WO2014034635A1 - Electrode material for lithium ion secondary batteries, method for producing same, and lithium ion secondary battery - Google Patents
Electrode material for lithium ion secondary batteries, method for producing same, and lithium ion secondary battery Download PDFInfo
- Publication number
- WO2014034635A1 WO2014034635A1 PCT/JP2013/072805 JP2013072805W WO2014034635A1 WO 2014034635 A1 WO2014034635 A1 WO 2014034635A1 JP 2013072805 W JP2013072805 W JP 2013072805W WO 2014034635 A1 WO2014034635 A1 WO 2014034635A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ion secondary
- lithium ion
- electrode material
- active material
- carbon
- Prior art date
Links
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/366—Composites as layered products
-
- 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
-
- 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
- H01M4/13—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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- 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 an electrode material for a lithium ion secondary battery, a manufacturing method thereof, and a lithium ion secondary battery. More specifically, the present invention relates to a technology for increasing the capacity of a lithium ion secondary battery.
- the lithium ion secondary battery in which the negative electrode is formed of a material capable of occluding and releasing lithium ions can suppress the deposition of dendride compared to the lithium battery in which the negative electrode is formed of metallic lithium. For this reason, the lithium ion secondary battery has an advantage that a battery having a high capacity and a high energy density can be provided while safety is improved by preventing a short circuit of the battery.
- olivine-type lithium iron phosphate (LiFePO 4 ) has been attracting attention as a positive electrode material for lithium ion secondary batteries from the viewpoint of safety and cost emphasis. Resistance is a major issue (see, for example, Patent Document 2). Therefore, in order to solve the problem of low resistance of olivine-type lithium iron phosphate, various studies have been made to combine olivine-type lithium iron phosphate and graphite, which is a conductive material, into electrode materials. (For example, see Patent Documents 3 and 4).
- the present invention provides an electrode material for a lithium ion secondary battery that can maintain a large current charge / discharge for a long period of time and can realize a high-capacity lithium ion secondary battery, and its production
- the main object is to provide a method and a lithium ion secondary battery.
- An electrode material for a lithium ion secondary battery according to the present invention is an electrode material for a lithium ion secondary battery containing an active material and a conductive material, and the active material is a lithium-containing composite oxide, tin oxide, or silicon oxide
- the conductive material is amorphous carbon, carbon nanotubes, and carbon black, and a part or all of the surface of the active material is covered with the amorphous carbon.
- the coverage of the active material surface with the amorphous carbon can be, for example, 10 to 95%.
- the amorphous carbon may be an organic pyrolysis product.
- the active material includes, for example, Li 4 Ti 5 O 12 ,
- the active material is a mixture of tin oxide containing metal tin or silicon oxide containing metal silicon and graphite. It may be used.
- a method for producing an electrode material for a lithium ion secondary battery according to the present invention includes a step of mixing an active material, an organic substance that forms amorphous carbon by thermal decomposition, a carbon nanotube, and carbon black in a solvent, After drying the mixture obtained by the mixing, the method further includes heating to form amorphous carbon derived from the organic matter on the surface of the active material, and crushing the mixture after heating. .
- Another method for producing an electrode material for a lithium ion secondary battery according to the present invention includes a step of mixing an active material, a carbon nanotube, and carbon black in a solvent, and after drying the mixture obtained by the mixing. And a step of further heating and a step of crushing the mixture after the heating, and either one or both of the carbon nanotubes and carbon black contain amorphous carbon.
- the lithium ion secondary battery according to the present invention uses the above-described electrode material for a lithium ion secondary battery.
- a large-capacity lithium ion secondary battery can be realized that can maintain a large current charge / discharge for a long period of time.
- the electrode material of the present embodiment is used for a lithium ion secondary battery, and contains lithium-containing composite oxide, tin oxide or silicon oxide as an active material, and amorphous carbon or carbon as a conductive material. Contains nanotubes and carbon black. In the electrode material of this embodiment, part or all of the surface of the active material is covered with amorphous carbon that is a conductive material.
- the amorphous carbon is electrically connected to the active material by covering the surface of the active material, and the carbon nanotubes are in contact with both the amorphous carbon and the carbon black. To electrically connect them. Furthermore, carbon black forms a conductive network throughout the electrode and is electrically connected to the current collector.
- Amorphous carbon which is a conductive material, is carbon having low crystallinity (low graphitization degree), and the surface of the active material can be covered by low crystallinity.
- carbon with high crystallinity high degree of graphitization
- the coverage of the active material surface with amorphous carbon is preferably 10 to 95%, more preferably 20 to 95%, assuming that the entire surface of the active material is 100%.
- the coverage is less than 10%, the electrical connection between the active material and the amorphous carbon may be insufficient. Note that the higher the coverage, the more advantageous for electrical connection, so the coverage by amorphous carbon may be 100%.
- the amorphous carbon used in the electrode material of the present embodiment is not particularly limited except that the crystallinity is low (the degree of graphitization is low), but it is preferably formed of a thermal decomposition product of organic matter. Thereby, the covering state of the active material surface by amorphous carbon can be made favorable.
- organic substances that form amorphous carbon by pyrolysis include glucose (C 6 H 12 O 6 ), sucrose (C 12 H 22 O 11 ), dextrin ((C 6 H 12 O 5 ) n ), and ascorbine.
- C 6 H 8 O 6 carboxymethylcellulose (CMC), polyvinylpyrrolidone (PVP), polyallylamine hydrochloride (PAH), polyacrylate (PAA), polyvinyl alcohol (PVA), silane coupling agent and coal Pitch and the like.
- CMC carboxymethylcellulose
- PVP polyvinylpyrrolidone
- PAH polyallylamine hydrochloride
- PAA polyacrylate
- PVA polyvinyl alcohol
- silane coupling agent silane coupling agent and coal Pitch and the like.
- amorphous carbon is formed on the active material surface using these organic materials, for example, after drying a mixture obtained by mixing an active material, carbon nanotubes, carbon black, and organic materials in a solvent. What is necessary is just to heat.
- the active material surface can be obtained without using an organic substance that decomposes to form amorphous carbon. It has been found that it can be satisfactorily coated with amorphous carbon. In that case, a mixture obtained by mixing an active material, carbon nanotubes, and carbon black in a solvent may be further heated after drying.
- the carbon nanotubes or carbon black containing amorphous carbon include carbon nanotubes having an amorphous carbon layer covering the surface of the tube body (see Japanese Patent Application Laid-Open No. 2004-299986).
- the carbon nanotube as the conductive material preferably has a fiber diameter of 5 to 50 nm and a specific surface area of 50 to 400 m 2 / g.
- the carbon nanotubes are electrically connected by being bonded to the amorphous carbon covering the surface of the active material. “Coupling” here includes covalent bonding and bonding by van der Waals force.
- carbon nanotubes are bonded to amorphous carbon.
- carbon nanotubes are fibrous particles and can be in line contact with the amorphous carbon layer covering the active material surface.
- carbon black is a spherical particle, it can only make point contact with amorphous carbon, and a sufficient bond cannot be obtained.
- the method for bonding the amorphous carbon and the carbon nanotube is not particularly limited.
