WO2006025600A1 - Procédé de maintien de composition de matériau d’électrode positive pour batterie secondaire au lithium - Google Patents

Procédé de maintien de composition de matériau d’électrode positive pour batterie secondaire au lithium Download PDF

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Publication number
WO2006025600A1
WO2006025600A1 PCT/JP2005/016466 JP2005016466W WO2006025600A1 WO 2006025600 A1 WO2006025600 A1 WO 2006025600A1 JP 2005016466 W JP2005016466 W JP 2005016466W WO 2006025600 A1 WO2006025600 A1 WO 2006025600A1
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Prior art keywords
positive electrode
electrode material
material composition
polymer
composition
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PCT/JP2005/016466
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English (en)
Japanese (ja)
Inventor
Alan Vallee
Paul-Andre Lavoie
Kazuhiko Murata
Fumihide Tamura
Hiromoto Katsuyama
Taketo Toba
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Nippon Shokubai Co., Ltd.
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Priority to JP2006532025A priority Critical patent/JPWO2006025600A1/ja
Publication of WO2006025600A1 publication Critical patent/WO2006025600A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/58—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method of storing a positive electrode material composition used for producing a lithium secondary battery. Specifically, when transporting and storing the positive electrode material composition for a lithium secondary battery, the positive electrode material composition such that the battery performance of the lithium secondary battery produced by the positive electrode material composition is not deteriorated. On how to save Ming background technology
  • the positive electrode used in the lithium secondary battery includes: a polymer as a matrix, an electrolyte salt for transporting ions, an electrode active material for storing ions, a conductive aid, and a solvent, if necessary.
  • a polymer as a matrix an electrolyte salt for transporting ions
  • an electrode active material for storing ions a conductive aid
  • a solvent if necessary.
  • it is generally manufactured using a composition obtained by kneading as a material, and so far, various batteries using a positive electrode formed using such a composition as a material have been proposed (for example, a patent) Reference 1 to 4).
  • the positive electrode is produced by extruding the composition as described above, or by casting it by solution casting and devolatizing the solvent.
  • Patent Document 1 Special Table 2 0 0 2-5 3 5 2 3 5
  • Patent Document 2 US Patent No. 5 7 5 5 9 8 5
  • Patent Document 3 International Publication No. 0 3 Z 7 5 3 7 5 Breadlet
  • Patent Document 4 International Publication No. 0 3 Z 9 2 0 1 7 Pamphlet Abstract of the Invention Problems to be Solved by the Invention
  • one or all of the electrolyte salt, the electrode active material and the conductive additive are mixed (kneaded) in a polymer in advance.
  • the battery performance is significantly inferior to the case where a battery is manufactured using a positive electrode obtained by individually procuring each raw material and mixing (kneading) immediately before molding.
  • Such problems usually occur when a polymer as a matrix is previously mixed (kneaded) with other raw materials and stored for a certain period before being used for molding for transportation or storage.
  • the problem to be solved by the present invention is that, in transporting and storing the positive electrode material composition, the battery performance of the lithium secondary battery using the positive electrode produced by the positive electrode material composition is not deteriorated.
  • An object of the present invention is to provide a method of storing a positive electrode material composition for a lithium secondary battery, which can store the positive electrode material composition. Means to solve the problem
  • the present inventors diligently studied to solve the above-mentioned problems.
  • the molecular weight of the polymer serving as the matrix tends to slightly decrease in the coexistence of the electrode active material and the conductive aid, and it is a minor level that does not cause any problems in applications other than such applications of the positive electrode material.
  • the decrease in molecular weight of the polymer has a significant adverse effect on cell performance in the positive electrode material for lithium secondary batteries.
  • the degree of molecular weight reduction of the polymer is acceptable so long as the battery performance is not adversely affected.
  • the first method for storing a positive electrode material composition for a lithium secondary battery according to the present invention is a method for storing a positive electrode material composition that essentially includes a polymer, an electrode active material and a conductive additive, Mw weight average molecular weight of the polymer in the previous composition.
  • Mw weight average molecular weight of the polymer in the composition when stored for 18 days
  • D Mw reduction rate of the weight average molecular weight represented by the following formula (1) is 10% or less It is characterized by
  • a second method of storing a positive electrode material composition for a lithium secondary battery according to the present invention is a method of storing a positive electrode material composition that essentially includes a polymer, an electrode active material, and a conductive additive, and includes an inert gas atmosphere. It is characterized in that temperature control is performed to 5 or less under an atmosphere.
  • a third method of storing a positive electrode material composition for a lithium secondary battery according to the present invention is a method of storing a positive electrode material composition that essentially includes a polymer, an electrode active material, and a conductive support agent, and is performed under an air atmosphere. Temperature control to 5 ° C or less. Effect of the invention
  • the decrease in molecular weight of the polymer in the positive electrode material composition is suppressed at the time of transportation, storage and the like, and the positive electrode manufactured by the positive electrode material composition.
  • the battery performance of the lithium secondary battery can be prevented from being degraded.
  • the storage method according to the present invention the method for storing the positive electrode material composition for a lithium secondary battery according to the present invention (hereinafter sometimes referred to as “the storage method according to the present invention”) will be described in detail.
  • the present invention is not bound to be clear, and modifications can be made as appropriate without departing from the spirit of the present invention other than the following examples.
  • the positive electrode material composition for a lithium secondary battery to be stored in the storage method of the present invention is a composition essentially comprising a polymer, an electrode active material and a conductive auxiliary.
  • the polymer which is an essential component of the positive electrode material composition is not particularly limited as long as it is usually used as a matrix of a positive electrode material for a lithium secondary battery, and is an ion conductive polyether polymer. Is preferred.
