WO2010026627A1 - 電極材料の製造方法と電極材料および電極並びに電池 - Google Patents
電極材料の製造方法と電極材料および電極並びに電池 Download PDFInfo
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- WO2010026627A1 WO2010026627A1 PCT/JP2008/065828 JP2008065828W WO2010026627A1 WO 2010026627 A1 WO2010026627 A1 WO 2010026627A1 JP 2008065828 W JP2008065828 W JP 2008065828W WO 2010026627 A1 WO2010026627 A1 WO 2010026627A1
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- 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
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a method for producing an electrode material, an electrode material, an electrode, and a battery, and in particular, a method for producing an electrode material suitable for use in a positive electrode material for a battery and further a positive electrode material for a lithium ion battery.
- the present invention relates to a manufactured electrode material, a positive electrode formed using the electrode material, and a battery including the positive electrode.
- non-aqueous electrolyte secondary batteries such as lithium ion batteries have been proposed and put into practical use as batteries that are expected to be reduced in size, weight, and capacity.
- This lithium ion battery is composed of a positive electrode and a negative electrode having a property capable of reversibly removing and inserting lithium ions, and a non-aqueous electrolyte.
- a Li-containing metal oxide having a property capable of reversibly removing and inserting lithium ions such as a carbon-based material or lithium titanate (Li 4 Ti 5 O 12 )
- a positive electrode material of a lithium ion battery As a positive electrode active material, a lithium-containing metal oxide such as lithium iron phosphate (LiFePO 4 ) having a property capable of reversibly removing and inserting lithium ions, a binder, and the like are used.
- the electrode material mixture containing is used.
- the positive electrode of a lithium ion battery is formed by apply
- Such lithium ion batteries are lighter and smaller than secondary batteries such as conventional lead batteries, nickel cadmium batteries, and nickel metal hydride batteries, and have high energy. It is used as a power source for portable electronic devices such as personal computers.
- lithium ion batteries have been studied as high-output power sources for electric vehicles, hybrid vehicles, electric tools, etc., and batteries used as these high-output power sources are required to have high-speed charge / discharge characteristics. Yes.
- an electrode active material for example, an electrode material containing a Li-containing metal oxide having a property capable of reversibly removing and inserting lithium ions has a problem that electron conductivity is low.
- the formula Li x A y B z PO 4 (where A is at least one selected from Cr, Mn, Fe, Co, Ni, Cu, B Is at least one selected from Mg, Ca, Sr, Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y, rare earth elements, 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1 .5, 0 ⁇ z ⁇ 1.5), a plurality of primary particles are aggregated into secondary particles, and carbon is interposed as an electron conductive material between the primary particles.
- A is at least one selected from Cr, Mn, Fe, Co, Ni, Cu
- B Is at least one selected from Mg, Ca, Sr, Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y, rare earth elements, 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1 .5, 0 ⁇ z ⁇ 1.5
- a plurality of primary particles are aggregated into secondary particles, and carbon is
- the primary particles comprising the formula Li x A y B z PO 4 of the by plurality aggregate and secondary particles, and the method of interposing the carbon between the primary particles, a sufficient electron conductivity In order to impart, the carbon content had to be high.
- the Li x A y B z PO 4 as an electrode active material, electrode materials made of carbon as a conductive additive to impart electronic conductivity, thus, the electrode material mixture containing an electrode material and a binder
- the content of the electrode active material decreased, the discharge capacity at a high speed charge / discharge rate was high, and a battery having sufficient charge / discharge rate performance could not be produced.
- the present invention has been made in view of the above circumstances, and has a high discharge capacity at a high-speed charge / discharge rate, a method for producing an electrode material capable of realizing sufficient charge / discharge rate performance, an electrode material and an electrode, and An object is to provide a battery.
- the present inventors have assembled a plurality of primary particles of the electrode active material into secondary particles, and the surface of the primary particles is made of thin film carbon. It is found that an electrode material capable of increasing the electron supply capability and realizing a sufficient charge / discharge rate performance can be produced by covering the substrate with carbon and interposing carbon between the primary particles, thereby completing the present invention. It came to. That is, the present inventors have found that an electrode material having specifically high conductivity can be obtained even with the same carbon amount by mixing and using a plurality of types of organic compounds having different properties, and complete the present invention. It came to.
- the method for producing an electrode material according to the present invention includes a slurry containing an electrode active material or a precursor of an electrode active material and an organic compound selected from at least two of the following groups A, B and C: Is sprayed and dried to produce a granulated body, and the granulated body is fired in a non-oxidizing atmosphere of 500 ° C. or higher and 1000 ° C. or lower.
- Group A polyvinyl alcohol, polyvinyl pyrrolidone, cellulose, starch, gelatin, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, polystyrene sulfonic acid, polyacrylamide, polyvinyl acetate
- Group B glucose, fructose, galactose, mannose , Maltose, sucrose, lactose, glycogen, pectin, alginic acid, glucomannan, chitin, hyaluronic acid, chondroitin, agarose
- Group C polyethers or polyhydric alcohols excluding organic compounds contained in Groups A and B
- the electrode active material lithium cobalt oxide, lithium nickel oxide, lithium manganate, lithium titanate, wherein Li x A y B z PO 4 (where, A is Co, Mn, Ni, Fe, Cu, from the group of Cr
- B is one selected from the group of Mg, Ca, Sr, Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y, rare earth elements
- the electrode material of the present invention is sprayed with a slurry containing an electrode active material or a precursor of the electrode active material and an organic compound selected from at least two of the following groups A, B and C, and dried: To produce a granulated body, and the granulated body is fired in a non-oxidizing atmosphere of 500 ° C. or higher and 1000 ° C. or lower.
- Group A polyvinyl alcohol, polyvinyl pyrrolidone, cellulose, starch, gelatin, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, polystyrene sulfonic acid, polyacrylamide, polyvinyl acetate
- Group B glucose, fructose, galactose, mannose , Maltose, sucrose, lactose, glycogen, pectin, alginic acid, glucomannan, chitin, hyaluronic acid, chondroitin, agarose
- Group C polyethers or polyhydric alcohols excluding organic compounds contained in Groups A and B
- the electrode of the present invention is sprayed with a slurry containing an electrode active material or a precursor of the electrode active material and an organic compound selected from at least two of the following groups A, B and C, and dried.
- a granulated body is produced, and the granulated body is formed using an electrode material formed by firing in a non-oxidizing atmosphere of 500 ° C. or higher and 1000 ° C. or lower.
- Group A polyvinyl alcohol, polyvinyl pyrrolidone, cellulose, starch, gelatin, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, polystyrene sulfonic acid, polyacrylamide, polyvinyl acetate
- Group B glucose, fructose, galactose, mannose , Maltose, sucrose, lactose, glycogen, pectin, alginic acid, glucomannan, chitin, hyaluronic acid, chondroitin, agarose
- Group C polyethers or polyhydric alcohols excluding organic compounds contained in Groups A and B
- the battery of the present invention is sprayed with a slurry containing an electrode active material or a precursor of the electrode active material and an organic compound selected from at least two of the following groups A, B and C, and dried.
- a slurry containing an electrode active material or a precursor of the electrode active material and an organic compound selected from at least two of the following groups A, B and C, and dried.
- an electrode formed by using an electrode material formed by firing the granulated body in a non-oxidizing atmosphere of 500 ° C. or higher and 1000 ° C. or lower is provided as a positive electrode. It is characterized by.
- Group A polyvinyl alcohol, polyvinyl pyrrolidone, cellulose, starch, gelatin, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, polystyrene sulfonic acid, polyacrylamide, polyvinyl acetate
- Group B glucose, fructose, galactose, mannose , Maltose, sucrose, lactose, glycogen, pectin, alginic acid, glucomannan, chitin, hyaluronic acid, chondroitin, agarose
- Group C polyethers or polyhydric alcohols excluding organic compounds contained in Groups A and B
- a slurry containing an electrode active material or a precursor of an electrode active material and an organic compound selected from at least two groups out of the groups A, B and C described above is produced a granulated body, and the granulated body is baked in a non-oxidizing atmosphere of 500 ° C. or higher and 1000 ° C. or lower.
- An electrode material capable of realizing charge / discharge rate performance can be provided.
- a slurry containing an electrode active material and an organic compound selected from at least two of the following groups A, B and C is sprayed.
- This is a method of synthesizing an electrode material by drying to produce a granulated body and firing the granulated body in a non-oxidizing atmosphere of 500 ° C. or higher and 1000 ° C. or lower.
- the organic compound contained in each group of A group, B group, and C group selects 1 type, or 2 or more types from each group.
- Group A organic compounds include polyvinyl alcohol, polyvinyl pyrrolidone, cellulose, starch, gelatin, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, polystyrene sulfonic acid, polyacrylamide, and polyvinyl acetate.