- the amorphous carbon is amorphous.
- a bond between the amorphous carbon and the carbon nanotube is formed at the same time.
- the carbon nanotubes are electrically connected by being bonded to carbon black.
- the method for bonding carbon nanotubes and carbon black is not particularly limited.
- carbon black is produced by pyrolyzing hydrocarbons
- carbon nanotubes are introduced and bonded, acetylene gas
- acetylene gas A method of supplying hydrocarbons containing a catalyst for forming carbon nanotubes and bonding them during pyrolysis of acetylene gas and / or in a state in which acetylene gas is pyrolyzed (see JP-T-2009-503182), carbon nanotubes and carbon black
- a method for bonding carbon nanotubes and carbon black by a mechanochemical method there is a method using a medium stirring type mixer such as a bead mill, a vibration mill, or a ball mill.
- a medium stirring type mixer such as a bead mill, a vibration mill, or a ball mill.
- the active material the organic substance that decomposes to form amorphous carbon
- the carbon nanotube, and the carbon black are mixed in a solvent, or the active material, either or both are amorphous.
- the carbon nanotubes and carbon black may be bonded using a mechanochemical method, or may be bonded during heating after mixing. .
- the carbon black as the conductive material is preferably acetylene black or furnace black, and more preferably acetylene black having a relatively small content of impurities that may affect battery performance.
- the specific surface area of carbon black is preferably smaller than the specific surface area of carbon nanotubes and is 10 to 200 m 2 / g.
- the carbon black used for the electrode material of the present embodiment preferably has an ash content defined by JIS K 1469 of 1.0% by mass or less.
- the carbon black is not only coupled and electrically connected to the carbon nanotubes as described above, but also forms a conductive network throughout the electrode and is electrically connected to the current collector. .
- the reason why carbon black can form a conductive network over the entire electrode is that carbon black is a spherical particle unlike carbon nanotubes and has good dispersibility, so that it easily spreads and distributes throughout the electrode.
- Carbon black can be electrically connected to carbon nanotubes and current collectors because it has a unique higher-order structure in which spherical primary particles are linked in a chain, and it is conductive despite being spherical particles. It is because it is easy to take.
- the active material of the electrode material of this embodiment is a lithium-containing composite oxide, tin oxide, or silicon oxide.
- the electrode material of this embodiment when used as a negative electrode material, Li 4 Ti 5 O 12 , tin oxide containing metal tin, silicon oxide containing metal silicon, or the like may be used as the active material. it can. Further, as the negative electrode active material, a mixture of tin oxide containing metal tin or silicon oxide containing metal silicon and graphite may be used.
- lithium-containing phosphates such as LiFePO 4 (olivine-type lithium iron phosphate), LiMnPO 4 , LiMnXFe (1-X) PO 4 are essentially difficult to improve the battery capacity per volume, It is not suitable for the active material of the electrode material of the embodiment.
- the method for producing the electrode material of the present embodiment is not particularly limited.
- an active material, an organic material that forms amorphous carbon by thermal decomposition, carbon nanotubes, and carbon black are mixed in a solvent.
- a step of drying the mixture obtained by mixing and further heating to form amorphous carbon derived from organic matter on the surface of the active material, and a step of crushing the mixture after heating. Can be manufactured.
- the electrode material of the present embodiment is a material containing amorphous carbon in one or both of carbon nanotubes and carbon black, and an active material, carbon nanotubes, and carbon black are mixed in a solvent. It can also be produced by performing a step of performing, a step of further heating after drying the mixture obtained by mixing, and a step of crushing the mixture after heating.
- the mixing step in each manufacturing method described above can be carried out using a mixer such as a cracker, universal mixer, Henschel mixer or ribbon blender, or a medium stirring mixer such as a bead mill, a vibration mill or a ball mill.
- the solvent used in the mixing step may be water, but in order to improve the dispersibility of carbon nanotubes and carbon black, a mixed solvent of water and alcohol or a nonaqueous solvent such as alcohol is preferable.
- the solvent used in the mixing step may be hydrolysis of metal tin or metal silicon. It is preferable to use a non-aqueous solvent such as alcohol in order to prevent the problem and improve the dispersibility of graphite.
- the solvent is removed by drying the obtained mixture.
- the method for drying the mixture is not particularly limited. However, when using an organic substance that forms amorphous carbon by thermal decomposition, be careful not to remove the organic substance as a filtrate together with the solvent when filtration is performed. There is a need to. Therefore, for the drying of the mixture, a method such as freeze drying, reduced pressure drying, vacuum drying or vibration fluidized drying can be applied in addition to filtration.
- amorphous carbon is formed from the organic material by heating, and the amorphous carbon covers the surface of the active material. Bonds of carbon nanotubes and bonds between carbon nanotubes and carbon black are formed.
- the amorphous carbon contained in the carbon nanotubes and / or carbon black covers the surface of the active material, A bond between amorphous carbon and carbon nanotubes, or a bond between carbon nanotubes and carbon black is formed.
- Conditions such as temperature and atmosphere when heating the mixture vary depending on the active material used.
- the atmosphere is preferably an inert atmosphere or a reducing atmosphere in order to prevent oxidation of the carbon-based material.
- an oxide-based positive electrode active material such as LiMO 2 (where 0 ⁇ x ⁇ 1) and LiNi g Mn (2-g) O 4 (where 0 ⁇ g ⁇ 2)
- the active material itself In order to prevent
- Li 4 Ti 5 O 12 which is a negative electrode active material
- Li 4 Ti 5 O 12 is not easily decomposed, and therefore it is preferable to heat at a slightly higher temperature of 300 to 500 ° C.
- an inert gas such as argon or nitrogen is present.
- the melting point of metallic tin is as low as 232 ° C., it is preferable to heat at a temperature lower than 232 ° C.
- the active material is silicon oxide containing metal silicon or a mixture of graphite with this, the active material is not decomposed even in an inert atmosphere or a reducing atmosphere, and the melting point of silicon is as high as 1410 ° C. Heating is possible over a wide temperature range up to around 1400 ° C., and an inert gas such as argon or nitrogen can be used. The mixture after heating is deagglomerated by crushing, and the electrode material of this embodiment is obtained.
- the electrode material of the present embodiment improves the electron conduction network in the electrode and facilitates the transfer of electrons between the active material, the conductive agent and the current collector of the metal foil. Compared with the electrode material manufactured by mixing the electrode, the electrode resistance is reduced, and large current charging / discharging becomes possible.
- the electrode material of the present embodiment has an optimized electrical connection among the active material, the conductive agent, and the current collector of the metal foil, and can conduct electricity with a small amount of the conductive agent. When used, the performance difference from the conventional electrode material becomes significant. In addition, the amount that can be used in a small amount greatly contributes to the improvement of battery capacity.
- the electrode material of the present embodiment it becomes possible to increase the ratio of the active material in the electrode material and increase the capacity of the lithium ion secondary battery.
- the lithium ion secondary battery of the present embodiment uses the electrode material of the first embodiment described above for the positive electrode material and / or the negative electrode material described above.
