WO2020095996A1 - 被覆粒子、正極、負極、全固体電池、及び、硫化物系全固体電池用コーティング組成物 - Google Patents
被覆粒子、正極、負極、全固体電池、及び、硫化物系全固体電池用コーティング組成物 Download PDFInfo
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- H01M4/04—Processes of manufacture in general
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates to coated particles, a positive electrode, a negative electrode, an all-solid-state battery, and a coating composition for a sulfide-based all-solid-state battery.
- Patent Document 1 describes coating a sulfide-based solid electrolyte with a fluorine-based compound such as (CH 3 ) 3 —Si— (CF 2 ) 6 —CF 3 or a perfluoroacrylic resin.
- Patent Document 2 describes coating a powder of a sulfide-based solid electrolyte containing no bridging sulfur with a water repellent containing a fluororesin.
- the present disclosure provides a sulfide-based particle that is not only less likely to generate hydrogen sulfide upon exposure to the air, but is also excellent in ionic conductivity and dispersibility in a solvent, a positive electrode, a negative electrode, and an all-solid-state battery including such a particle. With the goal.
- the present disclosure also aims to provide a novel sulfide-based all-solid-state battery coating composition.
- the present disclosure is a coated particle in which the surface of a sulfide-based particle is coated with a fluoropolymer
- the above-mentioned fluoropolymer comprises a structural unit (1) based on a monomer (1) represented by the following formula (1): A composition based on at least one selected from the group consisting of a monomer (2) represented by the following formula (2), an alkoxysilyl group-containing monomer (3) represented by the following formula (3), and a vinyl monomer. And a unit (2).
- Formula (1) (In the formula, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (provided that X 1 and X 2 are the same or different and each represents a hydrogen atom, a fluorine atom or a chlorine atom).
- Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a —CH 2 CH 2 N (R a ) SO 2 — group
- R a is an alkyl group having 1 to 4 carbon atoms, a —CH 2 CH (OY 1 ) CH 2 — group (provided that Y 1 is a hydrogen atom or an acetyl group), or — (CH 2 ) n SO 2 - is a group (n is 1 ⁇ 10)
- Rf A linear or branched fluoroalkyl group having 1 to 10 carbon atoms.
- a branched or branched alkyl group, and R 2 has 1 or more carbon atoms which may contain at least one atom selected from the group consisting of oxygen atom, nitrogen atom and sulfur atom in the structure.
- R 1 is H or CH 3
- R 2 has at least one atom selected from the group consisting of oxygen atom, nitrogen atom and sulfur atom in the structure.
- Formula (3) (In the formula, R 3 , R 4 and R 5 are the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and at least R 3 , R 4 and R 5 One is the above alkoxy group, and R 6 is a group containing a radically polymerizable unsaturated bond.)
- the present disclosure also relates to a positive electrode having the above-mentioned coated particles and a positive electrode active material.
- the present disclosure also relates to a negative electrode including the coated particles and the negative electrode active material.
- the present disclosure also relates to an all-solid-state battery having a positive electrode layer having the positive electrode, a negative electrode layer having the negative electrode, and a solid electrolyte layer having the coated particles formed between the positive electrode layer and the negative electrode layer. Concerned.
- the present disclosure contains a fluoropolymer and an organic solvent
- the above-mentioned fluoropolymer comprises a structural unit (1) based on a monomer (1) represented by the following formula (1): A composition based on at least one selected from the group consisting of a monomer (2) represented by the following formula (2), an alkoxysilyl group-containing monomer (3) represented by the following formula (3), and a vinyl monomer. It also relates to a coating composition for a sulfide-based all-solid-state battery, which comprises the unit (2).
- Formula (1) (In the formula, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (provided that X 1 and X 2 are the same or different and each represents a hydrogen atom, a fluorine atom or a chlorine atom).
- Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a —CH 2 CH 2 N (R a ) SO 2 — group
- R a is an alkyl group having 1 to 4 carbon atoms, a —CH 2 CH (OY 1 ) CH 2 — group (provided that Y 1 is a hydrogen atom or an acetyl group), or — (CH 2 ) n SO 2 - is a group (n is 1 ⁇ 10)
- Rf A linear or branched fluoroalkyl group having 1 to 10 carbon atoms.
- a branched or branched alkyl group, and R 2 has 1 or more carbon atoms which may contain at least one atom selected from the group consisting of oxygen atom, nitrogen atom and sulfur atom in the structure.
- R 1 is H or CH 3
- R 2 has at least one atom selected from the group consisting of oxygen atom, nitrogen atom and sulfur atom in the structure.
- Formula (3) (In the formula, R 3 , R 4 and R 5 are the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and at least R 3 , R 4 and R 5 One is the above alkoxy group, and R 6 is a group containing a radically polymerizable unsaturated bond.)
- sulfide-based particles which are not only less likely to generate hydrogen sulfide upon exposure to the air but also have excellent ionic conductivity and dispersibility in a solvent, a positive electrode, a negative electrode, and an all-solid-state battery including such particles. can do.
- a novel sulfide-based coating composition for all-solid-state batteries can also be provided.
- the present disclosure is a coated particle in which the surface of a sulfide-based particle containing a sulfur component is coated with a fluoropolymer, and the fluoropolymer is a structural unit (1) based on a specific monomer (1). And a structural unit (2) based on at least one selected from the group consisting of a specific monomer (2), a specific alkoxysilyl group-containing monomer (3) and a vinyl-based monomer. It relates to coated particles.
- the coated particles of the present disclosure are those in which the surface of the sulfide-based particles is coated with a specific fluorine-containing polymer, it is possible to suppress the reaction between the sulfide-based particles and water in the atmosphere during exposure to the atmosphere, Less likely to generate hydrogen sulfide (H 2 S). Therefore, it is possible to alleviate the dry environment and improve workability and safety in the production process (equipment) of the sulfide-based all-solid-state battery.
- the coated particles of the present disclosure can also exert these effects over a long period of time (for example, 20 minutes or longer, preferably 120 minutes or longer).
- the conventional coating agent it was necessary to thicken the coat layer in order to secure sufficient moisture-proof performance, but this causes a problem that the ion conductivity is hindered by the coat layer and the ion conductivity is lowered. It was In addition, there is a problem that the dispersibility in a solvent used for constructing a battery (for example, a solvent used for a paint for forming an electrode) is lowered. Since the coated particles of the present disclosure use a specific fluorine-containing polymer for coating, high moistureproof performance and ion conductivity (particularly lithium ion conductivity) can be secured even with a thin coating (small amount used), and at the time of battery construction. It is also possible to suppress deterioration of dispersibility in the solvent used.
- the sulfide-based particles are not particularly limited as long as they are solid particles containing a sulfur component.
- the sulfide-based particles may form an aggregate of the sulfide-based particles.
- the sulfide-based particles preferably function as a solid electrolyte.
- a material that can be used as a sulfide-based solid electrolyte for an all-solid-state battery can be used, but one containing Li is preferable, and one containing Li and P is more preferable.
- Examples of the sulfide-based particles include Li 2 S—SiS 2 , Li 2 S—P 2 S 5 , Li 2 S—GeS 2 , Li 2 S—B 2 S 3 , Li 2 S—Ga 2 S 3 , Li 2 S-Al 2 S 3 , Li 2 S-GeS 2 -P 2 S 5 , Li 2 S-Al 2 S 3 -P 2 S 5 , Li 2 S-P 2 S 3 , Li 2 S-P 2 S 3 -P 2 S 5 , LiX 0 -Li 2 S-P 2 S 5 , LiX 0 -Li 2 S-SiS 2 , LiX 0 -Li 2 S-B 2 S 3 , Li 3 PO 4 -Li 2 S-Si 2 S, Li 3 PO 4 -Li 2 S-SiS 2 , LiPO 4 -Li 2 S-SiS, LiX 0 -Li 2 S-P 2 O 5 , LiX 0 -
- X 0 is I, Br, or Cl.
- glass ceramics obtained by heat-treating amorphous sulfide-based particles can be used.