- polyvinyl alcohol and polyacrylic acid are particularly preferable because they have excellent film forming properties and can form a suitable carbon film with a small amount of addition.
- Group B organic compounds include glucose, fructose, galactose, mannose, maltose, sucrose, lactose, glycogen, pectin, alginic acid, glucomannan, chitin, hyaluronic acid, chondroitin, agarose and the like.
- organic compound of Group C polyethers or polyhydric alcohols excluding the organic compounds contained in Group A and Group B are used, and examples thereof include polyethylene glycol, polypropylene glycol, polyglycerin, and glycerin.
- lithium cobalt acid lithium nickel acid, lithium manganese oxide, lithium titanate, wherein Li x A y B z PO 4 (where, A is Co, Mn, Ni, Fe, Cu, from the group of Cr
- B is one selected from the group of Mg, Ca, Sr, Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y, rare earth elements
- examples of the rare earth element include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
- Li x A y B z PO 4 as the (Li x A y B z PO 4 powder), solid phase method, liquid phase method, the use of those produced by the conventional method such as vapor-phase method Can do.
- the compound represented by the formula Li x A y B z PO 4 is selected from the group consisting of lithium salts such as lithium acetate (LiCH 3 COO) and lithium chloride (LiCl), and lithium hydroxide (LiOH), for example.
- Li source divalent iron salts such as iron (II) chloride (FeCl 2 ), iron (II) acetate (Fe (CH 3 COO) 2 ), phosphoric acid (H 3 PO 4 ), phosphoric acid 2
- a slurry mixture obtained by mixing a phosphoric acid compound such as ammonium (NH 4 H 2 PO 4 ) or diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) with water is placed in a pressure-resistant sealed container.
- a hydrothermal synthesis is performed, and the resulting precipitate is washed with water to produce a cake-like precursor material.
- a cake-like precursor material synthesized by firing is suitably used.
- the Li x A y B z PO 4 powder may be crystalline particles, amorphous particles, or mixed particles of crystalline and amorphous.
- the reason why amorphous particles may be used is that the amorphous Li x A y B z PO 4 powder crystallizes when heat-treated in a non-oxidizing atmosphere of 500 ° C. or higher and 1000 ° C. or lower. .
- the size of the Li x A y B z PO 4 powder is not particularly limited, but the average primary particle diameter is preferably 0.01 ⁇ m to 20 ⁇ m, more preferably 0.02 ⁇ m to 5 ⁇ m. .
- the average particle size of the primary particles is less than 0.01 ⁇ m, it becomes difficult to sufficiently coat the surface of the primary particles with thin film carbon, the discharge capacity at a high-speed charge / discharge rate is lowered, and a sufficient charge / discharge rate is obtained. It becomes difficult to achieve performance.
- the average particle size of the primary particles exceeds 20 ⁇ m, the resistance inside the primary particles increases, and the discharge capacity at the high-speed charge / discharge rate becomes insufficient.
- the shape of the Li x A y B z PO 4 powder is not particularly limited, but it is easy to produce an electrode material composed of spherical, particularly spherical, secondary particles. Therefore, the Li x A y B z PO 4 powder A spherical shape, particularly a true spherical shape is preferable.
- the reason why the shape of the electrode material is preferably spherical is that it is possible to reduce the amount of solvent when preparing a paste for preparing a positive electrode by mixing the electrode material, a binder resin (binder) and a solvent. This is because it becomes easy to apply this positive electrode-forming paste to the current collector.
- the shape of the electrode material is spherical, the surface area of the electrode material is minimized, the amount of binder resin (binder) added to the electrode material mixture can be minimized, and the resulting positive electrode This is because the internal resistance can be reduced. Furthermore, since it is easy to close-pack, the filling amount of the positive electrode material per unit volume is increased and the electrode density can be increased, so that a high-capacity lithium ion battery can be provided.
- the compounding ratio of the electrode active material and the organic compounds of group A, B and C is such that when the amount of organic compound in groups A, B and C is converted to carbon, 100 parts by weight of electrode active material.
- Carbon is preferably 0.1 parts by weight or more and 30 parts by weight or less. If the compounding ratio of carbon is less than 0.1 parts by weight, the discharge capacity at a high-speed charge / discharge rate becomes low, and it becomes difficult to realize sufficient charge / discharge rate performance. On the other hand, when the blending ratio of carbon exceeds 30 parts by weight, the blending ratio of the electrode active material is lowered, and when a battery is formed, the capacity of the battery is lowered.
- the compounding ratio of the organic compound belonging to Group A, the organic compound belonging to Group B, and the organic compound belonging to Group C is as follows. That is, the amount of carbon produced by heat treating an organic compound belonging to Group A is C A , the amount of carbon produced by heat treating an organic compound belonging to Group B is C B , and the amount of carbon produced by heat treating an organic compound belonging to Group C is produced.
- the carbon amount is C C
- the value divided by ( C , weight conversion) is 0.05 or more. For the organic compound of the group with the smallest amount, if the above value is less than 0.05, a plurality of organic compounds having different properties are not used, but substantially one organic compound is used. It is none other than.
- a uniform slurry is prepared by dissolving or dispersing these electrode active materials and an organic compound selected from at least two of the groups A, B and C in water.
- the electrode active material is dispersed and the organic compounds of Group A, B and C are dissolved or dispersed.
- a method using a medium stirring type dispersion apparatus capable of stirring medium particles at high speed such as a planetary ball mill, a vibration ball mill, a bead mill, a paint shaker, and an attritor, is preferable.
- the electrode active material is dispersed in the primary particles and stirred so as to dissolve the organic compounds of Group A, Group B, and Group C.
- the surface of the primary particles of the electrode active material is coated with the organic compounds of Group A, Group B, and Group C.
- Group A, B The carbon derived from the organic compounds of the group C and the group C comes to intervene uniformly.
- the slurry is sprayed in a high-temperature atmosphere, for example, in the air of 70 ° C. or more and 250 ° C. or less, and dried to produce a granulated body.
- the particle diameter of the droplets during spraying is preferably 0.05 ⁇ m to 500 ⁇ m.
- the granulated body is fired in a non-oxidizing atmosphere of 500 ° C. or higher and 1000 ° C. or lower, preferably 600 ° C. or higher and 900 ° C. or lower.
- a non-oxidizing atmosphere 500 ° C. or higher and 1000 ° C. or lower, preferably 600 ° C. or higher and 900 ° C. or lower.
- the surface of the primary particles of the electrode active material is covered with carbon generated by the thermal decomposition of the organic compounds of the groups A, B, and C, and carbon is formed between the primary particles of the electrode active material.
- An intervening electrode material composed of secondary particles is obtained.
- the calcination temperature of the granulated material is less than 500 ° C.
- the decomposition / reaction of the organic compounds of the A group, the B group and the C group does not proceed sufficiently, the carbonization of the organic compound is insufficient, and the high resistance organic substance A decomposition product is produced.
- the firing temperature of the granulated body exceeds 1000 ° C.
- Li in the electrode active material evaporates and not only the composition shifts, but also the grain growth of the electrode active material is promoted, and the discharge at a high-speed charge / discharge rate.
- an inert atmosphere is preferred, such as Ar, if it is desired to suppress more oxidizing, reducing atmosphere such as a reducing gas such as H 2 Is preferred.
- “Second Embodiment of Electrode Material Manufacturing Method” 2nd embodiment of the manufacturing method of the electrode material of this invention is a slurry containing the precursor of an electrode active material, and the organic compound each selected from at least 2 group among said A group, B group, and C group Is sprayed and dried to produce a granulated body, and this granulated body is fired in a non-oxidizing atmosphere of 500 ° C. or higher and 1000 ° C. or lower to synthesize an electrode material.
- the precursor of the electrode active material refers to an intermediate material obtained by heat-treating a mixture of each raw material component of the electrode active material, which has not yet become a final electrode active material.
- the precursor of the compound represented by the formula Li x A y B z PO 4 is Li source, A source (where A is selected from the group of Co, Mn, Ni, Fe, Cu, Cr) Selected from the group consisting of Mg, Ca, Sr, Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y, and rare earth elements.
- a source (where A is selected from the group of Co, Mn, Ni, Fe, Cu, Cr) Selected from the group consisting of Mg, Ca, Sr, Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y, and rare earth elements.
- Intermediate material obtained by heat-treating a mixture of PO 4 source and water).
- the mixture is placed in a pressure-resistant airtight container and hydrothermally synthesized, and the resulting precipitate is washed with water to produce a cake-like substance, or the mixture is heated at a high temperature.
- the raw material used for generating the precursor of the electrode active material is not particularly limited as long as it is a combination in which a target substance can be usually obtained by a hydrothermal method. Soluble acetate, sulfate, chloride and the like are preferable.