  • the polymer is an ethylene oxide-based polymer in that the battery performance as a positive electrode material can be further improved.
  • the ethylene oxide-based polymer suitable as the polymer is, for example, ethylene oxide. Structural formula below (1)
  • R a (where R a represents a carbon number of 1 to 16, any of alkyl group, cycloalkyl group, aryl group, aralkyl group, (meth) ataryloyl group and alkenyl group) Or a single CH 2 — O— R e — R a group (where R e is a single (CH 2 — CH 2 — 0) p — structure (p is an integer from 0 to 10)) It can be obtained by polymerizing a mixture of monomers essentially comprising the substituted oxylan compound shown in the above).
  • the monomer mixture may contain other monomers in addition to ethylene oxide and the substituted alkoxy compound.
  • the proportion of each monomer in the monomer mixture is not particularly limited and may be set appropriately.
  • Examples of the substituted oxylan compound represented by the above structural formula (1) include propylene oxide, butylene oxide, 1,2- epoxypentane, 1,2-epoxyhexane, 1,2-epoxyoctane, cyclohexoxide and styrene oxide. Or methyl glycidyl ether, cetyl dalysidyl ether, ethylene glycol methyl glycidyl ether and the like.
  • the substituent is a crosslinkable substituent, for example, epoxy butene, 3, 4-epoxy 1 1-pentene, 1, 2-epoxy 1, 5 9-cyclododecadiene, 3, 4- Epoxy, 1-butyl cyclohexene, 1, 2-epoxy, 5-cyclo-Otene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate and glycidyl 1 ⁇ xanoate or or buli glycidyl ether, aryl Glycidyl ether, 4-vinylcyclohexyl glycidyl ether, a -terpenyl glycidyl ether, cyclohexenyl methyl dalysyl ether, 4-vinylbenzyl glycidyl ether, 4-arylbenzyl glycidyl ether.
  • a crosslinkable substituent for example, epoxy butene, 3, 4-
  • Sylkyl ether ethylene glycol palyl glycidyl ether, ethylene glycol vinyl glycidyl ether, diethylene glycol palyl glycidyl ether, diethylene glycol vinyl dalysyl ether, triethylene glycol palyl glycidyl ether, triethylene glycol vinyl dalysyl ether, oligo Examples thereof include ethylene glycol glycidyl ether and oligoethylene glycalyl vinyl dalysyl ether.
  • the number of substituted oxylan compounds may be one or two or more.
  • the monomer mixture may be polymerized while stirring in a solvent.
  • the method for such polymerization is not particularly limited, but preferred examples include a solution polymerization method and a precipitation polymerization method. Among them, the solution polymerization method is more preferable because it has excellent productivity.
  • a solution polymerization method in which polymerization is performed while supplying each monomer as a raw material to a previously charged solvent is particularly preferable because of safety such as easy removal of heat of reaction.
  • a commonly used polymerization initiator, an antioxidant (for example, a general-purpose phenol-based antioxidant etc.), a solubilizer, etc. may be added. ,.
  • the solvent examples include aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene; and aliphatic hydrocarbons such as heptane, octane, n-hexane, n-pentane and 2, 2, 4-trimethylpentane.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene
  • aliphatic hydrocarbons such as heptane, octane, n-hexane, n-pentane and 2, 2, 4-trimethylpentane.
  • Solvents Alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; Ether solvents such as jetyl ether, dibutyl ether and methyl butyl ether; Solvents for ethylene diallyl dialkyl ethers such as dimethoxetane; THF Organic solvents which do not contain active hydrogen such as hydroxyl groups such as cyclic ether solvents such as (tetrahydrofuran) and dioxan are preferable, and toluene, xylene and n-hexane are more preferable.
  • the solvent is an organic solvent which does not contain water at all, but the problem is that the hydroxide formed by the reaction of water and metal ions etc. becomes an insulating layer and the cycle characteristics of the battery are deteriorated. It is preferable to avoid it.
  • the weight average molecular weight (Mw) of the polymer is not particularly limited, but is preferably 2 0 0 0 5-5 0 0 0 0 0, more preferably 3 0 0 0 0 3 0 0 , 0 0 0, and more preferably 4 0, 0 0 0 to 2 0 0, 0 0 0. If the weight average molecular weight is less than 20, 00, there is a risk that tack will occur when forming into a positive electrode, while if it exceeds 500, the forming itself becomes difficult, Processability and handling may be reduced.
  • the molecular weight distribution (MwZMn) of the polymer is not particularly limited, but is preferably 3 or less, more preferably 2 or less. When the molecular weight distribution is more than 3, there is a risk that tackiness may occur during molding to form a positive electrode, or poor and indling properties may deteriorate.
  • the electrode active material which is an essential component of the positive electrode material composition, has an electrochemical effect on the insertion and desorption of Li ions, and is generally used to form a positive electrode.
  • the electrode active material may be only one type, or two or more types.
  • the proportion of the electrode active material in the positive electrode material composition is not particularly limited, but is preferably, for example, 0.1 to 50 times by weight the polymer, and more preferably 0.3 to 2 times. It is preferable that it is 0 times, more preferably 0.5 to 10 times. If the amount of the electrode active material is too small, the function as the positive electrode may not be sufficiently exhibited. On the other hand, if the amount of the electrode active material is too large, molding may be difficult.
  • the conductive auxiliary agent which is an essential component of the positive electrode material composition, is not particularly limited as long as it is generally used to form a positive electrode, and examples thereof include acetylene black, ketjen black, Graphite, etc. Can be mentioned.
