodes, does not occur, lithium ion secondary batteries using a carbon material as a negative electrode material have been developed and are rapidly spreading.
- Examples of the carbon material used for the negative electrode of the lithium ion secondary battery include crystalline natural and artificial graphite, soft carbon that is a precursor of artificial graphite, and hard carbon that does not become graphite even when subjected to high-temperature treatment.
- Soft carbon and hard carbon can be obtained by heat-treating organic matter such as pitch and resin in an inert atmosphere until the volatile content disappears at about 1000 ° C.
- Especially hard carbon has an amorphous structure with low crystallinity. It is a material with
- graphite can be obtained by refining naturally existing graphite or by heat-treating soft carbon at a temperature of about 2500 ° C. or higher.
- the negative electrode is formed by molding the powdered material, usually using a small amount of a binder, and pressing the material onto an electrode substrate to be a current collector.
- the limit capacity when graphite is used is 372 mAh / g.
- the actual discharge capacity Is much lower than this. For this reason, various attempts have been made to approach this limit capacity.
- Patent Document 1 discloses that boron is 0.1 to 2 masses. A carbonaceous material obtained by carbonizing an organic resin with a% added has been proposed.
- Patent Document 2 proposes a negative electrode material graphitized by adding a boron compound to pitch and then heat-treating it at a high temperature.
- Patent Document 3 proposes a carbon powder excellent in discharge capacity and charge / discharge efficiency obtained by adding a boron compound to carbon powder and graphitizing it at 2500 ° C. or higher.
- JP-A-3-245548 JP 2000-149947 A Japanese Patent Laid-Open No. 8-31422
- a nonaqueous electrolyte secondary battery used for an electric vehicle or the like is required to have excellent charge / discharge characteristics even under a high load, and a nonaqueous electrolyte having so-called high rate discharge performance.
- the charge / discharge capacity of the secondary battery can be improved and the energy density can be increased by increasing the degree of graphitization of the carbon material, it is insufficient from the viewpoint of high rate discharge performance.
- the inventors of the present invention have recently developed a negative electrode material having excellent discharge rate characteristics while maintaining excellent charge / discharge capacity by heat-treating a mixture of a carbon material having a sufficiently high degree of graphitization with a boron compound at a low temperature. I got the knowledge that it could be realized. The present invention is based on this finding.
- an object of the present invention is to provide a negative electrode material for a non-aqueous electrolyte secondary battery having a high charge / discharge capacity and excellent rate characteristics.
- the negative electrode material for a non-aqueous electrolyte secondary battery according to the present invention has a carbon atom content of 98.0% or more in terms of mass, and a C-axis direction plane distance (d 002 ) of 3.370 angstroms or less.
- a boron material represented by the general formula: HxBOy (wherein x represents a real number of 0 to 1.0 and y represents a real number of 1.5 to 3.0) The boron compound is bonded to some carbon atoms of the carbon material.
- the boron compound may be contained in an amount of 0.1 to 5.0% in terms of boron atom mass with respect to the carbon material.
- the carbon material may be natural graphite or artificial graphite obtained by heat-treating a hydrocarbon compound at a temperature of 2000 ° C. or higher.
- the negative electrode material for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention may have a structure in which carbon atoms of the carbon material and oxygen atoms of the boron compound are bonded by a covalent bond.
- the carbon atom content is 98.0% or more in terms of mass
- the C-axis direction spacing ( d 002 ) is not more than 3.370 ⁇
- boric acid is mixed and kneaded, The mixture is heat treated at a temperature of room temperature to 1400 ° C.
- the heat treatment may be performed in a vacuum or an inert gas atmosphere.
- boric acid is dehydrated by the heat treatment, and the general formula: HxBOy (where x is a real number of 0 to 1.0) And y represents a real number of 1.5 to 3.0.) Is formed.
- a negative electrode for a non-aqueous electrolyte secondary battery and a positive electrode, an electrolyte layer containing a non-aqueous electrolyte, and a negative electrode made of the material obtained by the above method are provided.
- the negative electrode comprises the negative electrode.
- Example 4 shows an FT-IR spectrum of the negative electrode material obtained in Example 1.
- 2 is a scanning electron micrograph of the negative electrode material obtained in Example 1.
- 4 is an FT-IR spectrum of the negative electrode material obtained in Example 2.
- the negative electrode material for a non-aqueous electrolyte secondary battery according to the present invention contains a carbon material and a boron compound as essential components. First, the carbon material will be described.
- a highly graphitized carbon material is used. That is, a carbon material having a carbon atom content of 98.0% or more in terms of mass and a plane spacing (d 002 ) in the C-axis direction of 3.370 mm or less is used.