- Li source examples include lithium chloride (LiCl), lithium bromide (LiBr), lithium carbonate (Li 2 CO 3 ), lithium nitrate (LiNO 3 ), lithium sulfate (Li 2 SO 4 ), and lithium phosphate (Li 3 PO 4 ), lithium inorganic acid salts such as lithium hydroxide (LiOH); lithium organic acid salts such as lithium acetate (LiCH 3 COO) and lithium oxalate ((COOLi) 2 ); lithium ethoxide (LiC 2 H 5 Li-containing organometallic compounds such as lithium alkoxides such as O); organolithium compounds such as (Li 4 (CH 3 ) 4 ) are used.
- LiCl lithium chloride
- LiBr lithium bromide
- Li 2 CO 3 lithium nitrate
- LiNO 3 lithium sulfate
- Li 3 PO 4 lithium phosphate
- Li inorganic acid salts such as lithium hydroxide (LiOH)
- the A source is preferably a compound containing one or more elements selected from the group consisting of Co, Mn, Ni, Fe, Cu and Cr, and in particular, any one of Mn, Fe, Co and Ni Alternatively, a compound containing two or more of these elements is preferable from the viewpoints of high discharge potential, abundant resources, safety, and the like. Examples of such compounds include iron sulfate (II) (FeSO 4 ), iron acetate (II) (Fe (CH 3 COO) 2 ), iron chloride (II) (FeCl 2 ), and the like. Can be mentioned.
- the B source is an element different from the A source and is selected from the group consisting of Mg, Ca, Sr, Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, Sc, Y, and rare earth elements.
- the compound containing one or more kinds of elements is preferable, and in particular, any one of Mg, Ca, Sr, Ti, Zn, and Al, or a compound containing two or more elements among these, It is preferable from the viewpoints of high discharge potential, abundant resources and safety.
- examples of the rare earth element include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
- Examples of the PO 4 source include phosphoric acids such as orthophosphoric acid (H 3 PO 4 ) and metaphosphoric acid (HPO 3 ); diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ), ammonium dihydrogen phosphate (NH And ammonium hydrogen phosphate such as 4 H 2 PO 4 ).
- phosphoric acids such as orthophosphoric acid (H 3 PO 4 ) and metaphosphoric acid (HPO 3 ); diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ), ammonium dihydrogen phosphate (NH And ammonium hydrogen phosphate such as 4 H 2 PO 4 ).
- orthophosphoric acid, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, and the like are preferable because of their relatively high purity and ease of composition control.
- an electrode material is synthesized in the same manner as in the first embodiment except that the precursor of the electrode active material is used instead of the electrode active material.
- an electrode active material or a precursor thereof As described above, according to the first and second embodiments of the method for producing an electrode material of the present invention, an electrode active material or a precursor thereof, and at least two groups among the A group, the B group, and the C group described above.
- a slurry in which each selected organic compound is uniformly dispersed in water is sprayed as fine droplets, dried to form a granulated body, and the granulated body is fired. Thermal decomposition occurs, and an electrode material composed of secondary particles having carbon interposed between primary particles of the electrode active material is formed.
- the electrode active material or its precursor by mixing the electrode active material or its precursor and an organic compound selected from at least two of the groups A, B and C, carbon derived from these organic compounds It becomes easy to design the thickness, form, and conductivity of the carbon film covering the electrode active material. That is, although the reason why the conductivity is specifically improved by mixing the electrode active material or its precursor and the above-mentioned plurality of organic compounds is not necessarily clear, for example, an organic compound belonging to Group A is manufactured. Since the film property is excellent, it is considered that a carbon film can be easily formed on the surface of the electrode active material, and a conductive path can be formed over a wide range in the electrode material with a small amount of carbon.
- the organic compounds belonging to Group B easily generate carbon even in a pyrolysis reaction at a lower temperature and exhibit good conductivity.
- the organic compound belonging to Group C improves the wettability of the surface of the electrode active material, carbon derived from the organic compound belonging to Group A and / or carbon derived from the organic compound belonging to Group B, In addition to improving the adhesion of the carbon, it is possible to convert the carbon derived from the organic compound belonging to the group A and / or the carbon derived from the organic compound belonging to the group B into an optimum form on the surface of the electrode active material ( It is considered that the film can be arranged with the thickness of the coating, the coverage, the coating area, the distance between the coating and the opening, and the like. Therefore, by mixing organic compounds selected from a plurality of groups, the effects of these organic compounds are combined, and the conductivity of the electrode material is specifically improved as compared with the case where it is used alone.
- the obtained electrode material has a plurality of primary particles of electrode active material covered with a thin film of carbon having a thickness of 50 nm or less to form secondary particles. Since it is covered with carbon, the portion of the primary particles constituting the secondary particles that are exposed to the outside are also covered with the thin film carbon, and the primary particles are bonded to each other via the thin film carbon. is doing.
- the primary particles are bonded to each other, so that the primary particles are not merely secondary particles in the form of aggregates, but at least the secondary particles behave as one particle. A state of being tightly coupled.
- FIG. 1 is a cross-sectional view showing an electrode material obtained by the first and second embodiments of the method for producing an electrode material of the present invention, in which a plurality of primary particles of an electrode active material are aggregated, The primary particles 1, 1,... Are joined to each other by a thin-layered carbon 2 having a three-dimensional network structure to form secondary particles 3 having a spherical shape as a whole.
- Such an electrode material is one of electrode active materials composed of a compound represented by the formula Li x A y B z PO 4 as compared with an electrode material having the same electron conductivity manufactured by another manufacturing method. The amount of carbon intervening between the secondary particles (covering the primary particle surface) is reduced.
- the formula Li x A y B z and a compound represented by PO 4 electrode materials made of carbon as a conductive aid for imparting electron conductivity as an electrode active material, and thus, the electrode material made of the electrode material and a binder resin Since the amount of the electrode active material contained in the mixture can be increased, the lithium ion battery manufactured using this electrode material mixture has a high discharge capacity at a high-speed charge / discharge rate and has sufficient charge / discharge rate performance. .
- the electrode of the present invention is an electrode formed using the electrode material of the present invention.
- the electrode material of the present invention a binder resin (binder), and a solvent are mixed to prepare a positive electrode preparation paint or paste.
- a conductive assistant such as carbon black may be added as necessary.
- the positive electrode preparation paint or paste is applied to one surface of the metal foil and then dried to obtain a metal foil in which the positive electrode active material is held on one surface.
- a positive electrode active material or the like held on one surface of the metal foil is pressure-bonded and dried to produce a current collector (positive electrode) having an electrode material layer.
- binder resin for example, polytetrafluoroethylene (PTFE) resin, polyvinylidene fluoride (PVdF) resin, or the like is used.
- PTFE polytetrafluoroethylene
- PVdF polyvinylidene fluoride
- the mixing ratio of the electrode material and the binder resin is not particularly limited.
- the binder resin is about 3 to 20 parts by weight with respect to 100 parts by weight of the electrode material.
- the battery of the present invention is a battery comprising the electrode of the present invention as a positive electrode.
- the negative electrode, electrolyte, separator, battery shape and the like are not particularly limited. Since the positive electrode of the battery of the present invention is formed by the electrode material of the present invention which is a fine spherical powder having a high purity and a uniform particle size, the discharge capacity at a high-speed charge / discharge rate is high. It has high and stable charge / discharge cycle performance and high output.
- Example 1 In 2 L (liter) of water, 4 mol of lithium acetate (LiCH 3 COO), 2 mol of iron (II) sulfate (FeSO 4 ), 2 mol of phosphoric acid (H 3 PO 4 ), the total amount becomes 4 L (liter). To prepare a uniform slurry mixture. Next, this mixture is placed in a pressure-resistant sealed container having a capacity of 8 L (liter), hydrothermally synthesized at 120 ° C. for 1 hour, and the resulting precipitate is washed with water to obtain a cake-like electrode active material precursor. It was.
- this electrode active material precursor in terms of solid content
- 4 g of polyvinyl alcohol and 1.5 g of polyethylene glycol as organic compounds are dissolved in 150 g of water, and 500 g of zirconia balls having a diameter of 5 mm are mixed as medium particles.
- Dispersion treatment was performed for 12 hours with a ball mill to prepare a uniform slurry.
- this slurry was sprayed into an air atmosphere at 180 ° C. and dried to obtain a granulated body having an average particle diameter of 6 ⁇ m.
- the obtained granulated body was fired in a nitrogen atmosphere at 700 ° C. for 1 hour to obtain an electrode material (A1).
- the electrode material (A1) was a spherical body having an average particle size of 5 ⁇ m.
- Example 2 An electrode material (A2) was obtained in the same manner as in Example 1 except that 4.8 g of glucose and 1.5 g of polyethylene glycol were used as the organic compound. When this electrode material (A2) was observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM), a plurality of primary particles gathered to form secondary particles, and the surface of these primary particles. was covered with a thin film of carbon, and it was observed that carbon was present between the primary particles.