  • the conductivity assistant may be only one kind or two or more kinds.
  • the proportion of the conductive auxiliary agent in the positive electrode material composition is not particularly limited, but is preferably 1 to 20 parts by weight, more preferably 2 parts by weight with respect to 100 parts by weight of the electrode active material, for example. It should be about 15 parts by weight. If the amount of the conductive additive is too small, the conductivity of the positive electrode may be insufficient. If the amount of the conductive additive is too large, molding may be difficult.
  • the positive electrode material composition preferably also contains an electrolyte salt required to form a positive electrode.
  • the electrolyte salt is not particularly limited as long as it is usually used to form a positive electrode, and examples thereof include, but are not limited to, for example, fluorine ion, chloride ion, bromine ion, iodine ion, heptafluoropropyl Sulfonate ion, bis (trifluoromethanesulfonyl) imide ion, bis (heptafluoropropione les / lephoni imidate ion, trifnoleoporte sulfonate ion, tetrafluoroboronate ion, nitrate ion, As s F 6- , PF 6- , stearyl sulfonate ion, octyl sulfonate ion, dodecyl benzene sulfonate ion
  • L i BF 4, L i PF 6, L i CF 3 S 0 3, L i C 4 F 9 S_ ⁇ 3, L i N (CF 3 S 0 2) 2 , L i N (C 2 F 6 S 0 2 ) 2 is more preferable
  • the number of electrolyte salts may be only one, and may be two or more.
  • the proportion is not particularly limited, but for example, when the polymer is a polyether polymer, the total number of moles of ether oxygen in the polyether polymer and the value of the number of moles of the electrolyte salt are 1 to 36. It is preferable that the ratio be 3 to 3, more preferably 6 to 3.
  • the amount of the electrolyte salt is too small, the ion conductivity may be reduced, On the other hand, even if the amount of electrolyte salt is too large, the effect of improving ion conductivity corresponding to the amount of electrolyte salt does not appear, which is economically disadvantageous. It is
  • the positive electrode material composition may contain a solvent.
  • the solvent is one that is finally removed by means such as degassing when molded into a positive electrode, but by including the solvent in the composition, the polymer such as the electrolyte salt etc. can be obtained.
  • the components that are difficult to dissolve can be dissolved in a solvent to facilitate mixing of the components, or the viscosity can be adjusted so that they can be easily handled during transport and storage.
  • the solvent is not particularly limited, and can be used, for example, when obtaining the above-mentioned ethylene oxide polymer. .
  • the proportion of the solvent in the positive electrode material composition is not particularly limited, and may be set as appropriate.
  • the polymerization reaction solution contains the solvent, so the polymerization reaction solution is used as it is for the positive electrode material. It may be mixed as a component of the composition, or after the solvent is once removed from the polymerization reaction solution, another solvent may be added as a component of the positive electrode material composition.
  • the positive electrode material composition further comprises, if necessary, for example, an antioxidant, a light stabilizer, a lubricant, an antistatic agent, a reinforcing agent, a filler, an antioxidant (for example, a general-purpose phenol-based antioxidant etc.), etc.
  • the additive may be suitably contained in the range which does not impair the effect of the present invention.
  • the positive electrode material composition may contain, for example, a component contained in a polymerization reaction solution obtained by polymerization when obtaining the polymer.
  • the positive electrode material composition to be stored in the storage method of the present invention is, for example, a solution, a slurry, a solution, particles, pellets, fine particles, a desired shape (a size larger than particles or pellets).
  • the polymer, the electrode active material and the conductive auxiliary agent may be mixed or kneaded, if necessary, to volatilize, granulate, dry, adjust, etc. It is obtained by applying moisture and the like. From the viewpoint of ease of handling, etc., the solidified material obtained by mixing or kneading each component and removing the solvent by devolatilization (particulate, pellet, fine particles, lump of desired shape, etc.
  • the water content in the positive electrode material composition is to avoid the problem that the hydroxide layer formed by the reaction of water and metal ion becomes an insulating layer and the cycle characteristics of the battery are deteriorated.
  • the lower one is preferable, and from this point of view, the composition obtained through at least one of devolatilization, drying and humidity control is said to be preferable.
  • the method of devolatilization For the method of mixing or kneading the above-described components that essentially contain the polymer, the electrode active material, and the conductive auxiliary agent, the method of devolatilization, the method of granulation, the method of drying, the method of humidity control, etc. A conventionally known method may be adopted as appropriate.
  • the weight average molecular weight of the polymer in the positive electrode material composition is Mw.
  • the reduction rate (D Mw ) of the weight average molecular weight represented by the following formula (1) is 10% or less It is characterized by Preferably, the reduction rate (D Mw ) when stored for 18 days is 5% or less.
  • the reduction rate (D Mw ) is 10% or less
  • a positive electrode material is prepared, and lithium is produced using the positive electrode material. Even when a secondary battery is manufactured, good battery performance can be exhibited.
  • the reduction rate (D Mw ) it is preferable to adopt the second or third storage method of the present invention described later.
  • the storage method in which the inert gas in the second storage method of the present invention described later is replaced with dry air having a dew point of 40 ° C. or less, preferably 50 ° C. or less is preferable.
  • the reduction rate (D Mw ) when stored for 18 days as described above is 10%.
  • the reduction rate of the molecular weight when stored for 3 days (when the weight average molecular weight of the polymer in the composition when stored for 3 days is Mw, it is represented by the above formula (1)
  • the weight-average molecular weight reduction rate is preferably 10% or less, preferably 5% or less.
  • the positive electrode material composition is stored in a space filled with an inert gas and temperature-controlled to 50 ° C. or less.
