WO2017199606A1 - Ｌｉイオン二次電池用負極材料、Ｌｉイオン二次電池用負極およびＬｉイオン二次電池 - Google Patents

Ｌｉイオン二次電池用負極材料、Ｌｉイオン二次電池用負極およびＬｉイオン二次電池 Download PDF

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WO2017199606A1
WO2017199606A1 PCT/JP2017/013962 JP2017013962W WO2017199606A1 WO 2017199606 A1 WO2017199606 A1 WO 2017199606A1 JP 2017013962 W JP2017013962 W JP 2017013962W WO 2017199606 A1 WO2017199606 A1 WO 2017199606A1
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negative electrode
ion secondary
particles
secondary battery
containing oxide
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PCT/JP2017/013962
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English (en)
French (fr)
Japanese (ja)
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田原　知之
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Ｊｆｅケミカル株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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

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  • a Li ion conductive metal oxide is coated on the surface of a Si particle that can be alloyed with Li, and a Li ion conductive metal oxide is coated on the surface of the Li ion conductive metal oxide film.
  • the present invention relates to a negative electrode material for a secondary battery.
  • Li-ion secondary batteries are widely used as power sources for electronic devices because of their excellent characteristics of high voltage and high energy density.
  • the current Li ion secondary batteries are mainly those using LiCoO 2 for the positive electrode and graphite for the negative electrode.
  • the graphite of the negative electrode is excellent in reversibility of charge and discharge, but the discharge capacity has already reached a value close to the theoretical value of 372 mAh / g corresponding to the intercalation compound LiC 6 . For this reason, in order to achieve higher energy density, it is necessary to develop a negative electrode material having a discharge capacity larger than that of graphite.
  • Si and SiO have attracted attention as active materials for forming an alloy with Li having a discharge capacity far exceeding that of graphite as a negative electrode material replacing graphite. Since the Si-based negative electrode has a large volume expansion associated with alloying at the time of charging, it easily deteriorates, and as a measure for reducing the expansion, atomization of particles is effective. However, the active material surface becomes active due to atomization, and the reductive decomposition of the electrolytic solution is promoted at the time of charging. Therefore, the practical cycle characteristics are not obtained.
  • Patent Document 1 proposes a carbon material characterized in that it is a metal-containing hollow carbon particle containing Si in an internal void, and Si is coated with Cu or Ni nanoparticles.
  • the surface of Si is only coated with a metal element that imparts conductivity. This metal element not only lowers Li ion conduction, but is also insufficient to suppress reductive decomposition of the electrolyte during charging. As a result, accumulation of decomposition product residues causes the electrode to expand and cause cycle deterioration.
  • the hollow carbon particles have a high bulk density and cannot increase the density of the negative electrode.
  • Patent Document 2 proposes a negative electrode material in which a composite of a nano-sized Si particle surrounded by an Li-containing oxide and a carbon material is coated with carbon.
  • the amount of oxide surrounding Si is excessive, about 35 to 88% by mass, so that the resistance of Li ion conduction and electron conduction becomes large, causing a decrease in capacity and rapid charge / discharge characteristics.
  • a negative electrode is formed by bonding a compound having conductivity and suppressing the expansion to the surface of nano-sized Si particles, and granulating the Si particles using a resin such as polyimide imparted with conductivity as a binder.
  • a resin such as polyimide imparted with conductivity as a binder.
  • Materials have been proposed.
  • the compound bonded to the Si surface not only lowers Li ion conduction, but also suppresses the reductive decomposition of the electrolyte during charging, so the electrode expands due to the accumulation of decomposition residue and cycle deterioration cause.
  • the present invention has been made in view of the above-described situation, and by covering the surface of the Si negative electrode active material with a Li-containing oxide, reductive decomposition of the electrolytic solution during charging is suppressed, and further, a Li-containing oxide film Li, which exhibits a high discharge capacity exceeding the theoretical capacity of graphite, and excellent initial charge / discharge efficiency and cycle characteristics, by relaxing the charge expansion of the Si negative electrode active material by constraining the surface of the electrode with a conductive binder. It aims at providing the negative electrode material for ion secondary batteries.