- the interplanar spacing (d 002 ) means the interplanar interstitial distance of the carbon material obtained by X-ray diffraction measurement.
- a carbon material having a low graphitization degree with a surface spacing exceeding 3.370 mm cannot be said to have sufficient crystallinity, and a high discharge capacity cannot be realized.
- Natural graphite has a C-axis surface spacing of 3.354 mm, and artificial graphite also has a C-axis surface spacing that decreases as graphitization proceeds and approaches 3.354 mm. Higher heat treatment temperature and longer heat treatment time tend to increase the degree of graphitization.
- a carbon material having a carbon atom content of 98.0% or more in terms of mass and having a plane spacing in the C-axis direction of 3.370 mm or less it has been conventionally used in addition to the above-mentioned natural graphite. Artificial graphite and quiche graphite can be used.
- any one or more of carbon materials such as hard carbon, soft carbon, pyrolytic carbon, coke, glassy carbon, organic polymer compound fired body, activated carbon, and carbon black can be used. These are obtained by graphitizing a hydrocarbon compound, and are usually performed by heat-treating the hydrocarbon compound at a temperature of 1500 to 3000 ° C. When the graphitization temperature is 2000 ° C. or higher, a carbon material having a C-axis direction surface spacing of 3.370 mm or less can be obtained.
- natural graphite can be preferably used. Although natural graphite is cheaper than artificial graphite and has a high charge / discharge capacity, discharge characteristics under high load are insufficient, and it has not been used as a negative electrode material for secondary batteries that require high rate performance. It was. However, in the present invention, as will be described later, by heat-treating a mixture of natural graphite and a boron compound at a specific temperature, the boron compound is bonded to some of the carbon atoms of the carbon material, and as a result, The rate characteristics can be remarkably improved.
- the negative electrode material according to the present invention can be obtained by heat-treating a mixture of the above carbon material and a boron compound at a temperature of room temperature to 1400 ° C.
- a boron compound is added to a precursor such as pitch or tar, and heat treatment is performed at a high temperature (1500 ° C. to 3000 ° C.).
- the boron compound is decomposed, and a part of the carbon element of the graphite is replaced with the boron element.
- the purpose is to obtain artificial graphite with a small interplanar spacing by reducing the tetracoordinate carbon element of the carbon network by substitution of boron element which is a tricoordinate element.
- a boron compound as described above is added to graphite having an interplanar spacing of 3.370 mm or less, which is a highly graphitized carbon material, and heat-treated at a low temperature.
- the rate characteristics can be remarkably improved while maintaining a high charge / discharge capacity. The reason for this is not clear, but is considered as follows.
- the boron compound bonded to a part of carbon atoms of the carbon material is represented by the general formula: HxBOy (wherein x represents a real number of 0 to 1.0 and y represents a real number of 1.5 to 3.0). Is represented.) It is considered that the following structure is formed when the oxygen atom of the boron compound is covalently bonded to a part of the carbon atom on the end surface of the graphene layer of graphite.
- the boron compound represented by the general formula: HxBOy bonded to a part of carbon atoms at the end of the graphene layer of graphite since the boron atom has an unshared electron pair, lithium ions are released from the negative electrode to the electrolyte. In doing so, the intercalated lithium ions move through the boron atoms. That is, the boron compound functions as a lithium ion transfer channel. As a result, it is considered that lithium ions are efficiently released even at a high load with a large amount of current, and the discharge rate characteristics are improved.
- the above logical consideration is only a process, and the present invention is not bound by the theory described above.
- the ratio of the carbon material to the boron compound is preferably 0.1 to 5.0% in terms of boron atom mass with respect to the carbon material. If the boron atom mass is less than 0.1%, the number of boron atoms having an unshared electron pair is small, and the boron compound may not function as a lithium ion transfer channel. On the other hand, when the proportion of the boron compound exceeds 5% in terms of boron atom mass, the discharge capacity is reduced because the content of graphite carbon per unit mass of the negative electrode material is reduced. In addition, the initial efficiency (ratio between discharge capacity and charge capacity) also decreases.
- the proportion of graphite as a charging site decreases, the amount of charge decreases, and the initial efficiency decreases due to the excessive content of the boron compound.
- the boron compound content is 7% in terms of boron atom mass
- the discharge capacity (0.1 C rate) is reduced to 266 mAh / g
- the initial efficiency is 62.8%.
- the method for producing a negative electrode material for a non-aqueous electrolyte secondary battery according to the present invention includes mixing the above-described carbon material with boric acid and kneading, and heat-treating the mixture at a temperature of room temperature to 1400 ° C.
