CN102714317A - Binder composition for all-solid-state battery and slurry for all-solid-state battery electrode - Google Patents

Binder composition for all-solid-state battery and slurry for all-solid-state battery electrode Download PDF

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CN102714317A
CN102714317A CN2011800059902A CN201180005990A CN102714317A CN 102714317 A CN102714317 A CN 102714317A CN 2011800059902 A CN2011800059902 A CN 2011800059902A CN 201180005990 A CN201180005990 A CN 201180005990A CN 102714317 A CN102714317 A CN 102714317A
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polymer
compound
electrode
construction unit
fully solid
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CN102714317B (en
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西村敏弘
大久保明彦
曾根卓男
丰岛司
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Yinnenshi Materials Co ltd
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JSR Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/622—Binders being polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
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Abstract

Disclosed are: a binder composition for an all-solid-state battery, which is capable of forming an electrode layer with high workability, said electrode layer having high adhesion to a collector and a solid electrolyte layer; and a binder composition for an all-solid-state battery, which is capable of providing a slurry for an all-solid-state battery electrode. Specifically disclosed is a binder composition for an all-solid-state battery, which is characterized by containing a nonpolar liquid organic medium and a binder resin that is composed of a hydrogenated conjugated diene polymer obtained by hydrogenating a polymer, which is selected from among the polymers (a1) and the polymers (a2) described below, and having a hydrogenation degree of not less than 70%. polymers (a1): polymers other than block polymers, which are composed only of structural units derived from a conjugated diene compound polymers (a2): random copolymers which contain structural units derived from a conjugated diene compound and structural units derived from an aromatic vinyl compound, while having a 1,2-vinyl bond content of not more than 70 mol% in the structural units derived from a conjugated diene compound and containing the structural units derived from an aromatic vinyl compound in an amount of less than 40 mass%.

Description

Fully solid adhesive for cell composition and fully solid battery electrode are used slurry
Technical field
The present invention relates to a kind of fully solid adhesive for cell composition and fully solid battery electrode and use slurry; This fully solid adhesive for cell composition uses the structure that this fully solid battery is served as reasons and between pair of electrodes, solid electrolyte layer is set and forms as the formation material in the fully solid battery.
Background technology
In recent years, in battery, be arranged on the electrolyte of the dielectric substrate between positive pole and negative pole,, proposed the use solid electrolyte and replaced liquid electrolyte from viewpoints such as fail safes as formation.
On the other hand; As the manufacturing approach of the electrode that constitutes battery, for example, known following method: the battery that will contain adhesive composition and electrode active material is applied to surface, the drying of collector body with slurry; To the extrusion process of filming that obtains; Thereby at collector body laminated electrode layer, form the electrode of this structure, this adhesive composition is that the adhesive that dissolving is made up of resin in liquid organic media forms.
As the adhesive composition that is used to form kind electrode, the resin that the hydride that use is for example formed by the hydrogenation of styrene-butadiene analog copolymer constitutes etc. are as adhesive (for example, with reference to patent documentation 1 and patent documentation 2).
Yet adaptation, the particularly adaptation to solid electrolyte layer that the electrode layer that is formed with slurry by this battery electrode has collector body are not sufficiently high problems.
In addition, forming with slurry in the process of electrode, particularly passing through methods such as scraper rubbing method and spin-coating method when collector body surface coated battery electrode is used slurry, having the problem that can't obtain enough operation property through battery electrode.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 11-86899 communique
Patent documentation 2: japanese kokai publication hei 08-157677 communique
Summary of the invention
The present invention is based on the problems referred to above proposition; Its purpose is to provide can be had high operation property ground and form electrode layer, can form fully solid adhesive for cell composition and fully solid battery electrode that collector body and solid electrolyte layer are obtained the electrode layer of high adaptation simultaneously and use slurry.
In addition, another purpose of the present invention provides can have high operation property ground formation solid electrolyte layer, can form the fully solid adhesive for cell composition that electrode is obtained the solid electrolyte layer of high adaptation simultaneously.
Fully solid adhesive for cell composition of the present invention uses as the formation material in the fully solid battery; The structure that this fully solid battery is served as reasons and between pair of electrodes, solid electrolyte layer is set and forms; It is characterized in that: this adhesive composition comprises adhesive resin and the nonpolar aqueous organic media that is formed by the hydrogenating conjugate diene base polymer; This hydrogenating conjugate diene base polymer is that the polymer hydrogenation that is selected from following polymer (a1) or following polymer (a2) is formed, and hydrogenation ratio is more than 70%.