- a typical lithium ion secondary battery is composed of an electrode group formed by laminating or winding an electrode composed of a negative electrode and a positive electrode via a separator, and an electrolyte solution in which the electrode group is immersed. ing.
- the electrode is formed by applying an electrode material for a lithium ion secondary battery to a current collector of a metal foil through an organic binder or the like.
- the electrode material is kneaded with a solvent or a binder to form an electrode mixture (slurry).
- a solvent or a binder For example, when forming a positive electrode, N-methylpyrrolidone (NMP) can be used as a solvent and polyvinylidene fluoride (PVDF) can be used as a binder.
- NMP N-methylpyrrolidone
- PVDF polyvinylidene fluoride
- water is often used as a solvent
- CMC carboxymethyl cellulose
- SBR styrene butadiene rubber
- an electrode can be produced by press-molding.
- an aluminum foil is used as the current collector.
- the active material is tin oxide oxide
- separators electrically insulates a positive electrode and a negative electrode, and hold
- the thing made from synthetic resins, such as polyethylene and a polypropylene, and the nonwoven fabric made from a cellulose can be used.
- the separator is preferably a porous film.
- nonaqueous electrolytic solution containing lithium salt or an ion conductive polymer examples include ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and methyl ethyl carbonate (MEC). Is mentioned.
- the lithium ion secondary battery of the present embodiment uses the electrode material of the first embodiment described above, large current charge / discharge can be maintained for a long period of time, and the capacity is high.
- an electrode material was produced by the method shown below, and its performance was evaluated.
- Examples 1 to 8 Using a mixer, active materials, organic substances, carbon nanotubes, carbon black and the like shown in Table 1 below were mixed in a solvent. Thereafter, the electrode materials of Examples 1 to 8 were obtained by drying, heating and crushing. Table 2 below shows the conditions in each step.
- Example 1 carbon nanotubes having a surface coated with an amorphous carbon layer were obtained by the method described in Example 1 of JP-A-2004-299986. This was mixed with the black powder and carbon black described above in a solvent using a mixer. Then, the electrode material of Example 9 was obtained by drying, heating, and crushing. The materials used are shown in Table 1 below. Table 2 below shows the conditions in each step.
- lithium carbonate Li 2 CO 3
- Li 2 CO 3 lithium carbonate
- further calcined at 700 ° C. for 48 hours in the air to obtain a black powder. Obtained.
- the obtained powder was subjected to elemental analysis and X-ray diffraction measurement. As a result, it was a compound having a composition of LiNi 0.5 Mn 1.5 O 4 .
- Example 1 carbon nanotubes having a surface coated with an amorphous carbon layer were obtained by the method described in Example 1 of JP-A-2004-299986. This was mixed with the black powder and carbon black described above in a solvent using a mixer. Then, the electrode material of Example 10 was obtained by drying, heating, and crushing. The materials used are shown in Table 1 below, and the conditions in each step are shown in Table 2 below.
- a reflection electron composition image was taken using a scanning electron microscope (JSM-7400F manufactured by JEOL Ltd.), and the active material was coated with amorphous carbon. The rate was measured. Also, using a transmission electron microscope (JEM-2010, manufactured by JEOL Ltd.), a transmission electron beam (TEM) image of the electrode material of Examples 1 to 10 was taken to bond amorphous carbon and carbon nanotubes. The presence / absence of carbon nanotubes and carbon black / carbon black were confirmed. The results are shown in Table 3 below.
- the electrode materials of Examples 1 to 10 had an amorphous carbon coverage of 10% or more. In addition, it was confirmed that all of the electrode materials of Examples 1 to 10 were bonded with amorphous carbon and carbon nanotubes, bonded with carbon nanotubes and carbon black, and formed a conductive network with carbon black.
- Electrodes positive electrode / negative electrode
- lithium ion secondary batteries of Examples 11 to 20 were produced.
- the electrode materials of Examples 1 to 10 and polyvinylidene fluoride (Kureha Co., Ltd. KF polymer solution) as a binder were blended at a mass ratio of 95: 5.
- N-methylpyrrolidone product number 328634, manufactured by Sigma-Aldrich
- kneading was performed using a kneader (Hibismix and homodisper manufactured by Primics) to prepare an electrode mixture (slurry).
- This electrode mixture (slurry) was applied to an aluminum foil or copper foil having a thickness of 20 ⁇ m, dried, and then cut into a 40 mm square by pressing to obtain an electrode for a lithium secondary battery.
- a 50 mm square olefin fiber nonwoven fabric was used as a separator for electrically isolating these.
- lithium hexafluorophosphate (stellar) was added to a solution in which EC (ethylene carbonate manufactured by Aldrich) and MEC (methyl ethyl carbonate manufactured by Aldrich) were mixed at a volume ratio of 30:70.
- EC ethylene carbonate manufactured by Aldrich
- MEC methyl ethyl carbonate manufactured by Aldrich
- graphite manufactured graphite MCMB6-28 manufactured by Osaka Gas Co., Ltd.
- acetylene black HS-100 manufactured by Denki Kagaku Kogyo Co., Ltd.
- binder a slurry was prepared in the same manner as the electrode material described above, applied to a copper foil having a thickness of 20 ⁇ m, dried, then pressed, and a negative electrode cut into a 40 mm square was used. After connecting the terminals to the positive electrode and the negative electrode, the whole was enclosed in an aluminum laminate package to make a 70 mm square laminate type battery.
- Electrode materials of Comparative Examples 1 to 10 shown in Table 4 below were produced.
- N-methylpyrrolidone was added as a dispersion solvent and kneaded using a kneader to prepare an electrode mixture (slurry).
- Comparative Examples 1 to 8 an organic substance that decomposes to form amorphous carbon is not added. Instead, the same amount of carbon is generated when the organic substance used in Examples 1 to 8 is decomposed. Carbon black was added in an increased amount relative to the amount of carbon black in Examples 1-8.
- Table 4 The types and blending amounts of the active material, carbon nanotube, and carbon black in the electrode materials of Comparative Examples 1 to 10 are summarized in Table 4 below.
- Comparative Examples 11-12 An electrode material of Comparative Example 11 was produced in the same manner as in Example 1 except that the amount of sucrose in Example 1 was changed from 3 g to 0.3 g. Specifically, a conductive agent, an organic substance that forms amorphous carbon by pyrolysis, carbon nanotubes, and carbon black are mixed in a solvent using a mixer, and then dried, heated, and crushed for a comparative example. Eleven electrode materials were obtained.
- the coverage of amorphous carbon on the active material of the obtained electrode material of Comparative Example 11 was measured by a reflection electron composition image obtained using a scanning electron microscope and found to be 5%.
- the transmission electron beam (TEM) image obtained using a transmission electron microscope (JEM-2010, manufactured by JEOL Ltd.) shows whether or not there is a bond between amorphous carbon and carbon nanotube, and the bond between carbon nanotube and carbon black. When the presence or absence of this was confirmed, the bond between the carbon nanotube and the carbon black was recognized, but the bond between the amorphous carbon and the carbon nanotube was not recognized.