- boric acid As boric acid, orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ), and hypoboric acid (H 2 B 4 O 7 ) can be preferably used. These boric acids are thermally decomposed by heat treatment at a high temperature such as 1500 to 3000 ° C., and boron atoms are replaced with part of carbon atoms constituting the graphene layer of graphite, resulting in the following structure. Therefore, since the lithium ion moving channel as described above is not formed, the discharge rate characteristics are not improved.
- boric acid is dehydrated by heat treatment at a temperature below thermal decomposition.
- orthoboric acid is known to undergo the following dehydration depending on the heat treatment temperature.
- the temperature of the heat treatment exceeds 1400 ° C.
- boric acid is oxidized to boron oxide (B 2 O 3 ) and further boron carbide, so that the above-described lithium ion transfer channel is not formed. Therefore, it is necessary to perform heat treatment at a temperature of 1400 ° C. or lower.
- a preferable heat treatment temperature is 1000 ° C. to 1200 ° C. In this temperature range, the discharge rate characteristic can be further improved by heat-treating the mixture of the carbon material and boric acid.
- boric acid is added to a carbon material (for example, natural graphite) having a carbon atom content of 100% in terms of mass and having a C-axis plane spacing (d 002 ) of 3.370 angstroms or less.
- a carbon material for example, natural graphite
- d 002 C-axis plane spacing
- a negative electrode is produced using a negative electrode material by applying a water-soluble coating liquid obtained by adding a suitable solvent and a binder to the negative electrode material to a current collector.
- the coating film is dried to evaporate water in the coating solution. It is considered that boric acid is dehydrated also by heat during the above process, and a supply bond is generated between the carbon atom in natural graphite and the oxygen atom of the boron compound as described above.
- the heat treatment of the mixture of the carbon material and boric acid is preferably performed in a vacuum or in an inert gas atmosphere such as nitrogen or argon. Under an oxygen atmosphere, the carbon material (graphite) may be oxidized even at a temperature of 1400 ° C. or lower.
- the lithium ion secondary battery is essentially a battery mechanism in which lithium ions are occluded in the negative electrode during charge and discharge and are desorbed from the negative electrode during discharge.
- a lithium ion secondary battery usually has a negative electrode, a positive electrode, and a non-aqueous electrolyte as main battery components.
- the positive and negative electrodes are composed of a lithium ion combination and a substance capable of forming an interlayer, respectively. Access to the negative electrode is made between the graphene layers constituting the graphite.
- the constituent elements of the lithium ion secondary battery may be the same as those of a general lithium secondary battery except that the above-described material is used as the negative electrode material.
- the negative electrode is prepared by adding a powder of a rubbery polymer such as styrene-butadiene rubber or a resin-based polymer such as carboxymethyl cellulose to the negative electrode material described above, and mixing and kneading in a solvent such as water.
- the negative electrode can be produced by applying to a current collector.
- the negative electrode may be formed by hot press molding in a mold.
- the shape of the current collector used for the negative electrode is not particularly limited, and examples thereof include a foil shape or a net shape such as a mesh or an expanded metal. Examples of the current collector include copper, stainless steel, and nickel.
- the thickness of the current collector is preferably about 5 to 20 ⁇ m in the case of a foil.
- the positive electrode active material examples include lithium-containing transition metal oxides LiM 1 1-x M 2 x O 2 or LiM 1 2y M 2 y O 4 (wherein X is 0 ⁇ X ⁇ 4, Y is 0 ⁇ Y ⁇ 1 and M 1 and M 2 represent transition metals and consist of at least one of Co, Ni, Mn, Cr, Ti, V, Fe, Zn, Al, In, and Sn), transition Metal chalcogenides, vanadium oxides (V 2 O 5 , V 6 O 13 , V 2 O 4 , V 3 O 8 etc.) and their lithium compounds, general formula M x Mo 6 S 8-y (where X is 0 ⁇ X ⁇ 4, Y is a numerical value in the range of 0 ⁇ Y ⁇ 1, and M represents a metal such as a transition metal) Further, activated carbon, activated carbon fiber, or the like is used. be able to.
- the organic solvent used for the non-aqueous electrolyte is not particularly limited.
- an organic or inorganic lithium compound soluble in the organic solvent to be used may be used.
- suitable lithium compounds LiClO 4, LiBF 4, LiPF 6, LiAsF 6, LiB (C 6 H 5), LiCl, LiBr, LiCF 3 SO 3, LiCH 3 SO 3 , and the like. You may use what mixed these 2 or more types.
- a separator can also be used. Although it does not specifically limit as a separator, for example, a woven fabric, a nonwoven fabric, a synthetic resin microporous film, etc. are mentioned. In particular, a synthetic resin porous membrane is preferably used. Among these, a polyolefin-based microporous membrane is preferable in terms of thickness, membrane strength, and membrane resistance. Specifically, it is a microporous film made of polyethylene and polypropylene, or a microporous film in which these are combined.
