JP5447154B2 - Lithium ion conductive solid electrolyte composition and all-solid secondary battery - Google Patents

Description

  The present invention relates to a lithium ion conductive solid electrolyte composition and an all solid state secondary battery using the composition.

  In recent years, secondary batteries such as lithium batteries have been used in various applications such as portable power terminals such as personal digital assistants and portable electronic devices, as well as small household power storage devices, motorcycles, electric vehicles, and hybrid electric vehicles. Has increased.

  As the use expands, further improvements in the safety of secondary batteries are required. In order to ensure safety, a method of preventing liquid leakage and a method of using an inorganic solid electrolyte instead of an organic solvent electrolyte having high flammability and extremely high ignition risk at the time of leakage are effective.

  Patent Document 1 describes an all-solid secondary battery using a slurry composition containing an inorganic solid electrolyte and a butadiene block copolymer (CBC) as a binder. Patent Document 2 describes an all solid state secondary battery using a slurry composition containing an inorganic solid electrolyte and a styrene-ethylene-butylene-styrene block copolymer (SEBS) as a binder. . Patent Document 3 describes a crystalline norbornene-based ring-opening polymer hydride used for packaging films, medical containers and the like.

JP-A-11-86899 Japanese Patent Publication No. 7-87045 WO2009 / 107784

  However, according to the study by the present inventors, it has been found that the slurry composition described in Patent Document 1 is easily gelled and thus has a problem of poor paintability. Further, it is found that when the electrode layer is formed from the slurry composition described in Patent Document 2, the strength of the electrode layer is reduced due to the flexibility of SEBS, and the adhesion of the electrode is deteriorated. It was. Further, in Patent Document 2, it has been found that there is a problem in that battery characteristics such as cycle life characteristics deteriorate due to oxidation of residual double bonds contained in SEBS.

  Accordingly, the present invention has been made in view of the above problems, and is a lithium ion conductive solid electrolyte composition having good paintability, electrode adhesion, and battery cycle life characteristics, and all solids using the composition. An object is to provide a secondary battery.

The gist of the present invention aimed at solving such problems is as follows.
(1) A lithium ion conductive solid electrolyte composition for a secondary battery comprising a solid electrolyte and a polymer,
The polymer opens a norbornene monomer composed of 90 to 100% by weight of 2-norbornene and 10 to 0% by weight of 2-norbornene having a substituent not containing an aliphatic carbon-carbon double bond. ring-opening polymer obtained by cyclic polymer, carbon - comprising more than 99% of the carbon-carbon double bond by hydrogenating the secondary crystalline norbornene ring-opening polymer hydrogenation product of melting point from 110 to 145 ° C. A lithium ion conductive solid electrolyte composition for a battery .

(2) The lithium ion conductive solid electrolyte composition according to (1), wherein a branching index of the crystalline norbornene-based ring-opening polymer hydride is 0.3 to 0.98.

(3) An all-solid secondary battery having a positive electrode having a positive electrode active material layer, a negative electrode having a negative electrode active material layer, and a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer,
At least one layer of the positive electrode active material layer, the negative electrode active material layer, or the solid electrolyte layer contains a lithium ion conductive solid electrolyte and a polymer,
The polymer opens a norbornene monomer composed of 90 to 100% by weight of 2-norbornene and 10 to 0% by weight of 2-norbornene having a substituent not containing an aliphatic carbon-carbon double bond. All solids which are hydrogenated crystalline norbornene-based ring-opening polymers having a melting point of 110 to 145 ° C. obtained by hydrogenating 99% or more of carbon-carbon double bonds of the ring-opening polymer obtained by ring polymerization. Secondary battery.

(4) The all-solid-state secondary battery according to (3), wherein a branching index of the crystalline norbornene-based ring-opening polymer hydride is 0.3 to 0.98.

  According to the present invention, since a gelation can be prevented by using a specific crystalline norbornene-based ring-opening polymer hydride as a binder, a lithium ion conductive solid electrolyte composition having good paintability Can be obtained. In addition, the specific crystalline norbornene-based ring-opening polymer hydride used in the present invention has high strength compared to SEBS and has few residual double bonds, so that an electrode with good adhesion can be obtained, The cycle life characteristics of the battery can be improved.

  Hereinafter, the present invention will be described in the order of (1) a lithium ion conductive solid electrolyte composition and (2) an all-solid secondary battery.

(1) Lithium ion conductive solid electrolyte composition The lithium ion conductive solid electrolyte composition of the present invention comprises a solid electrolyte and a polymer.

Solid electrolyte The solid electrolyte used in the present invention is a lithium ion conductive inorganic solid electrolyte, and is not particularly limited as long as it has lithium ion conductivity. However, a crystalline inorganic lithium ion conductor or an amorphous It is preferable that an inorganic lithium ion conductor is included.

Crystalline inorganic lithium ion conductors include Li ₃ N, LISICON (Li ₁₄ Zn (GeO ₄ ) ₄ , perovskite-type Li _0.5 La _0.5 TiO ₃ , LIPON (Li _{3 + y} PO _4−x N _x ), Thio-LISICON (Li _3.25 Ge _0.25 P _0.75 S ₄ ) and the like, and amorphous inorganic lithium ion conductors include glass Li—Si—S—O, Li—PS, and the like. Among them, from the viewpoint of conductivity, an amorphous inorganic lithium ion conductor is preferable, and sulfide glass composed of Li ₂ S and P ₂ S ₅ is particularly preferable.

Further, the solid electrolyte _preferably contains a _{Li 1 + X Al X Ti 2} -X (PO 4) 3 (0 ≦ x ≦ 2) phosphate compound represented by.

  The average particle size of the solid electrolyte is 1.5 μm or less, preferably 0.3 to 1.3 μm. The 90% cumulative particle size of the solid electrolyte is 2.5 μm or less, preferably 0.5 to 2.3 μm. When the average particle size of the solid electrolyte and the cumulative particle size of 90% are in the above ranges, a lithium ion conductive solid electrolyte composition having good dispersibility and coating property can be obtained. When the average particle size of the solid electrolyte is larger than 1.5 μm, the solid electrolyte in the lithium ion conductive solid electrolyte composition has a high sedimentation rate, and it becomes difficult to form a homogeneous thin film by a coating method or the like. Further, when the 90% cumulative particle size of the solid electrolyte is larger than 2.5 μm, the porosity of the mixture layer (positive / negative electrode active material layer or solid electrolyte layer) containing the solid electrolyte and the polymer increases. Ionic conductivity decreases. On the other hand, if the average particle size of the solid electrolyte or the cumulative 90% particle size is too small, the surface area of the particles increases, and the organic solvent in the composition is difficult to evaporate. For this reason, the drying time becomes longer, and the productivity of the battery decreases.

Polymer The polymer used in the present invention is a norbornene system comprising 90 to 100% by weight of 2-norbornene and 10 to 0% by weight of 2-norbornene having a substituent not containing an aliphatic carbon-carbon double bond. A crystalline norbornene-based ring-opening polymer hydrogen having a melting point of 110 to 145 ° C. obtained by hydrogenating 99% or more of carbon-carbon double bonds of a ring-opening polymer obtained by ring-opening polymerization of a monomer It is a monster. The “crystallinity” in the present invention can be determined by DSC measurement using a differential scanning calorimeter. Specifically, when a DSC curve is obtained by DSC measurement, the DSC curve has no shoulder, shows one maximum endothermic peak, and a single endothermic peak temperature (melting point Tm) can be specified, It can be determined that it is “crystalline”.

(Norbornene monomer)
The norbornene-based monomer used in the present invention is a monomer having a norbornene structure that does not generate a branched structure by an olefin and metathesis reaction, and does not contain 2-norbornene and an aliphatic carbon-carbon double bond. It is composed of 2-norbornene having a substituent.

  When these total amount is 100% by weight, 2-norbornene (bicyclo [2.2.1] hept-2-ene): 90 to 100% by weight, does not include aliphatic carbon-carbon double bond 2-Norbornene having a substituent: 10 to 0% by weight. The proportion of 2-norbornene is preferably 95 to 99% by weight, more preferably 97 to 99% by weight, and the proportion of 2-norbornene having a substituent other than the substituent capable of olefin metathesis reaction is preferably 1 to 5% by weight, more preferably 1 to 3% by weight. When the proportion of 2-norbornene having a substituent other than the substituent capable of undergoing 2-norbornene or olefin metathesis reaction is less than the above range or exceeds the above range, the mechanical properties of the polymer are lowered, and the solid electrolyte and the polymer are contained. The mechanical strength of the mixture layer may decrease.

  2-Norbornene is a known compound and can be obtained, for example, by reacting cyclopentadiene with ethylene.