- Li 2 S—P 2 S 5 is preferable.
- the surface of the sulfide-based particle is coated with the fluoropolymer.
- a part of the surface of the sulfide-based particles may be coated, or the entire surface may be coated.
- the coated particle of the present disclosure may be one in which an aggregate of the sulfide-based particles is coated with the fluoropolymer.
- the surface of the sulfide-based particles is coated with the fluoropolymer by, for example, observing the C1s orbital energy spectrum of the surface treatment layer using X-ray photoelectron spectroscopy (XPS). You can check. It can also be confirmed by energy dispersive X-ray spectroscopy (SEM-EDX) using a scanning electron microscope or time-of-flight secondary ion mass spectrometry (TOF-SIMS).
- SEM-EDX energy dispersive X-ray spectroscopy
- TOF-SIMS time-of-flight secondary ion mass spectrometry
- the fluoropolymer contains the structural unit (1) based on the monomer (1) represented by the following formula (1).
- Formula (1) (In the formula, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (provided that X 1 and X 2 are the same or different and each represents a hydrogen atom, a fluorine atom or a chlorine atom).
- Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a —CH 2 CH 2 N (R a ) SO 2 — group
- R a is an alkyl group having 1 to 4 carbon atoms, a —CH 2 CH (OY 1 ) CH 2 — group (provided that Y 1 is a hydrogen atom or an acetyl group), or — (CH 2 ) n SO 2 - is a group (n is 1 ⁇ 10)
- Rf A linear or branched fluoroalkyl group having 1 to 10 carbon atoms.
- the above-mentioned monomer (1) is one in which a fluoroalkyl group is ester-bonded directly or through a specific divalent organic group to acrylic acid which may have a substituent at the ⁇ -position.
- the hydrocarbon group may be cyclic or acyclic, and may be linear or branched.
- the fluoroalkyl group is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and also includes a perfluoroalkyl group in which all hydrogen atoms are substituted with a fluorine atom.
- X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (provided that X 1 and X 2 are the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom), Cyano group, C1-C21 linear or branched fluoroalkyl group, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, or C1-C20 linear or branched X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CF 3 group, a cyano group, an unsubstituted benzyl group, an unsubstituted phenyl group, or a carbon number of 1 to A linear or branched fluoroalkyl group having 10 carbon
- Rf is a linear or branched fluoroalkyl group having 4 to 6 carbon atoms in view of good solubility in a fluorine-based organic solvent described later, particularly in hydrofluoroether.
- a straight-chain or branched perfluoroalkyl group having 4 to 6 carbon atoms is particularly preferable.
- Rf is a linear or branched fluoroalkyl group having 4 to 6 carbon atoms, it is represented by X in the formula (1) in order to further improve the waterproof property of the coating film formed.
- the ⁇ -position-substituted acrylate is a group or atom other than a hydrogen atom.
- the substituent X at the ⁇ -position is a methyl group (CH 3 ) or a fluorine atom, it uses a low-cost raw material, has good waterproofness, and has an ionic conductivity and dispersion of the solid electrolyte. It is possible to form a film that does not impair the property.
- the substituent X at the ⁇ -position is preferably a methyl group. It is also preferable that Rf does not have a ring structure.
- Y is preferably a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, more preferably an alkylene group having 1 to 10 carbon atoms, An alkylene group having 1 to 5 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is further preferable. It is also preferable that Y does not have a ring structure.
- CH 2 C (CF 3 ) COOCH 2 CH 2 -Rf
- the said monomer (1) can be used individually by 1 type or in mixture of 2 or more types.
- the fluoropolymer is also selected from the group consisting of a monomer (2) represented by the following formula (2), an alkoxysilyl group-containing monomer (3) represented by the following formula (3), and a vinyl-based monomer. And a structural unit (2) based on at least one kind (hereinafter, also referred to as a second monomer).
- R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 3 X 4 group (provided that X 3 and X 4 are the same or different and each represents a hydrogen atom, a fluorine atom or a chlorine atom).
- Formula (3) (In the formula, R 3 , R 4 and R 5 are the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and at least R 3 , R 4 and R 5 One is the above alkoxy group, and R 6 is a group containing a radically polymerizable unsaturated bond.)
- R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 3 X 4 group (provided that X 3 and X 4 are the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom).
- a hydrogen atom, a fluorine atom, a CF 3 group, a CH 3 group, a linear or branched fluoroalkyl group having 1 to 10 carbon atoms, or a linear or branched alkyl group having 1 to 10 carbon atoms Is more preferable, a fluorine atom, a CF 3 group, H or CH 3 is further preferable, and H or CH 3 is even more preferable.
- the hydrocarbon group as R 2 may have at least one atom selected from the group consisting of oxygen atom, nitrogen atom, and sulfur atom in the structure,
- the number of carbon atoms is 1 or more.
- the carbon number is preferably 6 or more, and may be 7 or more. Further, it is preferably 20 or less, and more preferably 15 or less.
- the above-mentioned atom which the above-mentioned hydrocarbon group as R 2 may contain is preferably at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom, and more preferably an oxygen atom. preferable.
- Examples of the hydrocarbon group as R 2 include a group having a hydrocarbon ring such as a group having an aliphatic hydrocarbon ring, a group having an aromatic hydrocarbon ring, or an aliphatic hydrocarbon group having no ring. Be done.
- Examples of the group having an aliphatic hydrocarbon ring include a group having a heterocycle such as a cycloalkyl group and a glycidyl group, and a group having a crosslinked hydrocarbon ring such as isobornyl, bornyl, fensyl, adamantyl and norbornyl.
- Examples of the group having an aromatic hydrocarbon ring include a phenyl group and a benzyl group.
- hydrocarbon group a cycloalkyl group, a group having a bridged hydrocarbon ring and a benzyl group are preferable, and a group having a bridged hydrocarbon ring is more preferable.
- the hydrocarbon ring may be directly bonded to a carboxyl group, or may be bonded to a carboxyl group via a linear or branched alkylene group having 1 to 5 carbon atoms.
- the hydrocarbon ring may be further substituted with a hydroxyl group or an alkyl group (carbon number, for example, 1 to 5).
- Examples of the aliphatic hydrocarbon group having no ring include a linear or branched alkyl group which may have an ether bond.
- the hydrocarbon group as R 2 is preferably a group having an aliphatic hydrocarbon ring or a group having an aromatic hydrocarbon ring.
- the hydrocarbon group as R 2 may not contain a fluorine atom.
- R 1 is H or CH 3
- R 2 has 3 or more carbon atoms and contains at least one atom selected from the group consisting of oxygen atom, nitrogen atom, and sulfur atom in the structure.
- Formula (2) (In the formula, R 1 is H or CH 3 , and R 2 is a hydrocarbon group having a ring structure and having 6 or more carbon atoms.)
- the monomer (2) has a (meth) acrylate having a cyclohexyl group, a (meth) acrylate having a benzyl group, a (meth) acrylate having an isobornyl group, a (meth) acrylate having a norbornyl group, and an adamantyl group.
- (Meth) acrylate etc. can also be mentioned.
- cyclohexyl methacrylate and the like can be exemplified as the (meth) acrylate having a cyclohexyl group.
- Examples of the (meth) acrylate having a benzyl group include benzyl methacrylate and the like.
- Examples of the (meth) acrylate having an isobornyl group include isobornyl (meth) acrylate and isobornylmethyl (meth) acrylate.
- Examples of the (meth) acrylate having a norbornyl group include 3-methyl-norbornylmethyl (meth) acrylate, norbornylmethyl (meth) acrylate, norbornyl (meth) acrylate, 1,3,3-trimethyl-norbornyl (meth) acrylate.
- the above-mentioned monomer (2) above all, Is preferred, and at least one selected from the group consisting of (meth) acrylate having an isobornyl group, (meth) acrylate having a cyclohexyl group, and (meth) acrylate having an adamantyl group is preferred, and isobornyl (meth) acrylate, cyclohexyl ( More preferably, at least one selected from the group consisting of (meth) acrylate and 2-methyl-2-adamantyl (meth) acrylate.