- the electrode material of Comparative Example 11 was blended with polyvinylidene fluoride as a binder in the same manner as in Example 10, N-methylpyrrolidone was added as a dispersion solvent, and the mixture was kneaded using a kneader to prepare an electrode mixture ( Slurry). Furthermore, using this as an electrode, a laminate type battery of Comparative Example 12 was produced.
- Example 20 and Comparative Example 22 After the first charge / discharge, the charge was 4.3 V (Examples 12, 15, 17 and Comparative Examples 14, 17, 19 were 2.8 V, Example 19 and Comparative Example 21 were 4.8 V, Example 20 and Comparative Example 22) Is 5.0V) (finished at 0.2C constant current, 0.05C current), and discharge is 0.2C, 0.33C, 0.5C, 1C, 3C, 5C, 10C (constant current, 2C) for each cycle. 7V end, Examples 12, 15, 17 and Comparative Examples 14, 17 and 19 end at 1.2V, Example 20 and Comparative Example 22 end at 3.0V) and gradually increase the current value.
- the lithium ion secondary batteries of Examples 11 to 20 using the electrode materials of Examples 1 to 10 have a larger cell capacity than the lithium secondary batteries of Comparative Examples 12 to 22. Moreover, the direct current resistance in charging and discharging was low, and the discharging performance was excellent. From this result, according to the present invention, it was confirmed that large current charge / discharge can be maintained for a long period of time and a high capacity lithium ion secondary battery can be realized.
Abstract
Description
前記非晶質炭素による前記活物質表面の被覆率は、例えば10~95%とすることができる。
前記非晶質炭素は、有機物の熱分解物でもよい。
本発明のリチウムイオン二次電池用電極材を正極材に用いる場合、前記活物質としては、例えばLiCoO2、LiMn2O4、LiNiO2、Li(MnaNibCoc)O2(但し、a+b+c=1 かつ 0<a<1、0<b<1、0<c<1)、Li(AldNieCof)O2(但し、d+e+f=1 かつ 0<d<1、0<e<1、0<f<1)、xLi2MnO3-(1-x)LiMO2(但し、0<x<1)及びLiNigMn(2-g)O4(但し、0<g<2)からなる群から選択される1種のリチウム含有複合酸化物を使用することができる。
本発明のリチウムイオン二次電池用電極材を負極材に用いる場合、前記活物質には、例えばLi4Ti5O12、金属錫を内包した錫酸化物又は金属シリコンを内包したシリコン酸化物を使用することができる。
又は、本発明のリチウムイオン二次電池用電極材を負極材に用いる場合、前記活物質には、金属錫を内包した錫酸化物又は金属シリコンを内包したシリコン酸化物と、黒鉛との混合物を用いてもよい。 An electrode material for a lithium ion secondary battery according to the present invention is an electrode material for a lithium ion secondary battery containing an active material and a conductive material, and the active material is a lithium-containing composite oxide, tin oxide, or silicon oxide The conductive material is amorphous carbon, carbon nanotubes, and carbon black, and a part or all of the surface of the active material is covered with the amorphous carbon.
The coverage of the active material surface with the amorphous carbon can be, for example, 10 to 95%.
The amorphous carbon may be an organic pyrolysis product.
When using a lithium-ion secondary battery electrode material of the present invention in the positive electrode material, as the active material, for example LiCoO 2, LiMn 2 O 4, LiNiO 2, Li (Mn a Ni b Co c) O 2 ( where, a + b + c = 1 and 0 <a <1,0 <b < 1,0 <c <1), Li (Al d Ni e Co f) O 2 ( where, d + e + f = 1 and 0 <d <1,0 <e <1, 0 <f <1), xLi 2 MnO 3- (1-x) LiMO 2 (where 0 <x <1) and LiNi g Mn (2-g) O 4 (where 0 <g <2 One lithium-containing composite oxide selected from the group consisting of:
When the electrode material for a lithium ion secondary battery of the present invention is used as a negative electrode material, the active material includes, for example, Li 4 Ti 5 O 12 , tin oxide containing metal tin or silicon oxide containing metal silicon. Can be used.
Alternatively, when the electrode material for a lithium ion secondary battery of the present invention is used as a negative electrode material, the active material is a mixture of tin oxide containing metal tin or silicon oxide containing metal silicon and graphite. It may be used.
本発明に係る他のリチウムイオン二次電池用電極材の製造方法は、活物質と、カーボンナノチューブと、カーボンブラックとを溶媒中で混合する工程と、前記混合によって得た混合物を、乾燥した後、更に加熱する工程と、前記加熱後の混合物を解砕する工程と、を有し、前記カーボンナノチューブ及びカーボンブラックのいずれか一方又は両方は非晶質炭素を含有する。 A method for producing an electrode material for a lithium ion secondary battery according to the present invention includes a step of mixing an active material, an organic substance that forms amorphous carbon by thermal decomposition, a carbon nanotube, and carbon black in a solvent, After drying the mixture obtained by the mixing, the method further includes heating to form amorphous carbon derived from the organic matter on the surface of the active material, and crushing the mixture after heating. .
Another method for producing an electrode material for a lithium ion secondary battery according to the present invention includes a step of mixing an active material, a carbon nanotube, and carbon black in a solvent, and after drying the mixture obtained by the mixing. And a step of further heating and a step of crushing the mixture after the heating, and either one or both of the carbon nanotubes and carbon black contain amorphous carbon.
先ず、本発明の第1の実施形態に係る電極材について説明する。本実施形態の電極材は、リチウムイオン二次電池に用いられるものであり、活物質としてリチウム含有複合酸化物、錫酸化物又はシリコン酸化物を含有すると共に、導電材として非晶質炭素、カーボンナノチューブ及びカーボンブラックを含有する。そして、本実施形態の電極材では、導電材である非晶質炭素により、活物質の表面の一部又は全部が被覆されている。 (First embodiment)
First, the electrode material which concerns on the 1st Embodiment of this invention is demonstrated. The electrode material of the present embodiment is used for a lithium ion secondary battery, and contains lithium-containing composite oxide, tin oxide or silicon oxide as an active material, and amorphous carbon or carbon as a conductive material. Contains nanotubes and carbon black. In the electrode material of this embodiment, part or all of the surface of the active material is covered with amorphous carbon that is a conductive material.
導電材である非晶質炭素は、結晶性が低い(黒鉛化度が低い)炭素であり、結晶性が低いことによって活物質の表面を被覆することが可能になる。一方、結晶性が高い(黒鉛化度が高い)炭素は、黒鉛特有の層状構造を有し、その各層はファンデルワールス力により緩く結合しているため、層に垂直な方向に剥離が生じやすい。このため活物質の表面を被覆することには適さない。 [Amorphous carbon]
Amorphous carbon, which is a conductive material, is carbon having low crystallinity (low graphitization degree), and the surface of the active material can be covered by low crystallinity. On the other hand, carbon with high crystallinity (high degree of graphitization) has a layered structure peculiar to graphite, and since each layer is loosely bonded by van der Waals force, peeling is likely to occur in a direction perpendicular to the layer. . For this reason, it is not suitable for coating the surface of the active material.