  The 2-norbornene having a substituent that does not contain an aliphatic carbon-carbon double bond has a substituent that does not contain an aliphatic carbon-carbon double bond and does not have a ring condensed with the 2-norbornene ring. And a norbornene monomer having a ring structure fused to an intramolecular norbornene ring and having a substituent that does not contain an aliphatic carbon-carbon double bond. Separated.

Specific examples of the norbornene monomer having a substituent not containing an aliphatic carbon-carbon double bond and having no ring condensed with the norbornene ring in the molecule include 5-methyl-bicyclo [2.2 .1] Hept-2-ene (5-methyl-2-norbornene), 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept- 2-ene, 5-hexyl-bicyclo [2.2.1] hept-2-ene, 5-decyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2. 1] norbornenes having an alkyl group such as hept-2-ene, 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene;
Norbornenes having an aromatic ring such as 5-phenyl-bicyclo [2.2.1] hept-2-ene (5-phenyl-2-norbornene);
5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene (5-methoxycarbonyl-2-norbornene), 5-ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- Methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonyl-5-methyl-bicyclo [2.2.1] hept-2-ene, 2-methylpropionic acid 5 -Hydroxy-bicyclo [2.2.1] hept-2-ene, 2-methyloctanoic acid 5-hydroxy-bicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-bicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) -bicyclo [2.2.1] hept-2-ene, 5,5-di (hydroxymethyl) -bicyclo [2.2.1] ] Put-2-ene, 5-hydroxyisopropyl-bicyclo [2.2.1] hept-2-ene, 5,6-dicarboxy-bicyclo [2.2.1] hept-2-ene, 6-carboxy- Norbornenes having a polar group containing an oxygen atom such as 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene;
Norbornene having a polar group containing a nitrogen atom such as 5-cyano-bicyclo [2.2.1] hept-2-ene, 6-carboxy-5-cyano-bicyclo [2.2.1] hept-2-ene And the like.

Three or more polycyclic norbornene monomers having a substituent that does not contain an aliphatic carbon-carbon double bond include a norbornene ring in the molecule and one or more rings condensed with the norbornene ring. And a norbornene monomer.
Specifically, dicyclopentadiene such as tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), methyldicyclopentadiene, dimethyldicyclopentadiene;
Tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0 ^{2 , 11} . 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as “1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene”) and the like. Norbornenes;
Tetracyclododecenes having an unsubstituted or alkyl group such as tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyltetracyclododecene, etc. ;
Tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene;
8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid Tetracyclododecenes having a substituent containing an oxygen atom such as tetracyclododecene-8,9-dicarboxylic anhydride;
Tetracyclododecenes having a substituent containing a nitrogen atom such as 8-cyanotetracyclododecene, tetracyclododecene-8,9-dicarboxylic imide;
Tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene;
Tetracyclododecenes having a substituent containing a silicon atom, such as 8-trimethoxysilyltetracyclododecene;
Hexacycloheptadecenes having an unsubstituted or alkyl group such as hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene, etc. ;
Hexacycloheptadecenes having an aromatic ring such as 12-phenylhexacycloheptadecene;
12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene 12,13-dicarboxylic acid, Hexacycloheptadecenes having a substituent containing an oxygen atom such as hexacycloheptadecene 12,13-dicarboxylic anhydride;
Hexacycloheptadecenes having a substituent containing a nitrogen atom such as 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13-dicarboxylic imide;
Hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene;
And hexacycloheptadecenes having a substituent containing a silicon atom such as 12-trimethoxysilylhexacycloheptadecene; and the like.
Norbornene monomers having a substituent that does not contain an aliphatic carbon-carbon double bond can be used singly or in combination of two or more.

  The crystalline norbornene ring-opening polymer hydride used in the present invention preferably has a branched structure. This branched structure can be generated by ring-opening polymerization of a norbornene monomer in the presence of a branching agent. When the crystalline norbornene-based ring-opening polymer hydride has a branched structure, the flexibility of the mixture layer containing the solid electrolyte and the polymer can be improved.

  The branching agent contributes to the olefin metathesis reaction in which a recombination of the bond of two kinds of olefins occurs in the presence of a carbene complex catalyst and a new olefin is generated. The branching agent has an aliphatic carbon-carbon double bond, and has a cycloalkane structure or a cycloalkene structure. Specifically, (1) a compound having two or more cycloalkene structures in the molecule, and (2) one or more substituents containing a cycloalkene structure and an aliphatic carbon-carbon double bond in the molecule. (3) a cycloalkane compound having three or more substituents containing an aliphatic carbon-carbon double bond in the molecule.

  Examples of the substituent containing an aliphatic carbon-carbon double bond include alkenyl groups having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples include a vinyl group, an allyl group, a 3-butenyl group, a 4-pentenyl group, a 2-methyl-3-butenyl group, and a 5-heptyl group. Among these, a vinyl group and an allyl group are preferable because a hydride of a norbornene-based ring-opening polymer having more excellent fluidity can be obtained.

In addition, these alkenyl groups may be bonded to the mother nucleus through an arbitrary group, or may be bonded to the mother nucleus through an arbitrary group to form a ring structure. Specific examples of the arbitrary group include an alkylene group, —O—, —S—, —O—CO—, —O—CH ₂ —O—CO—, and phenylene. The number of elements constituting an arbitrary group is preferably 10 or less, more preferably 5 or less, and other than alkyl groups, because a norbornene-based ring-opening polymer hydride having excellent fluidity can be obtained. Those having no divalent group are preferred.

Such branching agents include 5-vinyl-bicyclo [2.2.1] hept-2-ene, 5-allyl-bicyclo [2.2.1] hept-2-ene, 5-vinyloxycarbonyl- Bicyclo [2.2.1] hept-2-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-allyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . A monomer having a norbornene structure having a substituent capable of undergoing an olefin metathesis reaction, such as 1 ^7,10 ] dodec-3-ene;
exo-trans-exo- pentacyclo [8.2.1.1 ^4,7. 0 ^2,9 . 0 ^3,8 ] tetradeca-5,11-diene (hereinafter sometimes referred to as “NB-dimer”), 4,4a, 4b, 5,8,8a, 9,9a-octahydro-1,4: 5 , 8-bismethano-1H-fluorene, 1α, 4α: 5α, 8α-dimethano-1,4,4a, 5,8,8a, 9,9a, 10,10a-decahydroanthracene, 5,5′-bi ( Norborna-2-ene), tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecane-4,9-diene, 1,4,4a, 5,8,8a, 9,9a, 10,10a-decahydro-1,4: 5,8: 9,10-trimethanoanthracene A monomer having two norbornene structures in the molecule such as
1,2,4-trivinylcyclohexane, 4- (2-propenyl) -1,6-heptadiene, 3-vinyl-1,4-pentadiene, 3-vinyl-1,5-hexadiene, 1,3,5- Monomers having three or more terminal carbon-carbon double bonds in the molecule such as trivinylbenzene, 1,2,4-trivinylbenzene, 1,2,4,5-tetravinylbenzene, etc. Is mentioned.

  For example, as a branching agent, 5-vinyl-bicyclo [2.2.1] hept-2 which is a compound having at least one substituent containing a cycloalkene structure and an aliphatic carbon-carbon double bond in the molecule. When 2-norbornene (2-NB), which is a norbornene-based monomer, is subjected to ring-opening polymerization in the presence of -ene (VNB), a three-branched polymer is generated as shown below.

  (In the formula, M represents a transition metal atom such as tungsten, L represents a ligand such as a halogen atom, R represents an alkyl group, and m, n, and p each represents a positive integer.) 2-norbornene (2-NB) and 5-vinylnorbornene (VNB) undergo a ring-opening metathesis reaction to form a polymer chain (1), and another polymer chain (2-1) undergoes a metathesis reaction. A tri-branched polymer (3) is formed.

  As a branching agent, ring-opening polymerization of 2-norbornene (2-NB), which is a norbornene monomer, in the presence of NB-dimer, which is a compound having two or more cycloalkene structures in the molecule, is as follows. As shown, a 4-branched polymer is produced.

(In the formula, M, L, R, m, n, and p have the same meaning as described above, and q represents a positive integer.)
That is, 2-norbornene (2-NB) and NB-dimer undergo a ring-opening metathesis reaction to produce a polymer chain (4), and another polymer chain (2-1) undergoes a metathesis reaction to form a polymer chain. (5) is generated. Furthermore, 4-norbornene (NB) causes a metathesis reaction to form a 4-branched polymer (6).

  In addition, norbornene is used as a branching agent in the presence of 1,2,4-trivinylcyclohexane (TVC), which is a cycloalkane compound having three or more substituents containing an aliphatic carbon-carbon double bond in the molecule. When ring-opening polymerization of 2-norbornene (2-NB), which is a system monomer, produces a 3-branched polymer as shown below.