Polymer (a1) is the polymer that construction unit beyond the block polymer, an origin self-conjugate diolefin compound constitutes.
Polymer (a2) is a random copolymer; Comprise from the construction unit of conjugated diene compound and construction unit from aromatic ethenyl compound; From 1 in the construction unit of this conjugated diene compound; The content of 2-ethylenic linkage is below the 70mol%, and is proportional less than 40 quality % from containing of the construction unit of this aromatic ethenyl compound.
In fully solid adhesive for cell composition of the present invention, the hydrogenating conjugate diene base polymer that constitutes aforementioned adhesion agent resin be preferably through by the compound shown in the compound shown in the formula (1), the formula (2), in molecule, have the compound of two above ester bonds, in molecule, have the compound of two above epoxy radicals and in molecule, have at least a kind of coupling agent modified material that obtains selecting in the compound of two above vinyl.
In this fully solid adhesive for cell composition, the coupling rate in the aforementioned hydrogenating conjugate diene base polymer is 10～80%.
General formula (1)
R 1 4-n1MX 1 n1
[in the formula, R 1The expression alkyl, M representes tin atom, silicon atom or germanium atom, X 1Expression halogen atom, alkoxyl or acyloxy.N1 is 2～4 integer.]
General formula (2)
R 2 4-n2CX 2 n2
[in the formula, R 2Expression hydrogen atom or alkyl, X 2The expression halogen atom.N2 is 2～4 integer.]
In fully solid adhesive for cell composition of the present invention, the hydrogenating conjugate diene base polymer preferable weight-average molecular weight that constitutes aforementioned adhesion agent resin is 50,000～1,700,000.
In fully solid adhesive for cell composition of the present invention, the construction unit from conjugated diene compound in aforementioned polymer (a1) and the aforementioned polymer (a2) is preferably from the construction unit of butadiene or from the construction unit of isoprene.
In fully solid adhesive for cell composition of the present invention, in the aforementioned polymer (a1) from 1 in the construction unit of conjugated diene compound, the content of 2-vinyl bonds is preferably below the 70mol%.
In fully solid adhesive for cell composition of the present invention, the construction unit from aromatic ethenyl compound in the aforementioned polymer (a2) is preferably from cinnamic construction unit.
Fully solid battery electrode of the present invention is characterised in that with slurry, comprises aforementioned fully solid adhesive for cell composition and electrode active material.
According to fully solid adhesive for cell composition of the present invention, owing to use specific hydrogenating conjugate diene base polymer as adhesive resin, so can be with high operation property formation electrode layer and solid electrolyte layer; And; Form material as electrode, can form the electrode layer that collector body and solid electrolyte layer is obtained high adaptation, in addition; Formation material as solid electrolyte layer can form the solid electrolyte layer that electrode is obtained high adaptation.
In fully solid adhesive for cell composition of the present invention; Pass through to use by the coupling agent modified material that forms as adhesive resin; So when using, can form the electrode layer that collector body and solid electrolyte layer is obtained higher adaptation as the formation material of electrode, and; When the formation material as solid electrolyte layer uses, can form the solid electrolyte layer that electrode is obtained higher adaptation.
Fully solid battery electrode of the present invention with slurry owing to contain electrode active material and aforementioned fully solid adhesive for cell composition; So can be high operation property ground form electrode layer, can form the electrode layer that collector body and solid electrolyte layer is obtained high adaptation simultaneously.
Description of drawings
Fig. 1 confirms electrochemical properties among the expression embodiment and the key diagram of the structure of the determinator that uses.
Embodiment
Below, embodiment of the present invention are described.
< fully solid adhesive for cell composition >
Fully solid adhesive for cell composition of the present invention is to use as the formation material in the fully solid battery; The structure that this fully solid battery is served as reasons and between pair of electrodes, solid electrolyte layer is set and forms; Particularly; Can be used to form electrode and solid electrolyte layer, be particularly suitable for using as the formation material of electrode.
And fully solid adhesive for cell composition of the present invention comprises adhesive resin and the nonpolar liquid organic media that is formed by specific hydrogenating conjugate diene base polymer.
