JP2015088479A5

JP2015088479A5 -

Info

Publication number: JP2015088479A5
Application number: JP2014190588A
Authority: JP
Filing date: 2014-09-18
Publication date: 2015-12-03
Anticipated expiration: 2034-09-18

Description

式（ｂ１）〜（ｂ４）において、Ｒ^１１およびＲ^１２はそれぞれ独立に水素原子またはアルキル基を表す。Ｘ^１１、Ｘ^２１、Ｘ^３１、Ｘ^３２およびＸ^４１〜Ｘ^４３はそれぞれ独立に酸素原子または硫黄原子を表す。ｌは１〜４の整数を表す。
〔７〕さらに、周期律表第１族または第２族に属する金属イオンの挿入放出が可能な活物質を含む〔１〕〜〔６〕のいずれか１つに記載の固体電解質組成物。
〔８〕重合性官能基を２つ以上有する化合物が、下記式（Ｂ−１）〜（Ｂ−５）のいずれかで表される〔１〕〜〔７〕のいずれか１つに記載の固体電解質組成物。
In formulas (b1) to (b4), R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group. X ¹¹ , X ²¹ , X ³¹ , X ³² and X ^{41 to} X ⁴³ each independently represent an oxygen atom or a sulfur atom. l represents an integer of 1 to 4;
[7] The solid electrolyte composition according to any one of [1] to [6], further including an active material capable of inserting and releasing metal ions belonging to Group 1 or Group 2 of the periodic table .
[8 ] The compound according to any one of [1] to [ 7 ], wherein the compound having two or more polymerizable functional groups is represented by any one of the following formulas (B-1) to (B-5): Solid electrolyte composition.

式（ｑ−１）〜（ｑ−５）において、Ｌ^４は、単結合、−Ｏ−、−ＣＯ−、−Ｏ（Ｃ＝Ｏ）−、炭素数１〜６のアルキレン基、−Ｏ−Ｒ^Ｌ−、−ＣＯ−Ｒ^Ｌ−、−Ｏ（Ｃ＝Ｏ）−Ｒ^Ｌ−または−（Ｃ＝Ｏ）Ｏ−Ｒ^Ｌ−を表す。ここで、Ｒ^Ｌは炭素数１〜６のアルキレン基を表す。Ｒは炭素数１〜６のアルキル基を表す。Ｐ１は０〜３の整数を表す。Ｐ２は０〜９の整数を表す。Ｐ３は０〜５の整数を表す。
〔９〕固体電解質１００質量部に対して、重合性官能基を２つ以上有する化合物を０．１質量部以上５０質量部以下含有する〔１〕〜〔８〕のいずれか１つに記載の固体電解質組成物。
〔１０〕〔１〕〜〔９〕のいずれか１つに記載の固体電解質組成物の膜を金属箔上に有する電池用電極シート。
〔１１〕〔１〕〜〔９〕のいずれか１つに記載の固体電解質組成物の重合硬化膜を金属箔上に有する〔１０〕に記載の電池用電極シート。
〔１２〕２００℃１時間保持前後での質量の減少が１％以下である〔１０〕または〔１１〕に記載の電池用電極シート。
〔１３〕〔１〕〜〔９〕のいずれか１つに記載の固体電解質組成物を金属箔上に配置し、固体電解質組成物を製膜する電池用電極シートの製造方法。
〔１４〕製膜時に、重合性官能基を２つ以上有する化合物を重合させる〔１３〕に記載の電池用電極シートの製造方法。
〔１５〕〔１４〕に記載の電池用電極シートの製造方法を介して、全固体二次電池を製造する全固体二次電池の製造方法。
In formulas (q-1) to (q-5), L ⁴ represents a single bond, —O—, —CO—, —O (C═O) —, an alkylene group having 1 to 6 carbon atoms, —O—. R ^L —, —CO—R ^L —, —O (C═O) —R ^L — or — (C═O) O—R ^L — is represented. Here, R ^L represents an alkylene group having 1 to 6 carbon atoms. R represents an alkyl group having 1 to 6 carbon atoms. P1 represents an integer of 0 to 3. P2 represents an integer of 0 to 9. P3 represents an integer of 0 to 5.
[ 9 ] The compound according to any one of [1] to [ 8 ], containing 0.1 to 50 parts by mass of a compound having two or more polymerizable functional groups with respect to 100 parts by mass of the solid electrolyte. Solid electrolyte composition.
[10] [1] The membrane cell electrode sheet that Yusuke on a metal foil of a solid electrolyte composition according to any one of to [9].
[11] [1] cell electrode sheet according to the polymerization cured film of the solid electrolyte composition that the Yusuke on a metal foil (10) according to any one of to [9].
[ 12 ] The battery electrode sheet according to [ 10 ] or [ 11 ], wherein a decrease in mass before and after holding at 200 ° C. for 1 hour is 1% or less .
[13 ] A method for producing a battery electrode sheet, wherein the solid electrolyte composition according to any one of [1] to [ 9 ] is disposed on a metal foil, and the solid electrolyte composition is formed into a film.
[ 14 ] The method for producing an electrode sheet for a battery according to [ 13 ], wherein a compound having two or more polymerizable functional groups is polymerized during film formation.
[ 15 ] A method for producing an all-solid secondary battery, comprising producing an all-solid secondary battery via the method for producing an electrode sheet for a battery according to [ 14] .