  • the surface of Si particles as an active material is coated with a thin film of Li-containing oxide containing Li and other specific metal elements, which has a high Li ion conductivity and is stable. It was found that a high discharge capacity and good cycle characteristics can be obtained by constraining the surface with a conductive binder and adjusting the size of the aggregated particles of the active material to a single micron. The reason why high discharge capacity and cycle characteristics can be obtained as described above is that the surface of Si particles as an active material is coated with the above-described Li-containing oxide thin film having high Li ion conductivity and stability.
  • the present invention provides the following.
  • a Li-containing oxide film having a composition containing Li and at least one metal element M selected from Si, Al, Ti, and Zr, and further the surface of the film
  • Li ion secondary characterized in that the average particle diameter of the aggregated particles formed by aggregating the Si particles having the Li-containing oxide film and the conductive binder is 0.5 to 10 ⁇ m.
  • Negative electrode material for batteries is 0.5 to 10 ⁇ m.
  • the negative electrode material for a Li ion secondary battery of the present invention can sufficiently suppress excessive reductive decomposition of the electrolytic solution due to the active material during charging, and further suppress the expansion of charging by making the conductive binder and aggregate particles fine. Therefore, it exhibits a high discharge capacity exceeding the theoretical charge capacity of graphite and excellent cycle characteristics.
  • the negative electrode material for a Li ion secondary battery of the present invention is a contact between an active material and an electrolytic solution by forming a stable and high Li ion conductive Li-containing oxide film on the surface of Si particles as an active material.
  • the reductive decomposition of the electrolyte by the active material can be suppressed during charging, and the charging / discharging reaction accompanied by Li ion conduction is not hindered.
  • the film thickness is preferably 10 nm or less.
  • the film thickness is more preferably 0.5 to 10 nm. If it is thinner than 0.5 nm, the contact between the active material and the electrolytic solution may not be sufficiently prevented.
  • the film thickness is more preferably 1 to 5 nm.
  • the coating amount by the Li-containing oxide that is, the content of the Li-containing oxide in the negative electrode material for the Li ion secondary battery of the present invention is affected by the specific surface area of the Si particles as the active material.
  • the coating amount by the Li-containing oxide that is, the content of the Li-containing oxide in the negative electrode material for the Li ion secondary battery of the present invention is preferably 10% by mass or less.
  • the content of the Li-containing oxide in the negative electrode material for a Li-ion secondary battery of the present invention is more than 10% by mass, the resistance of Li ion conduction increases and the responsiveness of the electrode reaction may be deteriorated.
  • the content of the Li-containing oxide in the negative electrode material for a Li ion secondary battery of the present invention is more preferably 0.5 to 10% by mass.
  • the content of the Li-containing oxide in the negative electrode material for a Li ion secondary battery of the present invention is less than 0.5% by mass, the contact between the active material and the electrolytic solution may not be sufficiently prevented.
  • the content of the Li-containing oxide in the negative electrode material for a Li ion secondary battery of the present invention is more preferably 1 to 5% by mass.
  • the coating film formed on the surface of the Si particles as the active material is made of a Li-containing oxide having a stable and high Li ion conductivity.
  • the matrix metal oxide containing Li is at least one selected from SiO 2 , Al 2 O 3 , TiO 2 and ZrO 2 .
  • composition is M / Li ⁇ 0.1 in terms of molar ratio, free Li 2 O is likely to be deposited on the Li-containing oxide film and defects may occur, and contact between the active material and the electrolyte may not be sufficiently restricted. There is. If the composition is M / Li> 20 in terms of molar ratio, the resistance of Li ion conduction increases and the responsiveness of the electrode reaction may deteriorate.
  • the crystal phase of the Li-containing oxide in the present invention is affected by the heat treatment temperature.
  • the heat treatment temperature is 200 to 600 ° C.
  • crystallization does not proceed and it is amorphous, and when it is 600 ° C. or higher, crystals begin to be formed.
  • the Li-containing oxide contains Si as the metal element M, it is amorphous or crystalline phase SiO 2 (tridymite type), Li 4 SiO 4 , Li 2 SiO 3 , Li 2 Si 2. O 5 single phase or mixed phase.
  • the Li-containing oxide contains Al as the metal element M, the amorphous or crystalline phase of Al 2 O 3 ( ⁇ type), LiAl 5 O 8 , LiAlO 5 , Li 5 AlO 4 single phase or It becomes a mixed phase.