  • the space filled with the inert gas ie, the inert gas atmosphere
  • the composition is stored.
  • the space is filled with an inert gas such that the oxygen concentration in the space to be reduced is 15 V o 1% or less, more preferably 10 V o 1% or less, and even more preferably 7 V o 1% or less.
  • the flow rate, time, and the like at the time of filling the inert gas may be appropriately set so that the oxygen concentration in the space falls within the above range, in consideration of the size of the space and the like.
  • a mixed gas of an inert gas and air may be filled so that the oxygen concentration in the space falls within the above range.
  • the inert gas is not particularly limited, and examples thereof include nitrogen gas, argon gas, and helium gas.
  • the inert gas may be only one kind or two or more kinds.
  • the positive electrode material composition is stored in a space filled with air and temperature-controlled to 5 ° C. or less.
  • the air filled in the space for storing the positive electrode material composition may be dry air having a low dew point (for example, a dew point of 40 ° C. or less) or normal air (a dew point is not high yet). It may be dry air). That is, if the temperature exceeds 5 ° C. (for example, room temperature), as described above, the space for storing the positive electrode material composition by filling with an inert gas or the following dry air with a dew point of 140 or the like.
  • the positive electrode material composition may be stored as it is, for example, in an apparatus used for preparing a composition such as mixing, kneading, devolatilization, drying, conditioning, granulation, etc.
  • the container or bag may be filled and stored, and the storage form is not limited, but in the first storage method, the inert gas atmosphere, ie, the space filled with the inert gas is maintained It is preferable to store in a sealed device, container, bag, etc.
  • a device in the case of storage with a device, it may be stored in a batch type storage device such as a hopper or silo, and in the case of storage in a container, it may be stored in a metal drum or container, etc.
  • a metal drum or container if you do, you may use an aluminum foil bag or a multilayer film bag containing an aluminum foil layer (in particular, in consideration of heat sealability, a bag made by laminating aluminum foil on resin film such as polyethylene or polypropylene) It is good if it preserve
  • the positive electrode material composition is a solidified material
  • the solidified materials adhere to each other and not form a lump, even if a plurality of such materials are stored.
  • the solidified material is not in the form of a solution or paste, but is, for example, in the form of particles, pellets, or lumps of a desired form.
  • a plurality of positive electrode material compositions which are in a solidified state are usually stored in a single container, bag or the like, in which case the solidified bodies adhere to each other to form a lump (so-called blocking) Easily).
  • the melting point of the composition is lowered compared to the case where the composition does not contain an electrolyte salt. It becomes easy to become.
  • the positive electrode material composition is in a so-called blocking state, the deflection when supplying the composition from the feeder 1 to the extruder becomes large when it is molded to produce a positive electrode, and stable feeding can not be performed, and molding is performed. The problem arises that the dimensions and the like of the subsequent molded product are not uniform. In order to make the solidified products of the composition adhere to each other and not form a lump, it is preferable that fine particles are added during storage.
  • the fine particles were attached to the surface of the positive electrode material composition which is a solidified product by adding and mixing it in a space (apparatus, container, bag, etc.) for storing the fine particles together with the solidified positive electrode material composition. If it is stored as a state, or when a positive electrode material composition which is a solidified product is obtained, fine particles are also added together with the above-mentioned components so as to be stored as a state in which fine particles are contained inside the positive electrode material composition. do it.
  • the fine particles are not particularly limited as long as the specific surface area of the particles is 10 m 2 / g or more in nitrogen adsorption specific surface area (BET method).
  • the specific surface area of the fine particles is a nitrogen adsorption specific surface area (BET method), preferably 2 O m 2 g or more, more preferably 40 m 2 / g or more, and further preferably 10 O n ⁇ Z g It is good that it is above. If the specific surface area of the fine particles is less than 10 m 2 Z g in nitrogen adsorption ratio surface area (BET method), the adhesion preventing effect of the solidified positive electrode material compositions is reduced, so the effect is sufficient. However, if the amount of the fine particles added is increased excessively, the battery characteristics will be impaired.
  • the fine particles for example, silica particles, carbon particles, alumina particles, titanium particles, magnesia particles and the like can be used. Among them, it is particularly preferable to use a silica particle from the viewpoint of having the least electrical influence and easy dissolution uniformly in the positive electrode material composition.
  • the silica particles are not particularly limited, but those having a particle diameter of less than 60 / im are preferable.
  • the silica particles are preferably hydrophobic, and for example, “Aerosil R 9 2 2” or “Aerosil R 9 7 4” manufactured by Nippon Aerosil Co., Ltd. is preferably used as a commercial product.
  • the addition amount of the fine particles is not particularly limited, for example, it is preferable to be 0.1 to 1% by weight with respect to the positive electrode material composition.
  • the positive electrode material composition stored by the storage method of the present invention may be formed according to the usual method after blending the components required for the positive electrode material as necessary, for example, including it if it does not contain an electrolyte salt. Can be used as the positive electrode.
  • the lithium battery produced by the usual method using the positive electrode obtained in this manner can be used in various batteries such as short test, cycle characteristics, etc. Example that becomes excellent in performance
  • the molecular weight reduction rate in the comparative example is Mw the initial weight average molecular weight of the polymer in the positive electrode material composition before storage.
  • the weight-average molecular weight of the polymer in the composition after storage is M w, which is calculated based on the following formula.