- the electrode material (A2) was a spherical body having an average particle size of 5 ⁇ m.
- Example 3 An electrode material (A3) was obtained in the same manner as in Example 1 except that 2 g of polyvinyl alcohol and 2.4 g of glucose were used as the organic compound. When this electrode material (A3) was observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM), a plurality of primary particles gathered to form secondary particles, and the surface of these primary particles. was covered with a thin film of carbon, and it was observed that carbon was present between the primary particles.
- the electrode material (A3) was a spherical body having an average particle size of 5 ⁇ m.
- Example 4 An electrode material (A4) was obtained in the same manner as in Example 1 except that 4 g of polyvinyl alcohol and 2.0 g of polyglycerin were used as the organic compound. When this electrode material (A4) was observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM), a plurality of primary particles gathered to form secondary particles, and the surface of these primary particles. was covered with a thin film of carbon, and it was observed that carbon was present between the primary particles.
- the electrode material (A4) was a sphere having an average particle diameter of 5 ⁇ m.
- Example 5" An electrode material (A5) was obtained in the same manner as in Example 1 except that 4 g of polyacrylic acid and 2.0 g of polyglycerin were used as the organic compound. When this electrode material (A5) was observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM), a plurality of primary particles gathered to form secondary particles, and the surface of these primary particles. was covered with a thin film of carbon, and it was observed that carbon was present between the primary particles.
- the electrode material (A5) was a spherical body having an average particle size of 5 ⁇ m.
- Example 6 An electrode material (A6) was obtained in the same manner as in Example 1 except that 2 g of polyacrylic acid and 2.4 g of glucose were used as the organic compound. When this electrode material (A6) was observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM), a plurality of primary particles gathered to form secondary particles, and the surface of these primary particles. was covered with a thin film of carbon, and it was observed that carbon was present between the primary particles.
- the electrode material (A6) was a spherical body having an average particle diameter of 5 ⁇ m.
- Example 7 An electrode material (A7) was obtained in the same manner as in Example 1 except that 2 g of polyvinyl acetate and 1.5 g of polyethylene glycol were used as the organic compound. When this electrode material (A7) was observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM), a plurality of primary particles gathered to form secondary particles, and the surface of these primary particles. was covered with a thin film of carbon, and it was observed that carbon was present between the primary particles.
- the electrode material (A7) was a spherical body having an average particle size of 5 ⁇ m.
- Example 8 An electrode material (A8) was obtained in the same manner as in Example 1 except that 2 g of polyvinyl alcohol and 2.4 g of sucrose were used as the organic compound. When this electrode material (A8) was observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM), a plurality of primary particles gathered to form secondary particles, and the surface of these primary particles. was covered with a thin film of carbon, and it was observed that carbon was present between the primary particles.
- the electrode material (A8) was a spherical body having an average particle size of 5 ⁇ m.
- Example 9 In 2 L (liter) of water, 4 mol of lithium acetate (LiCH 3 COO), 2 mol of iron (II) sulfate (FeSO 4 ), 2 mol of phosphoric acid (H 3 PO 4 ), the total amount becomes 4 L (liter). To prepare a uniform slurry mixture. Next, this mixture was placed in a pressure-resistant sealed container having a capacity of 8 L (liter), hydrothermally synthesized at 180 ° C. for 3 hours, and the resulting precipitate was washed with water to obtain a cake-like electrode active material.
- this electrode active material LiFePO 4 (solid content conversion)
- 4 g of polyvinyl alcohol and 1.5 g of polyethylene glycol as organic compounds are dissolved in 150 g of water, and 500 g of zirconia balls having a diameter of 5 mm are mixed as medium particles.
- dispersion treatment was performed for 12 hours in a ball mill to prepare a uniform slurry.
- this slurry was sprayed into an air atmosphere at 180 ° C. and dried to obtain a granulated body having an average particle diameter of 6 ⁇ m.
- the obtained granulated body was fired in a nitrogen atmosphere at 700 ° C. for 1 hour to obtain an electrode material (A9).
- the electrode material (A9) was a spherical body having an average particle diameter of 5 ⁇ m.
- Electrode material (B1) was obtained in the same manner as in Example 1 except that 4 g of polyvinyl alcohol was used as the organic compound.
- the electrode material (B1) was a spherical body having an average particle size of 5 ⁇ m.
- Example 2 An electrode material (B2) was obtained in the same manner as in Example 1 except that 4.8 g of glucose was used as the organic compound.
- the electrode material (B2) was a sphere having an average particle diameter of 5 ⁇ m.
- Electrode material powder The carbon content of the electrode material powders obtained in Examples 1 to 9 and Comparative Examples 1 and 2 was measured using a carbon analyzer (WC-200, manufactured by LECO). Further, the green compact resistivity (conductivity) of the electrode material powder was measured by a four-terminal method at 25 ° C. using a low resistivity meter (Loresta-GP, manufactured by Mitsubishi Chemical Corporation). A sample for measuring the green compact resistivity was molded at a pressure of 50 MPa. The results are shown in Table 1.
- the green compact resistivity is greatly different between the electrode materials (A1 to A9) of Examples 1 to 9 and the electrode materials 1 and 2 (B1 and B2) of Comparative Examples. It was found that the electrode materials (A1 to A9) of ⁇ 9 have high conductivity.
- Lithium ion batteries were prepared using the electrode materials obtained in Examples 1 to 3 and Comparative Examples 1 and 2. 90% by weight of an electrode material, 5% by weight of carbon black as a conductive assistant, 5% by weight of polyvinylidene fluoride (manufactured by Kureha Chemical) as a binder resin, and N-methyl-2-pyrrolidone as a solvent are mixed, A positive electrode preparation paste was prepared. Next, the positive electrode preparation paste was applied to one surface of an aluminum (Al) foil, and then dried to obtain an aluminum foil in which the positive electrode active material was held on one surface.
- Al aluminum
- a positive electrode active material or the like held on one surface of the aluminum foil is pressure-bonded, and then the aluminum foil is punched into a disk shape having a diameter of 16 mm and vacuum-dried to obtain a thickness of 60 ⁇ m and a density of 2.2 g /
- a current collector (positive electrode) having an electrode material layer of cm 2 was produced.
- a lithium ion battery was produced using a 2016 coin-type cell made of stainless steel (SUS) under a dry argon (Ar) atmosphere.
- metallic lithium (Li) is used as a negative electrode
- a porous polypropylene film is used as a separator
- the low charge / discharge rate of 0.1 C is 8 C compared to the lithium ion batteries using the electrode materials of Comparative Examples 1 and 2. It was found that the discharge capacity is high over the range of the high-speed charge / discharge rate, and sufficient charge / discharge rate performance can be realized.
- an electrode active material or a precursor thereof and an organic compound selected from at least two groups out of the groups A, B, and C are uniformly dispersed in water.
- the slurry is sprayed as fine droplets, dried to form a granulated body, and this granulated body is fired to form secondary particles having carbon interposed between primary particles of the electrode active material.