- the structure of the lithium ion secondary battery according to the present invention is arbitrary, and the shape and form thereof are not particularly limited, and can be arbitrarily selected from a cylindrical shape, a square shape, a coin shape, a button shape, and the like. .
- Example 1 negative electrode material using natural graphite
- Boric acid manufactured by Sigma-Aldrich
- d 002 C-axis surface spacing
- Boron dope was performed by heat-treating the thing.
- the boron doping amount was set to 5% in terms of boron atom mass with respect to natural graphite.
- Natural graphite mixed with boric acid was heat treated at 200 ° C., 300 ° C., 500 ° C., 1000 ° C., 1200 ° C., 1500 ° C., 1800 ° C., 2000 ° C., 2400 ° C., and 2800 ° C. to obtain a negative electrode material.
- a mixture was prepared in the same manner as described above except that the amount of boric acid added was 3% in terms of boron atom mass, and heat-treated at each temperature of 1000 ° C. and 1200 ° C. to obtain a negative electrode material.
- FT-IR Fourier transform infrared spectrophotometer
- the working electrode (WE) is made of the obtained negative electrode material
- the counter electrode (CE) and the reference electrode (RE) are made of lithium metal
- the electrolytic solution is ethylene carbonate and dimethyl carbonate at 1: 1.
- a coin-type secondary battery was manufactured by using LiPF 6 dissolved as an electrolyte salt (concentration of electrolyte salt: 1 mol / dm 3 ) in the mixed solvent. Using the thus obtained secondary battery, the rate characteristics were examined as follows.
- the obtained secondary battery was used in a constant current charge / discharge test.
- the discharge capacity was 37.2 mA / g (corresponding to 0.1 C), and the battery was charged until the potential with respect to the lithium reference electrode (vs Li / Li + ) became 0.0 V. It calculated
- the current density was 74.4 mA / g (corresponding to 0.2 C), 186.0 mA / g (corresponding to 0.5 C), 372.0 mA / g (corresponding to 1.0 C),
- the discharge capacity was determined by changing to 744 mA / g (corresponding to 2.0 C) and 1860 mA / g (corresponding to 5.0 C).
- the evaluation results were as shown in Table 1 and Table 2 below.
- surface means the boron content of the boron atom mass conversion with respect to natural graphite.
- FIG. 3 shows a sample with a boron content of 5%
- FIG. 4 shows a sample with a boron content of 3%.
- Example 2 (negative electrode material using artificial graphite)> Artificial graphite was obtained by heat-treating green coke (optical isotropic structure ratio of 25% or less) at 2800 ° C.
- the resulting artificial graphite (HDPC) had a carbon content of 99.90% and a C-axis direction spacing (d 002 ) of 3.369 mm.
- boric acid manufactured by Sigma-Aldrich
- boric acid manufactured by Sigma-Aldrich
- a negative electrode material was obtained by heat treatment at 1000 ° C, 1200 ° C, 1500 ° C, 1800 ° C, 2000 ° C, 2400 ° C, and 2800 ° C.
- FT-IR Fourier transform infrared spectrophotometer
- a working electrode is produced using the obtained negative electrode material, a counter electrode (CE) and a reference electrode (RE) are produced from lithium metal, and ethylene carbonate and dimethyl carbonate are used as an electrolytic solution in a 1: 1 ratio.
- a coin-type secondary battery was manufactured using a solution obtained by dissolving LiPF 6 as an electrolyte salt (concentration of electrolyte salt: 1 mol / dm 3 ) in the mixed solvent mixed in (1). Using the thus obtained secondary battery, the rate characteristics were examined as follows.
- the obtained secondary battery was used in a constant current charge / discharge test.
- the discharge capacity was 37.2 mA / g (corresponding to 0.1 C), and the battery was charged until the potential with respect to the lithium reference electrode (vs Li / Li + ) became 0.0 V. It calculated
- the current density was 74.4 mA / g (equivalent to 0.2 C), 186.0 mA / g (equivalent to 0.5 C), 372 mA / g (equivalent to 1.0 C), 744 mA / g.
- the discharge capacity was determined by changing to g (corresponding to 2.0C) and 1860 mA / g (corresponding to 5.0C).
- the evaluation results were as shown in Table 3 below.
- surface means the boron content of the boron atom mass conversion with respect to artificial graphite (HDPC).
- Example 3 negative electrode material using natural graphite
- Boric acid manufactured by Sigma-Aldrich
- natural graphite having a carbon atom content of 99.95% or more in terms of mass and a C-axis surface spacing (d 002 ) of 3.361 mm
- Boron dope was performed by heat-treating the thing.