- R 3 , R 4 and R 5 are the same or different and each is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R 3 , R 4 and R 5 At least one of the above is an alkoxy group.
- the alkoxy group is preferably a methoxy group, a methoxy group or the like, and it is particularly preferable that R 3 , R 4 and R 5 are all methoxy groups or ethoxy groups.
- R 6 is a group containing a radically polymerizable unsaturated bond.
- alkoxysilyl group-containing monomer (3) include monomers represented by the following formula.
- R 7 is a hydrogen atom, a methyl group or Cl, and n is an integer of 1-10.
- R 7 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
- n is preferably 1 to 5, more preferably 1 to 3.
- alkoxysilyl group-containing monomers (3) the following are preferable.
- vinyl monomers examples include vinyl compounds having a fluorine atom such as trifluoromethyl vinyl, perfluoroethyl vinyl and perfluoroethyl ether vinyl; vinyl compounds having a chlorine atom such as vinyl chloride and vinylidene chloride.
- the said 2nd monomer can be used individually by 1 type or in mixture of 2 or more types.
- the second monomer is preferably at least one selected from the group consisting of the monomer (2) and the alkoxysilyl group-containing monomer (3).
- the content of the structural unit (2) is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the structural unit (1).
- the above content is more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and 30 parts by mass. It may be the following or 20 parts by mass or less.
- the above content may also be 1 to 30 parts by mass.
- the above-mentioned fluoropolymer may further contain a structural unit (3) based on another monomer, if necessary.
- the structural unit (3) may be 20% by mass or less based on the total amount of all structural units constituting the fluoropolymer, and is preferably 10% by mass or less.
- the above-mentioned other monomer may be a monomer copolymerizable with the above-mentioned monomer (1) and the above-mentioned second monomer, and may be in a wide range as long as it does not adversely affect the performance of the obtained fluoropolymer. It is selectable.
- aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen-containing unsaturated compound, silicon-containing unsaturated compound, unsaturated dicarboxylic acid compound, vinyl ester compound, allyl ester compound, unsaturated group-containing ether compound, maleimide examples thereof include, but are not limited to, compounds, (meth) acrylic acid esters, acrolein, methacrolein, cyclopolymerizable monomers and N-vinyl compounds.
- the method of polymerizing each monomer is not particularly limited, but solution polymerization is preferably performed in a fluorine-based solvent. According to this method, since the formed fluoropolymer has good solubility in the fluorine-based solvent, it is possible to smoothly proceed the radical polymerization reaction without forming a precipitate.
- the weight average molecular weight of the fluoropolymer is preferably 3,000 to 500,000, more preferably 5,000 to 300,000.
- the amount of the fluoropolymer is preferably 0.01 to 40 parts by mass, and more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the sulfide-based particle. It is more preferably 1 to 10 parts by mass.
- the coated particles of the present disclosure can sufficiently suppress the generation of hydrogen sulfide upon exposure to the atmosphere even when the amount of the above-mentioned fluoropolymer as a coating agent is relatively small, and thus decrease in ion conductivity and dispersibility. Can be suppressed.
- the coated particles of the present disclosure include a method of immersing the sulfide-based particles in a liquid obtained by dissolving or dispersing the fluoropolymer in a solvent and then drying the sulfide-based particles (immersion method), after spraying the liquid on the sulfide-based particles.
- immersion method a method of immersing the sulfide-based particles in a liquid obtained by dissolving or dispersing the fluoropolymer in a solvent and then drying the sulfide-based particles (immersion method), after spraying the liquid on the sulfide-based particles.
- It can be manufactured by a drying method (spray drying method), a PVD method, a CVD method, or the like.
- the PVD method is to heat a raw material in a vacuum (vacuum vapor deposition) or to irradiate it with high-speed electrons or ions to give physical energy to atoms on a solid surface to vaporize it and
- the PVD method is not particularly limited, and examples thereof include a vapor deposition method (usually a vacuum vapor deposition method) and sputtering.
- a vapor deposition method usually a vacuum vapor deposition method
- sputtering Specific examples of the vapor deposition method (usually a vacuum vapor deposition method) include resistance heating, high frequency heating using electron beam, microwave, etc., ion beam and similar methods.
- Specific examples of the CVD method include plasma CVD, optical CVD, thermal CVD and similar methods. Among the above methods, the dipping method or the spray drying method is preferable.
- an organic solvent is preferable in that a uniform solution of the fluoropolymer can be obtained.
- the preferable organic solvent include fluorine-based solvents, toluene, xylene, dibutyl ether, heptane, n-butyl butyrate and the like. Of these, a fluorine-based solvent is more preferable.
- the said organic solvent can be used individually by 1 type or in mixture of 2 or more types.
- the fluorine-based solvent has a fluorine atom in the molecule, and may be any of hydrocarbon compounds, alcohols, ethers, etc., as long as the solubility of the fluoropolymer to be formed is good, It may be either aliphatic or aromatic.
- the fluorine-based solvent for example, the following solvents are used: C5-12 perfluoroaliphatic hydrocarbons (eg, perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); poly Fluoroaromatic hydrocarbon (for example, bis (trifluoromethyl) benzene); Polyfluoroaliphatic hydrocarbon (for example, C 6 F 13 CH 2 CH 3 (for example, Asahi Clin (registered trademark) AC- manufactured by Asahi Glass Co., Ltd.) 6000), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Nippon Zeon Co., Ltd.); Hydrofluorocarbon (HFC) (for example, 1,1, 1,3,3-Pentafluorobutane (HFC-365mfc)); Hydrochlorofluor Carbon (e.g., HCFC-
- Alkyl perfluoroal Kill ether (perfluoroalkyl group and alkyl group may be linear or branched), or CF 3 CH 2 OCF 2 CHF 2 (for example, Asahi Clin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.) ), 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, Bertrel (registered trademark) Sion manufactured by Mitsui DuPont Fluorochemicals Co., Ltd.), etc.
- These solvents may be used alone. Alternatively, two or more kinds may be combined and used as a mixture.
- fluorine-based ethers are preferable, and hydrofluoroethers are more preferable.
- hydrofluoroether a compound represented by the formula: C n F 2n + 1 —O—C x H 2x + 1 (in the formula, n is a number of 1 to 6 and x is a number of 1 to 6) is preferable.
- hydrofluoroethers include Novec HFE7100 (chemical formula C 4 F 9 OCH 3 ) (boiling point 61 ° C.), 7200 (chemical formula C 4 F 9 OC 2 H 5 ) (boiling point 76 ° C.) manufactured by 3M. 7300 (chemical formula C 6 F 13 OCH 3 ) (boiling point 98 ° C.) and the like.
- organic solvent it is preferable to use one that has been dehydrated to reduce the water content.
- coated particles of the present disclosure can be suitably used as a solid electrolyte. Further, it can be suitably used as a constituent material of an all-solid-state battery, particularly an all-solid-state secondary battery.
- the present disclosure also relates to a positive electrode having the above-described coated particles of the present disclosure and a positive electrode active material.
- the content of the coated particles is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and 30 to 50% by mass based on the positive electrode active material. More preferably,
- any material that can be used as a positive electrode active material in an all-solid-state battery can be used without particular limitation.
- the positive electrode of the present disclosure may further include a binder.
- the binder is preferably a thermoplastic resin or a thermosetting resin, and examples thereof include polysiloxane, polyalkylene glycol, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride, hydrogenated butylene rubber, and polysulfide.
- Rubber styrene butadiene rubber (SBR), styrene butadiene rubber / carboxymethyl cellulose (SBR / CMC), polyethylene oxide (PEO), branched PEO, polyphenylene oxide (PPO), PEO-PPO copolymer, branched PEO-PPO copolymer , Alkyl borane-containing polyethers and the like.
- the positive electrode of the present disclosure may further include a conductive auxiliary material.