導電材であるカーボンナノチューブは、繊維径が5~50nmであり、かつ、比表面積が50~400m2/gであるものが好ましい。本実施形態の電極材においてカーボンナノチューブは、活物質表面を被覆した非晶質炭素と結合することによって電気的に接続する。ここでいう「結合」は、共有結合やファンデルワールス力による結合も含む。 [carbon nanotube]
The carbon nanotube as the conductive material preferably has a fiber diameter of 5 to 50 nm and a specific surface area of 50 to 400 m 2 / g. In the electrode material of this embodiment, the carbon nanotubes are electrically connected by being bonded to the amorphous carbon covering the surface of the active material. “Coupling” here includes covalent bonding and bonding by van der Waals force.
導電材であるカーボンブラックは、アセチレンブラック又はファーネスブラックであることが好ましく、電池性能に影響を及ぼす可能性がある不純物含有量が比較的少ないアセチレンブラックであることがさらに好ましい。また、カーボンブラックの比表面積は、カーボンナノチューブの比表面積よりも小さく、かつ、10~200m2/gであることが好ましい。更に、本実施形態の電極材に用いるカーボンブラックは、JIS K 1469で規定される灰分が1.0質量%以下であることが好ましい。 [Carbon black]
The carbon black as the conductive material is preferably acetylene black or furnace black, and more preferably acetylene black having a relatively small content of impurities that may affect battery performance. The specific surface area of carbon black is preferably smaller than the specific surface area of carbon nanotubes and is 10 to 200 m 2 / g. Furthermore, the carbon black used for the electrode material of the present embodiment preferably has an ash content defined by JIS K 1469 of 1.0% by mass or less.
本実施形態の電極材の活物質は、リチウム含有複合酸化物、錫酸化物又はシリコン酸化物である。例えば本実施形態の電極材を正極材として用いる場合は、LiCoO2、LiMn2O4、LiNiO2、Li(MnaNibCoc)O2(但し、a+b+c=1 かつ 0<a<1、0<b<1、0<c<1)、Li(AldNieCof)O2(但し、d+e+f=1 かつ 0<d<1、0<e<1、0<f<1)、xLi2MnO3-(1-x)LiMO2(但し、0<x<1)及びLiNigMn(2-g)O4(但し、0<g<2)などの酸化物系の正極活物質を用いることができる。 [Active material]
The active material of the electrode material of this embodiment is a lithium-containing composite oxide, tin oxide, or silicon oxide. For example, when the electrode material of the present embodiment is used as the positive electrode material, LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , Li (Mn a Ni b Co c ) O 2 (where a + b + c = 1 and 0 <a <1, 0 <b <1,0 <c < 1), Li (Al d Ni e Co f) O 2 ( where, d + e + f = 1 and 0 <d <1,0 <e < 1,0 <f <1), Oxide-based positive electrode active materials such as xLi 2 MnO 3- (1-x) LiMO 2 (where 0 <x <1) and LiNi g Mn (2-g) O 4 (where 0 <g <2) Can be used.
本実施形態の電極材の製造方法は、特に限定されるものではないが、例えば活物質と、熱分解により非晶質炭素を形成する有機物と、カーボンナノチューブと、カーボンブラックとを溶媒中で混合する工程と、混合によって得た混合物を、乾燥した後、更に加熱して活物質の表面に有機物由来の非晶質炭素を形成する工程と、加熱後の混合物を解砕する工程と、を行うことにより製造することができる。この方法で製造する場合、溶媒に溶解し、かつ加熱時に分解して非晶質炭素を形成しやすい有機物を使用することが好ましい。 [Production method]
The method for producing the electrode material of the present embodiment is not particularly limited. For example, an active material, an organic material that forms amorphous carbon by thermal decomposition, carbon nanotubes, and carbon black are mixed in a solvent. And a step of drying the mixture obtained by mixing and further heating to form amorphous carbon derived from organic matter on the surface of the active material, and a step of crushing the mixture after heating. Can be manufactured. When manufacturing by this method, it is preferable to use an organic substance that dissolves in a solvent and easily decomposes upon heating to form amorphous carbon.
次に、本発明の第2の実施形態に係るリチウムイオン二次電池について説明する。本実施形態のリチウムイオン二次電池は、前述した正極材及び/又は負極材に、前述した第1の実施形態の電極材を用いたものである。 (Second Embodiment)
Next, a lithium ion secondary battery according to a second embodiment of the present invention will be described. The lithium ion secondary battery of the present embodiment uses the electrode material of the first embodiment described above for the positive electrode material and / or the negative electrode material described above.
混合機を用いて、下記表1に示す活物質、有機物、カーボンナノチューブ及びカーボンブラックなどを、溶媒中で混合した。その後、乾燥、加熱、解砕することによって実施例1~8の電極材を得た。下記表2に各工程における条件を示す。 <Examples 1 to 8>
Using a mixer, active materials, organic substances, carbon nanotubes, carbon black and the like shown in Table 1 below were mixed in a solvent. Thereafter, the electrode materials of Examples 1 to 8 were obtained by drying, heating and crushing. Table 2 below shows the conditions in each step.
硝酸マンガン(Mn(NO3)2・6H2O)、硝酸ニッケル(Ni(NO3)2・6H2O)及び硝酸コバルト(Co(NO3)2・6H2O)を、蒸留水に、モル比で、Mn:Ni:Co=4:1:1の割合になるよう添加し、溶解させた。その後、窒素雰囲気中で炭酸リチウム(Li2CO3)を、モル比で、Li2CO3:(Mn+Ni+Co)=1.75:1の割合になるように添加して充分に撹拌後、濾過、洗浄、乾燥して粉末を得た。 <Example 9>
Manganese nitrate (Mn (NO 3 ) 2 .6H 2 O), nickel nitrate (Ni (NO 3 ) 2 .6H 2 O) and cobalt nitrate (Co (NO 3 ) 2 .6H 2 O) are added to distilled water. It was added and dissolved in a molar ratio of Mn: Ni: Co = 4: 1: 1. Thereafter, lithium carbonate (Li 2 CO 3 ) was added in a nitrogen atmosphere at a molar ratio of Li 2 CO 3 : (Mn + Ni + Co) = 1.75: 1, and after sufficient stirring, filtered, The powder was obtained by washing and drying.
塩化ニッケル(NiCl2・6H2O)及び塩化マンガン(MnCl2・4H2O)を、モル比で、Ni:Mn=1:3になるように混合した後、シュウ酸アンモニウム((NH4)2C2O4・H2O)を、モル比で、(Ni+Mn):C2O4=5:6になるように加えて混合した。混合物を、110℃で2時間乾燥した後、大気中、400℃で4時間焼成した。 <Example 10>
After mixing nickel chloride (NiCl 2 · 6H 2 O) and manganese chloride (MnCl 2 · 4H 2 O) in a molar ratio of Ni: Mn = 1: 3, ammonium oxalate ((NH 4 ) 2 C 2 O 4 .H 2 O) was added and mixed so that the molar ratio was (Ni + Mn): C 2 O 4 = 5: 6. The mixture was dried at 110 ° C. for 2 hours and then calcined in the atmosphere at 400 ° C. for 4 hours.