  • the Li-containing oxide contains Ti as the metal element M, the amorphous or crystalline phase of TiO 2 (anatase type, rutile type), Li 4 Ti 5 O 12 , Li 2 TiO 3 single phase or It becomes a mixed phase.
  • the Li-containing oxide contains Zr as the metal element M, it is amorphous or crystalline ZrO 2 (monoclinic, tetragonal), Li 2 ZrO 3 , Li 6 Zr 2 O 7 , Li 8 ZrO. 6 mixed or single phase.
  • a conductive material may be included in the film.
  • a conductive binding material is adhered to the surface of the Li-containing oxide film that covers the active material Si particles.
  • the conductive binding material restrains the active material Si particles to relieve the charge expansion, and adjusts the size of the aggregated particles made of the coated Si active material to a fine particle having an average particle diameter of 0.5 to 10 ⁇ m. This disperses the local expansion of the electrode and further imparts electron conduction.
  • the average particle diameter of the aggregated particles exceeds 10 ⁇ m, the influence of the charge expansion is locally increased and the deterioration of the electrode is promoted.
  • the average particle size is less than 0.5 ⁇ m, the handling of the powder becomes worse.
  • the average particle diameter is more preferably in the range of 1 to 5 ⁇ m.
  • the particle shape may be any of spherical, flat and crushed, and is not particularly limited.
  • the matrix of the binder material having conductivity is at least one selected from carbon, inorganic materials, and resins, and the conductive material that develops conductivity is used by dispersing carbon or graphite in the matrix. Therefore, the conductive binding material contains carbon.
  • the carbon which is the matrix of the binding material in the present invention is hard carbon having a low expansion and high capacity
  • the inorganic material is glass (eg, sulfide glass Li 10 GeP 2 S 12 ), the crystalline oxide, and the resin is polyimide. Silicone and the like are preferable, but not limited thereto.
  • the hard carbon of the carbon matrix can be obtained by heat-treating a precursor such as a phenol resin or an infusible pitch at 600 to 1200 ° C. in an inert atmosphere.
  • the inorganic matrix can be obtained by using a mechanochemical method, a sol-gel method or the like as a raw material sulfide or oxide. In the case of the sol-gel method, an intermediate hydroxide is heat-treated at 600 to 1200 ° C. in an inert atmosphere to generate an oxide.
  • the resin matrix can be obtained by drying and curing the precursor varnish at 200 to 500 ° C.
  • the conductivity imparted to the binder material can be expressed by dispersing a carbon or graphite conductive material in the matrix material, and the shape of the conductive material may be any of a fiber shape, a scale shape, and a tuft shape, and is not particularly limited. .
  • Specific examples of the conductive material include carbon nanotubes, scale graphite, earthy graphite, hard carbon, and carbon black.
  • the content of the conductive binder of the present invention is preferably 10% by mass or more. If the content of the conductive binder is less than 10% by mass, the charge expansion of the coated Si particles may not be sufficiently relaxed. When the content of the conductive binder is more than 50% by mass, the resistance of Li ion conduction increases and the responsiveness of the electrode reaction may be deteriorated.
  • the content of the conductive binder of the present invention is more preferably 10 to 50% by mass. When the content of the conductive binder is more than 50% by mass, the resistance of Li ion conduction increases and the responsiveness of the electrode reaction may be deteriorated.
  • Si particles are used as the active material.
  • the Si crystal phase may be either amorphous or crystalline, and is not particularly limited.
  • the average particle size of the Si particles is preferably 1 ⁇ m or less. When the average particle diameter exceeds 1 ⁇ m, the influence of the charge expansion is locally increased and the deterioration of the electrode is promoted.
  • the average particle size is preferably 0.01 ⁇ m or more.
  • the Si particles as the active material have high surface activity, and it is difficult to suppress the reductive decomposition of the electrolytic solution with a film during charging.
  • the average particle diameter is more preferably in the range of 0.01 ⁇ m to 0.2 ⁇ m.
  • the particle shape may be any of a spherical shape, a flake shape or a fiber shape synthesized by a gas phase method, and a pulverized shape obtained by pulverization in a lump shape, and is not particularly limited.