- the conductive auxiliary material is not particularly limited and may be a conventionally used material such as graphite; carbon black; acetylene black (AB); ketjen black (KB); vapor grown carbon fiber (VGCF). Carbon fiber; carbon nanotube (CNT); carbon nanofiber (CNF) and the like can be used.
- the thickness of the positive electrode of the present disclosure may be, for example, 10 to 500 ⁇ m.
- the coated particles and the positive electrode active material, and optionally other components are mixed with a solvent, and the obtained mixed liquid (slurry) is used as a base material (for example, a positive electrode current collector described later). It can be produced by a method of coating on the body and drying. You may press further if needed.
- a blast method, an aerosol deposition method, a cold spray method, a sputtering method, a vapor phase growth method, a pressure pressing method, a thermal spraying method and the like can be used.
- an organic solvent is preferable.
- the organic solvent include non-polar solvents such as hexane, heptane, toluene, xylene, decalin; tertiary amine solvents such as triethylamine; ether solvents such as dibutyl ether and cyclopentyl methyl ether; thiol solvents such as ethanemercaptan.
- Solvents Ester solvents such as butyl butyrate and the like can be mentioned. The organic solvent is preferably dehydrated to reduce the water content.
- the present disclosure also relates to a negative electrode having the above-described coated particles of the present disclosure and a negative electrode active material.
- the content of the coated particles is preferably 20 to 100% by mass, more preferably 30 to 90% by mass, and 40 to 80% by mass based on the negative electrode active material. More preferably,
- the negative electrode active material is not particularly limited, and a known negative electrode active material that can be used in all-solid-state batteries can be used.
- a known negative electrode active material that can be used in all-solid-state batteries can be used.
- simple substances / alloys / compounds of metals or semimetals into / from which lithium ions can be inserted / desorbed can be cited.
- the carbonaceous material include graphite (natural graphite, artificial graphite, etc.), hard carbon, amorphous carbon and the like.
- lithium metal or alloy As a simple substance or alloy of metal or semimetal, lithium metal or alloy; metal powder such as Sn, Si, Al, Sb, Zn, Bi; Sn 5 Cu 6 , Sn 2 Co, Sn 2 Fe, Ti-Sn, Ti -Metal alloy powder such as Si; and other amorphous alloys, plated alloys, and the like.
- the compound include oxides, sulfides, nitrides, hydrides, silicides (lithium silicide, etc.), and the like.
- oxide include titanium oxide, lithium titanium oxide (Li 4/3 Ti 5/3 O, etc.), silicon oxide and the like.
- the nitride include lithium cobalt nitride (LiCoN) and the like.
- the negative electrode active material one type may be used alone, or two or more types may be used in combination.
- a silicon oxide and a carbonaceous material may be used together.
- the particle size is not particularly limited, but those having an average particle size of 0.1 to 8 ⁇ m can be preferably used.
- the negative electrode of the present disclosure may further include a binder and a conductive auxiliary material.
- the binder and the conduction aid include binders and conduction aids that can be used in the positive electrode of the present disclosure.
- the thickness of the negative electrode of the present disclosure may be, for example, 10 to 500 ⁇ m.
- the negative electrode of the present disclosure can be manufactured by the same method as the positive electrode of the present disclosure.
- the present disclosure includes a positive electrode layer having the positive electrode of the present disclosure described above, a negative electrode layer having the negative electrode of the present disclosure described above, and the coated particles of the present disclosure described above formed between the positive electrode layer and the negative electrode layer. And a solid electrolyte layer having the same.
- the all solid state battery of the present disclosure is preferably an all solid state secondary battery.
- the positive electrode layer may have a positive electrode current collector together with the positive electrode of the present disclosure.
- the positive electrode current collector can be used without particular limitation as long as it is used as a positive electrode current collector for all-solid-state batteries. Examples of the form of such a positive electrode current collector include a foil-like body, a plate-like body, a net-like body, an aggregate of powders, and the like. Good.
- the foil-shaped body may be an electrolytic foil, an etched foil or the like.
- Examples of the material of the positive electrode current collector include materials that are stable at the redox potential of the positive electrode, such as aluminum, magnesium, stainless steel, titanium, iron, cobalt, zinc, tin, copper, nickel, germanium, indium, and alloys thereof. , Carbon, etc. are exemplified.
- the positive electrode current collector may have a thickness of 1 to 300 ⁇ m, for example.
- the negative electrode layer may have a negative electrode current collector together with the negative electrode of the present disclosure.
- Examples of the form and material of the negative electrode current collector include those described for the positive electrode current collector.
- the negative electrode current collector may have a thickness of 1 to 300 ⁇ m, for example.
- the solid electrolyte layer may include a binder together with the coated particles of the present disclosure.
- the binder is preferably a thermoplastic resin or a thermosetting resin, and examples thereof include polysiloxane, polyalkylene glycol, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and tetrafluoroethylene-hexafluoro.
- the solid electrolyte layer can be produced, for example, by a method in which the coated particles and, if necessary, other components are mixed with a solvent, the resulting mixed liquid is applied onto a base material, and dried. You may press further if needed.
- a blast method, an aerosol deposition method, a cold spray method, a sputtering method, a vapor phase growth method, a pressure pressing method, a thermal spraying method and the like can be used.
- An organic solvent is preferable as the solvent used for producing the solid electrolyte layer.
- the organic solvent include heptane, toluene, hexane, xylene, decalin, tetrahydrofuran (THF), N-methylpyrrolidone, acetonitrile, dimethoxyethane, dimethyl carbonate, tertiary amine solvents (triethylamine, etc.), ether solvents ( Cyclopentyl methyl ether, etc.), thiol-based solvents (ethane mercaptan, etc.), and butyl butyrate.
- the organic solvent it is preferable to use one that has been dehydrated to reduce the water content.
- the positive electrode layer, the solid electrolyte layer, and the negative electrode layer are laminated in this order, and a laminate is produced by pressing if desired, and the laminate is formed inside a battery case. It can be manufactured by, for example, a method of caulking the battery case and caulking the battery case.
- the present disclosure contains a fluoropolymer and an organic solvent, and the fluoropolymer comprises a structural unit (1) based on a monomer (1) represented by the following formula (1) and a following formula (2).
- Formula (1) (In the formula, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (provided that X 1 and X 2 are the same or different and each represents a hydrogen atom, a fluorine atom or a chlorine atom).
- Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a —CH 2 CH 2 N (R a ) SO 2 — group
- R a is an alkyl group having 1 to 4 carbon atoms, a —CH 2 CH (OY 1 ) CH 2 — group (provided that Y 1 is a hydrogen atom or an acetyl group), or — (CH 2 ) n SO 2 - is a group (n is 1 ⁇ 10)
- Rf A linear or branched fluoroalkyl group having 1 to 10 carbon atoms.
- a branched or branched alkyl group, and R 2 has 1 or more carbon atoms which may contain at least one atom selected from the group consisting of oxygen atom, nitrogen atom and sulfur atom in the structure.
- R 1 is H or CH 3
- R 2 has at least one atom selected from the group consisting of oxygen atom, nitrogen atom and sulfur atom in the structure.
- Formula (3) (In the formula, R 3 , R 4 and R 5 are the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and at least R 3 , R 4 and R 5 One is the above alkoxy group, and R 6 is a group containing a radically polymerizable unsaturated bond.)
- the coating composition of the present disclosure contains a specific fluorine-containing polymer, when used as a coating agent for a sulfide-based solid electrolyte used in a sulfide-based all-solid-state battery, hydrogen sulfide (H 2 S ) Is less likely to occur, the dry environment in the production process (equipment) of the sulfide-based all-solid-state battery can be alleviated, workability and safety can be improved, and it can be performed for a long time (for example, 20 minutes or more, preferably 120 minutes). Above, it is possible to exert these effects.
