Solid electrolyte composition, sheet for all-solid state secondary battery, electrode sheet for all-solid state secondary battery and method for manufacturing same, all-solid state secondary battery and method for manufacturing same
Provided are a solid electrolyte composition including an inorganic solid electrolyte, binder particles which include a polymer having an SP value of 10.5 cal 1/2 cm −3/2 or more and have an average particle diameter of 10 nm or more and 50,000 nm or less, and a dispersion medium, a sheet for an all-solid state secondary battery, an electrode sheet for an all-solid state secondary battery, and an all-solid state secondary battery for which the same solid electrolyte composition is used, and methods for manufacturing the electrode sheet for an all-solid state secondary battery and the all-solid state secondary battery.
1. A solid electrolyte composition comprising:
an inorganic solid electrolyte having conductivity for ions of metal elements belonging to Group I or II of the periodic table;
binder particles which include a polymer having an SP value of 11 cal 1/2 cm −3/2 or more and have an average particle diameter of 10 nm or more and 50,000 nm or less, wherein the SP value of the polymer is a value that is computed from the SP values of individual repeating units obtained using the Hoy method; and
a dispersion medium,
wherein the mass-average molecular weight of the polymer forming the binder particles is 5,000 or more, and
the polymer is an acrylic resin and said acrylic resin includes a repeating unit of at least one of monomers represented by the following Formulae (a-1) to (a-3) and (a-7),
wherein the acrylic resin including a repeating unit of a monomer represented by the Formula (a-1) has the repeating unit of a monomer represented by the Formula (a-1) in its main chain and a repeating unit of a macromonomer having a mass-average molecular weight of 1,000 or more and 500,000 or less as the side chain component, said macromonomer containing a repeating unit of a (meth)acrylic acid ester monomer,
in the Formula (a-1), R 11 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, X represents O or >NH, L 11 represents a single bond or an unsubstituted alkylene group having 1 to 3 carbon atoms, and R 12 represents a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or a hydroxyl group (—OH),
in the Formulae (a-2), (a-3) and (a-7), L 11 represents a single bond or a linking group that is selected from a group consisting of a hydrocarbon linking group selected from a group consisting of an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene groups having 2 to 10 carbon atoms, an arylene groups having 6 to 22 carbon atoms, and a combination thereof; a hetero linking group selected from a group consisting of a carbonyl group (—CO—), a thiolcarbonyl group (—CS—), a thioether group (—S—), an imino group (—NR N —), an ammonium linking group (—NR N 2 + —), a polysulfide group having 1 to 8 sulfur atoms, an imine linking group (R N —N═C<, —N═C(R N )—), a sulfonyl group (—SO 2 —), a sulfinyl group (—SO—), a phosphoric acid linking group (—O—P(OH)(O)—O—), a phosphonic acid linking group (—P(OH)(O)—O—), and a combination thereof, wherein R N has the same meaning as R 12 ; and a linking group made of a combination thereof, X represents —O— or >NH, R 11 represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, R 12 represents a hydrogen atom or a substituent, R 13 represents a hydrogen atom, an alkyl group, a hydroxy group-containing group, or a carboxy group-containing group and R 13 may be the linking group of L 11 and constitute a dimer at this portion, and R 15 and R 16 each independently represent a substituent.
2. The solid electrolyte composition according to claim 1 ,
wherein the polymer includes a repeating unit derived from a monomer having an SP value of 12 cal 1/2 cm −3/2 or more or a partial structure derived from a condensation component having an SP value of 12 cal 1/2 cm −3/2 or more in an amount of 35% by mass or more and 100% by mass or less of the entirety of the polymer.
3. The solid electrolyte composition according to claim 1 ,
wherein a glass transition temperature of the polymer is 30° C. or lower.
4. The solid electrolyte composition according to claim 1 ,
wherein the polymer includes a hydroxy group or a carbamoyl group.
5. The solid electrolyte composition according to claim 1 ,
wherein the inorganic solid electrolyte is represented by Formula (1),
L a1 M b1 P c1 S d1 A e1 (1)
in the formula, L represents an element selected from Li, Na, and K, M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge, A represents I, Br, Cl, or F, a1 to e1 represent the compositional ratios among the respective elements, and a1:b1:c1:d1:e1 satisfies 1 to 12:0 to 5:1:2 to 12:0 to 10.