次に、実施例1~10の電極材を使用して電極(正極・負極)を形成し、実施例11~20のリチウムイオン二次電池を作製した。具体的には、実施例1~10の電極材と、バインダーとしてポリフッ化ビニリデン(株式会社クレハ製 KFポリマー溶液)を、質量比で、95:5の割合で配合した。これに分散溶媒としてN-メチルピロリドン(シグマアルドリッチ社製 品番328634)を添加し、混練機(プライミクス社製 ハイビスミックス及びホモディスパー)を用いて混練して電極合剤(スラリー)を作製した。 <Examples 11 to 20>
Next, electrodes (positive electrode / negative electrode) were formed using the electrode materials of Examples 1 to 10, and lithium ion secondary batteries of Examples 11 to 20 were produced. Specifically, the electrode materials of Examples 1 to 10 and polyvinylidene fluoride (Kureha Co., Ltd. KF polymer solution) as a binder were blended at a mass ratio of 95: 5. To this was added N-methylpyrrolidone (product number 328634, manufactured by Sigma-Aldrich) as a dispersion solvent, and kneading was performed using a kneader (Hibismix and homodisper manufactured by Primics) to prepare an electrode mixture (slurry).
前述した実施例1~10と同じ活物質、カーボンナノチューブ及びカーボンブラックを使用し、下記表4に示す比較例1~10の電極材を作製した。比較例1~10の電極材は、そのままバインダであるポリフッ化ビニリデン(株式会社クレハ製 KFポリマー溶液)に、質量比で、バインダー:残部=5:95の割合となるように配合し、これに分散溶媒としてN-メチルピロリドンを添加し、混練機を用いて混練して電極合剤(スラリー)を作製した。 <Comparative Examples 1 to 10>
Using the same active materials, carbon nanotubes, and carbon black as in Examples 1 to 10 described above, electrode materials of Comparative Examples 1 to 10 shown in Table 4 below were produced. The electrode materials of Comparative Examples 1 to 10 were blended into polyvinylidene fluoride as a binder as it is (a KF polymer solution manufactured by Kureha Co., Ltd.) at a mass ratio of binder: remainder = 5: 95. N-methylpyrrolidone was added as a dispersion solvent and kneaded using a kneader to prepare an electrode mixture (slurry).
実施例1におけるショ糖の量を3gから0.3gに変更した以外は実施例1と同様にして比較例11の電極材を作製した。具体的には、導電剤、熱分解により非晶質炭素を形成する有機物、カーボンナノチューブ及びカーボンブラックを、溶媒中で混合機を用いて混合した後、乾燥、加熱、解砕することによって比較例11の電極材を得た。 <Comparative Examples 11-12>
An electrode material of Comparative Example 11 was produced in the same manner as in Example 1 except that the amount of sucrose in Example 1 was changed from 3 g to 0.3 g. Specifically, a conductive agent, an organic substance that forms amorphous carbon by pyrolysis, carbon nanotubes, and carbon black are mixed in a solvent using a mixer, and then dried, heated, and crushed for a comparative example. Eleven electrode materials were obtained.
比較例1~10で作製した電極合剤を電極に用いた以外は、それぞれ実施例11~20と全く同様にして比較例13~22のラミネート型電池を作製した。 <Comparative Examples 13 to 22>
Laminated batteries of Comparative Examples 13 to 22 were prepared in exactly the same manner as in Examples 11 to 20, respectively, except that the electrode mixture prepared in Comparative Examples 1 to 10 was used for the electrodes.
次に、前述した方法で作製した実施例11~20及び比較例12~22のリチウムイオン二次電池(ラミネート型電池)について放電性能試験を行った。具体的には、各電池を初回充電後、充放電効率が100%近傍になることを確認し、0.7mA/cm2の電流密度にて定電流放電を2.7V(実施例12、15、17及び比較例14、17、19は1.2V、実施例20及び比較例22は3.0V)まで行った際の放電容量を測定した。この容量(mAh)を1時間で充放電可能な電流値を「1C」とした。 [Discharge performance evaluation]
Next, discharge performance tests were conducted on the lithium ion secondary batteries (laminated batteries) of Examples 11 to 20 and Comparative Examples 12 to 22 manufactured by the above-described method. Specifically, after each battery was charged for the first time, it was confirmed that the charge / discharge efficiency was close to 100%, and constant current discharge was performed at 2.7 V at a current density of 0.7 mA / cm 2 (Examples 12 and 15). , 17 and Comparative Examples 14, 17, and 19 were measured at 1.2 V, and Example 20 and Comparative Example 22 were measured at 3.0 V). The current value at which this capacity (mAh) can be charged and discharged in 1 hour was defined as “1C”.
Claims (9)
- 活物質及び導電材を含有するリチウムイオン二次電池用電極材であって、
前記活物質はリチウム含有複合酸化物、錫酸化物又はシリコン酸化物であり、
前記導電材は、非晶質炭素、カーボンナノチューブ及びカーボンブラックであり、
前記非晶質炭素により前記活物質の表面の一部又は全部が被覆されている
リチウムイオン二次電池用電極材。 An electrode material for a lithium ion secondary battery containing an active material and a conductive material,
The active material is a lithium-containing composite oxide, tin oxide or silicon oxide,
The conductive material is amorphous carbon, carbon nanotube and carbon black,
An electrode material for a lithium ion secondary battery, wherein a part or all of the surface of the active material is coated with the amorphous carbon. - 前記非晶質炭素による前記活物質表面の被覆率は10~95%である請求項1に記載のリチウムイオン二次電池用電極材。 The electrode material for a lithium ion secondary battery according to claim 1, wherein the coverage of the active material surface with the amorphous carbon is 10 to 95%.
- 前記非晶質炭素は有機物の熱分解物である請求項1又は2に記載のリチウムイオン二次電池用電極材。 3. The electrode material for a lithium ion secondary battery according to claim 1 or 2, wherein the amorphous carbon is an organic pyrolysis product.