Abstract
Description
このリチウムイオン電池は、リチウムイオンを可逆的に脱挿入可能な性質を有する正極および負極と、非水系の電解質により構成されている。
一方、リチウムイオン電池の正極材料としては、正極活物質として、鉄リン酸リチウム(LiFePO4)などの、リチウムイオンを可逆的に脱挿入可能な性質を有するLi含有金属酸化物や、バインダーなどを含む電極材料合剤が用いられている。そして、集電体と呼ばれる金属箔の表面に、この電極材料合剤を塗布することにより、リチウムイオン電池の正極が形成されている。
A群:ポリビニルアルコール、ポリビニルピロリドン、セルロース、デンプン、ゼラチン、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ポリアクリル酸、ポリスチレンスルホン酸、ポリアクリルアミド、ポリ酢酸ビニル
B群:グルコース、フルクトース、ガラクトース、マンノース、マルトース、スクロース、ラクトース、グリコーゲン、ペクチン、アルギン酸、グルコマンナン、キチン、ヒアルロン酸、コンドロイチン、アガロース
C群:A群、B群に含まれる有機化合物を除くポリエーテルまたは多価アルコール類
A群:ポリビニルアルコール、ポリビニルピロリドン、セルロース、デンプン、ゼラチン、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ポリアクリル酸、ポリスチレンスルホン酸、ポリアクリルアミド、ポリ酢酸ビニル
B群:グルコース、フルクトース、ガラクトース、マンノース、マルトース、スクロース、ラクトース、グリコーゲン、ペクチン、アルギン酸、グルコマンナン、キチン、ヒアルロン酸、コンドロイチン、アガロース
C群:A群、B群に含まれる有機化合物を除くポリエーテルまたは多価アルコール類
A群:ポリビニルアルコール、ポリビニルピロリドン、セルロース、デンプン、ゼラチン、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ポリアクリル酸、ポリスチレンスルホン酸、ポリアクリルアミド、ポリ酢酸ビニル
B群:グルコース、フルクトース、ガラクトース、マンノース、マルトース、スクロース、ラクトース、グリコーゲン、ペクチン、アルギン酸、グルコマンナン、キチン、ヒアルロン酸、コンドロイチン、アガロース
C群:A群、B群に含まれる有機化合物を除くポリエーテルまたは多価アルコール類
A群:ポリビニルアルコール、ポリビニルピロリドン、セルロース、デンプン、ゼラチン、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ポリアクリル酸、ポリスチレンスルホン酸、ポリアクリルアミド、ポリ酢酸ビニル
B群:グルコース、フルクトース、ガラクトース、マンノース、マルトース、スクロース、ラクトース、グリコーゲン、ペクチン、アルギン酸、グルコマンナン、キチン、ヒアルロン酸、コンドロイチン、アガロース
C群:A群、B群に含まれる有機化合物を除くポリエーテルまたは多価アルコール類
2 炭素、
3 2次粒子
なお、この形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
本発明の電極材料の製造方法の第一の実施形態は、電極活物質と、下記のA群、B群およびC群のうち少なくとも2群からそれぞれ選択された有機化合物とを含むスラリーを噴霧し、乾燥して造粒体を生成し、この造粒体を500℃以上かつ1000℃以下の非酸化性雰囲気下にて焼成することにより、電極材料を合成する方法である。
ここで、A群、B群、C群の各群に含まれる有機化合物は、それぞれの群から1種または2種以上が選択される。
C群の有機化合物としては、A群、B群に含まれる有機化合物を除くポリエーテルまたは多価アルコール類が用いられ、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリグリセリン、グリセリンなどが挙げられる。
ここで、希土類元素としては、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Luなどが挙げられる。
式LixAyBzPO4で示される化合物としては、例えば、酢酸リチウム(LiCH3COO)、塩化リチウム(LiCl)などのリチウム塩、および、水酸化リチウム(LiOH)からなる群から選択されたLi源と、塩化鉄(II)(FeCl2)、酢酸鉄(II)(Fe(CH3COO)2)などの2価の鉄塩と、リン酸(H3PO4)、リン酸2アンモニウム(NH4H2PO4)、リン酸水素二アンモニウム((NH4)2HPO4)などのリン酸化合物と、水とを混合して得られたスラリー状の混合物を、耐圧密閉容器に入れて水熱合成し、得られた沈殿物を水洗してケーキ状の前駆体物質を生成し、このケーキ状の前駆体物質を焼成して合成したものを好適に用いることができる。
1次粒子の平均粒径が0.01μm未満では、1次粒子の表面を薄膜状の炭素で充分に被覆することが困難となり、高速充放電レートにおける放電容量が低くなり、充分な充放電レート性能を実現することが困難となる。一方、1次粒子の平均粒径が20μmを超えると、1次粒子内部の抵抗が大きくなるため、高速充放電レートにおける放電容量が不充分となる。
電極材料の形状が球状であることが好ましい理由は、電極材料とバインダー樹脂(結着剤)と溶剤とを混合して正電極作製用ペーストを調製する際の溶剤量を低減させることができるとともに、この正電極作製用ペーストの集電体への塗工も容易となるからである。
また、電極材料の形状が球状であれば、電極材料の表面積が最小となり、電極材料合剤に添加するバインダー樹脂(結着剤)の配合量を最小限にすることができ、得られる正電極の内部抵抗を小さくすることができるからである。さらに、最密充填し易いために、単位体積当たりの正極材料の充填量が多くなり、電極密度を高くすることができるので、高容量のリチウムイオン電池を提供できるからである。
炭素の配合比が0.1重量部未満では、高速充放電レートにおける放電容量が低くなり、充分な充放電レート性能を実現することが困難となる。一方、炭素の配合比が30重量部を超えると、電極活物質の配合比が低くなり、電池を形成した場合、その電池の容量が低くなる。
すなわち、A群に属する有機化合物を熱処理して生成する炭素量をCA、B群に属する有機化合物を熱処理して生成する炭素量をCB、C群に属する有機化合物を熱処理して生成する炭素量をCCとしたとき、炭素量CA、CB、CCのうち、最も少ない炭素量(重量換算、但し、0ではない。)を全炭素量(=炭素量CA+CB+CC、重量換算)で除した値が0.05以上となるようにすることが好ましい。
配合量が最も少ない群の有機化合物について、上記の値が0.05未満では、性状の異なる複数種の有機化合物を使用することにはならず、実質的に1種の有機化合物を使用することに他ならない。
水に、電極活物質と、A群、B群およびC群の有機化合物とを分散する方法としては、電極活物質が分散し、A群、B群およびC群の有機化合物が溶解または分散する方法であれば、特に限定されないが、例えば、遊星ボールミル、振動ボールミル、ビーズミル、ペイントシェーカー、アトライタなどの媒体粒子を高速で攪拌できる媒体攪拌型分散装置を用いる方法が好ましい。
この時、電極活物質を1次粒子に分散し、A群、B群およびC群の有機化合物を溶解するように攪拌することが好ましい。このようにすれば、電極活物質の1次粒子の表面がA群、B群およびC群の有機化合物で被覆され、その結果として、電極活物質の1次粒子の間に、A群、B群およびC群の有機化合物由来の炭素が均一に介在するようになる。
噴霧の際の液滴の粒径を、0.05μm~500μmとすることが好ましい。
造粒体の焼成温度が500℃未満では、上記のA群、B群およびC群の有機化合物の分解・反応が充分に進行せず、有機化合物の炭化が不充分であり、高抵抗の有機物分解物が生成する。一方、造粒体の焼成温度が1000℃を超えると、電極活物質中のLiが蒸発して組成のズレが起こるだけでなく、電極活物質の粒成長が促進され、高速充放電レートにおける放電容量が低くなり、充分な充放電レート性能を実現することが困難となる。
本発明の電極材料の製造方法の第二の実施形態は、電極活物質の前駆体と、上記のA群、B群およびC群のうち少なくとも2群からそれぞれ選択された有機化合物とを含むスラリーを噴霧し、乾燥して造粒体を生成し、この造粒体を500℃以上かつ1000℃以下の非酸化性雰囲気下にて焼成することにより、電極材料を合成する方法である。
ここで、電極活物質の前駆体とは、電極活物質の各原料成分の混合物を熱処理するなどして得た中間原料であって、未だ最終的な電極活物質となっていないものをいう。
この中間物質を生成する方法としては、例えば、その混合物を耐圧密閉容器に入れて水熱合成し、得られた沈殿物を水洗し、ケーキ状の物質を生成する方法、あるいは、その混合物を高温雰囲気中に噴霧し、乾燥して粒状物を生成する方法が挙げられる。
また、電極活物質の前駆体の生成に用いる原料としては、特に限定されず、通常水熱法で目的とする物質が得られる組み合わせであればよいが、水中で反応させることを考慮すると、水に可溶な酢酸塩、硫酸塩、塩化物などが好適である。
このような化合物としては、例えば、Fe成分としては、硫酸鉄(II)(FeSO4)、酢酸鉄(II)(Fe(CH3COO)2)、塩化鉄(II)(FeCl2)などが挙げられる。
ここで、希土類元素としては、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Luなどが挙げられる。
このような化合物としては、上記の元素のうちA源とは異なる元素の金属塩のうち1種または2種以上が用いられ、例えば、硫酸マグネシウム(MgSO4)、硫酸チタン(Ti(SO4)2)などの硫酸塩;酢酸マグネシウム(Mg(CH3COO)2)などの酢酸塩;塩化カルシウム(CaCl2)、四塩化チタン(TiCl4)などの塩化物などが好適に用いられる。
中でも、比較的純度が高く、組成制御を行うことが容易な点から、オルトリン酸、リン酸水素2アンモニウム、リン酸2水素アンモニウムなどが好ましい。