- the boron doping amount was 3% in terms of boron atom mass with respect to natural graphite.
- Natural graphite mixed with boric acid was heat treated at 1000 ° C. and 2800 ° C. to obtain a negative electrode material.
- a working electrode is produced using the obtained negative electrode material, a counter electrode (CE) and a reference electrode (RE) are produced from lithium metal, and ethylene carbonate and dimethyl carbonate are used as an electrolytic solution in a 1: 1 ratio.
- a coin-type secondary battery was manufactured using a solution obtained by dissolving LiPF 6 as an electrolyte salt (concentration of electrolyte salt: 1 mol / dm 3 ) in the mixed solvent mixed in (1). Using the thus obtained secondary battery, the rate characteristics were examined as follows.
- the obtained secondary battery was used in a constant current charge / discharge test.
- the discharge capacity was 37.2 mA / g (corresponding to 0.1 C), and the battery was charged until the potential with respect to the lithium reference electrode (vs Li / Li + ) became 0.0 V. It calculated
- the current density was 74.4 mA / g (corresponding to 0.2 C), 186 mA / g (corresponding to 0.5 C), 372 mA / g (corresponding to 1.0 C), 744 mA / g (
- the discharge capacity was obtained by changing to 1860 mA / g (corresponding to 5.0C).
- the evaluation results were as shown in Table 4 below.
- surface means the boron content of the boron atom mass conversion with respect to natural graphite.
Abstract
Description
前記混合物を、室温~1400℃の温度で熱処理することを含んでなることを特徴とするものである。
炭素原子の含有量が質量換算で99.995%以上であり、C軸方向の面間隔(d002)が3.354Åである天然黒鉛にホウ酸(シグマアルドリッチ製)を加えてボールミルで混練したものを熱処理することによりホウ素ドープを行った。ホウ素ドープ量は、天然黒鉛に対して、ホウ素原子質量換算で5%となるようにした。ホウ酸を混合した天然黒鉛を200℃、300℃、500℃、1000℃、1200℃、1500℃、1800℃、2000℃、2400℃、2800℃の各温度で熱処理して負極材料を得た。また、ホウ酸添加量がホウ素原子質量換算で3%となるようにした以外は上記と同様にして混合物を調製し、1000℃および1200℃の各温度で熱処理して負極材料を得た。
作用極(WE)を得られた負極材料で作製し、対極 (CE)および参照電極(RE)をリチウム金属で作製し、また、電解液としては、炭酸エチレンと炭酸ジメチルとを1:1で混合した混合溶媒に電解質塩としてLiPF6 を溶解(電解質塩の濃度:1mol/dm3)させたものを用い、コイン型2次電池を作製した。このようにして得られた2次電池を用いて、下記のようにしてレート特性を調べた。
グリーンコークス(光学等方性組織率が25%以下)を2800℃で熱処理することにより、人造黒鉛を得た。得られた人造黒鉛(HDPC)は、炭素含有量が99.90%であり、C軸方向の面間隔(d002)が3.369Åであった。
炭素原子の含有量が質量換算で99.95%以上であり、C軸方向の面間隔(d002)が3.361Åである天然黒鉛にホウ酸(シグマアルドリッチ製)を加えてボールミルで混練したものを熱処理することによりホウ素ドープを行った。ホウ素ドープ量は、天然黒鉛に対して、ホウ素原子質量換算で3%となるようにした。ホウ酸を混合した天然黒鉛を1000℃および2800℃の各温度で熱処理して負極材料を得た。
Claims (9)
- 炭素原子の含有量が質量換算で98.0%以上であって、且つC軸方向の面間隔(d002)が3.370オングストローム以下である炭素材料、および、一般式:HxBOy(式中、xは0~1.0の実数を表し、yは1.5~3.0の実数を表す。)で表されるホウ素化合物を含んでなり、前記炭素材料の炭素原子の一部に、前記ホウ素化合物が結合していることを特徴とする、非水電解質系2次電池用負極材料。
- 前記ホウ素化合物が、前記炭素材料に対して、ホウ素原子質量換算で0.1~5.0%含まれてなる、請求項1に記載の非水電解質系2次電池用負極材料。
- 前記炭素材料が、天然黒鉛、または炭化水素化合物を2000℃以上の温度で熱処理して得られた人造黒鉛である、請求項1または2に記載の非水電解質系2次電池用負極材料。
- 前記炭素材料の炭素原子と、前記ホウ素化合物の酸素原子とが、共有結合によって結合した構造を有する、請求項1~3のいずれか一項に記載の非水電解質系2次電池用負極材料。
- 請求項1~4のいずれか一項に記載の非水電解質系2次電池用負極材料を製造する方法であって、
炭素原子の含有量が質量換算で98.0%以上であって、且つC軸方向の面間隔(d002)が3.370Å以下である炭素材料に、ホウ酸を混合して混練し、
前記混合物を、室温~1400℃の温度で熱処理する、
ことを含んでなることを特徴とする、非水電解質系2次電池用負極材料の製造方法。 - 前記熱処理を、真空または不活性ガス雰囲気下で行う、請求項5に記載の方法。
- 前記熱処理により、ホウ酸が脱水和して、一般式:HxBOy(式中、xは0~1.0の実数を表し、yは1.5~3.0の実数を表す。)で表されるホウ素化合物が形成される、請求項5または6に記載の方法。