This fully solid adhesive for cell composition is that adhesive resin dissolves in nonpolar liquid organic media or disperses and forms.
(hydrogenating conjugate diene base polymer)
The hydrogenating conjugate diene base polymer that constitutes the adhesive resin in the fully solid adhesive for cell composition of the present invention be with the conjugated diolefine polymer that forms by following polymer (a1) and/or following polymer (a2) (below; Be called " specific conjugated diolefine polymer ") hydrogenation formation, its hydrogenation ratio is more than 70%.
Just, the adhesive resin that constitutes fully solid adhesive for cell composition of the present invention is that the hydride by polymer (a1) forms, formed or the hydride of mixed polymer (a1) and the hydride of polymer (a2) form by the hydride of polymer (a2).
Polymer (a1) is that the construction unit of an origin self-conjugate diolefin compound constitutes, and is the polymer (below, be called " non-block polymer ") beyond the block polymer.
Polymer (a2) is a random copolymer; Comprise from the construction unit of conjugated diene compound with from the construction unit of aromatic ethenyl compound; From 1 in the construction unit of this conjugated diene compound; The content of 2-vinyl bonds is below the 70mol%, and is proportional less than 40 quality % from containing of the construction unit of this aromatic ethenyl compound.
Wherein, The non-block polymer of described polymer (a1) representes not have the polymer of block structure, comprises and for example only contain a kind of homopolymers from the construction unit of conjugated diene compound, has random copolymer from the construction unit of two or more conjugated diene compounds etc.
In addition, in this manual, described " random copolymer " is the polymer with two or more various structure unit, according to ASTM D3418, demonstrates 1 glass transition temperature of measuring through differential scanning calorimetry (DSC) (Tg).
Wherein, when DSC measures, observe 1 glass transition temperature (Tg) in the random copolymer; With respect to this; Observe plural glass transition temperature (Tg) in the block copolymer, based on this reason, the glass transition temperature that observes (Tg) is that 1 material is a random copolymer.
In polymer (a2), must be preferably below the 35 quality % less than 40 quality % from the content of the construction unit of aromatic ethenyl compound, be preferably especially below the 30 quality %.
Proportional when excessive from containing of the construction unit of aromatic ethenyl compound, kinetic property worsens, and just polymer is hard; Can't obtain enough character as adhesive resin; The result is that the electrode layer of formation and the pliability of solid electrolyte layer are little, particularly; When using, produce following problems: in electrode layer and solid electrolyte layer, produce slight crack or in electrode layer, peel off from the collector body generation as the electrode of winding type battery and solid electrolyte layer.
In addition, proportional being preferably more than the 60 quality % that contain from the construction unit of conjugated diene compound in the polymer (a2) is more preferably more than the 80 quality %.
As the conjugated diene compound that is used for obtaining specific conjugated diolefine polymer of the present invention from the construction unit of conjugated diene compound; Use has the straight chain shape of aliphat conjugated double bond or the compound of branched; When specific conjugated diolefine polymer is polymer (a2), use can with the compound of aromatic ethenyl compound copolymerization.
Particularly, can enumerate out for example 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene etc., they can two or more alone or in combination uses.
Among them, preferred butadiene and isoprene are particularly as the preferred 1,3-butadiene of butadiene.
Wherein, Particularly; Polymer (a1) preferably contains the construction unit from butadiene; Be the polymer that only constitutes, contain as the preferred object lesson of polymer (a1), be preferably the polymer (polybutadiene) that only constitutes especially by construction unit from butadiene from the construction unit of butadiene with from the polymer of the construction unit of isoprene by construction unit from butadiene.
In addition, in polymer (a2), be preferably from the construction unit of butadiene or from the construction unit of isoprene from the construction unit of conjugated diene compound.
In addition; Be used for obtaining the aromatic ethenyl compound from the construction unit of aromatic ethenyl compound of specific conjugated diolefine polymer of the present invention; Just be used for obtaining the aromatic vinyl polymer from the construction unit of aromatic ethenyl compound of polymer (a2), use compound or derivatives thereof with the vinyl more than 1 that is connected to the aromatic group that contains aromatic ring or heterocycle.
Particularly, for example can enumerate out styrene, t-butyl styrene, AMS, p-methylstyrene, to ethyl styrene, divinylbenzene, 1,1-diphenyl benzene ethene, vinyl naphthalene etc., they can two or more alone or in combination uses.