- H 2 S hydrogen sulfide
- the coating composition of the present disclosure can also be used as a coating agent for a sulfide-based all-solid-state battery or a constituent member thereof (a positive electrode layer, a negative electrode layer, a solid electrolyte layer, etc.). Water can be prevented from entering the inside of the. Therefore, it is possible to prevent performance deterioration due to moisture not only in the manufacturing process of the all-solid-state battery and its constituent members but also after manufacturing.
- fluoropolymer in the coating composition of the present disclosure the same as the fluoropolymer in the coated particles of the present disclosure can be used, and preferred examples are also the same.
- Examples of the organic solvent in the coating composition of the present disclosure include those exemplified as the organic solvent that can be used in the production of the coated particles of the present disclosure, and the preferable examples are also the same.
- the fluoropolymer be dissolved in the organic solvent.
- the content of the fluoropolymer is preferably 0.001 to 30 mass% with respect to the total amount of the fluoropolymer and the organic solvent.
- the content is more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, more preferably 20% by mass or less, and 10% by mass or less. It is more preferable that the content is 5% by mass or less.
- the coating composition of the present disclosure is for a sulfide-based all-solid-state battery, and preferably for a sulfide-based all-solid-state secondary battery.
- the coating composition of the present disclosure can be used as a coating agent for a sulfide-based solid electrolyte used in a sulfide-based all-solid-state battery or as a coating agent for a sulfide-based all-solid-state battery. It can also be used as a coating agent for a constituent member of a sulfide-based all-solid-state battery.
- a coating material for a constituent member of a sulfide-based all-solid-state battery it is preferably used as a coating material for a member containing a sulfide-based solid electrolyte (positive electrode, negative electrode, solid electrolyte layer, etc.).
- the coating composition of the present disclosure may be applied to a sulfide-based solid electrolyte (for example, powder) as a raw material, or may be applied to the sulfide-based all-solid-state battery or any of the constituent members thereof at any stage of manufacturing the sulfide-based all-solid-state battery or its constituent members. You may apply to the structural member. When applied to a sulfide-based all-solid-state battery or a constituent member thereof, it may be applied to an all-solid-state battery during or after formation, or may be applied to a constituent member during or after formation.
- the method of applying the coating composition of the present disclosure to an object is not particularly limited as long as it is a method capable of adhering the fluoropolymer to the object, but the object is immersed in the coating composition of the present disclosure. Then, a method of drying, a method of spraying the coating composition of the present disclosure on an object, and then drying, and the like can be mentioned.
- a sulfide-based solid electrolyte powder as a raw material is immersed in the coating composition of the present disclosure, or the coating composition of the present disclosure is applied to the sulfide-based solid electrolyte powder.
- a mode of drying after spraying (2) at the time of applying or drying a slurry containing a sulfide-based solid electrolyte for forming a positive electrode, a negative electrode or a solid electrolyte layer, the coating composition is sprayed with the coating composition of the present disclosure And (3) a mode in which the positive electrode, the negative electrode or the solid electrolyte layer thus formed is dipped in the coating composition of the present disclosure, or sprayed with the coating composition of the present disclosure, and then dried. (4) After the formation of the sulfide-based all-solid-state battery, the battery is immersed in the coating composition of the present disclosure, or the coating composition of the present disclosure is sprayed on the battery, and then dried. Aspects to, but and the like, but is not limited thereto.
- a method for producing coated particles which includes the step of applying the coating composition of the present disclosure to sulfide-based particles, is also one of the preferred embodiments of the present disclosure.
- a method for producing a sulfide-based all-solid-state battery or a constituent member thereof including is also one of the preferred embodiments of the present disclosure.