- 請求項6または7に記載の方法により得られた材料からなる、非水電解質系2次電池用負極。
- 正極、非水電解液を含有する電解質層、および負極を備えた非水電解質系2次電池であって、前記負極が、請求項8に記載の負極からなる、非水電解質系2次電池。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12851061.7A EP2784860A4 (en) | 2011-11-24 | 2012-11-20 | NEGATIVE ELECTRODE MATERIAL FOR A SECONDARY BATTERY WITH NON-ACID ELECTROLYTE AND METHOD OF MANUFACTURING THEREOF |
CN201280057917.4A CN103975469A (zh) | 2011-11-24 | 2012-11-20 | 非水电解质二次电池用负极材料及其制造方法 |
KR1020147013451A KR20140096067A (ko) | 2011-11-24 | 2012-11-20 | 비수전해질계 2차 전지용 부극재료 및 그 제조 방법 |
US14/360,074 US20140335420A1 (en) | 2011-11-24 | 2012-11-20 | Negative-electrode material for rechargeable batteries with nonaqueous electrolyte, and process for producing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011256575 | 2011-11-24 | ||
JP2011-256575 | 2011-11-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013077325A1 true WO2013077325A1 (ja) | 2013-05-30 |
Family
ID=48469769
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/080082 WO2013077325A1 (ja) | 2011-11-24 | 2012-11-20 | 非水電解質系2次電池用負極材料およびその製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20140335420A1 (ja) |
EP (1) | EP2784860A4 (ja) |
JP (1) | JPWO2013077325A1 (ja) |
KR (1) | KR20140096067A (ja) |
CN (1) | CN103975469A (ja) |
WO (1) | WO2013077325A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020521718A (ja) * | 2017-05-31 | 2020-07-27 | ハイドロゲン イン モーション インコーポレイテッド (エイチ2エム) | 水素貯蔵生成物およびその製造方法 |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106611840A (zh) * | 2015-10-22 | 2017-05-03 | 松下知识产权经营株式会社 | 电池负极材料和电池 |
CN107437614B (zh) | 2016-05-27 | 2022-04-05 | 松下知识产权经营株式会社 | 负极活性物质和电池 |
US10332693B2 (en) | 2016-07-15 | 2019-06-25 | Nanotek Instruments, Inc. | Humic acid-based supercapacitors |
US11254616B2 (en) | 2016-08-04 | 2022-02-22 | Global Graphene Group, Inc. | Method of producing integral 3D humic acid-carbon hybrid foam |
US10731931B2 (en) | 2016-08-18 | 2020-08-04 | Global Graphene Group, Inc. | Highly oriented humic acid films and highly conducting graphitic films derived therefrom and devices containing same |
US10014519B2 (en) | 2016-08-22 | 2018-07-03 | Nanotek Instruments, Inc. | Process for producing humic acid-bonded metal foil film current collector |
US10597389B2 (en) | 2016-08-22 | 2020-03-24 | Global Graphene Group, Inc. | Humic acid-bonded metal foil film current collector and battery and supercapacitor containing same |
US10584216B2 (en) | 2016-08-30 | 2020-03-10 | Global Graphene Group, Inc. | Process for producing humic acid-derived conductive foams |
US20180061517A1 (en) * | 2016-08-30 | 2018-03-01 | Nanotek Instruments, Inc. | Highly Conductive Graphitic Films and Production Process |
US10593932B2 (en) | 2016-09-20 | 2020-03-17 | Global Graphene Group, Inc. | Process for metal-sulfur battery cathode containing humic acid-derived conductive foam |
US10647595B2 (en) | 2016-08-30 | 2020-05-12 | Global Graphene Group, Inc. | Humic acid-derived conductive foams and devices |
JP2018195560A (ja) * | 2017-05-16 | 2018-12-06 | パナソニックIpマネジメント株式会社 | 非水二次電池用負極活物質、及び、非水二次電池 |