  • the weight average molecular weight of the polymer in the positive electrode material composition was measured as follows. That is, acetonitrile is added to the composition to make a 1% solution, and after sufficiently stirring with a Tutch mixer and shaker to dissolve the polymer component, the insoluble matter is filtered by a filter (non-aqueous system, 0.45 ⁇ ). The resulting filtrate is diluted with an eluent (acetonitrile / water-water-sodium borate mixture solution) to give a sample, and a GPC apparatus (Tosoh “HCL_8120GPC”) is used as a sample, and a standard molecular weight sample of polyethylene oxide. It calculated
  • this reactor After replacing the air in a 100 L reactor (this reactor is called “Reactor A”) equipped with Max Blend wings, a hot water jacket, and an addition port with nitrogen gas, the hot water jacket temperature is raised to 70 ° C.
  • Polymer Ethylene butylene butylene oxide copolymer: weight average molecular weight (Mw) 124, 000, molecular weight distribution (MwZMn) 1 which had been warmed and kept at 80 ° C. in advance. 33. 30 parts of a solution of 45) in toluene (solid content 45.8%) was added.
  • Li 3 N (CF 3 S 0 2 ) 2 lithium bis (trifluoromethanesulfone) imide
  • Reactor B this reactor is referred to as “Reactor B”) equipped with a stirring blade (“Super blend wing”, Sumitomo Heavy Industries, Ltd.), a warm water jacket, and an addition port.
  • the reactor is replaced with nitrogen, and then, in the reactor, 0.50 076 parts of a phenol-based antioxidant (“Cysnox BB” manufactured by AP Corporation, 30 parts of toluene, and a mixture of an electrode active material and a conductive aid (“L um oxide / carbonblend "(US AVE S TOR LLC) 31. 68 parts were introduced one by one. After that, the residue remaining in the hopper and piping etc.
  • the piping of the reactor A is made via the piping previously attached to connect the reactor A and the reactor B.
  • Contents (mixed solution of polymer and lithium salt) 42. 58 parts are charged into reactor B, then heated with a water jacket and stirred at 50 for 2 hours to obtain a uniform slurry solution did.
  • BT_30-S 2 manufactured by BLASTIC INSTRUMENT RESEARCH INSTITUTE
  • the above reactor via a gear pump at a biaxial rotation speed of 100 rpm and an internal temperature of 100 ° C.
  • the slurry solution was fed, and degassing was applied under a reduced pressure of 349 Torr, and the solvent (toluene) was distilled off. Then, the rod-like body extruded from the outlet of the twin-screw extruder is formed into a sheet of 2 mm in thickness using a rolling two-roll ("8 x 20 BOX type roll machine" manufactured by Kansai Roll Co., Ltd.). The sheet was placed in a nitrogen-replaced bag, heat sealed, and stored in a refrigerator at 10 ° C. or less overnight. Next, the sheet material cooled to 9 ° C.
  • a phenol-based antioxidant (“Y-Sinox BB” manufactured by AP Corporation) was charged into the reactor. After that, connect a pressure reduction line to the reactor, and apply a pressure reduction of 60 to 69 Torr at 47 to 49 ° C while stirring with inner blade rotation 75 rpm and outer blade rotation 29 rpm to distill off toluene. The mixture was de-pressurized with nitrogen to form a slurry solution having a solid content of about 64. 4%.
  • the melt extruded from the outlet of the KRC kneader is sent to the strand die (2 mm in diameter, 2 holes) via a gear pump, The mixture was extruded into a stream to obtain a 3 mm-diameter string.
  • the string-like material is first placed on a belt conveyor ("San Ye concha SJ Y_15-200" manufactured by Sanei Mfg. Co., Ltd.) installed under a nitrogen stream at room temperature, allowed to cool, and then surfaced under a nitrogen stream. It was placed on a single-belt crater at a temperature of 10 ° C. (“Steel-belt single cooler” manufactured by Nippon Steel Conveyor Co., Ltd.) and cooled, and then allowed to stand overnight under nitrogen flow for drying.
  • the obtained string was cut into a round pellet having a length of about 3.65 mm using a strand cutter ("SFC-100” manufactured by Izu Chemical Co., Ltd.).
  • the pellet is placed in a conical dryer ("vacuum tumble dryer” manufactured by Nissan Kogyo Co., Ltd.)
  • a sealable container (volume 30 OmL) equipped with a thermometer, a gas inlet and a valve outlet, and a lid, close the lid, and open the gas inlet and outlet valves.
  • nitrogen gas is introduced into the vessel from the inlet at a flow rate of 1 O OmL Z minutes for 3.5 minutes to replace the air in the vessel with nitrogen gas, and then the gas outlet valve is closed immediately and the inlet valve is closed. Closed and sealed the container.
  • the container was placed in a thermostat so as to maintain the temperature in the container at 25 ⁇ 5 ° C. (room temperature), and stored for 18 days.
  • the composition in the container was immediately analyzed by a GPC apparatus which prepared a calibration curve using a standard molecular weight sample of polyethylene oxide, and the weight average molecular weight of the polymer in the composition was measured to be 122,000. There was a molecular weight reduction rate of 1.6% with respect to the initial weight average molecular weight of 14,000 of the polymer in the positive electrode material composition (A).
  • Example 1 2 The positive electrode material composition (A) was stored in the same manner as in Example 1-1 except that nitrogen gas was changed to argon gas. Thereafter, in the same manner as in Example 1-1, the composition in the container was immediately analyzed, and the weight average molecular weight of the polymer in the composition was measured to be 123,000, indicating that the positive electrode material composition (A) The molecular weight reduction rate was 0.8% with respect to the initial weight-average molecular weight of 124,000 of the polymer contained therein.