すなわち、電極活物質またはその前駆体と前記の複数種の有機化合物を混合することにより、特異的に導電性が向上する理由は必ずしも明確ではないものの、例えば、A群に属する有機化合物は、造膜性に優れることから、電極活物質の表面に炭素被膜を形成し易く、少量の炭素量で電極材料中に広範囲に亘って導電パスを形成することができると考えられる。また、B群に属する有機化合物は、より低温における熱分解反応でも炭素を生成し易く、良好な導電性を示すと考えられる。また、C群に属する有機化合物は、電極活物質表面の濡れ性を向上し、A群に属する有機化合物に由来する炭素および/またはB群に属する有機化合物に由来する炭素と、電極活物質との密着性を向上するとともに、その分子形態の作用により、A群に属する有機化合物に由来する炭素および/またはB群に属する有機化合物に由来する炭素を、電極活物質の表面に最適な形態(被膜の厚み、被覆率、被覆面積、被覆部・開口部間距離など)で配置することができると考えられる。したがって、複数の群から選ばれた有機化合物を混合することにより、これらの有機化合物による効果が相まって、単独で用いた場合に比べて、特異的に電極材料の導電性が向上する。
このような電極材料は、他の製造方法で製造された同一の電子伝導性を有する電極材料に比較して、式LixAyBzPO4で示される化合物などからなる電極活物質の1次粒子間に介在する(1次粒子表面を被覆する)炭素量が少なくなっている。したがって、電極活物質である式LixAyBzPO4で示される化合物と、電子伝導性を付与する導電助剤である炭素からなる電極材料、ひいては、電極材料とバインダー樹脂からなる電極材料合剤に含まれる電極活物質量を多くすることができるので、この電極材料合剤を用いて製造したリチウムイオン電池は、高速充放電レートにおける放電容量が高く、充分な充放電レート性能を有する。
本発明の電極は、本発明の電極材料を用いて形成してなる電極である。
本発明の電極を製造するには、本発明の電極材料と、バインダー樹脂(結着剤)と、溶剤とを混合して、正電極作製用塗料またはペーストを調製する。この際、必要に応じてカーボンブラックなどの導電助剤を添加してもよい。
次いで、金属箔の一方の面に、この正電極作製用塗料またはペーストを塗布した後、乾燥して、正極活物質が一方の面に保持された金属箔を得る。
次いで、金属箔の一方の面に保持された正極活物質などを加圧圧着し、乾燥して、電極材料層を有する集電体(正電極)を作製する。
電極材料とバインダー樹脂との配合比は、特に限定されないが、例えば、電極材料100重量部に対してバインダー樹脂を3重量部~20重量部程度とする。
本発明の電池は、本発明の電極を正電極として備えてなる電池である。
本発明の電池において、負電極、電解質、セパレータおよび電池形状などは特に限定されるものではない。
本発明の電池は、その正電極が、高純度であり、粒径が揃った微細な球状粉体である本発明の電極材料によって形成されたものであるから、高速充放電レートにおける放電容量が高く、安定した充放電サイクル性能を有し、かつ、高出力化が達成されたものである。
水2L(リットル)に、4molの酢酸リチウム(LiCH3COO)、2molの硫酸鉄(II)(FeSO4)、2molのリン酸(H3PO4)を、全体量が4L(リットル)になるように混合し、均一なスラリー状の混合物を調製した。
次いで、この混合物を容量8L(リットル)の耐圧密閉容器に収容し、120℃にて1時間、水熱合成し、得られた沈殿物を水洗し、ケーキ状の電極活物質の前駆体を得た。
次いで、この電極活物質の前駆体150g(固形分換算)、および、有機化合物としてポリビニルアルコール4gとポリエチレングリコール1.5gを水150gに溶解し、媒体粒子として直径5mmのジルコニアボール500gを混合し、ボールミルにて12時間分散処理を行い、均一なスラリーを調製した。
次いで、このスラリーを180℃の大気雰囲気中に噴霧し、乾燥して、平均粒径が6μmの造粒体を得た。
得られた造粒体を700℃の窒素雰囲気下にて1時間、焼成し、電極材料(A1)を得た。
この電極材料(A1)を走査型電子顕微鏡(SEM)および透過型電子顕微鏡(TEM)にて観察したところ、1次粒子が複数個集合して2次粒子となり、かつ、これら1次粒子の表面は薄膜状の炭素で被覆されており、1次粒子間に炭素が介在していることが観察された。また、電極材料(A1)は、平均粒径が5μmの球状体であった。
有機化合物としてグルコース4.8gとポリエチレングリコール1.5gを用いた以外は、実施例1と同様にして、電極材料(A2)を得た。
この電極材料(A2)を走査型電子顕微鏡(SEM)および透過型電子顕微鏡(TEM)にて観察したところ、1次粒子が複数個集合して2次粒子となり、かつ、これら1次粒子の表面は薄膜状の炭素で被覆されており、1次粒子間に炭素が介在していることが観察された。また、電極材料(A2)は、平均粒径が5μmの球状体であった。
有機化合物としてポリビニルアルコール2gとグルコース2.4gを用いた以外は、実施例1と同様にして、電極材料(A3)を得た。
この電極材料(A3)を走査型電子顕微鏡(SEM)および透過型電子顕微鏡(TEM)にて観察したところ、1次粒子が複数個集合して2次粒子となり、かつ、これら1次粒子の表面は薄膜状の炭素で被覆されており、1次粒子間に炭素が介在していることが観察された。また、電極材料(A3)は、平均粒径が5μmの球状体であった。
有機化合物としてポリビニルアルコール4gとポリグリセリン2.0gを用いた以外は、実施例1と同様にして、電極材料(A4)を得た。
この電極材料(A4)を走査型電子顕微鏡(SEM)および透過型電子顕微鏡(TEM)にて観察したところ、1次粒子が複数個集合して2次粒子となり、かつ、これら1次粒子の表面は薄膜状の炭素で被覆されており、1次粒子間に炭素が介在していることが観察された。また、電極材料(A4)は、平均粒径が5μmの球状体であった。
有機化合物としてポリアクリル酸4gとポリグリセリン2.0gを用いた以外は、実施例1と同様にして、電極材料(A5)を得た。
この電極材料(A5)を走査型電子顕微鏡(SEM)および透過型電子顕微鏡(TEM)にて観察したところ、1次粒子が複数個集合して2次粒子となり、かつ、これら1次粒子の表面は薄膜状の炭素で被覆されており、1次粒子間に炭素が介在していることが観察された。また、電極材料(A5)は、平均粒径が5μmの球状体であった。
有機化合物としてポリアクリル酸2gとグルコース2.4gを用いた以外は、実施例1と同様にして、電極材料(A6)を得た。
この電極材料(A6)を走査型電子顕微鏡(SEM)および透過型電子顕微鏡(TEM)にて観察したところ、1次粒子が複数個集合して2次粒子となり、かつ、これら1次粒子の表面は薄膜状の炭素で被覆されており、1次粒子間に炭素が介在していることが観察された。また、電極材料(A6)は、平均粒径が5μmの球状体であった。
有機化合物としてポリ酢酸ビニル2gとポリエチレングリコール1.5gを用いた以外は、実施例1と同様にして、電極材料(A7)を得た。
この電極材料(A7)を走査型電子顕微鏡(SEM)および透過型電子顕微鏡(TEM)にて観察したところ、1次粒子が複数個集合して2次粒子となり、かつ、これら1次粒子の表面は薄膜状の炭素で被覆されており、1次粒子間に炭素が介在していることが観察された。また、電極材料(A7)は、平均粒径が5μmの球状体であった。
有機化合物としてポリビニルアルコール2gとスクロース2.4gを用いた以外は、実施例1と同様にして、電極材料(A8)を得た。
この電極材料(A8)を走査型電子顕微鏡(SEM)および透過型電子顕微鏡(TEM)にて観察したところ、1次粒子が複数個集合して2次粒子となり、かつ、これら1次粒子の表面は薄膜状の炭素で被覆されており、1次粒子間に炭素が介在していることが観察された。また、電極材料(A8)は、平均粒径が5μmの球状体であった。
水2L(リットル)に、4molの酢酸リチウム(LiCH3COO)、2molの硫酸鉄(II)(FeSO4)、2molのリン酸(H3PO4)を、全体量が4L(リットル)になるように混合し、均一なスラリー状の混合物を調製した。
次いで、この混合物を容量8L(リットル)の耐圧密閉容器に収容し、180℃にて3時間、水熱合成し、得られた沈殿物を水洗し、ケーキ状の電極活物質を得た。
次いで、この電極活物質(LiFePO4)150g(固形分換算)、および、有機化合物としてポリビニルアルコール4gとポリエチレングリコール1.5gを水150gに溶解し、媒体粒子として直径5mmのジルコニアボール500gを混合し、ボールミルにて12時間分散処理を行い、均一なスラリーを調製した。
次いで、このスラリーを180℃の大気雰囲気中に噴霧し、乾燥して、平均粒径が6μmの造粒体を得た。
得られた造粒体を700℃の窒素雰囲気下にて1時間、焼成し、電極材料(A9)を得た。
この電極材料(A9)を走査型電子顕微鏡(SEM)および透過型電子顕微鏡(TEM)にて観察したところ、1次粒子が複数個集合して2次粒子となり、かつ、これら1次粒子の表面は薄膜状の炭素で被覆されており、1次粒子間に炭素が介在していることが観察された。また、電極材料(A9)は、平均粒径が5μmの球状体であった。
有機化合物としてポリビニルアルコール4gを用いた以外は、実施例1と同様にして、電極材料(B1)を得た。
電極材料(B1)は、平均粒径が5μmの球状体であった。
有機化合物としてグルコース4.8gを用いた以外は、実施例1と同様にして、電極材料(B2)を得た。
電極材料(B2)は、平均粒径が5μmの球状体であった。
実施例1~9および比較例1、2で得られた電極材料粉末の炭素量を、カーボン分析装置(WC-200、LECO社製)を用いて測定した。
また、電極材料粉末の圧粉体抵抗率(導電性)を、低抵抗率計(Loresta-GP、三菱化学社製)を用い、25℃にて、四端子法により測定した。なお、圧粉体抵抗率の測定用試料を、50MPaの圧力で成形した。
以上の結果を表1に示す。
実施例1~3および比較例1、2で得られた電極材料を用いてリチウムイオン電池を作製した。
電極材料90重量%と、導電助剤としてカーボンブラック5重量%と、バインダー樹脂としてポリフッ化ビニリデン(呉羽化学社製)5重量%と、溶剤としてN-メチル-2-ピロリドンとを混合して、正電極作製用ペーストを調製した。
次いで、アルミニウム(Al)箔の一方の面に、この正電極作製用ペーストを塗布した後、乾燥して、正極活物質が一方の面に保持されたアルミニウム箔を得た。
次いで、アルミニウム箔の一方の面に保持された正極活物質などを加圧圧着した後、このアルミニウム箔を直径16mmの円盤状に打ち抜き、それを真空乾燥して、厚み60μm、密度2.2g/cm2の電極材料層を有する集電体(正電極)を作製した。
次いで、乾燥アルゴン(Ar)雰囲気下、ステンレススチール(SUS)製の2016コイン型セルを用いてリチウムイオン電池を作製した。