  • Li-containing oxide precursor solution in which a Li compound, which is a precursor of a Li-containing oxide, and a compound of at least one metal element M selected from Si, Al, Ti, and Zr are dispersed, Is an organic solvent, the Li compound serving as the Li source is preferably Li acetate, Li nitrate, Li chloride, etc. dissolved in the organic solvent, and the metal element M compound serving as the metal element M source is an alkoxide dissolved in the organic solvent, Nitrate, chloride and the like are preferred.
  • alkoxides those in which the metal element M is Al, Ti, or Zr are easily hydrolyzed and unstable, and thus are preferably stabilized with a chelating agent.
  • Chelating agents include, but are not limited to, ethyl acetoacetate, acetylacetone, triatanolamine, and the like.
  • organic solvent ethanol, isopropyl alcohol, ethyl acetate, toluene and the like can be used.
  • the Li source compound is preferably Li acetate dissolved in water, Li nitrate, Li chloride, or the like, and the metal element M source metal element M source is nitrate, chloride, Oxyacid salts, peroxo acids and the like are preferred.
  • the metal element M is Si, an aqueous solution of Li silicate can also be used.
  • the carbon raw material that is the matrix of the binding substance in the present invention is preferably a phenol resin, an infusible pitch, or the like that generates hard carbon by heat treatment.
  • the phenol resin may be either a resol type or a novolac type.
  • the infusibilized pitch can be obtained, for example, by heat treating a coal tar pitch in air at 200 to 600 ° C. and crosslinking the polycyclic aromatic compound in the pitch with oxygen.
  • the inorganic matrix material is preferably a sulfide or oxide powder containing a constituent element when prepared by a mechanochemical method, and an alkoxide, nitrate or chloride soluble in a solvent containing the constituent element when prepared by a sol-gel method.
  • the resin matrix material can be obtained by dissolving, in a solvent, polyamic acid obtained by polymerizing tetracarboxylic dianhydride and diamine in equimolar amounts.
  • a silicone varnish it can be obtained by dissolving a highly branched three-dimensional polymer comprising a siloxane bond having a methyl group, a phenyl group or the like in a solvent.
  • Carbon nanotubes, scale graphite, earth graphite, hard carbon, carbon black, and the like can be used as the conductive material that imparts conductivity to the binder.
  • the method for producing a negative electrode material for a Li-ion secondary battery according to the present invention includes: a Li compound that is a precursor of a Li-containing oxide; and a compound of at least one metal element M selected from Si, Al, Ti, and Zr.
  • Si particles that can be alloyed with Li are added to the dispersed solution (Li-containing oxide precursor solution), dried, and heat-treated in a temperature range of 200 to 1200 ° C., and the surface of the Li-containing oxide film is further electrically conductive. After adhering the binder material or precursor material, heat treatment is performed in a temperature range of 200 to 1200 ° C. to adjust the aggregated particles made of the coated Si particles into fine particles having a size of single micron.
  • a solution (Li-containing oxide precursor solution) in which a Li compound that is a precursor of a Li-containing oxide and a compound of at least one metal element M selected from Si, Al, Ti, and Zr is dispersed is a metal element.
  • M is Al, Ti, or Zr
  • the alkoxide of these elements is stabilized by chelating with an chelating agent: ethyl acetoacetate, acetylacetone, tritananolamine, etc. in an alcohol solvent, and rapid hydrolysis reaction is performed. It is preferable to suppress and improve the film forming property.
  • the chelated alkoxide solution further promotes hydrolysis by adding water in order to further improve the film forming property.
  • the Li compound is dissolved in a solvent and mixed with the above solution to prepare a solution in which the precursor of the Li-containing oxide is dispersed.
  • the metal element M is Si
  • the alkoxide is stable, so a chelating agent is unnecessary.
  • the Li compound is dissolved in a solvent and mixed with the above solution.
  • a solution in which the precursor of the Li-containing oxide is dispersed can be prepared.
  • Si particles that can be alloyed with Li are added to the solution containing the precursor of the Li-containing oxide.
  • the Si particles may be in the form of a dry powder or a dispersed slurry.
  • the dry powder can be obtained by dry pulverizing the raw material Si or removing the solvent after wet pulverization.