  • the positive electrode material composition (A) Place the positive electrode material composition (A) in a sealable container (volume 30 OmL) equipped with a thermometer and a lid, close the lid, and close the container without replacing the inside of the container with nitrogen gas (at this time,
  • the water content of the air in the container was about 6000 ppm) and the container was placed in a thermostat so as to maintain the temperature in the container at 25 ⁇ 5 ° C. (room temperature), and stored for 18 days.
  • the composition in the container was immediately analyzed, and the weight average molecular weight of the polymer in the composition was measured in the same manner as in Example 11 and found to be 111,000, and the positive electrode material composition (A).
  • the molecular weight reduction rate to the initial weight average molecular weight 124,000 of the polymer contained was 10.5%.
  • the positive electrode material composition (B) placed in a sealable container (volume 30 OmL) equipped with a thermometer, a gas inlet with a valve and a gas outlet, and a lid, close the lid, and open the valves for the gas inlet and outlet.
  • nitrogen gas is introduced into the vessel from the inlet at a flow rate of 1 O OmL Z minutes for 3.5 minutes to replace the air in the vessel with nitrogen gas, and then the gas outlet valve is closed immediately and then the inlet Closed the container and sealed the container.
  • the container was placed in a thermostat so as to maintain the temperature in the container at 25 ⁇ 5 ° C. (room temperature), and stored for 18 B.
  • Example 1-1 Thereafter, in the same manner as in Example 1-1, the composition in the container was immediately analyzed, and the weight average molecular weight of the polymer in the composition was measured, to be 119,000.
  • Cathode Material Composition (B) The molecular weight reduction rate with respect to the initial weight average molecular weight of 124,000 of the polymer in was 4.0%.
  • the weight average molecular weight of the polymer in the composition when stored for 3 days was measured to be 123,000, and the percentage reduction in molecular weight relative to the initial weight average molecular weight 124,000 of the polymer in the positive electrode material composition (B) was 0.8%.
  • the positive electrode material composition (B) was stored in the same manner as in Example 1-3 except that nitrogen gas was changed to argon gas. Thereafter, in the same manner as in Example 11, the composition in the container was immediately analyzed, and the weight average molecular weight of the polymer in the composition was measured, and it was 123,000, and the positive electrode material composition (B) The molecular weight reduction rate was 0.8% with respect to the initial weight-average molecular weight of 124,000 of the polymer contained therein.
  • the weight average molecular weight of the polymer in the composition when stored for 3 days and 16 days was measured, it was 124,000 in each case, and the initial weight of the polymer in the positive electrode material composition (B) was measured.
  • the rate of decrease in molecular weight relative to the average molecular weight of 124,000 was all at 0. 0%.
  • the positive electrode material composition (B) Place the positive electrode material composition (B) in a sealable container (volume 300 mL) equipped with a thermometer and a lid, close the lid, and immediately seal the container without replacing the inside of the container with nitrogen gas (at this time, The water content of the air in the container was about 6000 ppm), the container was placed in a thermostat so that the temperature in the container was maintained at 25 ⁇ 5 ° C. (room temperature), and stored for 16. days did. Thereafter, in the same manner as in Example 11, the composition in the container was immediately analyzed, and the weight average molecular weight of the polymer in the composition was measured to be 98,000. In the positive electrode material composition (B) The molecular weight reduction rate was 21.0% relative to the initial weight average molecular weight of 124,000 of the polymer.
  • the positive electrode material composition (B) was stored in the same manner as Comparative Example 1-2 except that the storage period was changed from 16 days to 9 days. Thereafter, the composition in the container was immediately analyzed in the same manner as in Example 1-1, and the weight average molecular weight of the polymer in the composition was measured to be 104,000, and it was found in the positive electrode material composition (B). The rate of decrease in molecular weight relative to the initial weight average molecular weight of 124,000 of the polymer was 16.1%.
  • the positive electrode material composition (A) was stored in the same manner as in Example 11 except that nitrogen gas was changed to dry air with a dew point of 50 ° C. (content of water content: 39 ppm). Thereafter, in the same manner as in Example 11, the composition in the container was immediately analyzed, and the weight average molecular weight of the polymer in the composition was measured, to be 118, 000, and the positive electrode material composition (A) The molecular weight reduction rate was 4.8% with respect to the initial weight-average molecular weight of 124,000 of the polymer contained therein.
  • the positive electrode material composition (A) is placed in a sealable container (volume 300 mL) equipped with a thermometer and a lid and the lid is closed, and the container is closed (at this time, the amount of ice contained in the container is about ice) 3000
  • the container was put in a thermostat so that the temperature in the container was maintained at 0 to 5 ° C., and stored for 18 days. Thereafter, in the same manner as in Example 11, the composition in the container was immediately analyzed, and the weight average molecular weight of the polymer in the composition was measured, and it was 123,000. The molecular weight reduction rate was 0.8% with respect to the initial weight average molecular weight of 124,000 of the polymer in.
  • Example 1_1 Thereafter, in the same manner as in Example 1_1, the composition in the container was immediately analyzed, and the weight average molecular weight of the polymer in the composition was measured to be 122,000.
  • the polymer in the positive electrode material composition (A) The molecular weight reduction rate to an initial weight average molecular weight of 120,000 was 1.6%.
  • the positive electrode material composition (B) is placed in a sealable container (volume 300 mL) equipped with a thermometer and a lid, the lid is closed, and the container is closed (at this time, the moisture content of the air in the container is about
  • the container was placed in a thermostat so that the temperature in the container was maintained at 0-5 ° C., and stored for 18 days. Thereafter, the composition in the container was immediately analyzed and the weight average molecular weight of the polymer in the composition was measured in the same manner as in Example 11 and found to be 118, 000.