なお、負極としては金属リチウム(Li)を、セパレータとしては多孔質ポリプロピレン膜を、電解質溶液としては1mol/LのLiPF6溶液(溶媒:炭酸エチレン/炭酸ジエチル=1/1(体積比))を、それぞれ用いた。
実施例1~3および比較例1、2各々のリチウムイオン電池について充放電試験を実施した。
この充放電試験において、環境温度を室温(25℃)、カットオフ電圧を2.0~4.2V、充電レートを0.2Cの定電流、放電レートを0.1C~8Cとした。
結果を図2に示した。
Claims (5)
- 電極活物質または電極活物質の前駆体と、下記のA群、B群およびC群のうち少なくとも2群からそれぞれ選択された有機化合物とを含むスラリーを噴霧し、乾燥して造粒体を生成し、該造粒体を500℃以上かつ1000℃以下の非酸化性雰囲気下にて焼成することを特徴とする電極材料の製造方法。
A群:ポリビニルアルコール、ポリビニルピロリドン、セルロース、デンプン、ゼラチン、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ポリアクリル酸、ポリスチレンスルホン酸、ポリアクリルアミド、ポリ酢酸ビニル
B群:グルコース、フルクトース、ガラクトース、マンノース、マルトース、スクロース、ラクトース、グリコーゲン、ペクチン、アルギン酸、グルコマンナン、キチン、ヒアルロン酸、コンドロイチン、アガロース
C群:A群、B群に含まれる有機化合物を除くポリエーテルまたは多価アルコール類 - 前記電極活物質は、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウム、チタン酸リチウム、式LixAyBzPO4(但し、AはCo、Mn、Ni、Fe、Cu、Crの群から選択された1種または2種以上、BはMg、Ca、Sr、Ba、Ti、Zn、B、Al、Ga、In、Si、Ge、Sc、Y、希土類元素の群から選択された1種または2種以上、0≦x<2、0<y<1.5、0≦z<1.5)で示される化合物の群から選択された1種を主成分とすることを特徴とする請求項1に記載の電極材料の製造方法。
- 電極活物質または電極活物質の前駆体と、下記のA群、B群およびC群のうち少なくとも2群からそれぞれ選択された有機化合物とを含むスラリーを噴霧し、乾燥して造粒体を生成し、該造粒体を500℃以上かつ1000℃以下の非酸化性雰囲気下にて焼成してなることを特徴とする電極材料。
A群:ポリビニルアルコール、ポリビニルピロリドン、セルロース、デンプン、ゼラチン、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ポリアクリル酸、ポリスチレンスルホン酸、ポリアクリルアミド、ポリ酢酸ビニル
B群:グルコース、フルクトース、ガラクトース、マンノース、マルトース、スクロース、ラクトース、グリコーゲン、ペクチン、アルギン酸、グルコマンナン、キチン、ヒアルロン酸、コンドロイチン、アガロース
C群:A群、B群に含まれる有機化合物を除くポリエーテルまたは多価アルコール類 - 電極活物質または電極活物質の前駆体と、下記のA群、B群およびC群のうち少なくとも2群からそれぞれ選択された有機化合物とを含むスラリーを噴霧し、乾燥して造粒体を生成し、該造粒体を500℃以上かつ1000℃以下の非酸化性雰囲気下にて焼成してなる電極材料を用いて形成してなることを特徴とする電極。
A群:ポリビニルアルコール、ポリビニルピロリドン、セルロース、デンプン、ゼラチン、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ポリアクリル酸、ポリスチレンスルホン酸、ポリアクリルアミド、ポリ酢酸ビニル
B群:グルコース、フルクトース、ガラクトース、マンノース、マルトース、スクロース、ラクトース、グリコーゲン、ペクチン、アルギン酸、グルコマンナン、キチン、ヒアルロン酸、コンドロイチン、アガロース
C群:A群、B群に含まれる有機化合物を除くポリエーテルまたは多価アルコール類 - 電極活物質または電極活物質の前駆体と、下記のA群、B群およびC群のうち少なくとも2群からそれぞれ選択された有機化合物とを含むスラリーを噴霧し、乾燥して造粒体を生成し、該造粒体を500℃以上かつ1000℃以下の非酸化性雰囲気下にて焼成してなる電極材料を用いて形成してなる電極を正電極として備えてなることを特徴とする電池。
A群:ポリビニルアルコール、ポリビニルピロリドン、セルロース、デンプン、ゼラチン、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ポリアクリル酸、ポリスチレンスルホン酸、ポリアクリルアミド、ポリ酢酸ビニル
B群:グルコース、フルクトース、ガラクトース、マンノース、マルトース、スクロース、ラクトース、グリコーゲン、ペクチン、アルギン酸、グルコマンナン、キチン、ヒアルロン酸、コンドロイチン、アガロース
C群:A群、B群に含まれる有機化合物を除くポリエーテルまたは多価アルコール類
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2735248A CA2735248C (en) | 2008-09-03 | 2008-09-03 | Method for producing electrode material, electrode material, electrode and battery |
US13/060,849 US8580155B2 (en) | 2008-09-03 | 2008-09-03 | Method for producing electrode material, electrode material, electrode and battery |
CN2008801307024A CN102119457A (zh) | 2008-09-03 | 2008-09-03 | 电极材料的制造方法、电极材料及电极、以及电池 |
KR1020117002971A KR20110053958A (ko) | 2008-09-03 | 2008-09-03 | 전극 재료의 제조 방법, 전극 재료, 전극 및 전지 |
PCT/JP2008/065828 WO2010026627A1 (ja) | 2008-09-03 | 2008-09-03 | 電極材料の製造方法と電極材料および電極並びに電池 |
EP08809883A EP2343760A4 (en) | 2008-09-03 | 2008-09-03 | PROCESS FOR PRODUCING ELECTRODE MATERIAL, ELECTRODE MATERIAL, ELECTRODE AND BATTERY |
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JP2013069566A (ja) * | 2011-09-22 | 2013-04-18 | Sumitomo Osaka Cement Co Ltd | 電極材料及びその製造方法並びに電極、リチウムイオン電池 |
JP2013541141A (ja) * | 2010-09-08 | 2013-11-07 | エスケー イノベーション カンパニー リミテッド | リチウム二次電池用陽極活物質及びその製造方法 |
JP2015512126A (ja) * | 2012-02-28 | 2015-04-23 | エスジーエル・カーボン・エスイー | コーティングされた活性材料を製造するための方法、及びバッテリーのためのその使用 |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004014340A (ja) | 2002-06-07 | 2004-01-15 | Sumitomo Osaka Cement Co Ltd | 電極材料及びそれを用いたリチウムイオン電池並びに電極材料の製造方法 |
JP2004014341A (ja) | 2002-06-07 | 2004-01-15 | Sumitomo Osaka Cement Co Ltd | 電極材料の製造方法及びリチウムイオン電池 |
JP2005276609A (ja) * | 2004-03-24 | 2005-10-06 | Tdk Corp | 電極用複合粒子、電極及び電気化学素子、並びに、電極用複合粒子の製造方法、電極の製造方法及び電気化学素子の製造方法 |
JP2005285382A (ja) * | 2004-03-26 | 2005-10-13 | Toyota Motor Corp | リチウム二次電池用活物質の製造方法及びリチウム二次電池用活物質並びにリチウム二次電池 |
JP2007048692A (ja) * | 2005-08-12 | 2007-02-22 | Hitachi Vehicle Energy Ltd | リチウム二次電池用正極材料、リチウム二次電池用正極板及びこれを用いたリチウム二次電池 |
WO2007094240A1 (ja) * | 2006-02-17 | 2007-08-23 | Matsushita Electric Industrial Co., Ltd. | 導電性複合粒子およびその製造方法、並びにそれを用いた電極板、リチウムイオン二次電池 |
JP2008186732A (ja) * | 2007-01-30 | 2008-08-14 | Nippon Carbon Co Ltd | リチウム二次電池用負極活物質、それを使用した負極及び製造方法 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5976489A (en) * | 1996-04-10 | 1999-11-02 | Valence Technology, Inc. | Method for preparing lithium manganese oxide compounds |
JP2000353644A (ja) | 1999-04-06 | 2000-12-19 | Asahi Chem Ind Co Ltd | 電気二重層キャパシタ電極用炭素材料の製造方法 |
JP2001015114A (ja) | 1999-06-28 | 2001-01-19 | Hitachi Powdered Metals Co Ltd | 非水系電解液二次電池の負極塗膜形成用スラリーおよび非水系電解液二次電池の負極塗膜 |
EP1288160B1 (en) | 2000-04-27 | 2008-03-12 | Institute of Physics Chinese Academy of Sciences | Pyrolyzed hard carbon material, preparation and its applications |