6. The solid electrolyte composition according to claim 1 ,
wherein a C log P value of the dispersion medium is 1 or more.
7. The solid electrolyte composition according to claim 1 ,
wherein the dispersion medium is selected from an ether compound solvent, an aromatic compound solvent, and an aliphatic compound solvent.
8. The solid electrolyte composition according to claim 1 , further comprising:
an active material capable of intercalating and deintercalating ions of metal elements belonging to Group I or Group II of the periodic table.
9. The solid electrolyte composition according to claim 8 ,
wherein the active material is a transition metal oxide or a metal oxide.
10. A sheet for an all-solid state secondary battery, comprising:
a film of the solid electrolyte composition according to claim 1 formed on a base material.
11. An electrode sheet for an all-solid state secondary battery, comprising:
a film of the solid electrolyte composition according to claim 8 formed on a metal foil.
12. The solid electrolyte composition according to claim 1 , wherein L 11 represents the hydrocarbon linking group or the hetero linking group.
13. The solid electrolyte composition according to claim 1 , wherein an SP value of the polymer is 11.5 cal 1/2 cm −3/2 or more.
14. An all-solid state secondary battery comprising:
a positive electrode active material layer;
a solid electrolyte layer; and
a negative electrode active material layer in this order,
wherein at least one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer including an inorganic solid electrolyte having conductivity for ions of metal elements belonging to Group I or II of the periodic table and binder particles which include a polymer having an SP value of 11 cal 1/2 cm −3/2 or more and have an average particle diameter of 10 nm or more and 50,000 nm or less,
wherein the mass-average molecular weight of the polymer forming the binder particles is 5,000 or more, and
the polymer is an acrylic resin and said acrylic resin includes a repeating unit of at least one of monomers represented by the following Formulae (a-1) to (a-3) and (a-7),
wherein the acrylic resin including a repeating unit of a monomer represented by the Formula (a-1) has the repeating unit of a monomer represented by the Formula (a-1) in its main chain and a repeating unit of a macromonomer having a mass-average molecular weight of 1,000 or more and 500,000 or less as the side chain component, said macromonomer containing a repeating unit of a (meth)acrylic acid ester monomer,
in the Formula (a-1), R 11 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, X represents O or >NH, L 11 represents a single bond or an unsubstituted alkylene group having 1 to 3 carbon atoms, and R 12 represents a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or a hydroxyl group (—OH),
in the Formulae (a-2), (a-3) and (a-7), L 11 represents a single bond or a linking group that is selected from a group consisting of a hydrocarbon linking group selected from a group consisting of an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene groups having 2 to 10 carbon atoms, an arylene groups having 6 to 22 carbon atoms, and a combination thereof; a hetero linking group selected from a group consisting of a carbonyl group (—CO—), a thiolcarbonyl group (—CS—), a thioether group (—S—), an imino group (—NR N —), an ammonium linking group (—NR N 2 + —), a polysulfide group having 1 to 8 sulfur atoms, an imine linking group (R N —N═C<, —N═C(R N )—), a sulfonyl group (—SO 2 —), a sulfinyl group (—SO—), a phosphoric acid linking group (—O—P(OH)(O)—O—), a phosphonic acid linking group (—P(OH)(O)—O—), and a combination thereof, wherein R N has the same meaning as R 12 ; and a linking group made of a combination thereof, X represents —O— or >NH, R 11 represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, R 12 represents a hydrogen atom or a substituent, R 13 represents a hydrogen atom, an alkyl group, a hydroxy group-containing group, or a carboxy group-containing group and R 13 may be the linking group of L 11 and constitute a dimer at this portion, and R 15 and R 16 each independently represent a substituent.
15. The all-solid state secondary battery according to claim 14 , wherein L 11 represents the hydrocarbon linking group or the hetero linking group.
16. The all-solid state secondary battery according to claim 14 , wherein an SP value of the polymer is 11.5 cal 1/2 cm −3/2 or more.