  • the positive electrode material composition (B) The decrease in molecular weight was 4.8% relative to the initial weight-average molecular weight of 124,00 ° of the polymer contained therein.
  • the positive electrode material compositions lightly adhere to each other and maintain the shape as they were in the container, but when lightly adhere, they easily separate.
  • the positive electrode material composition adheres firmly to each other and maintains its shape as it was in the container, and it does not easily come apart even if it slightly sticks
  • a sealable container volume 300 mm
  • the lid closed and with the gas inlet and outlet valves open, introduce nitrogen gas into the vessel from the inlet at a flow rate of 1 OO m LZ minutes for 3.5 minutes to make the air in the vessel nitrogen
  • the gas outlet valve was closed and the inlet valve was closed to seal the vessel.
  • the container was placed in a thermostat so that the temperature in the container was maintained at 40 ° C., and stored for 18 days.
  • Example 1_1 the composition in the container was immediately analyzed in the same manner as in Example 1_1, and the weight average molecular weight of the polymer in the composition was measured to be 1 18, 00, and the composition of the positive electrode material was The molecular weight reduction rate with respect to the initial weight average molecular weight 1 2 4 0 0 0 0 of the polymer in substance ( ⁇ ') was 4 8%.
  • Example 3-1 In the same manner as in Example 3-1, a mixture of positive electrode material composition ( ⁇ ') particles and silica particles was obtained.
  • Example 3-1 In the sealable glove box, put together with the above-mentioned mixture, a balance, a cylindrical container, a plastic bag with a chuck, a weight, etc. necessary for the subsequent operation, and adjust the temperature in a thermostat at 20 ° C.
  • the same procedure as in Example 3-1 was performed except that the battery was placed in a constant temperature bath at 0 ° C. and stored for 9 days, and the positive electrode material composition ( ⁇ ') was stored. Thereafter, in the same manner as in Example 3-1, the state of blocking was evaluated. The result was ⁇ .
  • the close the lid put, 3 nitrogen gas into the container from the conductor inlet in a state of spaced valve of the gas inlet and outlet flow rate 1 0 0 m L / / min. introduced in the container 5 minutes
  • the gas outlet valve was closed and the inlet valve was closed to seal the container.
  • the container was placed in a thermostat so that the temperature in the container was maintained at 20 ° C., and stored for 18 days.
  • composition (A The molecular weight reduction rate to the initial weight average molecular weight of 1,204, 0 0 0 of the polymer in b) was 1.6%.
  • Example 3-1 In the same manner as in Example 3-1, a mixture of positive electrode material composition ( ⁇ ') particles and silica particles was obtained.
  • the items required for the subsequent operation such as Tendon, cylindrical container, plastic bag with chuck, weight, etc. From this point on, carry out the operation of circulating nitrogen gas in the glove box. Do not do this (at this time, the amount of moisture contained in the air in the glove box was about 100 ppm), and the temperature in 0 to 5 ° C and the temperature in 0 to 5 ° C.
  • the same procedure as in Example 3-1 was carried out except that the inside was changed to storage for 9 days, and the state of blocking was evaluated. The result was ⁇ .
  • the mixture of the positive electrode material composition ( ⁇ ′) particles and the silica particles described above is put into a sealable container (volume 300 mm) equipped with a thermometer and a lid, the lid is closed, and the container is sealed. After that (at this time, the moisture content of the air in the container was about 100 ppm), the container was placed in a thermostat so that the temperature in the container was maintained at 0 to 5 ° C. It was stored for 18 days. Thereafter, the composition in the container was immediately analyzed in the same manner as in Example 1-1, and the weight average molecular weight of the polymer in the composition was measured. The molecular weight reduction rate with respect to the initial weight average molecular weight of the polymer in the substance ( ⁇ ') was 1024%.
  • the positive electrode material composition ( ⁇ ′) 68.5 g) was changed to weighing), and that the temperature was controlled in a constant temperature bath at 23.degree. C., and it was put in a constant temperature bath at 23.degree. C. and stored for eight days.
  • the state of blocking was evaluated in the same manner as in 3-1. The result was X.
  • Example 3-4 the positive electrode was prepared in the same manner as in Example 3-4, except that the temperature was controlled in a thermostat of 13.degree. C., and then stored in a thermostat of 13.degree. C. for 8 days.
  • the material composition ( ⁇ ') was saved. Thereafter, in the same manner as in Example 3-1, the state of blocking was evaluated. The result was ⁇ ⁇ > ⁇ .
  • Example 3-4 the operation of circulating nitrogen gas in the glove box was not performed (at this time, the water content of the air in the glove box was about 150 ppm), and
  • the positive electrode material composition ( ⁇ ′) was prepared in the same manner as in Example 3-4 except that the temperature was controlled in a thermostat of 5 ° C., and stored in a thermostat of 0 to 5 ° C. and stored for 8 days. Saved. Thereafter, in the same manner as in Example 3-1, the state of blocking was evaluated. The result was ⁇ .
  • Example 3-6 In the same manner as in Example 3-6 except that the temperature was controlled in a thermostat at 110 ° C., and the temperature was changed to storage for 10 days in a thermostat at 110 ° C. , The positive electrode material composition (A,) was stored. Thereafter, in the same manner as in Example 3-1, the state of blocking was evaluated. The result was ⁇ . Above example ⁇ Table 1 summarizes the results for the comparative example,
  • the positive electrode material compositions (A) and ( ⁇ ′) of the positive electrode material compositions stored in each of the above Examples and Comparative Examples are used as they are as lithium salt in the positive electrode material composition ( ⁇ ) as an electrolyte salt.