- Fluoropolymer 2: Rf (C6) methacrylate / iBMA / 3- (trimethoxysilyl) propyl methacrylate (hereinafter abbreviated as “TMSMA”) 100 / 14.49 / 2.373 (mass ratio) copolymer (polymer weight average molecular weight: 118 , 800)
- Production Example 16 The fluoropolymer 5 and the HFE7200 solvent were used to adjust the solid content concentration shown in Table 1 to prepare a coating solution. 21 g of the coating solution was put in 9 g of the solid electrolyte powder obtained above in a juicer mixer, and after stirring, the treated powder was dried and the solvent was removed to obtain polymer-coated particles. Production Example 17 The fluorine-containing polymer 6 and the HFE7200 solvent were used to adjust the solid content concentration shown in Table 1 to prepare a coating solution. 21 g of the coating solution was put in 9 g of the solid electrolyte powder obtained above in a juicer mixer, and after stirring, the treated powder was dried and the solvent was removed to obtain polymer-coated particles.
- the polymer coated particles was 100mg weighed Ar gas-filled glove box, using a pelleting machine area of 1 cm 2 was molded into pellets at a pressure of 4.3ton / cm 2, the ion conductivity by using the AC impedance method was measured.
- Comparative Example 1 The ionic conductivity was measured, the amount of H 2 S generated was measured, and the dispersibility in the electrolyte paint was evaluated in the same manner as in Example 1 except that the solid electrolyte particles not coated with the polymer were used. The results are shown in Table 2.
- Comparative Examples 2 and 3 The ionic conductivity was measured, the amount of H 2 S generated was measured, and the dispersibility in the electrolyte coating was evaluated in the same manner as in Example 1 except that the polymer-coated particles obtained in Comparative Production Examples 1 and 2 were used. The results are shown in Table 2.
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Abstract
Description
本開示は、新規な硫化物系全固体電池用コーティング組成物を提供することも目的とする。
上記含フッ素ポリマーは、下記式(1)で表される単量体(1)に基づく構成単位(1)と、
下記式(2)で表される単量体(2)、下記式(3)で表されるアルコキシシリル基含有モノマー(3)及びビニル系モノマーからなる群より選択される少なくとも1種に基づく構成単位(2)とを含む
ことを特徴とする被覆粒子に関する。
式(1):
式(2):
式(3):
上記含フッ素ポリマーは、下記式(1)で表される単量体(1)に基づく構成単位(1)と、
下記式(2)で表される単量体(2)、下記式(3)で表されるアルコキシシリル基含有モノマー(3)及びビニル系モノマーからなる群より選択される少なくとも1種に基づく構成単位(2)とを含む
ことを特徴とする硫化物系全固体電池用コーティング組成物にも関する。
式(1):
式(2):
式(3):
本開示によれば、新規な硫化物系全固体電池用コーティング組成物を提供することもできる。
本開示は、硫黄成分を含有する硫化物系粒子の表面が含フッ素ポリマーで被覆された被覆粒子であって、上記含フッ素ポリマーは、特定の単量体(1)に基づく構成単位(1)と、特定の単量体(2)、特定のアルコキシシリル基含有モノマー(3)及びビニル系モノマーからなる群より選択される少なくとも1種に基づく構成単位(2)とを含むことを特徴とする被覆粒子に関する。
また、従来の被覆剤では、充分な防湿性能を確保するためにコート層を厚くする必要があったが、それによりイオン伝導性がコート層により阻害され、イオン伝導性が低下するという問題があった。また、電池構築時に使用する溶剤(例えば、電極を形成するための塗料に使用する溶剤)における分散性が低下するという問題があった。
本開示の被覆粒子は、被覆に特定の含フッ素ポリマーを使用するので、薄い被膜(少ない使用量)でも高い防湿性能とイオン伝導性(特にリチウムイオン伝導性)を確保でき、また、電池構築時に使用する溶剤への分散性の低下を抑えることもできる。
上記硫化物系粒子としては、例えば、Li2S-SiS2、Li2S-P2S5、Li2S-GeS2、Li2S-B2S3、Li2S-Ga2S3、Li2S-Al2S3、Li2S-GeS2-P2S5、Li2S-Al2S3-P2S5、Li2S-P2S3、Li2S-P2S3-P2S5、LiX0-Li2S-P2S5、LiX0-Li2S-SiS2、LiX0-Li2S-B2S3、Li3PO4-Li2S-Si2S、Li3PO4-Li2S-SiS2、LiPO4-Li2S-SiS、LiX0-Li2S-P2O5、LiX0-Li3PO4-P2S5等が挙げられる。X0は、I、Br、又はClである。
また、非晶質の硫化物系粒子を熱処理して得られるガラスセラミックスを用いることもできる。
上記硫化物系粒子としては、なかでも、Li2S-P2S5が好ましい。
本開示の被覆粒子は、上記硫化物系粒子の集合体が上記含フッ素ポリマーで被覆されたものであってもよい。
また、走査型電子顕微鏡を用いたエネルギー分散型X線分光法(SEM-EDX)、又は、飛行時間型二次イオン質量分析法(TOF-SIMS)によっても、確認することができる。
式(1):
特に、α位の置換基Xが、メチル基(CH3)、フッ素原子である場合には、低価格の原料を用いて、良好な防水性を有し、かつ固体電解質のイオン伝導性及び分散性を損なわない被膜を形成できる。特に、α位の置換基Xがメチル基であることが好ましい。また、Rfは、環構造を有さないことも好ましい。
式(2):
式(3):
上記脂肪族炭化水素環を有する基としては、シクロアルキル基、グリシジル基等のヘテロ環を有する基、イソボルニル、ボルニル、フェンシル、アダマンチル、ノルボルニル等の架橋炭化水素環を有する基、等が挙げられる。
上記芳香族炭化水素環を有する基としては、フェニル基、ベンジル基等が挙げられる。
上記炭化水素基としては、シクロアルキル基、架橋炭化水素環を有する基及びベンジル基が好ましく、架橋炭化水素環を有する基がより好ましい。
上記炭化水素環は、カルボキシル基に直接結合してもよく、炭素数1~5の直鎖状又は分枝鎖状のアルキレン基を介して、カルボキシル基に結合していてもよい。上記炭化水素環には、更に、水酸基やアルキル基(炭素数、例えば1~5)が置換していてもよい。
上記環を有さない脂肪族炭化水素基としては、エーテル結合を有してもよい直鎖または分岐状のアルキル基が挙げられる。
R2としての上記炭化水素基としては、なかでも、脂肪族炭化水素環を有する基又は芳香族炭化水素環を有する基が好ましい。
R2としての上記炭化水素基は、フッ素原子を含まないものであってもよい。
CH2=C(-F)-C(=O)-O-CH3、
CH2=C(-CF3)-C(=O)-O-CH3、
CH2=C(-CN)-C(=O)-O-CH3、
CH2=C(-C6H5)-C(=O)-O-CH3、
CH2=C(-F)-C(=O)-O-CH2CH3、
CH2=C(-CF3)-C(=O)-O-CH2CH3、
CH2=C(-CN)-C(=O)-O-CH2CH3、
CH2=C(-C6H5)-C(=O)-O-CH2CH3、
CH2=C(-F)-C(=O)-O-CH(CH3)2、
CH2=C(-CF3)-C(=O)-O-CH(CH3)2、
CH2=C(-CN)-C(=O)-O-CH(CH3)2、
CH2=C(-C6H5)-C(=O)-O-CH(CH3)2、
CH2=C(-F)-C(=O)-O-C(CH3)3、
CH2=C(-CF3)-C(=O)-O-C(CH3)3、
CH2=C(-CN)-C(=O)-O-C(CH3)3、
CH2=C(-C6H5)-C(=O)-O-C(CH3)3、
CH2=C(-F)-C(=O)-O-CH2CH(CH3)2、
CH2=C(-CF3)-C(=O)-O-CH2CH(CH3)2、
CH2=C(-CN)-C(=O)-O-CH2CH(CH3)2、
CH2=C(-C6H5)-C(=O)-O-CH2CH(CH3)2、
CH2=C(-F)-C(=O)-O-CH2CH2OCH3、
CH2=C(-CF3)-C(=O)-O-CH2CH2OCH3、