US20230163300A1 (en) * | 2020-04-03 | 2023-05-25 | Toyo Ink Sc Holdings Co., Ltd. | Boron-doped carbon material, conductive composition, conductive film, and electric storage device |
CN114843470B (zh) * | 2022-05-10 | 2023-11-03 | 长沙理工大学 | 一种硼、镧共修饰mcmb作为锂离子电池负极材料的制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03245548A (ja) | 1990-02-23 | 1991-11-01 | Sharp Corp | 半田付け検査装置 |
JPH0831422A (ja) | 1994-07-19 | 1996-02-02 | Nippon Steel Corp | リチウム二次電池負極用炭素材料とその製造方法 |
JP2000149947A (ja) | 1998-11-12 | 2000-05-30 | Mitsubishi Gas Chem Co Inc | リチウムイオン電池負極用グラファイト粉末 |
JP2002124256A (ja) * | 2000-10-12 | 2002-04-26 | Mitsubishi Gas Chem Co Inc | 非水溶媒二次電池 |
JP2002164051A (ja) * | 1993-03-10 | 2002-06-07 | Toshiba Corp | リチウム二次電池及び負極材料 |
JP2004134658A (ja) * | 2002-10-11 | 2004-04-30 | Fdk Corp | 充放電可能な電気化学素子 |
JP2004362789A (ja) * | 2003-06-02 | 2004-12-24 | Nec Corp | 負極材料及びそれを用いた二次電池 |
JP2005019397A (ja) * | 2003-06-05 | 2005-01-20 | Showa Denko Kk | 電池電極用炭素材料、その製造方法及び用途 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05251080A (ja) * | 1992-03-06 | 1993-09-28 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池用負極およびその製造法 |
DE69311170T2 (de) * | 1992-03-18 | 1997-12-04 | Matsushita Electric Ind Co Ltd | Negative Elektrode für eine Speicherbatterie mit einem nichtwässrigen Elektrolyt und Verfahren zu seiner Herstellung |
JPH06163080A (ja) * | 1992-11-19 | 1994-06-10 | Sanyo Electric Co Ltd | 二次電池 |
CN1225196A (zh) * | 1996-05-07 | 1999-08-04 | 东洋炭素株式会社 | 锂离子二次电池负极用材料及其制造方法以及使用该负极材料的锂离子二次电池 |
JP4379925B2 (ja) * | 1998-04-21 | 2009-12-09 | 住友金属工業株式会社 | リチウムイオン二次電池の負極材料に適したグラファイト粉末 |
US6391495B1 (en) * | 1998-11-25 | 2002-05-21 | Samsung Display Devices Co., Ltd. | Negative active material for lithium secondary battery, method of preparing the same and lithium secondary battery comprising the same |
JP4147671B2 (ja) * | 1999-03-02 | 2008-09-10 | ソニー株式会社 | 非水電解液二次電池および負極材料の製造方法 |
JP4945029B2 (ja) * | 2001-03-06 | 2012-06-06 | 新日鐵化学株式会社 | リチウム二次電池負極用材料とその製造方法およびリチウム二次電池 |
JP2002324550A (ja) * | 2001-04-26 | 2002-11-08 | Japan Storage Battery Co Ltd | 非水電解質二次電池 |
EP1629554A2 (en) * | 2003-06-05 | 2006-03-01 | Showa Denko K.K. | Carbon material for battery electrode and production method and use thereof |
JP5262175B2 (ja) * | 2008-02-21 | 2013-08-14 | ソニー株式会社 | 負極および二次電池 |
JP5573559B2 (ja) * | 2010-09-30 | 2014-08-20 | 三菱化学株式会社 | リチウムイオン二次電池用炭素材料 |
-
2012
- 2012-11-20 CN CN201280057917.4A patent/CN103975469A/zh active Pending
- 2012-11-20 EP EP12851061.7A patent/EP2784860A4/en not_active Withdrawn
- 2012-11-20 KR KR1020147013451A patent/KR20140096067A/ko not_active Application Discontinuation
- 2012-11-20 JP JP2013545932A patent/JPWO2013077325A1/ja active Pending
- 2012-11-20 US US14/360,074 patent/US20140335420A1/en not_active Abandoned
- 2012-11-20 WO PCT/JP2012/080082 patent/WO2013077325A1/ja active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03245548A (ja) | 1990-02-23 | 1991-11-01 | Sharp Corp | 半田付け検査装置 |
JP2002164051A (ja) * | 1993-03-10 | 2002-06-07 | Toshiba Corp | リチウム二次電池及び負極材料 |
JPH0831422A (ja) | 1994-07-19 | 1996-02-02 | Nippon Steel Corp | リチウム二次電池負極用炭素材料とその製造方法 |
JP2000149947A (ja) | 1998-11-12 | 2000-05-30 | Mitsubishi Gas Chem Co Inc | リチウムイオン電池負極用グラファイト粉末 |