Claims

Containing an inorganic solid electrolyte having conductivity of ions of metals belonging to Group 1 or Group 2 of the Periodic Table and a compound having two or more polymerizable functional groups, wherein at least one of the polymerizable functional groups is sulfur A solid electrolyte composition which is a functional group having an atom or a cyclic functional group having an oxygen atom.

The solid electrolyte composition according to claim 1, further comprising a light or thermal polymerization initiator.

The solid electrolyte composition according to claim 1, further comprising a lithium salt and a dispersion medium.

The solid electrolyte composition according to any one of claims 1 to 3, wherein the functional group having a sulfur atom or the cyclic functional group having an oxygen atom is a cyclic functional group having 2 to 4 carbon atoms or a mercapto group.

The solid electrolyte composition according to claim 1, wherein the polymerizable functional group other than the functional group having a sulfur atom or the cyclic functional group having an oxygen atom is a group containing a polymerizable unsaturated bond.

6. The compound according to claim 1, wherein the compound having two or more polymerizable functional groups has at least one structure of formulas (b1) to (b4) in the following structural group (b). The solid electrolyte composition described in 1.

In formulas (b1) to (b4), R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group. X ¹¹ , X ²¹ , X ³¹ , X ³² and X ^{41 to} X ⁴³ each independently represent an oxygen atom or a sulfur atom. l represents an integer of 1 to 4;

The solid electrolyte composition according to any one of claims 1 to 6, further comprising an active material capable of inserting and releasing metal ions belonging to Group 1 or Group 2 of the Periodic Table.

The solid electrolyte composition according to any one of claims 1 to 7 , wherein the compound having two or more polymerizable functional groups is represented by any one of the following formulas (B-1) to (B-5). .

In the formulas (B-1) to (B-5), L ¹ is —O—, —S—, —NR ^N —, —CO—, —O (C═O) —, having 1 to 6 carbon atoms. It represents an alkylene group, an alkenylene group having 2 to 6 carbon atoms, an arylene group having 6 to 14 carbon atoms, or a linking group obtained by combining these. Here, ^RN represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. L ² represents an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, an arylene group having 6 to 14 carbon atoms, an aralkylene group having 7 to 15 carbon atoms, or —Si (R ^Si ) ₂ —. . Here, R ^Si represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. L ³ is an alkyl group having 1 to 12 carbon atoms and a q + 1 valence, an alkenyl group having 2 to 12 carbon atoms and a q + 1 valence, an aryl group having 6 to 14 carbon atoms and a q + 1 valence, and an aralkyl having 7 to 15 carbon atoms and a q + 1 valence. Represents a group or a q + 1-valent isocyanuric acid residue. n represents an integer of 1 to 300. m represents an integer of 0 to 300. q represents an integer of 1 to 5. Q ¹ represents a group having a polymerizable functional group, and at least one of the groups having the polymerizable functional group in the molecule is any of the following formulas (q-1) to (q-5). Q ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogen atom, or Q ^1- (L ¹ ) _m- . However, Q ² may be a linking group L ¹ to be dimerized.

In formulas (q-1) to (q-5), L ⁴ represents a single bond, —O—, —CO—, —O (C═O) —, an alkylene group having 1 to 6 carbon atoms, —O—. R ^L —, —CO—R ^L —, —O (C═O) —R ^L — or — (C═O) O—R ^L — is represented. Here, R ^L represents an alkylene group having 1 to 6 carbon atoms. R represents an alkyl group having 1 to 6 carbon atoms. P1 represents an integer of 0 to 3. P2 represents an integer of 0 to 9. P3 represents an integer of 0 to 5.

The solid electrolyte composition according to any one of claims 1 to 8 , comprising 0.1 to 50 parts by mass of a compound having two or more polymerizable functional groups with respect to 100 parts by mass of the solid electrolyte. object.

The membrane electrode sheet for batteries that Yusuke on a metal foil of a solid electrolyte composition according to any one of claims 1-9.

Cell electrode sheet according to claim 10 that having a polymerization curing layer of a solid electrolyte composition according to the metal foil to any one of claims 1-9.

The battery electrode sheet according to claim 10 or 11 , wherein a decrease in mass before and after holding at 200 ° C for 1 hour is 1% or less.

According to Section 1 solid electrolyte composition according to any one of 9 placed on a metal foil, a manufacturing method of the battery electrode sheets forming a film of the solid electrolyte composition.

The method for producing an electrode sheet for a battery according to claim 13 , wherein a compound having two or more polymerizable functional groups is polymerized during the film formation.

The manufacturing method of the all-solid-state secondary battery which manufactures an all-solid-state secondary battery via the manufacturing method of the electrode sheet for batteries of Claim 14 .