(In the formula, M, L, m, n and p have the same meaning as described above.)
That is, the polymer chain (2) obtained from 2-norbornene (2-NB) and the three vinyl groups of 1,2,4-trivinylcyclohexane (TVC) each cause a metathesis reaction to form a three-branched polymer (7) is generated.

  In addition, when the branching agent to be used has a mother nucleus capable of ring-opening metathesis polymerization, this monomer also contributes to the ring-opening polymerization together with a norbornene monomer having no substituent capable of undergoing olefin metathesis reaction.

  The branching index of the crystalline norbornene ring-opening polymer hydride used in the present invention is preferably 0.3 to 0.98, more preferably 0.40 to 0.95. By appropriately adjusting the blending amount of the branching agent in the ring-opening polymerization, a crystalline norbornene-based ring-opening polymer hydride having a desired branching index can be obtained. By setting the branching index to 0.3 or more, gelation when the polymer is dissolved in an organic solvent can be suppressed. Moreover, the flexibility of the mixture layer containing the solid electrolyte layer and the polymer can be maintained by setting the branching index to 0.98 or less.

The branching index is defined by g = [η] Bra / [η] Lin.
[Η] Bra is the limiting viscosity of the branched crystalline norbornene ring-opening polymer hydride, and [η] Lin is the limit of the linear crystalline norbornene ring-opening polymer hydride having the same weight average molecular weight. Viscosity. Here, the intrinsic viscosity [η] is a value obtained by measuring a sample dissolved in cyclohexane at 60 ° C.

  The blending amount of the branching agent is preferably 0.01 to 5 mol%, more preferably 0.05 to 5 mol%, particularly preferably 0.1 when the total amount of norbornene-based monomers is 100 mol%. ~ 5 mol%.

(Metathesis polymerization catalyst)
Examples of the metathesis polymerization catalyst used for the ring-opening polymerization of the norbornene monomer include, for example, Japanese Patent Publication No. 41-20111, Japanese Patent Application Laid-Open No. 46-14910, Japanese Patent Publication No. 57-17834, and Japanese Patent Publication No. 57-61044. (A) a transition metal compound catalyst component and (b) a metal compound described in JP-A-54-86600, JP-A-58-127728, JP-A-1-240517, etc. General metathesis polymerization catalyst comprising a co-catalyst component; Schrock type polymerization catalyst (Japanese Patent Laid-Open No. 7-179575, Schrock et al., J. Am. Chem. Soc., 1990, 112, 3875-etc.) ) And Grubbs type polymerization catalyst (Fu et al., J. Am. Chem. Soc., 1993, 115, 9856-; Nguye n et al., J. Am.Chem.Soc., 1992, 114, 3974-; Grubbs et al., WO 98/21214 pamphlet etc.) and the like.
Among these, a metathesis polymerization catalyst comprising (a) a transition metal compound catalyst component and (b) a metal compound promoter component is preferable in order to adjust the molecular weight distribution of the obtained polymer to a suitable range.

The (a) transition metal compound catalyst component is a compound of a transition metal of Groups 3 to 11 of the periodic table. For example, halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, derivatives of these, or derivatives of these transition metals. A complexed product of a complexing agent such as P (C ₆ H ₅ ) ₃ can be mentioned.
Specific examples include TiCl ₄ , TiBr ₄ , VOCl ₃ , WBr ₃ , WCl ₆ , WOCl ₄ , MoCl ₅ , MoOCl ₄ , WO ₃ , H ₂ WO _{4 and the} like. Of these, W, Mo, Ti, or V is preferable from the viewpoint of polymerization activity and the like, and these halides, oxyhalides, and alkoxy halides are particularly preferable.

The (b) metal compound promoter component is a metal compound of Groups 1 to 2 and Groups 12 to 14 of the periodic table, and has at least one metal element-carbon bond or metal element-hydrogen bond. is there. Examples thereof include organic compounds such as Al, Sn, Li, Na, Mg, Zn, Cd, and B.
Specific examples include organoaluminum compounds such as trimethylaluminum, triisobutylaluminum, diethylaluminum monochloride, methylaluminum sesquichloride, and ethylaluminum dichloride; organotin compounds such as tetramethyltin, diethyldimethyltin, tetrabutyltin, and tetraphenyltin. Organic lithium compounds such as n-butyl lithium; organic sodium compounds such as n-pentyl sodium; organic magnesium compounds such as methyl magnesium iodide; organic zinc compounds such as diethyl zinc; organic cadmium compounds such as diethyl cadmium; Organic boron compounds; and the like. Of these, Group 13 metal compounds are preferred, and Al organic compounds are particularly preferred.

  In addition to the components (a) and (b), a metathesis polymerization activity can be increased by adding a third component. As the third component to be used, aliphatic tertiary amine, aromatic tertiary amine, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound , Halogen-containing compounds, and other Lewis acids.

  The compounding ratio of these components is the molar ratio of the (a) component: (b) component to the metal element, and is usually in the range of 1: 1 to 1: 100, preferably 1: 2 to 1:10. Moreover, (a) component: 3rd component is the range of 1: 0.005-1: 50 normally by molar ratio, Preferably it is the range of 1: 1-1: 10.

  The polymerization catalyst is used in a molar ratio of (transition metal in the polymerization catalyst) :( total monomer), usually 1: 100 to 1: 2,000,000, preferably 1: 1,000 to 1: 20,000, more preferably 1: 5,000 to 1: 8,000. If the amount of the catalyst is too large, it may be difficult to remove the catalyst after the polymerization reaction or the molecular weight distribution may be widened. On the other hand, if the amount is too small, sufficient polymerization activity cannot be obtained.

(Molecular weight regulator)
In the ring-opening polymerization, a molecular weight regulator can be added to the reaction system. The molecular weight of the resulting ring-opening polymer can be adjusted by adding a molecular weight regulator.

  It does not specifically limit as a molecular weight regulator to be used, A conventionally well-known thing can be used. For example, α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; allyl chloride and the like A halogen-containing vinyl compound such as glycidyl methacrylate; a nitrogen-containing vinyl compound such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2 Non-conjugated dienes such as methyl-1,4-pentadiene and 2,5-dimethyl-1,5-hexadiene, or 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1 , 3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc. Mention may be made of the ene or the like. Among these, α-olefins are preferable because of easy molecular weight adjustment.

  The addition amount of the molecular weight regulator may be an amount sufficient to obtain a polymer having a desired molecular weight, and is usually 1:50 to 1: 1 in a molar ratio of (molecular weight regulator) :( total monomer). 1,000,000, preferably 1: 100 to 1: 5,000, more preferably 1: 300 to 1: 3,000.

(Ring-opening polymerization)
Ring-opening polymerization can be initiated by mixing a norbornene monomer, a branching agent, a metathesis polymerization catalyst, and optionally a molecular weight regulator.

  Ring-opening polymerization is usually performed in a solvent. The organic solvent to be used is not particularly limited as long as the polymer and the polymer hydride are dissolved or dispersed under predetermined conditions and do not affect the polymerization and the hydrogenation reaction. Is preferred.

  Examples of such an organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, Alicyclic hydrocarbons such as tricyclodecane, hexahydroindenecyclohexane and cyclooctane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane Halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; diethyl ether and tetrahydrofuran It can be used solvents such as, ethers. These organic solvents can be used alone or in combination of two or more. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and ethers that are widely used in industry are preferable.

  When the polymerization is performed in an organic solvent, the concentration of the monomer (monomer mixture) is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and particularly preferably 3 to 40% by weight. If the concentration of the monomer is less than 1% by weight, the productivity may be lowered, and if it is more than 50% by weight, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction may be difficult.

Although the temperature which performs ring-opening polymerization is not specifically limited, Usually, -20- + 100 degreeC, Preferably it is 10-80 degreeC. If the polymerization temperature is too low, the reaction rate decreases, and if it is too high, the molecular weight distribution may be widened due to side reactions.
The polymerization time is not particularly limited, and is usually 1 minute to 100 hours.
Although the pressure conditions at the time of superposition | polymerization are not specifically limited, When superposing | polymerizing on pressurization conditions, the pressure to apply is 1 MPa or less normally.
After completion of the reaction, the desired norbornene-based ring-opening polymer can be isolated by ordinary post-treatment operation.

(Hydrogenation reaction)
The obtained norbornene-based ring-opening polymer is subjected to the next hydrogenation reaction step. As will be described later, the hydrogenation reaction can be continuously performed without adding a hydrogenation catalyst to the reaction solution subjected to the ring-opening polymerization and isolating the norbornene-based ring-opening polymer.

  The hydrogenation reaction of the norbornene-based ring-opening polymer is a reaction in which hydrogenation is performed on a carbon-carbon double bond existing in the main chain and / or side chain of the norbornene-based ring-opening polymer.