JP2002124256A (ja) * | 2000-10-12 | 2002-04-26 | Mitsubishi Gas Chem Co Inc | 非水溶媒二次電池 |
JP2004134658A (ja) * | 2002-10-11 | 2004-04-30 | Fdk Corp | 充放電可能な電気化学素子 |
JP2004362789A (ja) * | 2003-06-02 | 2004-12-24 | Nec Corp | 負極材料及びそれを用いた二次電池 |
JP2005019397A (ja) * | 2003-06-05 | 2005-01-20 | Showa Denko Kk | 電池電極用炭素材料、その製造方法及び用途 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2784860A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020521718A (ja) * | 2017-05-31 | 2020-07-27 | ハイドロゲン イン モーション インコーポレイテッド (エイチ2エム) | 水素貯蔵生成物およびその製造方法 |
JP7136889B2 (ja) | 2017-05-31 | 2022-09-13 | ハイドロゲン イン モーション インコーポレイテッド (エイチ2エム) | 水素貯蔵生成物およびその製造方法 |
US11634321B2 (en) | 2017-05-31 | 2023-04-25 | Hydrogen In Motion Inc. (H2M) | Hydrogen storage product and method for manufacturing same |
Also Published As
Publication number | Publication date |
---|---|
CN103975469A (zh) | 2014-08-06 |
EP2784860A1 (en) | 2014-10-01 |
US20140335420A1 (en) | 2014-11-13 |
JPWO2013077325A1 (ja) | 2015-04-27 |
EP2784860A4 (en) | 2015-07-22 |
KR20140096067A (ko) | 2014-08-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2013077325A1 (ja) | 非水電解質系2次電池用負極材料およびその製造方法 | |
US10164240B2 (en) | Composite anode active material, anode including the composite anode active material, and lithium secondary battery including the anode | |
JP2020529709A (ja) | 負極活物質、これを含む負極及びリチウム二次電池 | |
KR101331916B1 (ko) | 리튬 보레이트계 화합물의 제조 방법, 리튬 이온 2차 전지용 정극 활물질, 리튬 이온 2차 전지용 정극 및 리튬 이온 2차 전지 | |
KR102380023B1 (ko) | 이차전지 | |
CN105280880B (zh) | 非水电解质二次电池用正极、非水电解质二次电池以及其系统 | |
Cho et al. | Physical and electrochemical properties of La-doped LiFePO 4/C composites as cathode materials for lithium-ion batteries | |
JP2005149957A (ja) | 非水電解質二次電池 | |
JP2009295465A (ja) | リチウム二次電池用正極活物質及びその製造方法 | |
US20190334173A1 (en) | Composite graphite particles, method for producing same, and use thereof | |
Wang et al. | A facile method of improving the high rate cycling performance of LiNi1/3Co1/3Mn1/3O2 cathode material | |
KR101763478B1 (ko) | 리튬 이차전지용 음극활물질, 이의 제조방법, 및 이를 포함하는 리튬 이차전지 | |
KR102519438B1 (ko) | 복합 음극 활물질, 이를 포함하는 리튬 전지, 및 상기 복합 음극 활물질의 제조방법 | |
JP7334735B2 (ja) | 非水系二次電池用負極材、非水系二次電池用負極及び非水系二次電池 | |
JP2016004708A (ja) | リチウムイオン二次電池用正極活物質およびその製造方法、ならびにそれを用いたリチウムイオン二次電池 | |
JP2005243431A (ja) | 非水電解質二次電池 | |
JP6957127B1 (ja) | リチウムイオン二次電池の負極用炭素材料およびその製造方法並びにそれを用いた負極およびリチウムイオン二次電池 | |
JP7117536B2 (ja) | 負極活物質及び電池 | |
JP4354723B2 (ja) | 黒鉛質粒子の製造方法 | |
JP2000231933A (ja) | リチウムイオン二次電池 | |
JP2005050556A (ja) | リチウム二次電池用正極材料、リチウム二次電池用正極及びリチウム二次電池 | |
JP2012022933A (ja) | 二次電池用負極材料、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 | |
JP2005197175A (ja) | 正極、負極、電解質および電池 | |
JP2003263982A (ja) | 黒鉛質粒子の製造方法およびリチウムイオン二次電池用負極材料 | |
JP6941782B2 (ja) | 負極活物質および電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12851061 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20147013451 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14360074 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2013545932 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012851061 Country of ref document: EP |