  • the dispersion slurry can be obtained by wet pulverization.
  • the mixed slurry of the Li-containing oxide precursor dispersion and the Si particles removes the solvent and forms a Li-containing oxide precursor film on the surface of the Si particles.
  • methods such as spray drying and drying under reduced pressure can be used.
  • the Li-containing oxide precursor film is preferably heat-treated at 200 to 1200 ° C. in order to accelerate curing.
  • the atmosphere during the heat treatment is preferably a non-oxidizing atmosphere, and a non-reactive gas such as Ar or a low-reactive gas such as N 2 is the main component, and the concentration of the oxidizing gas such as O 2 is more preferably 1000 ppm or less.
  • FIG. 2- (1) is an aggregated particle obtained by the above procedure, in which Si particles 20 having a coating of Li-containing oxide 30 on the surface and the conductive binder 40 on the surface of the coating are aggregated.
  • a schematic diagram of 10A is shown.
  • FIG. 2 (2) shows an aggregated particle obtained by the above-described procedure, in which Si particles 20 having a coating of the Li-containing oxide 30 on the surface and the conductive binder 40 on the surface of the coating are aggregated.
  • a schematic diagram of 10B is shown.
  • the atmosphere during the heat treatment is preferably a non-oxidizing atmosphere, and a non-reactive gas such as Ar or a low-reactive gas such as N 2 is the main component, and the concentration of the oxidizing gas such as O 2 is more preferably 1000 ppm or less.
  • the negative electrode material for Li ion secondary batteries of the present invention is used by mixing with carbon materials such as different types of graphite materials and hard carbon in order to adjust battery characteristics such as capacity, density and efficiency of the electrodes to be produced. Also good.
  • the negative electrode for Li ion secondary batteries of this invention is a negative electrode for lithium ion secondary batteries containing said negative electrode material for Li ion secondary batteries.
  • the negative electrode for a lithium ion secondary battery of the present invention is produced according to a normal method for forming a negative electrode.
  • the binder preferably has chemical and electrochemical stability with respect to the electrolyte.
  • fluorine resin powders such as polytetrafluoroethylene and polyvinylidene fluoride, resin powders such as polyethylene and polyvinyl alcohol, Carboxymethylcellulose and the like are used. These can also be used together.
  • the binder is usually 1 to 20% by mass in the total amount of the negative electrode mixture.
  • the negative electrode material for a Li ion secondary battery of the present invention is adjusted to a desired particle size by classification or the like, and mixed with a binder and a solvent to prepare a slurry negative electrode mixture. That is, the negative electrode material for the Li ion secondary battery of the present invention, a binder and a solvent such as water, isopropylpyrrolidone, N-methylpyrrolidone, dimethylformamide, and the like, using a known stirrer, mixer, kneader, kneader Use to stir and mix to prepare slurry. The slurry is applied to one or both sides of the current collector and dried to obtain a negative electrode in which the negative electrode mixture layer is uniformly and firmly bonded.
  • the film thickness of the negative electrode mixture layer is 10 to 200 ⁇ m, preferably 20 to 100 ⁇ m.
  • the shape of the current collector used for producing the negative electrode is not particularly limited, but may be a foil shape, a mesh shape, a net shape such as expanded metal, or the like.
  • the material of the current collector is preferably copper, stainless steel, nickel or the like, and the thickness of the current collector is usually 5 to 20 ⁇ m.
  • the negative electrode for Li ion secondary batteries of this invention may mix carbonaceous materials, such as graphite material and hard carbon, and electrically conductive materials, such as CNT, in the range which does not impair the objective of this invention.
  • the Li ion secondary battery of the present invention includes the above-described negative electrode for a Li ion secondary battery, a positive electrode, and a nonaqueous electrolyte, for example, laminated in the order of the negative electrode, the nonaqueous electrolyte, and the positive electrode, and is accommodated in the battery outer packaging material. It is composed by doing.
  • a separator is disposed between the negative electrode and the positive electrode.
  • the structure, shape, and form of the Li-ion secondary battery of the present invention are not particularly limited, and can be arbitrarily selected from a cylindrical shape, a square shape, a coin shape, a button shape, a laminate shape, and the like depending on the application.