  This hydrogenation reaction is performed by adding a hydrogenation catalyst to an inert solvent solution of a norbornene-based ring-opening polymer and supplying hydrogen into the reaction system.

  As the hydrogenation catalyst, either a homogeneous catalyst or a heterogeneous catalyst can be used as long as it is generally used for hydrogenation of olefin compounds. Considering the removal of residual metals in the resulting polymer, a heterogeneous catalyst is preferable.

  Examples of homogeneous catalysts include cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, etc. Catalyst systems comprising combinations of transition metal compounds and alkali metal compounds such as combinations; dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, bis (tricyclohexylphosphine) And a noble metal complex catalyst such as benzylidine ruthenium (IV) dichloride.

Examples of heterogeneous catalysts include nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, nickel, palladium, platinum, rhodium, ruthenium, Alternatively, a solid catalyst system in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide or the like can be mentioned.
The usage-amount of a catalyst is 0.05-10 weight part normally with respect to 100 weight part of norbornene-type ring-opening polymers.

  As the inert organic solvent used for the hydrogenation reaction, the same aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons as those exemplified as the organic solvent that can be used in the ring-opening polymerization described above. Halogen-containing aromatic hydrocarbons, nitrogen-containing hydrocarbons, ethers and the like.

  The temperature of the hydrogenation reaction varies depending on the hydrogenation catalyst used, but is usually -20 to + 300 ° C, preferably 0 to + 250 ° C. If the hydrogenation temperature is too low, the reaction rate may be slow, and if it is too high, side reactions may occur.

  The hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.1 to 10 MPa, more preferably 1 to 5 MPa. If the hydrogen pressure is too low, the hydrogen addition rate is slow, and if it is too high, a high pressure reactor is required, which is not preferable.

  After completion of the hydrogenation reaction, the hydrogenation catalyst and the like are filtered off from the reaction solution, and the target crystalline norbornene-based ring-opening polymer hydrogen is removed by removing volatile components such as a solvent from the polymer solution after the filtration. The compound can be obtained. In addition, in the hydrogenation reaction liquid, an antioxidant (stabilizer), a nucleating agent, a foaming agent, a flame retardant, a compound such as a thermoplastic resin or a soft polymer, a compounding agent such as a lubricant, Other compounding agents usually used in the resin industry field such as dyes, antistatic agents, ultraviolet absorbers, light stabilizers, waxes and the like may be added, followed by heating as necessary, followed by filtration.

As a method for removing volatile components such as a solvent, a known method such as a coagulation method or a direct drying method can be employed.
The coagulation method is a method in which a polymer is precipitated by mixing a polymer solution with a poor solvent for the polymer. Examples of the poor solvent to be used include polar solvents such as alcohols such as ethyl alcohol, n-propyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate;
The particulate component obtained by solidification is dried by heating, for example, in vacuum, nitrogen or air, or is extruded into a pellet from a melt extruder as necessary. be able to.
The direct drying method is a method in which the polymer solution is heated under reduced pressure to remove the solvent. This method can be carried out using a known apparatus such as a centrifugal thin film continuous evaporation dryer, a scratched heat exchange type continuous reactor type dryer, a high viscosity reactor device or the like. The degree of vacuum and temperature are appropriately selected depending on the device and are not limited.
As described above, the crystalline norbornene-based ring-opening polymer hydride used in the present invention can be obtained.

(Crystalline norbornene ring-opening polymer hydride)
The crystalline norbornene ring-opening polymer hydride used in the present invention has a hydrogenation rate of carbon-carbon double bonds in the norbornene ring-opening polymer of usually 99% or more, preferably 99.9% or more. When in the above range, the crystalline norbornene-based ring-opening polymer hydride has almost no residual double bond, and therefore has excellent oxidation resistance during charge and discharge of the battery. When the hydrogenation rate is less than the above range, resistance to electrochemical oxidation at the time of charging / discharging of the battery is lowered, and battery characteristics such as cycle life characteristics are lowered.
The hydrogenation rate of the crystalline norbornene-based ring-opening polymer hydride can be determined by measuring by ¹ H-NMR using deuterated chloroform as a solvent.

  The isomerization rate of the crystalline norbornene ring-opening polymer hydride used in the present invention is usually 25% or less, preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. By setting the isomerization rate to 25% or less, crystallinity is imparted, and the heat resistance and mechanical strength of the mixture layer containing the solid electrolyte and the polymer are maintained in an appropriate range.

The isomerization rate can be calculated from 33.0 ppm peak integrated value / (31.8 ppm peak integrated value + 33.0 ppm peak integrated value) × 100 measured by ¹³ C-NMR using deuterated chloroform as a solvent. ^{In the 13} C-NMR spectrum, the 31.8 ppm peak is derived from a cis isomer of a repeating unit derived from 2-norbornene in the polymer, and the 33.0 ppm peak is a repeating unit derived from 2-norbornene in the polymer. It is derived from the trans form.

  In order to make the isomerization ratio within the above range, in the hydrogenation reaction of the norbornene-based ring-opening polymer, the reaction temperature is preferably 100 to 230 ° C, more preferably 130 to 220 ° C, and particularly preferably 150 to 210 ° C. The amount of the hydrogenation catalyst used is preferably 0.2 to 5 parts by weight, more preferably 0.2 to 2 parts by weight with respect to 100 parts by weight of the norbornene-based ring-opening polymer. Within such a range, the balance between the hydrogenation reaction rate and the heat resistance of the resulting polymer is excellent and suitable.

  The proportion of the repeating unit (A) derived from 2-norbornene in the crystalline norbornene ring-opening polymer hydride used in the present invention is usually 90% by weight or more, preferably 95% by weight or more, more preferably The proportion of the repeating unit (B) derived from the norbornene monomer having a substituent not containing an aliphatic carbon-carbon double bond is 97% by weight or more, preferably 10% by weight or less, preferably 5 wt% or less, more preferably 3 wt% or less. When the abundance ratio of the repeating unit (A) and the repeating unit (B) is in such a range, the mechanical properties and heat resistance of the mixture layer containing the polymer are improved.

  The crystalline norbornene-based ring-opening polymer hydride used in the present invention has a weight average molecular weight (Mw) measured by a square laser light scattering photometric method by gel permeation chromatography (GPC) using cyclohexane as an eluent. And preferably 50,000 to 200,000, more preferably 70,000 to 180,000, still more preferably 80,000 to 150,000. When the weight average molecular weight (Mw) is less than 50,000, the mechanical properties of the mixture layer containing a polymer are deteriorated. Moreover, when a weight average molecular weight (Mw) exceeds 200,000, the solubility to the organic solvent of a polymer will fall.

  The crystalline norbornene ring-opening polymer hydride used in the present invention has a molecular weight distribution (Mw / Mn) of preferably 1.5 to 10.0, more preferably 2.0 to 9.0, and still more preferably. 3.0 to 8.0, particularly preferably 4.0 to 7.0. When the molecular weight distribution (Mw / Mn) is less than 1.5, the mechanical properties of the mixture layer containing the solid electrolyte and the polymer are deteriorated. Moreover, when molecular weight distribution (Mw / Mn) exceeds 10.0, the workability of a solid electrolyte composition will fall.

  The melting point of the crystalline norbornene-based ring-opening polymer hydride used in the present invention is usually 110 to 145 ° C, preferably 120 to 145 ° C, more preferably 130 ° C to 145 ° C. When the melting point of the crystalline norbornene-based ring-opening polymer hydride is less than 110 ° C., the heat resistance of the crystalline norbornene-based ring-opening polymer hydride is lowered, so that the cycle life characteristics of the battery are lowered. Moreover, when the melting point of the crystalline norbornene ring-opening polymer hydride exceeds 145 ° C., the flexibility of the mixture layer containing the solid electrolyte and the polymer is lowered. The melting point of the crystalline norbornene ring-opening polymer hydride varies depending on the molecular weight, molecular weight distribution, isomerization rate, etc. of the norbornene ring-opening polymer hydride.

  The melt flow rate of the crystalline norbornene-based ring-opening polymer hydride used in the present invention at 230 ° C. and a load of 21.18 N is usually 15 g / 10 min or less, preferably 10 g / 10 min or less. The melt flow rate at 280 ° C. and a load of 21.18 N is usually 100 g / 10 min or less, preferably 70 g / 10 min or less. When the metro flow rate is outside this range, the processability of the mixture layer containing the solid electrolyte and the polymer is lowered.

  It is preferable that the crystalline norbornene-based ring-opening polymer hydride used in the present invention has few foreign matters. Metal residues, foreign matters, and the like may cause deterioration of battery characteristics. After the polymerization reaction or after the hydrogenation reaction, metal residues and foreign matters can be precisely removed by filtering the polymer solution with a filter having a pore size of 0.2 μm or less.