- 前記活物質は、
LiCoO2、
LiMn2O4、
LiNiO2、
Li(MnaNibCoc)O2
但し、a+b+c=1 かつ 0<a<1、0<b<1、0<c<1、
Li(AldNieCof)O2
但し、d+e+f=1 かつ 0<d<1、0<e<1、0<f<1、
xLi2MnO3-(1-x)LiMO2
但し、0<x<1、
及びLiNigMn(2-g)O4
但し、0<g<2、
からなる群から選択される1種のリチウム含有複合酸化物であり、
正極材に用いられる請求項1~3のいずれか1項に記載のリチウムイオン二次電池用電極材。 The active material is
LiCoO 2 ,
LiMn 2 O 4 ,
LiNiO 2 ,
Li (Mn a Ni b Co c ) O 2
However, a + b + c = 1 and 0 <a <1, 0 <b <1, 0 <c <1,
Li (Al d Ni e Co f ) O 2
Where d + e + f = 1 and 0 <d <1, 0 <e <1, 0 <f <1,
xLi 2 MnO 3- (1-x) LiMO 2
However, 0 <x <1,
And LiNi g Mn (2-g) O 4
However, 0 <g <2,
A lithium-containing composite oxide selected from the group consisting of:
The electrode material for a lithium ion secondary battery according to any one of claims 1 to 3, which is used for a positive electrode material. - 前記活物質は、Li4Ti5O12、金属錫を内包した錫酸化物又は金属シリコンを内包したシリコン酸化物であり、
負極材に用いられる請求項1~3のいずれか1項に記載のリチウムイオン二次電池用電極材。 The active material is Li 4 Ti 5 O 12 , tin oxide containing metal tin or silicon oxide containing metal silicon,
The electrode material for a lithium ion secondary battery according to any one of claims 1 to 3, which is used for a negative electrode material. - 前記活物質は、金属錫を内包した錫酸化物又は金属シリコンを内包したシリコン酸化物と、黒鉛との混合物であり、
負極材に用いられる請求項1~3のいずれか1項に記載のリチウムイオン二次電池用電極材。 The active material is a mixture of tin oxide encapsulating metal tin or silicon oxide encapsulating metal silicon and graphite,
The electrode material for a lithium ion secondary battery according to any one of claims 1 to 3, which is used for a negative electrode material. - 活物質と、熱分解により非晶質炭素を形成する有機物と、カーボンナノチューブと、カーボンブラックとを溶媒中で混合する工程と、
前記混合によって得た混合物を、乾燥した後、更に加熱して前記活物質の表面に前記有機物由来の非晶質炭素を形成する工程と、
前記加熱後の混合物を解砕する工程と、
を有するリチウムイオン二次電池用電極材の製造方法。 Mixing an active material, an organic substance that forms amorphous carbon by thermal decomposition, a carbon nanotube, and carbon black in a solvent;
A step of drying the mixture obtained by the mixing and further heating to form amorphous carbon derived from the organic matter on the surface of the active material;
Crushing the mixture after heating;
The manufacturing method of the electrode material for lithium ion secondary batteries which has this. - 活物質と、カーボンナノチューブと、カーボンブラックとを溶媒中で混合する工程と、
前記混合によって得た混合物を、乾燥した後、更に加熱する工程と、
前記加熱後の混合物を解砕する工程と、
を有し、
前記カーボンナノチューブ及びカーボンブラックのいずれか一方又は両方は非晶質炭素を含有するリチウムイオン二次電池用電極材の製造方法。 Mixing an active material, carbon nanotubes, and carbon black in a solvent;
A step of further heating after drying the mixture obtained by the mixing;
Crushing the mixture after heating;
Have
The method for producing an electrode material for a lithium ion secondary battery, wherein either one or both of the carbon nanotube and carbon black contains amorphous carbon. - 請求項1~6のいずれか1項に記載の電極材を用いたリチウムイオン二次電池。 A lithium ion secondary battery using the electrode material according to any one of claims 1 to 6.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020157003780A KR102121868B1 (en) | 2012-08-28 | 2013-08-27 | Electrode material for lithium ion secondary batteries, method for producing same, and lithium ion secondary battery |
JP2014533007A JP6344740B2 (en) | 2012-08-28 | 2013-08-27 | ELECTRODE MATERIAL FOR LITHIUM ION SECONDARY BATTERY, ITS MANUFACTURING METHOD, AND LITHIUM ION SECONDARY BATTERY |
CN201380045468.6A CN104603992B (en) | 2012-08-28 | 2013-08-27 | Electrode for lithium ion secondary battery material, its manufacturing method and lithium rechargeable battery |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-188098 | 2012-08-28 | ||
JP2012188098 | 2012-08-28 | ||
JP2012273610 | 2012-12-14 | ||
JP2012-273610 | 2012-12-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014034635A1 true WO2014034635A1 (en) | 2014-03-06 |
Family
ID=50183447
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/072805 WO2014034635A1 (en) | 2012-08-28 | 2013-08-27 | Electrode material for lithium ion secondary batteries, method for producing same, and lithium ion secondary battery |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6344740B2 (en) |
KR (1) | KR102121868B1 (en) |
CN (1) | CN104603992B (en) |
TW (1) | TWI628836B (en) |
WO (1) | WO2014034635A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014099295A (en) * | 2012-11-13 | 2014-05-29 | Nippon Chemicon Corp | Electrode material for lithium ion secondary battery, manufacturing method of the electrode material and lithium ion secondary battery |
JP2015191688A (en) * | 2014-03-27 | 2015-11-02 | 三菱マテリアル株式会社 | Negative-electrode active material for lithium ion secondary battery and manufacturing method for the same |
JP2018518541A (en) * | 2015-02-27 | 2018-07-12 | ゲイツ コーポレイション | Carbon nanostructure pre-blend and use thereof |
JP2020527290A (en) * | 2017-07-20 | 2020-09-03 | 日本電気株式会社 | Carbon Conductive Additive for Lithium Ion Batteries |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PL3678228T3 (en) * | 2017-12-01 | 2023-01-16 | Lg Energy Solution, Ltd. | Negative electrode and secondary battery including the same |
KR20200094428A (en) * | 2019-01-30 | 2020-08-07 | 에스케이이노베이션 주식회사 | Secondary Battery and the Fabrication Method Thereof |
KR102244226B1 (en) * | 2019-10-22 | 2021-04-26 | 주식회사 그랩실 | Silicon Composite Anode Active Material including Network of Conductive Fibers, Manufacturing method thereof and Lithium Secondary Battery Comprising the Same |
KR20210153997A (en) * | 2020-06-11 | 2021-12-20 | 주식회사 엘지에너지솔루션 | Negative electrode and secondary battery comprising the same |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005158721A (en) * | 2003-10-31 | 2005-06-16 | Hitachi Maxell Ltd | Electrode material of nonaqueous secondary battery, its process of manufacture, and nonaqueous secondary battery using electrode material |
WO2011056847A2 (en) * | 2009-11-03 | 2011-05-12 | Envia Systems, Inc. | High capacity anode materials for lithium ion batteries |
JP2011108522A (en) * | 2009-11-18 | 2011-06-02 | Denki Kagaku Kogyo Kk | Cathode material for lithium ion secondary battery and method of manufacturing the same |
WO2011112042A2 (en) * | 2010-03-11 | 2011-09-15 | 주식회사 엘지화학 | Organic polymer-silicon composite particle, preparation method for same, and cathode and lithium secondary battery including same |
JP2011192563A (en) * | 2010-03-16 | 2011-09-29 | Hitachi Maxell Energy Ltd | Nonaqueous secondary battery |
JP2011238586A (en) * | 2010-05-06 | 2011-11-24 | Samsung Sdi Co Ltd | Cathode active material for lithium secondary battery and lithium secondary battery having the same |
WO2012140790A1 (en) * | 2011-04-13 | 2012-10-18 | エス・イー・アイ株式会社 | Electrode material for lithium secondary battery and lithium secondary battery |
WO2013002162A1 (en) * | 2011-06-30 | 2013-01-03 | 三洋電機株式会社 | Nonaqueous electrolyte secondary cell and method for manufacturing same |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5910382A (en) | 1996-04-23 | 1999-06-08 | Board Of Regents, University Of Texas Systems | Cathode materials for secondary (rechargeable) lithium batteries |