  • a battery equipped with means for detecting an increase in the internal pressure of the battery and shutting off the current when an abnormality such as overcharging occurs it is preferable to use a battery equipped with means for detecting an increase in the internal pressure of the battery and shutting off the current when an abnormality such as overcharging occurs.
  • the positive electrode is formed, for example, by applying a positive electrode mixture composed of a positive electrode material, a binder, and a solvent to the surface of the current collector.
  • a positive electrode active material it is preferable to select a lithium-containing transition metal oxide capable of inserting / extracting a sufficient amount of lithium.
  • the lithium-containing transition metal oxide is a composite oxide of lithium and a transition metal, and may contain four or more elements.
  • the composite oxide may be used alone or in combination of two or more. Specifically, there are LiCoO 2 , LiNiO 2 , LiMnO 2 , LiNi 0.9 Co 0.1 O 2 , LiNi 0.5 Co 0.5 O 2 , LiFePO 4 and the like.
  • the positive electrode active material may be used alone or in combination of two or more.
  • various additives such as a conductive agent and a binder can be appropriately used.
  • the shape of the current collector is not particularly limited, but a foil shape or a mesh shape such as a mesh or expanded metal is used.
  • the material of the current collector is aluminum, stainless steel, nickel or the like, and its thickness is usually 10 to 40 ⁇ m.
  • Nonaqueous electrolyte used in Li-ion secondary battery of the present invention, an electrolyte salt used in the conventional non-aqueous electrolyte, LiPF 6, LiBF 4, LiAsF 6, LiClO 4, LiB (C 6 H 5 ), LiCl, LiBr, LiCF 3 SO 3 , LiCH 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiN (CF 3 CH 2 OSO 2 ) 2 , LiN (CF 3 CF 2 OSO 2) 2, LiN ( HCF 2 CF 2 CH 2 OSO 2) 2, LiN ((CF 3) 2 CHOSO 2) 2, LiB [ ⁇ C 6 H 3 (CF 3) 2 ⁇ ] 4, LiAlCl 4, Lithium salts such as LiSiF 6 can be used.
  • the electrolyte salt concentration in the electrolytic solution is preferably from 0.1 to 5 mol / L, more preferably from 0.5 to 3.0 mol / L.
  • the non-aqueous electrolyte may be a liquid non-aqueous electrolyte or a polymer electrolyte such as a solid electrolyte or a gel electrolyte.
  • the non-aqueous electrolyte battery is configured as a so-called Li ion secondary battery
  • the non-aqueous electrolyte battery is configured as a polymer electrolyte battery such as a polymer solid electrolyte or a polymer gel electrolyte battery.
  • Examples of the electrolyte for preparing the non-aqueous electrolyte include carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate, 1,1- or 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran 2-methyltetrahydrofuran, ⁇ -butyrolactone, 1,3-dioxolane, 4-methyl-1,3-dioxolane, ethers such as anisole and diethyl ether, thioethers such as sulfolane and methylsulfolane, acetonitrile, chloronitrile, propionitrile Nitrile such as trimethyl borate, tetramethyl silicate, nitromethane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, trimethyl orthoformate, nitrobenzene, benzoic chloride , It can be used benzoyl bromide,
  • an additive may be added to prevent the electrolytic solution from being reduced and decomposed during charging to deteriorate the battery.
  • Known additives include, but are not limited to, fluoroethylene carbonate (FEC), vinylene carbonate (VC), ethylene sulfite (ES), and the like.
  • FEC fluoroethylene carbonate
  • VC vinylene carbonate
  • ES ethylene sulfite
  • the addition amount is usually about 0.5 to 10% by mass.
  • a separator is disposed between the negative electrode and the positive electrode.
  • a separator is not specifically limited, For example, a woven fabric, a nonwoven fabric, a synthetic resin microporous film, etc. can be used.
  • a microporous membrane made of synthetic resin is suitable.
  • a polyolefin microporous membrane is preferable in terms of thickness, membrane strength, and membrane resistance. Specifically, polyethylene and polypropylene microporous membranes, or microporous membranes combining these are preferred.
  • a button type secondary battery for single electrode evaluation composed of (positive electrode) 4 was prepared and evaluated.
  • An actual battery can be produced according to a known method based on the concept of the present invention.
  • the measurement methods used in the examples are as follows.