  Since the crystalline norbornene ring-opening polymer hydride used in the present invention is a polymer having a melting point, that is, a polymer that forms a crystal structure, a crystal part is formed (crystallized) inside the molded body, and Combined with the amorphous part, the mechanical properties of the mixture layer containing the solid electrolyte and the polymer are improved.

  The content of the polymer (crystalline norbornene ring-opening polymer hydride) in the lithium ion conductive solid electrolyte composition of the present invention is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the solid electrolyte. More preferably, it is 0.5-15 mass parts, Most preferably, it is 1-10 mass parts. When the content of the polymer is in the above range, the mechanical strength can be maintained while maintaining the ionic conductivity of the mixture layer containing the solid electrolyte and the polymer.

  The manufacturing method of a lithium ion conductive solid electrolyte composition is not specifically limited, It can obtain by mixing the solid electrolyte and polymer mentioned above. The mixing method is not particularly limited, and examples thereof include mixing by a planetary mixer using a solvent and mixing by a bead mill.

(2) All-solid secondary battery The all-solid-state secondary battery of the present invention is a solid electrode between a positive electrode having a positive electrode active material layer, a negative electrode having a negative electrode active material layer, and the positive electrode active material layer and the negative electrode active material layer. The solid electrolyte and the polymer are included in at least one layer of the positive electrode active material layer, the negative electrode active material layer, or the solid electrolyte layer. Hereinafter, the solid electrolyte layer, the positive electrode active material layer, and the negative electrode active material layer will be described in this order.

Solid electrolyte layer The solid electrolyte layer is formed by applying a lithium ion conductive solid electrolyte composition comprising the solid electrolyte and the polymer on a positive electrode active material layer or a negative electrode active material layer and drying it. The

  A lithium ion conductive solid electrolyte composition for forming a solid electrolyte layer (hereinafter sometimes referred to as “composition (A)”) is a solid electrolyte, a polymer, an organic solvent, and other additives added as necessary. Manufactured by mixing the ingredients.

(Organic solvent)
Examples of the organic solvent include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene. These solvents can be used singly or in combination of two or more, and can be appropriately selected from the viewpoint of drying speed and environment. In particular, in the present invention, aromatic carbonization is performed from the viewpoint of reactivity with the solid electrolyte. It is preferable to use a nonpolar solvent selected from hydrogens.

  The content of the organic solvent in the composition (A) is preferably 10 to 700 parts by mass, more preferably 30 to 500 parts by mass with respect to 100 parts by mass of the solid electrolyte. By setting the content of the organic solvent in the above range, good coating properties can be obtained while maintaining the dispersibility of the solid electrolyte in the composition.

  The composition (A) may contain components having functions of a dispersant, a leveling agent, and an antifoaming agent as other components added as necessary in addition to the above components. These components are not particularly limited as long as they do not affect the battery reaction.

(Dispersant)
Examples of the dispersant include an anionic compound, a cationic compound, a nonionic compound, and a polymer compound. A dispersing agent is selected according to the solid electrolyte to be used. The content of the dispersant in the composition is preferably in a range that does not affect the battery characteristics, and specifically 10 parts by mass or less with respect to 100 parts by mass of the solid electrolyte.

(Leveling agent)
Examples of the leveling agent include surfactants such as alkyl surfactants, silicone surfactants, fluorine surfactants, and metal surfactants. By mixing the surfactant, it is possible to prevent repelling that occurs when the composition (A) is applied to the surface of the positive electrode active material layer or the negative electrode active material layer described later, and improve the smoothness of the positive and negative electrodes. be able to. The content of the leveling agent in the composition is preferably in a range that does not affect the battery characteristics, and specifically 10 parts by mass or less with respect to 100 parts by mass of the solid electrolyte.

(Defoamer)
Examples of the antifoaming agent include mineral oil antifoaming agents, silicone antifoaming agents, and polymer antifoaming agents. The antifoaming agent is selected according to the solid electrolyte used. The content of the antifoaming agent in the composition is preferably within a range that does not affect the battery characteristics. Specifically, it is 10 parts by mass or less with respect to 100 parts by mass of the solid electrolyte.

Positive electrode active material layer The positive electrode active material layer is formed by applying a lithium ion conductive solid electrolyte composition comprising the solid electrolyte and the polymer to the surface of a current collector, which will be described later, and drying.

  A lithium ion conductive solid electrolyte composition for forming a positive electrode active material layer (hereinafter sometimes referred to as “composition (B)”) is a solid electrolyte, a polymer, a positive electrode active material, a conductive agent, an organic solvent, and necessary It is manufactured by mixing other components added depending on the case. Moreover, the organic solvent used by the composition (B) and the other component added as needed can use the same thing as what is illustrated by said solid electrolyte layer.

(Positive electrode active material)
The positive electrode active material is a compound that can occlude and release lithium ions. The positive electrode active material is roughly classified into those made of inorganic compounds and those made of organic compounds.

Examples of the positive electrode active material made of an inorganic compound include transition metal oxides, composite oxides of lithium and transition metals, and transition metal sulfides. As the transition metal, Fe, Co, Ni, Mn and the like are used. Specific examples of the inorganic compound used for the positive electrode active material include LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , LiMn ₂ O ₄ , LiFePO ₄ , LiFeVO ₄ and other lithium-containing composite metal oxides; TiS ₂ , TiS ₃ , non- Transition metal sulfides such as crystalline MoS ₂ ; transition metal oxides such as Cu ₂ V ₂ O ₃ , amorphous V ₂ O—P ₂ O ₅ , MoO ₃ , V ₂ O ₅ , V ₆ O ₁₃ It is done. These compounds may be partially element-substituted.

  Examples of the positive electrode active material made of an organic compound include polyaniline, polypyrrole, polyacene, disulfide compounds, polysulfide compounds, and N-fluoropyridinium salts. The positive electrode active material may be a mixture of the above inorganic compound and organic compound.

  The average particle diameter of the positive electrode active material used in the present invention is usually 0.1 to 50 μm, preferably 1 to 20 μm, from the viewpoint of improving battery characteristics such as load characteristics and cycle characteristics. When the average particle size is in the above range, an all-solid secondary battery having a large charge / discharge capacity can be obtained, and handling of the composition and handling when producing the positive electrode are easy. The average particle size can be determined by measuring the particle size distribution by laser diffraction.

  The weight ratio of the positive electrode active material to the solid electrolyte is positive electrode active material: solid electrolyte = 90: 10 to 50:50, preferably 60:40 to 80:20. When the weight ratio of the positive electrode active material is less than the above range, the amount of the positive electrode active material in the battery is reduced, leading to a decrease in capacity as a battery. In addition, when the weight ratio of the solid electrolyte is less than the above range, sufficient conductivity cannot be obtained, and the positive electrode active material cannot be used effectively, leading to a decrease in capacity as a battery.

(Conductive agent)
The conductive agent is not particularly limited as long as it can impart conductivity, and usually includes carbon powders such as acetylene black, carbon black and graphite, and fibers and foils of various metals.

  The content of the conductive agent is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass with respect to 100 parts by mass of the electrode active material. By setting the content of the conductive agent in the above range, it is possible to impart sufficient electron conductivity to the electrode active material layer while keeping the battery capacity high.

  As the organic solvent in the composition and other components added as necessary, those similar to those exemplified in the solid electrolyte layer can be used. The content of the organic solvent in the composition is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass with respect to 100 parts by mass of the positive electrode active material. When the content of the organic solvent in the composition is in the above range, good coating properties can be obtained while maintaining the dispersibility of the solid electrolyte.

  In addition to the above components, the composition (B) may contain additives that exhibit various functions, such as a reinforcing material, as other components added as necessary. These are not particularly limited as long as they do not affect the battery reaction.

Negative electrode active material layer The negative electrode active material layer is formed by applying a lithium ion conductive solid electrolyte composition comprising the solid electrolyte and the polymer to the surface of a current collector, which will be described later, and drying.

  A lithium ion conductive solid electrolyte composition for forming a negative electrode active material layer (hereinafter sometimes referred to as “composition (C)”) includes a solid electrolyte, a polymer, a negative electrode active material, a conductive agent, an organic solvent, and necessary It is manufactured by mixing other components added depending on the case. Moreover, the thing similar to what is illustrated with said positive electrode active material layer can be used for the electrically conductive agent used with a composition (C), the organic solvent, and the other component added as needed.

(Negative electrode active material)
Examples of the negative electrode active material include carbon allotropes such as graphite and coke. The negative electrode active material composed of the allotrope of carbon can also be used in the form of a mixture with a metal, a metal salt, an oxide, or the like or a cover. Moreover, as a negative electrode active material, lithium alloys, such as oxides and sulfates, such as silicon, tin, zinc, manganese, iron, nickel, lithium metal, Li-Al, Li-Bi-Cd, Li-Sn-Cd, Lithium transition metal nitride, silicon, etc. can be used. The average particle diameter of the negative electrode active material is usually 1 to 50 μm, preferably 15 to 30 μm, from the viewpoint of improving battery characteristics such as initial efficiency, load characteristics, and cycle characteristics.