  • a cathode was prepared by adding a methanemethane) imide (L i N (CF 3 S 0 2 ) 2 ) so that the amount of the electrolyte salt was 7% by weight in the composition (B), and forming immediately. Then, a lithium battery is produced using the positive electrode, and the performance of the obtained battery (short test and And all the batteries based on the positive electrode material composition stored in each example exhibited better performance than the batteries based on the positive electrode material composition stored in each comparative example. It is hot. Industrial applicability
  • the method of storing a positive electrode material composition of a lithium secondary battery according to the present invention can be used when transporting or storing a material for producing a positive electrode used for a lithium secondary battery.

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Abstract

L’invention porte sur un procédé de maintien d’une composition de matériau d’électrode positive pour batteries secondaires au lithium pendant le transport/le stockage permettant de maintenir la composition de matériau d’électrode positive dans une condition préservant les performances d’une batterie secondaire au lithium faisant appel à une électrode positive fabriquée à partir de la composition de matériau d’électrode positive. L’invention porte spécifiquement sur un premier procédé de maintien d’une composition de matériau d’électrode positive pour batteries secondaires au lithium, à savoir un procédé de maintien d’une composition de matériau d’électrode positive contenant essentiellement un polymère, un matériau actif d’électrode et un assistant conducteur. Ce procédé est caractérisé en ce que lorsque le poids moléculaire moyen en poids du polymère dans la composition avant stockage est représenté par Mw0 et le poids moléculaire moyen en poids du polymère dans la composition après stockage de 18 jours est représenté par Mw, la vitesse de réduction (DMw) du poids moléculaire moyen en poids représentée par la formule (1) ci-dessous ne dépasse pas 10%. DMw(%) = [(Mw0 - Mw)/Mw0] × 100 (1)
PCT/JP2005/016466 2004-09-03 2005-09-01 Procédé de maintien de composition de matériau d’électrode positive pour batterie secondaire au lithium WO2006025600A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008251776A (ja) * 2007-03-30 2008-10-16 Nippon Zeon Co Ltd 電気化学素子用電極の製造方法
JP2011513924A (ja) * 2008-03-07 2011-04-28 バシウム・カナダ・インコーポレーテッド リチウム系電気化学セル用電極の製造方法
JP2011093753A (ja) * 2009-10-30 2011-05-12 Murata Mfg Co Ltd リチウム遷移金属複合酸化物の製造方法
JP2011154915A (ja) * 2010-01-28 2011-08-11 Panasonic Corp ドライエアーの供給方法及び装置
WO2015029835A1 (fr) * 2013-08-29 2015-03-05 日本ゼオン株式会社 Procédé de préservation de composition de liant aqueux pour pile rechargeable au lithium
JP2018088306A (ja) * 2016-11-28 2018-06-07 富士フイルム株式会社 固体電解質組成物、固体電解質含有シートおよび全固体二次電池、ならびに、固体電解質含有シートおよび全固体二次電池の製造方法
US20220199963A1 (en) * 2020-12-23 2022-06-23 Volkswagen Aktiengesellschaft Method for the production of an electrode powder mixture for a battery cell
WO2023059273A1 (fr) * 2021-10-04 2023-04-13 İzmi̇r Eği̇ti̇m Sağlik Sanayi̇ Yatirim A.Ş. Anode monocouche composite à base de thermoplastique dans des batteries secondaires

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JPS61124053A (ja) * 1984-11-19 1986-06-11 Sanyo Electric Co Ltd アルカリ蓄電池用カドミウム陰極の保存方法
JPS63307663A (ja) * 1987-06-05 1988-12-15 Bridgestone Corp 非水電解質二次電池
JPH04500883A (ja) * 1989-07-20 1992-02-13 ドウティー　エレクトロニック　コンポーネンツ　リミテッド 活性物質としてリチウムバナジウム酸化物を含有する電池
JPH07176305A (ja) * 1993-12-21 1995-07-14 Toshiba Battery Co Ltd アルカリ二次電池用ペースト式水素吸蔵合金負極の保管方法
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008251776A (ja) * 2007-03-30 2008-10-16 Nippon Zeon Co Ltd 電気化学素子用電極の製造方法
JP2011513924A (ja) * 2008-03-07 2011-04-28 バシウム・カナダ・インコーポレーテッド リチウム系電気化学セル用電極の製造方法
JP2011093753A (ja) * 2009-10-30 2011-05-12 Murata Mfg Co Ltd リチウム遷移金属複合酸化物の製造方法
JP2011154915A (ja) * 2010-01-28 2011-08-11 Panasonic Corp ドライエアーの供給方法及び装置
WO2015029835A1 (fr) * 2013-08-29 2015-03-05 日本ゼオン株式会社 Procédé de préservation de composition de liant aqueux pour pile rechargeable au lithium
JPWO2015029835A1 (ja) * 2013-08-29 2017-03-02 日本ゼオン株式会社 リチウム二次電池用水系バインダー組成物の保存方法
JP2018088306A (ja) * 2016-11-28 2018-06-07 富士フイルム株式会社 固体電解質組成物、固体電解質含有シートおよび全固体二次電池、ならびに、固体電解質含有シートおよび全固体二次電池の製造方法
US20220199963A1 (en) * 2020-12-23 2022-06-23 Volkswagen Aktiengesellschaft Method for the production of an electrode powder mixture for a battery cell
WO2023059273A1 (fr) * 2021-10-04 2023-04-13 İzmi̇r Eği̇ti̇m Sağlik Sanayi̇ Yatirim A.Ş. Anode monocouche composite à base de thermoplastique dans des batteries secondaires

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