  • Measurement method (1) Measurement of average particle diameter The average particle diameter was a particle diameter at which the cumulative frequency measured with a laser diffraction particle size meter was 50% by volume.
  • Example 1 A first solution is prepared by dissolving 0.02 mol of Al-sec butoxide and 0.02 mol of ethyl acetoacetate in an isopropanol solvent, and then an ethanol solution in which 0.002 mol of acetic acid Li dihydrate is dissolved is used as the first solution. In addition, a second solution was prepared. Next, 29 g of Si particles having an average particle size of 0.15 ⁇ m was added to the second solution, and after removing the solvent, the mixture was baked at 1000 ° C. in a non-oxidizing atmosphere of nitrogen, and Li containing Li as a metal element M and Li containing Al Si particles having an oxide coating film were obtained.
  • the above-mentioned coated Si particles were added to an aqueous solution in which a resol-type phenol resin solution (nonvolatile content: 71% by mass), which is a precursor of the conductive binder, was dissolved to prepare a slurry.
  • a resol-type phenol resin solution nonvolatile content: 71% by mass
  • the phenol resin solution / coated Si particles 1/2 mass ratio.
  • the slurry was spray-dried with a spray-drying apparatus, and then fired at 1000 ° C. in a non-oxidizing atmosphere of nitrogen to obtain a spherical dry granulated body.
  • Example 2 Spherical dry granules were obtained in the same manner as in Example 1 except that Ti-isopropoxide was used instead of Al-sec butoxide in Example 1.
  • Example 3 Spherical dry granules were obtained in the same manner as in Example 1 except that Zr-propoxide was used instead of Al-sec butoxide in Example 1.
  • Example 4 A first solution is prepared by dissolving in 0.02 mol of Si-methoxide and an isopropanol solvent, and then an ethanol solution in which 0.002 mol of Lithium acetate dihydrate is dissolved is added to the first solution and refluxed for 2 hours. A spherical dry granulated body was obtained in the same manner as in Example 1 except that it was produced.
  • Example 5 As in Example 1, except that a polyamic acid solution in which carbon black was dispersed was used as a precursor of the conductive binder of Example 1 and the heat treatment after spray drying was performed at 300 ° C. using a spray dryer. Thus, a spherical dry granulated body was obtained.
  • Example 6 A spherical dry granule was obtained in the same manner as in Example 1 except that the coating amount of the Li-containing oxide was adjusted to 7.0%.
  • Example 7 Spherical dry granulated material as in Example 1 except that the spraying conditions of the spray drying apparatus in Example 1 were adjusted so that the average spherical particle size of the obtained spherical dry granulated material was 9.5 ⁇ m. Got.
  • Example 1 A spherical dry granulated body was obtained in the same manner as in Example 1 except that Si particles having an average particle diameter of 0.15 ⁇ m that were not coated were used.
  • Example 2 A spherical dried granulated body was obtained in the same manner as in Example 1 except that the average particle size of the granulated body spray-dried with a spray drying apparatus was adjusted to 15 ⁇ m.
  • Example 3 A spherical dry granule was obtained in the same manner as in Example 5 except that a polyimide resin containing no carbon black was used as the binder.
  • the copper foil and the negative electrode mixture layer were punched into a cylindrical shape having a diameter of 15.5 mm and pressed to produce a working electrode (negative electrode) having a negative electrode mixture layer adhered to the copper foil.
  • the density of the negative electrode mixture layer was 1.65 g / cm 3 .
  • the electrolyte was prepared by dissolving LiPF 6 at a concentration of 1 mol / L in a mixed solvent of 33% by volume of ethylene carbonate (EC) and 67% by volume of methyl ethyl carbonate (MEC) to prepare a non-aqueous electrolyte.
  • the prepared non-aqueous electrolyte was impregnated into a 20 ⁇ m thick polypropylene porous separator to produce a separator impregnated with the electrolyte.
  • it can produce according to a well-known method based on the concept of this invention.
  • FIG. 2 shows a button type secondary battery as a configuration of the evaluation battery.
  • the exterior cup 1 and the exterior can 3 were sealed by interposing an insulating gasket 6 at the peripheral portion thereof and caulking both peripheral portions.