  The weight ratio of the negative electrode active material to the solid electrolyte is negative electrode active material: solid electrolyte = 90: 10 to 50:50, preferably 60:40 to 80:20. When the weight ratio of the negative electrode active material is less than the above range, the amount of the negative electrode active material in the battery is reduced, leading to a decrease in capacity as a battery. In addition, when the weight ratio of the solid electrolyte is less than the above range, sufficient conductivity cannot be obtained, and the negative electrode active material cannot be used effectively, leading to a decrease in capacity as a battery.

(Current collector)
The current collector is not particularly limited as long as it is an electrically conductive and electrochemically durable material. From the viewpoint of having heat resistance, for example, iron, copper, aluminum, nickel, stainless steel, etc. Metal materials such as titanium, tantalum, gold, and platinum are preferable. Among these, aluminum is particularly preferable for the positive electrode, and copper is particularly preferable for the negative electrode. The shape of the current collector is not particularly limited, but a sheet shape having a thickness of about 0.001 to 0.5 mm is preferable. In order to increase the adhesive strength between the current collector and the positive and negative electrode active material layers described above, the current collector is preferably used after being subjected to a roughening treatment. Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method. In the mechanical polishing method, an abrasive cloth paper with a fixed abrasive particle, a grindstone, an emery buff, a wire brush provided with a steel wire or the like is used. Further, an intermediate layer may be formed on the surface of the current collector in order to increase the adhesive strength and conductivity between the current collector and the positive / negative electrode active material layer.

(Production of compositions (A) to (C))
Compositions (A) to (C) are obtained by mixing the components described above.

  Although the mixing method of composition (A)-(C) is not specifically limited, For example, the method using mixing apparatuses, such as a stirring type, a shaking type, and a rotary type, is mentioned. In addition, a method using a dispersion kneader such as a homogenizer, a ball mill, a bead mill, a planetary mixer, a sand mill, a roll mill, and a planetary kneader may be used, and a planetary mixer, ball mill or A method using a bead mill is preferred.

  The all-solid-state secondary battery of the present invention includes a positive electrode having a positive electrode active material layer, a negative electrode having a negative electrode active material layer, and a solid electrolyte layer between the positive and negative electrode active material layers. The coalescence is contained in at least one layer of the positive electrode active material layer, the negative electrode active material layer, or the solid electrolyte layer, preferably in the negative electrode active material layer or the solid electrolyte layer, and more preferably in the negative electrode active material layer. By including a lithium ion conductive solid electrolyte composition in at least one of the positive electrode active material layer, the negative electrode active material layer, or the solid electrolyte layer, an electrode having good adhesion can be obtained and the cycle life characteristics of the battery can be obtained. Can be improved.

  The positive electrode in the all solid state secondary battery of the present invention is produced by applying the above composition (B) onto a current collector and drying to form a positive electrode active material layer. Moreover, the negative electrode in the all-solid-state secondary battery of the present invention is obtained by applying the composition (C) on a current collector different from the positive electrode current collector and drying to form a negative electrode active material layer. Manufactured. Subsequently, a composition (A) is apply | coated on the formed positive electrode active material layer or negative electrode active material layer, and it dries, and forms a solid electrolyte layer. In addition, a solid electrolyte layer can also be formed by apply | coating a composition (A) on a carrier film, drying, and transcribe | transferring on a positive electrode active material layer or a negative electrode active material layer. And an all-solid-state secondary battery element is manufactured by bonding together the electrode which did not form a solid electrolyte layer, and the electrode which formed said solid electrolyte layer.

  The method of applying the composition (B) and the composition (C) to the current collector is not particularly limited. For example, a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush It is applied by painting. The amount to be applied is not particularly limited, but is such an amount that the thickness of the active material layer formed after removing the organic solvent is usually 5 to 300 μm, preferably 10 to 250 μm. The drying method is not particularly limited, and examples thereof include drying with warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams. The drying conditions are usually adjusted so that the organic solvent volatilizes as quickly as possible within a speed range in which stress concentration occurs and the active material layer cracks or the active material layer does not peel from the current collector. Furthermore, you may stabilize an electrode by pressing the electrode after drying. Examples of the pressing method include, but are not limited to, a mold press and a calendar press.

  Drying is performed at a temperature at which the organic solvent is sufficiently volatilized. Specifically, the drying temperature is preferably 50 to 250 ° C, more preferably 80 to 200 ° C. By setting it as the said range, it becomes possible to form a favorable active material layer without thermal decomposition of a binder. Although it does not specifically limit about drying time, Usually, it is performed in the range for 10 to 60 minutes.

  The method for applying the composition (A) to the positive electrode active material layer, the negative electrode active material layer, or the carrier film is not particularly limited, and the method for applying the above-described composition (B) and composition (C) to the current collector is not limited. The gravure method is preferable from the viewpoint that a thin solid electrolyte layer can be formed. The amount to be applied is not particularly limited, but is an amount such that the thickness of the solid electrolyte layer formed after removing the organic solvent is usually 1 to 15 μm, preferably 3 to 14 μm. The drying method, drying conditions, and drying temperature are also the same as those of the composition (B) and the composition (C) described above.

  Furthermore, you may pressurize the laminated body which bonded together the electrode which formed said solid electrolyte layer, and the electrode which did not form a solid electrolyte layer. The pressurizing method is not particularly limited, and examples thereof include a flat plate press, a roll press, and CIP (Cold Isostatic Press). The pressure for pressing is preferably 5 to 700 MPa, more preferably 7 to 500 MPa. This is because by setting the pressure of the pressure press within the above range, the resistance at each interface between the electrode and the solid electrolyte layer, and further, the contact resistance between particles in each layer is lowered, and good battery characteristics are exhibited.

  There is no particular limitation on whether the composition (A) is applied to the positive electrode active material layer or the negative electrode active material layer, but the composition (A) is applied to the active material layer having the larger particle diameter of the electrode active material to be used. It is preferable to do. When the particle diameter of the electrode active material is large, unevenness is formed on the surface of the active material layer. Therefore, the unevenness on the surface of the active material layer can be reduced by applying the composition. Therefore, when the electrode formed with the solid electrolyte layer and the electrode not formed with the solid electrolyte layer are bonded and laminated, the contact area between the solid electrolyte layer and the electrode is increased, and the interface resistance can be suppressed. .

  The obtained all-solid-state secondary battery element is put into a battery container as it is or wound or folded according to the shape of the battery, and sealed to obtain an all-solid-state secondary battery. If necessary, an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate or the like can be placed in the battery container to prevent an increase in pressure inside the battery and overcharge / discharge. The shape of the battery may be any of a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like.

  Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to these examples. Each characteristic is evaluated by the following method. In the examples, “parts” and “%” are “parts by mass” and “% by weight”, respectively, unless otherwise specified.

<Measurement of hydrogenation rate>
The hydrogenation rate of the crystalline norbornene-based ring-opening polymer hydride is obtained by using deuterated chloroform as the solvent, and the peak intensity derived from the carbon-carbon double bond before hydrogenation in ¹ H-NMR, and after hydrogenation The peak intensity derived from the carbon-carbon double bond was measured and determined by the ratio thereof.

<Measurement of melting point>
The melting point was measured by using a differential scanning calorimeter (product name “DSC6220SII”, manufactured by Nanotechnology) based on JIS K 7121 (1987), after heating the sample to a temperature 30 ° C. higher than the melting point, It cooled to room temperature at 10 degreeC / min, and measured at the temperature increase rate of 10 degreeC / min after that.

<Calculation of branching index>
The branching index is obtained by dividing the intrinsic viscosity [η] Bra of a branched norbornene ring-opening polymer hydride by the intrinsic viscosity [η] Lin of a linear norbornene ring-opening polymer hydride having the same weight average molecular weight. It was calculated as a value.

  Intrinsic viscosity [η] is obtained by measuring the viscosity at four points of concentration adjustment with a multi-point method using a Ubbelohde viscometer at 60 ° C for a sample dissolved in cyclohexane, and extrapolating the relationship between each measurement point to zero concentration. Asked.

The intrinsic viscosity of the linear norbornene-based ring-opening polymer hydride having the same weight average molecular weight is the absolute viscosity of the linear norbornene-based ring-opening polymer hydride having a different absolute weight average molecular weight of 4 points or more [η ] Lin = KMw ^a (where [η] Lin is the intrinsic viscosity, Mw is the absolute average molecular weight, and K and a are constants) and are obtained by interpolation.