CA2270771A1 (en) * | 1999-04-30 | 2000-10-30 | Hydro-Quebec | New electrode materials with high surface conductivity |
JP4151210B2 (en) | 2000-08-30 | 2008-09-17 | ソニー株式会社 | Positive electrode active material and method for producing the same, non-aqueous electrolyte battery and method for producing the same |
JP4040606B2 (en) | 2003-06-06 | 2008-01-30 | Jfeケミカル株式会社 | Negative electrode material for lithium ion secondary battery and production method thereof, and negative electrode for lithium ion secondary battery and lithium ion secondary battery |
KR100796687B1 (en) * | 2005-11-30 | 2008-01-21 | 삼성에스디아이 주식회사 | Active material for rechargeable lithium battery, method of preparing thereof and rechargeable lithium battery comprising same |
CN102576873B (en) * | 2009-10-09 | 2016-05-11 | 东洋油墨Sc控股株式会社 | Positive active material for lithium secondary battery material, its manufacture method and use its lithium secondary battery |
WO2011140150A1 (en) * | 2010-05-03 | 2011-11-10 | Georgia Tech Research Corporation | Alginate-containing compositions for use in battery applications |
-
2013
- 2013-08-27 CN CN201380045468.6A patent/CN104603992B/en active Active
- 2013-08-27 JP JP2014533007A patent/JP6344740B2/en active Active
- 2013-08-27 WO PCT/JP2013/072805 patent/WO2014034635A1/en active Application Filing
- 2013-08-27 KR KR1020157003780A patent/KR102121868B1/en active IP Right Grant
- 2013-08-28 TW TW102130729A patent/TWI628836B/en active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005158721A (en) * | 2003-10-31 | 2005-06-16 | Hitachi Maxell Ltd | Electrode material of nonaqueous secondary battery, its process of manufacture, and nonaqueous secondary battery using electrode material |
WO2011056847A2 (en) * | 2009-11-03 | 2011-05-12 | Envia Systems, Inc. | High capacity anode materials for lithium ion batteries |
JP2011108522A (en) * | 2009-11-18 | 2011-06-02 | Denki Kagaku Kogyo Kk | Cathode material for lithium ion secondary battery and method of manufacturing the same |
WO2011112042A2 (en) * | 2010-03-11 | 2011-09-15 | 주식회사 엘지화학 | Organic polymer-silicon composite particle, preparation method for same, and cathode and lithium secondary battery including same |
JP2011192563A (en) * | 2010-03-16 | 2011-09-29 | Hitachi Maxell Energy Ltd | Nonaqueous secondary battery |
JP2011238586A (en) * | 2010-05-06 | 2011-11-24 | Samsung Sdi Co Ltd | Cathode active material for lithium secondary battery and lithium secondary battery having the same |
WO2012140790A1 (en) * | 2011-04-13 | 2012-10-18 | エス・イー・アイ株式会社 | Electrode material for lithium secondary battery and lithium secondary battery |
WO2013002162A1 (en) * | 2011-06-30 | 2013-01-03 | 三洋電機株式会社 | Nonaqueous electrolyte secondary cell and method for manufacturing same |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014099295A (en) * | 2012-11-13 | 2014-05-29 | Nippon Chemicon Corp | Electrode material for lithium ion secondary battery, manufacturing method of the electrode material and lithium ion secondary battery |
JP2015191688A (en) * | 2014-03-27 | 2015-11-02 | 三菱マテリアル株式会社 | Negative-electrode active material for lithium ion secondary battery and manufacturing method for the same |
JP2018518541A (en) * | 2015-02-27 | 2018-07-12 | ゲイツ コーポレイション | Carbon nanostructure pre-blend and use thereof |
US20180223052A1 (en) * | 2015-02-27 | 2018-08-09 | Gates Corporation | Carbon nanostructure preblends and their applications |
US10308773B2 (en) | 2015-02-27 | 2019-06-04 | Gates Corporation | Carbon nanostructure preblends and their applications |
JP2020527290A (en) * | 2017-07-20 | 2020-09-03 | 日本電気株式会社 | Carbon Conductive Additive for Lithium Ion Batteries |
US11349152B2 (en) | 2017-07-20 | 2022-05-31 | Nec Corporation | Carbon conductive additives for lithium ion battery |
Also Published As
Publication number | Publication date |
---|---|
CN104603992A (en) | 2015-05-06 |
CN104603992B (en) | 2018-08-21 |
KR102121868B1 (en) | 2020-06-11 |
KR20150052004A (en) | 2015-05-13 |
TW201415697A (en) | 2014-04-16 |
JP6344740B2 (en) | 2018-06-20 |
JPWO2014034635A1 (en) | 2016-08-08 |
TWI628836B (en) | 2018-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10559811B2 (en) | Graphene-enhanced anode particulates for lithium ion batteries | |
JP6344740B2 (en) | ELECTRODE MATERIAL FOR LITHIUM ION SECONDARY BATTERY, ITS MANUFACTURING METHOD, AND LITHIUM ION SECONDARY BATTERY | |
CN107636868B (en) | Secondary battery, negative electrode, active material, and method for producing active material particles | |
JP5486907B2 (en) | Positive electrode material for lithium ion secondary battery and method for producing the same | |
TWI574914B (en) | A composite particle and a method for producing the same, an electrode material for a secondary battery, and a secondary battery | |
JP6188158B2 (en) | Negative electrode for lithium ion secondary battery, negative electrode slurry for lithium ion secondary battery, and lithium ion secondary battery | |
JP6596779B2 (en) | COMPOSITE PARTICLE, PROCESS FOR PRODUCING THE SAME, ELECTRODE MATERIAL FOR SECONDARY BATTERY, AND SECONDARY BATTERY | |
CN103918109A (en) | Positive-electrode materials: methods for their preparation and use in lithium secondary batteries | |
JP5155498B2 (en) | Method for producing positive electrode active material for lithium secondary battery | |
KR20120129816A (en) | Accumulator device and positive electrode | |
KR20130086077A (en) | Negative electrode active material for lithium ion secondary battery | |
CN102136574A (en) | Cathode active material and lithium secondary battery containing the same | |
KR20130129819A (en) | Lithium ion secondary battery | |
JP3816799B2 (en) | Lithium secondary battery | |
KR101093242B1 (en) | Mixed Cathode Material for Lithium Secondary Battery and High Power Lithium Secondary Battery Employed with the Same | |
WO2020065832A1 (en) | Electrically conductive substance, positive electrode, and secondary battery | |
KR101115390B1 (en) | Mixed Cathode Material for Lithium Secondary Battery and High Power Lithium Secondary Battery Employed with the Same | |
JP2024058944A (en) | Anode mixture, method of manufacturing anode, anode and secondary battery | |
JP2024502362A (en) | Positive electrode active material for lithium secondary batteries, method for producing the same, and lithium secondary batteries containing the same | |
KR20080036254A (en) | Anode material of excellent conductivity and high power secondary battery employed with the same |
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: 13832167 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014533007 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20157003780 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13832167 Country of ref document: EP Kind code of ref document: A1 |