CA2320661A1 (fr) * | 2000-09-26 | 2002-03-26 | Hydro-Quebec | Nouveau procede de synthese de materiaux limpo4 a structure olivine |
JP2003157851A (ja) * | 2001-08-30 | 2003-05-30 | Hitachi Chem Co Ltd | 熱硬化性ポリビニルアルコール系バインダ樹脂組成物、合剤スラリー、電極、非水電解液系二次電池及び電極材料用の熱硬化性ポリビニルアルコール系バインダ樹脂 |
JP4997674B2 (ja) * | 2001-09-03 | 2012-08-08 | 日本電気株式会社 | 二次電池用負極および二次電池 |
US6913855B2 (en) * | 2002-07-22 | 2005-07-05 | Valence Technology, Inc. | Method of synthesizing electrochemically active materials from a slurry of precursors |
KR100569239B1 (ko) * | 2003-10-25 | 2006-04-07 | 한국과학기술연구원 | 이산화탄소와 탄화수소의 내부개질반응에 의해 전기와 합성가스를 동시에 생성하는 고체산화물 연료전지, 및 이를 이용한 전기화학적 전환반응시스템 |
JP2006261061A (ja) | 2005-03-18 | 2006-09-28 | Sumitomo Osaka Cement Co Ltd | 電極材料及びそれを用いた電極並びにリチウム電池と電極材料の製造方法 |
JP2006339184A (ja) | 2005-05-31 | 2006-12-14 | Nippon Zeon Co Ltd | 電気化学素子電極用複合粒子の製造方法 |
JP2007095495A (ja) * | 2005-09-29 | 2007-04-12 | Hitachi Metals Ltd | リチウム二次電池用正極活物質及び非水系リチウム二次電池 |
KR100774263B1 (ko) | 2006-07-04 | 2007-11-08 | 건국대학교 산학협력단 | 구형 형상을 갖는 리튬 2차 전지용 양극 소재 분말의 제조방법 |
JP2008044816A (ja) | 2006-08-17 | 2008-02-28 | Tokai Carbon Co Ltd | 多孔質炭素材の製造方法 |
EP2131422B1 (en) * | 2007-03-29 | 2020-05-27 | Mitsubishi Materials Corporation | Positive electrode-forming material, component thereof, method for producing the same, and rechargeable lithium-ion battery |
JP4317239B2 (ja) * | 2007-04-27 | 2009-08-19 | Tdk株式会社 | 電極用複合粒子の製造方法 |
KR101080956B1 (ko) * | 2009-04-13 | 2011-11-08 | 국립대학법인 울산과학기술대학교 산학협력단 | 리튬 이차 전지용 음극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지 |
KR101182273B1 (ko) * | 2010-08-12 | 2012-09-12 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 음극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지 |
-
2008
- 2008-09-03 CA CA2735248A patent/CA2735248C/en not_active Expired - Fee Related
- 2008-09-03 EP EP08809883A patent/EP2343760A4/en not_active Withdrawn
- 2008-09-03 US US13/060,849 patent/US8580155B2/en active Active
- 2008-09-03 WO PCT/JP2008/065828 patent/WO2010026627A1/ja active Application Filing
- 2008-09-03 KR KR1020117002971A patent/KR20110053958A/ko not_active Application Discontinuation
- 2008-09-03 CN CN2008801307024A patent/CN102119457A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004014340A (ja) | 2002-06-07 | 2004-01-15 | Sumitomo Osaka Cement Co Ltd | 電極材料及びそれを用いたリチウムイオン電池並びに電極材料の製造方法 |
JP2004014341A (ja) | 2002-06-07 | 2004-01-15 | Sumitomo Osaka Cement Co Ltd | 電極材料の製造方法及びリチウムイオン電池 |
JP2005276609A (ja) * | 2004-03-24 | 2005-10-06 | Tdk Corp | 電極用複合粒子、電極及び電気化学素子、並びに、電極用複合粒子の製造方法、電極の製造方法及び電気化学素子の製造方法 |
JP2005285382A (ja) * | 2004-03-26 | 2005-10-13 | Toyota Motor Corp | リチウム二次電池用活物質の製造方法及びリチウム二次電池用活物質並びにリチウム二次電池 |
JP2007048692A (ja) * | 2005-08-12 | 2007-02-22 | Hitachi Vehicle Energy Ltd | リチウム二次電池用正極材料、リチウム二次電池用正極板及びこれを用いたリチウム二次電池 |
WO2007094240A1 (ja) * | 2006-02-17 | 2007-08-23 | Matsushita Electric Industrial Co., Ltd. | 導電性複合粒子およびその製造方法、並びにそれを用いた電極板、リチウムイオン二次電池 |
JP2008186732A (ja) * | 2007-01-30 | 2008-08-14 | Nippon Carbon Co Ltd | リチウム二次電池用負極活物質、それを使用した負極及び製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2343760A4 * |
Cited By (7)
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CN102280612A (zh) * | 2010-08-25 | 2011-12-14 | 深圳市比克电池有限公司 | 锂电池负极浆料制备方法及制备得到的锂离子电池 |
JP2013541141A (ja) * | 2010-09-08 | 2013-11-07 | エスケー イノベーション カンパニー リミテッド | リチウム二次電池用陽極活物質及びその製造方法 |
JP2013069566A (ja) * | 2011-09-22 | 2013-04-18 | Sumitomo Osaka Cement Co Ltd | 電極材料及びその製造方法並びに電極、リチウムイオン電池 |
JP2015512126A (ja) * | 2012-02-28 | 2015-04-23 | エスジーエル・カーボン・エスイー | コーティングされた活性材料を製造するための方法、及びバッテリーのためのその使用 |
WO2017168947A1 (ja) * | 2016-03-30 | 2017-10-05 | 住友精化株式会社 | 非水電解質二次電池電極用バインダー、非水電解質二次電池用電極合剤、非水電解質二次電池用電極、非水電解質二次電池、および電気機器 |
JPWO2017168947A1 (ja) * | 2016-03-30 | 2019-02-07 | 住友精化株式会社 | 非水電解質二次電池電極用バインダー、非水電解質二次電池用電極合剤、非水電解質二次電池用電極、非水電解質二次電池、および電気機器 |
US10873086B2 (en) | 2016-03-30 | 2020-12-22 | Sumitomo Seika Chemicals Co., Ltd. | Binder for nonaqueous electrolyte secondary battery electrodes, electrode mixture for nonaqueous electrolyte secondary batteries, electrode for nonaqueous electrolyte secondary batteries, nonaqueous electrolyte secondary battery and electrical device |
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CN102119457A (zh) | 2011-07-06 |
CA2735248A1 (en) | 2010-03-11 |
EP2343760A4 (en) | 2012-11-14 |
US20110163272A1 (en) | 2011-07-07 |
KR20110053958A (ko) | 2011-05-24 |
CA2735248C (en) | 2014-03-11 |
EP2343760A1 (en) | 2011-07-13 |
US8580155B2 (en) | 2013-11-12 |
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