  The linear norbornene-based ring-opening polymer hydride is a branched norbornene-based ring-opening in the absence of a compound having a substituent capable of olefin metathesis reaction (hereinafter sometimes referred to as “branching agent”). A linear norbornene-based ring-opening polymer having a different weight average molecular weight can be obtained by changing the amount of the molecular weight regulator by copolymerizing the same monomer as the polymer hydride and then hydrogenating it. Obtained.

<Evaluation of paint properties>
It was visually determined whether the compositions obtained in Examples and Comparative Examples showed fluidity at 25 ° C. immediately after preparation. A composition exhibiting fluidity was defined as “good”, and a composition exhibiting no fluidity was defined as “bad”.

<Plate properties: Peel strength>
The electrode on which the solid electrolyte layer is formed is cut into a rectangle having a width of 2.5 cm and a length of 10 cm to form a test piece, which is fixed with the solid electrolyte layer surface facing up. After applying the cellophane tape to the surface of the solid electrolyte layer of the test piece, the stress was measured when the cellophane tape was peeled from the end of the test piece in the direction of 180 ° at a speed of 50 mm / min. The measurement is performed 10 times, the average value is obtained, and this is taken as the peel strength (N / m) and evaluated according to the following criteria. The larger this value is, the better the adhesion strength of the electrode on which the solid electrolyte layer is formed to the current collector and the mechanical strength of the mixture layer containing the solid electrolyte and the polymer.
A: 15 N / m or more B: 10 N / m or more to less than 15 N / m C: 5.0 N / m or more to less than 10 N / m D: less than 5.0 N / m

<Electrode characteristics: flexibility>
The winding characteristics of the produced solid electrolyte layer were evaluated by the following procedure.
The film on which the solid electrolyte layer was produced was subjected to a flexibility test according to a mandrel test (JIS K 5600 (1999)). A mandrel having a diameter of 3 mmφ was used, the solid electrolyte layer was placed on the mandrel on the outside, and the surface was observed with a digital microscope. A ten-sheet flexibility test was performed to determine whether the test was acceptable. The smaller the number of cracks, the better the flexibility of the mixture layer containing the solid electrolyte and the polymer.
A: 1 out of 10 sheets is not broken.
B: Cracks are observed in 1 to 3 sheets out of 10 sheets.
C: Cracks are observed in 4 to 9 sheets out of 10 sheets.
D: Cracks are observed in all 10 sheets.

<Battery characteristics: Battery cycle life characteristics>
The produced all solid state secondary battery was subjected to a charge / discharge test at a current density of 130 μA / cm ² and a voltage range of 3.0 to 4.2 V, and an initial capacity was measured. Furthermore, the capacity retention rate (%) ((discharge capacity at the 20th cycle / discharge capacity at the first cycle) × 100) with the number of charge / discharge cycles was measured. The higher the capacity retention rate, the better the battery cycle life characteristics.

Example 1
Polymer production (ring-opening polymerization)
Under a nitrogen atmosphere, 700 parts of dehydrated cyclohexane was mixed with 0.89 part of 1-hexene, 1.06 part of diisopropyl ether, 0.34 part of triisobutylaluminum, and 0.13 part of isobutyl alcohol in a reactor at room temperature. . There, 250 parts of 2-norbornene (2-NB), 1.25 parts of 5-vinyl-2-norbornene (hereinafter sometimes referred to as “VNB”) and 26 parts of a tungsten hexachloride 1.0% toluene solution. Was continuously added over 2 hours while maintaining the temperature at 55 ° C. to carry out polymerization to obtain a ring-opening polymer. The polymerization conversion rate was almost 100%. In addition, the compounding quantity of VNB which is a branching agent was 0.39 mol% when it was set as 100 mol% in total of 2-NB which is a norbornene-type monomer.

(Hydrogenation reaction)
The reaction solution containing the ring-opening polymer obtained above was transferred to a pressure-resistant hydrogenation reactor, and 1.0 part of diatomaceous earth-supported nickel catalyst (T8400, nickel support rate 58%, manufactured by Zudhemy Catalyst Co., Ltd.) was added thereto. In addition, the reaction was performed at 200 ° C. and a hydrogen pressure of 4.5 MPa for 6 hours. This solution was filtered through a filter equipped with a stainless steel wire mesh using diatomaceous earth as a filter aid to remove the catalyst. The obtained reaction solution was poured into 3000 parts of isopropyl alcohol with stirring to precipitate a hydride, which was collected by filtration. Further, after washing with 500 parts of acetone, it was dried in a vacuum drier set at 0.13 × 10 ³ Pa or less and 100 ° C. for 48 hours to obtain 190 parts of a crystalline norbornene-based ring-opening polymer hydride as a polymer. Obtained.

(Polymer physical properties)
The hydrogenation rate of the obtained crystalline norbornene-based ring-opening polymer hydride was 99.9%, the melting point was 136 ° C., and the branching index was 0.64.

Preparation of Lithium Ion Conductive Solid Electrolyte Composition Sulfide glass ceramic (Li ₂ S—P ₂ S ₅ ) is used as the solid electrolyte, p-xylene is used as the organic solvent, 100 parts of the solid electrolyte, and the above crystalline norbornene ring opening 5 parts of polymer hydride is diluted with p-xylene to a solid content concentration of 50%, mixed with a 1 mmφ zirconia bead in a bead mill for 5 minutes, and a lithium ion conductive solid for forming a solid electrolyte layer. An electrolyte composition was obtained. The paint property of the obtained lithium ion conductive solid electrolyte composition was evaluated. The results are shown in Table 1.

  In addition, in order to perform a flexibility test of the solid electrolyte layer, the obtained lithium ion conductive solid electrolyte composition was applied onto a carrier film made of polyester by a doctor blade method, dried at 120 ° C. for 20 minutes, and then the carrier film The solid electrolyte layer formed above was obtained. The obtained solid electrolyte layer was evaluated for flexibility according to the above flexibility test method. The results are shown in Table 1.

Production of positive electrode 30 parts of LiCoO ₂ as a positive electrode active material, sulfide glass ceramics (Li ₂ S—P ₂ S ₅ ) having an average particle diameter of 1.2 μm and a cumulative 90% particle diameter of 2.3 μm as a solid electrolyte 14 parts, 0.6 part of powdery acetylene black (manufactured by Denki Kagaku Kogyo) as a conductive agent, 1.5 parts of the crystalline norbornene-based ring-opening polymer hydride, and p-xylene 46.1 as an organic solvent Parts are put into a resin container, 130 parts of Zr beads are added, and mixed for 10 minutes (autorotation: 2200 rpm revolution: 500 rpm) with a bead mill to obtain a lithium ion conductive solid electrolyte composition for forming a positive electrode active material layer. It was. An aluminum foil (thickness 20 μm) was used as a current collector, and the composition was applied on the aluminum foil and dried at 120 ° C. for 20 minutes to obtain a positive electrode. The thickness of the positive electrode active material layer after drying was 30 μm.

Production of negative electrode 12.5 parts of graphite as a negative electrode active material, 12.5 parts of sulfide-based glass ceramics (Li ₂ S—P ₂ S ₅ ) as a solid electrolyte, and the crystalline norbornene-based ring-opening polymer hydride described above 0.63 parts and 25.6 parts of p-xylene as an organic solvent are put into a resin container, 130 parts of Zr beads are added, and mixed for 2 minutes (rotation: 2200 rpm revolution: 500 rpm) in a bead mill. A lithium ion conductive solid electrolyte composition for forming a material layer was obtained. A copper foil (thickness 20 μm) was used as a current collector, and the composition was applied on the copper foil and dried at 120 ° C. for 20 minutes to obtain a negative electrode. The film thickness of the negative electrode active material layer after drying was 20 μm.

Preparation of all-solid-state secondary battery A lithium ion conductive solid electrolyte composition for forming a solid electrolyte layer is applied on the surface of the positive electrode active material layer and dried at 120 ° C. for 30 minutes. An electrode on which a solid electrolyte layer was formed was produced. The film thickness of the solid electrolyte layer after drying was 6 μm. The peel strength of the obtained electrode was measured and evaluated according to the above criteria. The results are shown in Table 1.

  The positive electrode on which the solid electrolyte layer is laminated and the negative electrode are punched out to 12 mmφ each, and then the solid electrolyte layer and the negative electrode active material layer surface of the negative electrode are combined and press-pressed at a pressure of 10 MPa, Thus, a positive electrode / solid electrolyte layer / negative electrode laminate was obtained. The capacity ratio was positive electrode: negative electrode = 1: 1.2, and the charge / discharge capacity was regulated to be positive. A coin-type battery was produced from the obtained laminate, and the battery cycle life characteristics were evaluated. The results are shown in Table 1.