  • a copper current collector 7 a made of nickel net, a cylindrical counter electrode (positive electrode) 4 made of lithium foil, a separator 5 impregnated with an electrolytic solution, and a negative electrode mixture 2 are attached to the inside of the outer can 3 in that order.
  • a battery in which a current collector 7b made of foil is laminated.
  • the separator 5 impregnated with the electrolytic solution was sandwiched between the current collector 7b and the working electrode (negative electrode) made of the negative electrode mixture 2, and the counter electrode 4 in close contact with the current collector 7a.
  • the current collector 7b is accommodated in the exterior cup 1
  • the counter electrode 4 is accommodated in the exterior can 3
  • the exterior cup 1 and the exterior can 3 are combined, and an insulating gasket is provided at the peripheral edge between the exterior cup 1 and the exterior can 3. 6 was interposed, and both peripheral portions were caulked and sealed.
  • the Li ion secondary battery using the negative electrode material for the Li ion secondary battery of the present invention has a high Li ion conductivity because the coating film has a high Li ion conductivity, and the electrolyte solution is reduced. It can be seen that since the decomposition is suppressed, and the charge expansion of the Si particles themselves and the local charge expansion are suppressed by the single micron aggregate particles by the conductive binder, the capacity retention rate after the cycle is high.
  • the uncoated Si particles of Comparative Example 1 have poor cycle characteristics due to large decomposition of the electrolyte. In Comparative Example 2, since the average particle diameter of the aggregated particles is large, the expansion of the electrode film increases and the cycle characteristics are poor. In Comparative Example 3, since the binder material is not conductive, the resistance of electron conduction is large and the capacity is low.
  • the surface of Si particles as an active material is coated with a thin film of Li-containing oxide containing Li and other specific metal elements, which has a high Li ion conductivity and is stable.
  • a conductive binder By constraining the surface with a conductive binder and adjusting the average particle diameter of the aggregated particles of the active material to a fine particle of 0.5 to 10 ⁇ m, excessive reductive decomposition of the electrolyte by the active material during charging can be achieved.
  • a negative electrode material which can be sufficiently suppressed and can suppress charge expansion of Si particles, and thus exhibits a high discharge capacity exceeding the theoretical charge capacity of graphite and excellent cycle characteristics.
  • the Li ion secondary battery using the negative electrode material for Li ions of the present invention satisfies the recent demand for higher energy density of the battery, and is useful for downsizing and higher performance of the equipment to be mounted.
  • the negative electrode material for Li ions of the present invention can be used for high-performance Li ion secondary batteries ranging from small to large, taking advantage of its characteristics.

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PCT/JP2017/013962 2016-05-17 2017-04-03 Ｌｉイオン二次電池用負極材料、Ｌｉイオン二次電池用負極およびＬｉイオン二次電池 WO2017199606A1 (ja)

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CN108539147A (zh) * 2018-03-21 2018-09-14 同济大学 一种锂离子电池负极材料SiO@Al@C的制备方法及应用
JP2020068191A (ja) * 2017-12-27 2020-04-30 東ソー株式会社 リチウム二次電池用複合活物質およびその製造方法
CN113363445A (zh) * 2021-06-15 2021-09-07 广东凯金新能源科技股份有限公司 一种网状γ-氧化铝包覆改性石墨负极材料、其制备方法及其应用
WO2022113500A1 (ja) * 2020-11-30 2022-06-02 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用負極材料および非水電解質二次電池
WO2022163099A1 (ja) * 2021-01-29 2022-08-04 パナソニックＩｐマネジメント株式会社 活物質粒子、電気化学素子、および電気化学デバイス
WO2022168408A1 (ja) * 2021-02-03 2022-08-11 パナソニックＩｐマネジメント株式会社 活物質粒子、電気化学素子、および電気化学デバイス
WO2023162716A1 (ja) * 2022-02-28 2023-08-31 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用負極活物質および非水電解質二次電池
WO2023162689A1 (ja) * 2022-02-28 2023-08-31 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用負極活物質および非水電解質二次電池
WO2023175731A1 (ja) * 2022-03-15 2023-09-21 株式会社 東芝 電極、電池、及び電池パック

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WO2023162716A1 (ja) * 2022-02-28 2023-08-31 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用負極活物質および非水電解質二次電池
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