CH2=C(-F)-C(=O)-O-CH2CH2CH2CH3、
CH2=C(-CF3)-C(=O)-O-CH2CH2CH2CH3、
CH2=C(-CN)-C(=O)-O-CH2CH2CH2CH3、
CH2=C(-C6H5)-C(=O)-O-CH2CH2CH2CH3、
CH2=C(-F)-C(=O)-O-CH2CH(CH2CH3)CH2CH2CH2CH3、
CH2=C(-CF3)-C(=O)-O-CH2CH(CH2CH3)CH2CH2CH2CH3、
CH2=C(-R1)-C(=O)-O-CH2CH2OCH3、
CH2=C(-R1)-C(=O)-O-CH2CH(CH2CH3)CH2CH2CH2CH3、
CH2=C(-R1)-C(=O)-O-(CH2)17CH3、
CH2=C(-R1)-C(=O)-O-CH2CH2N(CH3)CH3、
CH2=C(-R1)-C(=O)-O-CH2CH2NCO
これらの内で、シクロヘキシル基を有する(メタ)アクリレートとしては、シクロヘキシルメタクリレート等を例示できる。
ベンジル基を有する(メタ)アクリレートとしては、ベンジルメタクリレート等を例示できる。
イソボルニル基を有する(メタ)アクリレートとしては、イソボルニル(メタ)アクリレート、イソボルニルメチル(メタ)アクリレート等を例示できる。
ノルボルニル基を有する(メタ)アクリレートとしては、3-メチル-ノルボルニルメチル(メタ)アクリレート、ノルボルニルメチル(メタ)アクリレート、ノルボルニル(メタ)アクリレート、1,3,3-トリメチル-ノルボルニル(メタ)アクリレート、ミルタニルメチル(メタ)アクリレート、イソピノカンファニル(メタ)アクリレート、2-{[5-(1’,1’,1’-トリフルオロ-2’-トリフルオロメチル-2’-ヒドロキシ)プロピル]ノルボルニル}(メタ)アクリレート等を例示できる。
アダマンチル基を有する(メタ)アクリレートとしては、2-メチル-2-アダマンチル(メタ)アクリレート、2-エチル-2-アダマンチル(メタ)アクリレート、3-ヒドロキシ-1-アダマンチル(メタ)アクリレート、1-アダマンチル-α-トリフルオロメチル(メタ)アクリレート等を例示できる。
R7は、水素原子又はメチル基であることが好ましく、メチル基であることがより好ましい。
nは、1~5であることが好ましく、1~3であることがより好ましい。
本開示の被覆粒子は、被覆剤である上記含フッ素ポリマーが比較的少量であっても、大気暴露時に硫化水素の発生を充分に抑制することができるので、イオン伝導性や分散性の低下を抑制することができる。
上記の方法のなかでも、浸漬法又はスプレードライ法が好ましい。
上記好ましい有機溶剤としては、フッ素系溶剤、トルエン、キシレン、ジブチルエーテル、ヘプタン、n-酪酸ブチル等が挙げられる。なかでもフッ素系溶剤がより好ましい。上記有機溶剤は、1種を単独で、又は2種以上を混合して用いることができる。
上記フッ素系溶剤としては、例えば以下の溶媒が使用される:C5-12のパーフルオロ脂肪族炭化水素(例えば、パーフルオロヘキサン、パーフルオロメチルシクロヘキサン及びパーフルオロ-1,3-ジメチルシクロヘキサン);ポリフルオロ芳香族炭化水素(例えば、ビス(トリフルオロメチル)ベンゼン);ポリフルオロ脂肪族炭化水素(例えば、C6F13CH2CH3(例えば、旭硝子株式会社製のアサヒクリン(登録商標)AC-6000)、1,1,2,2,3,3,4-ヘプタフルオロシクロペンタン(例えば、日本ゼオン株式会社製のゼオローラ(登録商標)H);ハイドロフルオロカーボン(HFC)(例えば、1,1,1,3,3-ペンタフルオロブタン(HFC-365mfc));ハイドロクロロフルオロカーボン(例えば、HCFC-225(アサヒクリン(登録商標)AK225));ヒドロフルオロエーテル(HFE)(例えば、パーフルオロプロピルメチルエーテル(C3F7OCH3)(例えば、住友スリーエム株式会社製のNovec(商標名)7000)、パーフルオロブチルメチルエーテル(C4F9OCH3)(例えば、住友スリーエム株式会社製のNovec(商標名)7100)、パーフルオロブチルエチルエーテル(C4F9OC2H5)(例えば、住友スリーエム株式会社製のNovec(商標名)7200)、パーフルオロヘキシルメチルエーテル(C2F5CF(OCH3)C3F7)(例えば、住友スリーエム株式会社製のNovec(商標名)7300)等のアルキルパーフルオロアルキルエーテル(パーフルオロアルキル基及びアルキル基は直鎖又は分枝状であってよい)、あるいはCF3CH2OCF2CHF2(例えば、旭硝子株式会社製のアサヒクリン(登録商標)AE-3000))、1,2-ジクロロ-1,3,3,3-テトラフルオロ-1-プロペン(例えば、三井・デュポンフロロケミカル社製のバートレル(登録商標)サイオン)等。これらの溶媒は、単独で、又は、2種以上を組み合わせて混合物として用いることができる。
例えば、コバルト酸リチウム(LiCoO2)、ニッケル酸リチウム(LiNiO2)、マンガン酸リチウム(LiMn2O4)、LiNiCoO2、ニッケルコバルトマンガン酸リチウム(LiCo1/3Ni1/3Mn1/3O2等)、アルミニウム含有ニッケルコバルト酸リチウム(LiNi0.8Co0.15Al0.05O2等)、Li1+xMn2-x-yMyO4(Mは、Al、Mg、Co、Fe、Ni、及びZnから選ばれる1種以上の金属元素)で表される組成の異種元素置換Li-Mnスピネル、チタン酸リチウム(LixTiOy)、リン酸金属リチウム(LiMPO4、MはFe、Mn、Co、又はNi)、遷移金属酸化物(V2O5、MoO3等)、イオウ含有化合物(Li2S、TiS2等)、リチウムシリコン酸化物(LixSiyOz)、リチウム金属(Li)、リチウム合金(LiM、Mは、Sn、Si、Al、Ge、Sb、又はP)、リチウム貯蔵性金属間化合物(MgxM又はLySb、MはSn、Ge、又はSb、LはIn、Cu、又はMn)、Li過剰の複合酸化物(Li2MnO3-LiMO2)、Li2PtO3、LiNiVO4、LiCoVO4、LiCrMnO4、LiFe(SO4)3等、並びにこれらの誘導体を挙げることができる。
粒径は特に限定されないが、平均粒径が0.1~20μmのものを好適に用いることができる。
上記バインダーとしては、熱可塑性樹脂又は熱硬化性樹脂が好ましく、例えば、ポリシロキサン、ポリアルキレングリコール、ポリテトラフルオロエチレン(PTFE)、ポリフッ化ビニリデン(PVDF)、ポリフッ化ビニル、水素添加ブチレンゴム、多硫化ゴム、スチレンブタジエンゴム(SBR)、スチレンブタジエンゴム/カルボキシメチルセルロース(SBR/CMC)、ポリエチレンオキシド(PEO)、分岐PEO、ポリフェニレンオキサイド(PPO)、PEO-PPO共重合体、分岐PEO-PPO共重合体、アルキルボラン含有ポリエーテル等が挙げられる。
上記の方法以外に、ブラスト法、エアロゾルデポジション法、コールドスプレー法、スパッタリング法、気相成長法、加圧プレス法、溶射法等も用いることができる。
例えば、リチウムイオンを挿入及び脱離可能な炭素質材料の他、リチウムイオンを挿入及び脱離可能な金属や半金属の単体・合金、化合物等が挙げられる。炭素質材料としては、黒鉛(天然黒鉛、人造黒鉛等)、ハードカーボン、非晶質炭素等が例示できる。金属や半金属の単体・合金としては、リチウム金属や合金;Sn、Si、Al、Sb、Zn、Bi等の金属粉;Sn5Cu6、Sn2Co、Sn2Fe、Ti-Sn、Ti-Si等の金属合金粉;その他アモルファス合金やメッキ合金等が挙げられる。上記化合物としては、例えば、酸化物、硫化物、窒化物、水素化物、シリサイド(リチウムシリサイド等)等が挙げられる。酸化物としては、チタン酸化物、リチウムチタン酸化物(Li4/3Ti5/3O等)、ケイ素酸化物等が挙げられる。窒化物としては、リチウムコバルト窒化物(LiCoN)等が挙げられる。負極活物質は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。例えば、ケイ素酸化物と炭素質材料とを併用してもよい。
粒径は特に限定されないが、平均粒径が0.1~8μmのものを好適に用いることができる。
上記バインダー及び上記導電助材としては、本開示の正極に使用可能なバインダー及び導電助材を挙げることができる。
本開示の全固体電池は、全固体二次電池であることが好ましい。
上記正極集電体の厚みは、例えば、1~300μmであってよい。
上記負極集電体の厚みは、例えば、1~300μmであってよい。
上記の方法以外に、ブラスト法、エアロゾルデポジション法、コールドスプレー法、スパッタリング法、気相成長法、加圧プレス法、溶射法等も用いることができる。
式(1):
式(2):
式(3):
また、薄い被膜(少ない使用量)でも高い防湿性能とイオン伝導性(特にリチウムイオン伝導性)を確保でき、また、電池構築時に使用する溶剤への分散性の低下を抑えることもできる。
また、本開示のコーティング組成物は、硫化物系全固体電池又はその構成部材(正極層、負極層、固体電解質層等)の被覆剤として使用することもでき、上記全固体電池又はその構成部材の内部に水分が侵入することを防止することができる。したがって、上記全固体電池やその構成部材の製造工程においてだけでなく、製造後にも、水分に起因する性能低下を防止することができる。
上述したように、本開示のコーティング組成物は、硫化物系全固体電池に用いられる硫化物系固体電解質の被覆剤として使用することもできるし、硫化物系全固体電池の被覆剤として使用することもできるし、硫化物系全固体電池の構成部材の被覆剤として使用することもできる。
硫化物系全固体電池の構成部材の被覆剤として使用する場合は、硫化物系固体電解質を含む部材(正極、負極、固体電解質層等)の被覆剤として使用することが好ましい。
硫化物系全固体電池又はその構成部材に適用する場合、形成途中又は形成後の全固体電池に適用してもよく、形成途中又は形成後の構成部材に適用してもよい。
硫化物系固体電解質を用いて硫化物系全固体電池又はその構成部材を形成する工程、及び、形成途中又は形成後の上記全固体電池又はその構成部材に本開示のコーティング組成物を適用する工程を含む硫化物系全固体電池又はその構成部材の製造方法も、本開示の好適な態様の1つである。
Arガス充填グローブボックス内で硫化リチウム(Li2S)と五硫化リン(P2S5)の粉末をLi2S:P2S5=75:25のモル比となるように秤量し、混合した後、遊星ボールミル(ジルコニア製45mL容器、ジルコニアボールφ=10mm×10)により、回転速度370rpmで、40時間メカニカルミリングし、固体電解質粒子(粉体)を得た。
各製造例では、以下の含フッ素ポリマーを使用した。
含フッ素ポリマー1:
メタクリル酸パーフルオロヘキシルエチル(CH2=C(CH3)COOCH2CH2C6F13:以下「Rf(C6)メタクリレート」と省略)/メタクリル酸イソボルニル(以下「iBMA」と省略)=100/14.3(質量比)共重合体(ポリマー重量平均分子量:115,500)
含フッ素ポリマー2:
Rf(C6)メタクリレート/iBMA/メタクリル酸3-(トリメトキシシリル)プロピル(以下「TMSMA」と省略)=100/14.49/2.373(質量比)共重合体(ポリマー重量平均分子量:118,800)
含フッ素ポリマー3:
Rf(C6)メタクリレート/メタクリル酸ブチル(以下「BMAと省略)=100/15.2(質量比)共重合体(ポリマー重量平均分子量:115,000)
含フッ素ポリマー4:
Rf(C6)メタクリレート/iBMA=100/66.67(質量比)共重合体(ポリマー重量平均分子量:138,000)
含フッ素ポリマー5:
α―フルオロアクリル酸パーフルオロヘキシルエチル(CH2=C(F)COOCH2CH2C6F13/2-メチル-2-アダマンチルメタアクリレート=100/25.0(質量比)共重合体(ポリマー重量平均分子量:105,500)
含フッ素ポリマー6:
α―トリフルオロメチルアクリル酸パーフルオロブチルエチル(CH2=C(CF3)COOCH2CH2C4F9/シクロヘキシルメタクリレート=100/5(質量比)共重合体(ポリマー重量平均分子量:182,900)
上記含フッ素ポリマーとHFE7200溶媒を用いて表1に示す固形分濃度に調整し、コーティング溶液を作製した。コーティング溶液21gを上記で得られた固体電解質粉体9gをジューサーミキサーに入れ、撹拌後、処理粉体を乾燥させ、溶媒を除去し、ポリマー被覆粒子を得た。
上記含フッ素ポリマー4とヘプタンを用いて、表1に示す固形分濃度に調整し、コーティング溶液を作製した。コーティング溶液21gを上記で得られた固体電解質粉体9gをジューサーミキサーに入れ、撹拌後、処理粉体を乾燥させ、溶媒を除去し、ポリマー被覆粒子を得た。
上記含フッ素ポリマー5とHFE7200溶媒を用いて、表1に示す固形分濃度に調整し、コーティング溶液を作製した。コーティング溶液21gを上記で得られた固体電解質粉体9gをジューサーミキサーに入れ、撹拌後、処理粉体を乾燥させ、溶媒を除去し、ポリマー被覆粒子を得た。
製造例17
上記含フッ素ポリマー6とHFE7200溶媒を用いて、表1に示す固形分濃度に調整し、コーティング溶液を作製した。コーティング溶液21gを上記で得られた固体電解質粉体9gをジューサーミキサーに入れ、撹拌後、処理粉体を乾燥させ、溶媒を除去し、ポリマー被覆粒子を得た。
製造例1~17で得られた各ポリマー被覆粒子を用いて、以下の方法でイオン伝導度測定、H2S発生量の測定、電解質塗料中の分散性の評価を実施した。結果を表2に示す。
Arガス充填グローブボックス内でポリマー被覆粒子を100mg秤量し、1cm2の面積のペレット成型機を用いて4.3ton/cm2の圧力でペレット状に成型し、交流インピーダンス法を用いてイオン伝導度を測定した。
ポリマー被覆粒子100mgを、温度25℃、相対湿度40%に保ったデシケーター内で暴露し、硫化水素センサーを用いて、暴露20分後と120分後の硫化水素の発生量を測定した。
ポリマー被覆粒子49質量%とスチレンブタジエンゴム(SBR)1質量%とヘプタン50質量%を混合し、超音波(37kHz)で1時間処理して電解質塗料を作製し、アルミニウム箔状に塗布した。目視で均一に塗布できた場合は〇、均一に塗布できなかった場合は×と評価した。
ポリマー被覆しなかった固体電解質粒子を用いること以外は実施例1と同様にしてイオン伝導度測定、H2S発生量の測定、電解質塗料中の分散性の評価を実施した。結果を表2に示す。
比較製造例1、2で得られたポリマー被覆粒子を用いる以外は実施例1と同様にしてイオン伝導度測定、H2S発生量の測定、電解質塗料中の分散性の評価を実施した。結果を表2に示す。
Claims (5)
- 硫化物系粒子の表面が含フッ素ポリマーで被覆された被覆粒子であって、
前記含フッ素ポリマーは、下記式(1)で表される単量体(1)に基づく構成単位(1)と、
下記式(2)で表される単量体(2)、下記式(3)で表されるアルコキシシリル基含有モノマー(3)及びビニル系モノマーからなる群より選択される少なくとも1種に基づく構成単位(2)とを含む
ことを特徴とする被覆粒子。
式(1):
式(2):
式(3):
- 請求項1記載の被覆粒子及び正極活物質を有する正極。
- 請求項1記載の被覆粒子及び負極活物質を有する負極。
- 請求項2記載の正極を有する正極層と、請求項3記載の負極を有する負極層と、前記正極層及び前記負極層の間に形成された、請求項1記載の被覆粒子を有する固体電解質層とを有する全固体電池。
- 含フッ素ポリマー及び有機溶剤を含有し、
前記含フッ素ポリマーは、下記式(1)で表される単量体(1)に基づく構成単位(1)と、
下記式(2)で表される単量体(2)、下記式(3)で表されるアルコキシシリル基含有モノマー(3)及びビニル系モノマーからなる群より選択される少なくとも1種に基づく構成単位(2)とを含む
ことを特徴とする硫化物系全固体電池用コーティング組成物。
式(1):
式(2):
式(3):
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KR1020217012018A KR102605125B1 (ko) | 2018-11-08 | 2019-11-07 | 피복 입자, 정극, 부극, 전고체 전지, 및 황화물계 전고체 전지용 코팅 조성물 |
EP19881270.3A EP3854826A4 (en) | 2018-11-08 | 2019-11-07 | COATED PARTICLES, POSITIVE ELECTRODE, NEGATIVE ELECTRODE, ALL-SOLID BATTERY, AND COATING COMPOSITION FOR ALL-SOLID SULPHIDE BATTERIES |
JP2020555585A JP7239846B2 (ja) | 2018-11-08 | 2019-11-07 | 被覆粒子、正極、負極、全固体電池、及び、硫化物系全固体電池用コーティング組成物 |
CN201980072114.8A CN112969730B (zh) | 2018-11-08 | 2019-11-07 | 被覆颗粒、正极、负极、全固态电池以及硫化物系全固态电池用涂布组合物 |
US17/240,053 US20210249700A1 (en) | 2018-11-08 | 2021-04-26 | Coated particles, positive electrode, negative electrode, all-solid-state battery, and coating composition for sulfide-based all-solid-state batteries |
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US17/240,053 Continuation US20210249700A1 (en) | 2018-11-08 | 2021-04-26 | Coated particles, positive electrode, negative electrode, all-solid-state battery, and coating composition for sulfide-based all-solid-state batteries |
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EP (1) | EP3854826A4 (ja) |
JP (1) | JP7239846B2 (ja) |
KR (1) | KR102605125B1 (ja) |
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KR20230129943A (ko) * | 2022-03-02 | 2023-09-11 | 주식회사 엘지화학 | 복합 고체 전해질 및 이를 포함하는 전고체 전지 |
WO2024049097A1 (ko) * | 2022-08-30 | 2024-03-07 | 주식회사 엘지화학 | 복합 고체 전해질, 이의 제조 방법 및 이를 포함하는 전고체 전지 |
KR20240110399A (ko) * | 2023-01-06 | 2024-07-15 | 삼성에스디아이 주식회사 | 고체 전해질, 고체 전해질 막, 양극 및 전고체 이차 전지 |
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- 2019-11-07 CN CN201980072114.8A patent/CN112969730B/zh active Active
- 2019-11-07 JP JP2020555585A patent/JP7239846B2/ja active Active
- 2019-11-07 EP EP19881270.3A patent/EP3854826A4/en active Pending
- 2019-11-07 WO PCT/JP2019/043679 patent/WO2020095996A1/ja unknown
- 2019-11-07 KR KR1020217012018A patent/KR102605125B1/ko active IP Right Grant
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See also references of EP3854826A4 |
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EP3854826A1 (en) | 2021-07-28 |
KR20210065147A (ko) | 2021-06-03 |
CN112969730A (zh) | 2021-06-15 |
KR102605125B1 (ko) | 2023-11-27 |
JPWO2020095996A1 (ja) | 2021-10-07 |
EP3854826A4 (en) | 2022-06-22 |
CN112969730B (zh) | 2023-02-28 |
JP7239846B2 (ja) | 2023-03-15 |
US20210249700A1 (en) | 2021-08-12 |
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