(Example 2)
When the blending amount of the branching agent (VNB) in Example 1 is 100 mol% in total of 2-NB that is a norbornene monomer, it is the same as Example 1 except that it is 3.6 mol%. An all-solid secondary battery was fabricated and evaluated. The results are shown in Table 1. The hydrogenation rate of the obtained crystalline norbornene-based ring-opening polymer hydride was 99.9%, the melting point was 134 ° C., and the branching index was 0.43.

(Example 3)
When the blending amount of the branching agent (VNB) in Example 1 is 100 mol% in total of 2-NB that is a norbornene-based monomer, it is the same as Example 1 except that it is 0.14 mol%. An all-solid secondary battery was fabricated and evaluated. The results are shown in Table 1. The hydrogenation rate of the obtained crystalline norbornene-based ring-opening polymer hydride was 99.9%, the melting point was 135 ° C., and the branching index was 0.93.

Example 4
Under a nitrogen atmosphere, 700 parts of dehydrated cyclohexane was mixed with 0.89 part of 1-hexene, 1.06 part of diisopropyl ether, 0.34 part of triisobutylaluminum, and 0.13 part of isobutyl alcohol in a reactor at room temperature. . There, 240 parts of 2-norbornene (2-NB), 10 parts of dicyclopentadiene (DCP), 0.75 parts of 5-vinyl-2-norbornene (VNB) and 26 parts of a tungsten hexachloride 1.0% toluene solution Was continuously added over 2 hours while maintaining the temperature at 55 ° C. to carry out polymerization to obtain a ring-opening polymer. The polymerization conversion rate was almost 100%. In addition, the compounding quantity of VNB which is a branching agent was 0.23 mol% when it was set as 100 mol% in total of 2-NB and DCP which are norbornene-type monomers.

  An all-solid secondary battery was prepared and evaluated in the same manner as in Example 1 except that the ring-opening polymer obtained above was used. The results are shown in Table 1. The hydrogenation rate of the obtained crystalline norbornene-based ring-opening polymer hydride was 99.9%, the melting point was 139 ° C., and the branching index was 0.85.

(Example 5)
An all-solid secondary battery was prepared and evaluated in the same manner as in Example 1 except that the branching agent (VNB) in Example 1 was not blended. The results are shown in Table 1. The hydrogenation rate of the obtained crystalline norbornene-based ring-opening polymer hydride was 99.9%, the melting point was 132 ° C., and the branching index was 0.99.

(Comparative Example 1)
An all-solid secondary battery was prepared and evaluated in the same manner as in Example 1 except that a butadiene block copolymer (CBC) was used as the polymer. The results are shown in Table 1.

(Comparative Example 2)
An all-solid secondary battery was prepared and evaluated in the same manner as in Example 1 except that a styrene-ethylene-butylene-styrene block copolymer (SEBS) was used as the polymer. The results are shown in Table 1.

(Comparative Example 3)
The amount of the branching agent (VNB) in Example 1 was the same as Example 1 except that the amount was 11.72 mol% when the total amount of 2-NB, which is a norbornene monomer, was 100 mol%. An all-solid secondary battery was fabricated and evaluated. The results are shown in Table 1. The hydrogenation rate of the obtained crystalline norbornene-based ring-opening polymer hydride was 99.9%, the melting point was 108 ° C., and the branching index was 0.13.

(Comparative Example 4)
In Example 1, an all-solid-state secondary battery was prepared and evaluated in the same manner as in Example 1 except that a ring-opening polymer was obtained without blending a branching agent and the hydrogenation reaction was performed as follows. It was. The results are shown in Table 1. The hydrogenation rate of the obtained crystalline norbornene-based ring-opening polymer hydride was 99.9%, the melting point was 148 ° C., and the branching index was 0.99.

(Hydrogenation reaction)
The reaction solution containing the ring-opening polymer obtained above was transferred to a pressure-resistant hydrogenation reactor, and 5.25 parts of Pd / CaCO ₃ (Pd amount: 5%) (manufactured by Strem) was added as a catalyst. And a hydrogen pressure of 3.5 MPa for 48 hours. This solution was filtered with a filter equipped with a stainless steel wire mesh using diatomaceous earth as a filter aid to remove the catalyst. The obtained reaction solution was poured into 3000 parts of isopropyl alcohol with stirring to precipitate a hydride, which was collected by filtration. Furthermore, after washing with 500 parts of acetone, it was dried in a vacuum dryer set at 0.13 × 10 ³ Pa or less and 100 ° C. for 48 hours to obtain 190 parts of crystalline norbornene ring-opening polymer hydride as a polymer. Obtained.

(Comparative Example 5)
In Example 1, an all-solid secondary battery was prepared and evaluated in the same manner as in Example 1 except that the hydrogenation reaction was performed using the following ring-opening polymer as the ring-opening polymer. The results are shown in Table 1. The hydrogenation rate of the obtained born norbornene-based ring-opening polymer hydride was 99.9% and the branching index was 1.00. Further, there was no clear melting point, and the glass transition point (Tg) was 100 ° C.

(Ring-opening polymerization)
Under a nitrogen atmosphere, 700 parts of dehydrated cyclohexane were mixed with 0.89 part of 1-hexene, 0.18 part of diisopropyl ether, 0.59 part of triisobutylaluminum, and 0.45 part of isobutyl alcohol in a reactor at room temperature. . Thereto, 85 parts by weight of DCP and 8-ethyltetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] 15 parts of dodec-3-ene (ETD) and 10 parts of tungsten hexachloride 1.0% toluene solution are continuously added over 2 hours while maintaining the temperature at 55 ° C. A ring polymer was obtained. The polymerization conversion rate was almost 100%. In addition, the branching agent was not mix | blended.

(Comparative Example 6)
The same ring-opened polymer as in Example 1 was used, and all the same procedures as in Example 1 were carried out except that the hydrogenation rate of the obtained crystalline norbornene-based ring-opened polymer hydride was 90%. A solid secondary battery was fabricated and evaluated. The results are shown in Table 1. The crystalline norbornene ring-opening polymer hydride had a melting point of 120 ° C. and a branching index of 0.64.

From Table 1, the lithium ion conductive solid electrolyte composition comprising the hydrogenated crystalline norbornene ring-opening polymer of Examples 1 to 5 with a hydrogenation rate of 99% or more and a melting point of 110 ° C to 145 ° C, and all It can be seen that the solid secondary battery is excellent in all of paint properties, electrode plate characteristics, and battery life characteristics.
On the other hand, the lithium ion conductive solid electrolyte composition and the all solid secondary battery containing the hydrogenated polydiene polymer of Comparative Examples 1 and 2 are inferior in at least one of paintability, electrode plate characteristics, and battery life characteristics. It was.
In Comparative Examples 3, 4, and 5, it was found that when the melting point is less than 110 ° C., exceeds 145 ° C., or has no melting point, the electrode plate characteristics are inferior and the battery life characteristics are also deteriorated.
In Comparative Example 6, it was found that when the hydrogenation rate of the crystalline norbornene-based ring-opening polymer hydride was less than 99%, the battery life characteristics were significantly lowered.
From the above, the crystalline norbornene ring-opening polymer hydrides of the examples are excellent in terms of the coating properties, electrode plate characteristics, and battery life characteristics of the solid electrolyte composition required for all-solid secondary batteries. I can say that.

Claims (4)

A lithium ion conductive solid electrolyte composition for a secondary battery comprising a solid electrolyte and a polymer,
The polymer opens a norbornene monomer composed of 90 to 100% by weight of 2-norbornene and 10 to 0% by weight of 2-norbornene having a substituent not containing an aliphatic carbon-carbon double bond. ring-opening polymer obtained by cyclic polymer, carbon - comprising more than 99% of the carbon-carbon double bond by hydrogenating the secondary crystalline norbornene ring-opening polymer hydrogenation product of melting point from 110 to 145 ° C. A lithium ion conductive solid electrolyte composition for a battery .   The lithium ion conductive solid electrolyte composition according to claim 1, wherein a branching index of the crystalline norbornene-based ring-opening polymer hydride is 0.3 to 0.98. An all-solid secondary battery having a positive electrode having a positive electrode active material layer, a negative electrode having a negative electrode active material layer, and a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer,
At least one layer of the positive electrode active material layer, the negative electrode active material layer, or the solid electrolyte layer contains a lithium ion conductive solid electrolyte and a polymer,
The polymer opens a norbornene monomer composed of 90 to 100% by weight of 2-norbornene and 10 to 0% by weight of 2-norbornene having a substituent not containing an aliphatic carbon-carbon double bond. All solids which are hydrogenated crystalline norbornene-based ring-opening polymers having a melting point of 110 to 145 ° C. obtained by hydrogenating 99% or more of carbon-carbon double bonds of the ring-opening polymer obtained by ring polymerization. Secondary battery. The all-solid-state secondary battery according to claim 3, wherein the branching index of the crystalline norbornene-based ring-opening polymer hydride is 0.3 to 0.98.