Among them, optimization styrene.
In addition, in polymer (a2), can contain together with other construction unit with from the construction unit of conjugated diene compound and from the construction unit of aromatic ethenyl compound.
As the compound that is used to obtain this other construction unit, can use can with the compound of conjugated diene compound and aromatic ethenyl compound copolymerization.
Particularly; As can with the compound of conjugated diene compound and aromatic ethenyl compound copolymerization, can enumerate out for example acrylonitrile, methyl methacrylate, EMA, methyl acrylate, ethyl acrylate, hydroxyethyl methacrylate, hydroxy-ethyl acrylate etc.
In addition, other construction unit in the polymer (a2) contains proportional being preferably below the 40 quality %.
In this specific conjugated diolefine polymer, from 1 in the construction unit of conjugated diene compound, the amount of 2-vinyl bonds is chosen following scope.
In polymer (a1), from 1 in the construction unit of conjugated diene compound, the content of 2-vinyl bonds is preferably below the 70mol%, and more preferably 30mol% is above and be below the 70mol%, is preferably 30～60mol% especially.
1, when the content of 2-vinyl bonds was too small, adhesive resin possibly diminish to the dissolubility of nonpolar liquid organic media.
On the other hand, 1, when the content of 2-vinyl bonds is excessive,, might in the electrode layer that forms, can't obtain enough adaptations to collector body and solid electrolyte layer as the material that forms electrode.In addition, as the material that forms solid electrolyte layer, might in the solid electrolyte layer that forms, can't can't have enough adaptations to electrode layer particularly to electrode.
In addition, in polymer (a2), from 1 in the construction unit of conjugated diene compound, the content of 2-vinyl bonds is necessary for below the 70mol%, and it is above and for below the 70mol% to be preferably 30mol%, is preferably 30～60mol% especially.
1, when the content of 2-vinyl bonds was too small, adhesive resin possibly diminish to the dissolubility of nonpolar liquid organic media.
1, when the content of 2-vinyl bonds is excessive,, might in the electrode layer that forms, can't obtain enough adaptations to collector body and solid electrolyte layer as the material that forms electrode.In addition, as the material that forms solid electrolyte layer, might in the solid electrolyte layer that forms, can't can't have enough adaptations to electrode layer particularly to electrode.
Wherein, described " from 1 in the construction unit of conjugated diene compound, the content of 2-vinyl bonds " is meant that in the entire infrastructure unit from conjugated diene compound, containing of the construction unit shown in the following formula (i) is proportional.In addition, described do not have 1, and the construction unit of 2-vinyl bonds is the construction unit of following formula shown in (ii).
[formula (i) and formula (ii) in, R 3～R 8Represent hydrogen atom or monovalence alkyl independently of one another.]
In addition, from 1 in the construction unit of conjugated diene compound, the content of 2-vinyl bonds can use infrared analysis, measures through the Hampton method.
And the hydrogenation ratio of hydrogenating conjugate diene base polymer of the present invention is necessary for more than 70%, is preferably more than 80%, is preferably more than 90% especially.
When hydrogenation ratio is too small, in the electrode layer that forms, can't obtain enough adaptations to collector body and solid electrolyte layer as the formation material of electrode.In addition, as the formation material of solid electrolyte layer, in the solid electrolyte layer that forms, can't can't have enough adaptations to electrode layer particularly to electrode.
Wherein, the hydrogenation interpolation rate of hydrogenating conjugate diene base polymer can be measured through nulcear magnetic resonance (NMR) optical spectroscopy (NMR).
Particularly, can calculate from the H-NMR spectrogram.
In addition, hydrogenating conjugate diene base polymer of the present invention is preferably through at least a kind of coupling agent modified formation from following (a)～(e).
(a) compound shown in the above-mentioned general formula (1) (below, be called " compound that contains the 14th family's element ")
(b) compound shown in the above-mentioned general formula (2) (below, be called " halogenated hydrocarbon compound ")
(c) in molecule, has the ester group compound that contains of two above ester bonds
(d) in molecule, has the epoxy compounds that contains of two above epoxy radicals
(e) in molecule, has the vinyl compound that contains of two above vinyl
Contain in the general formula (1) of the compound of the 14th family's element R in expression 1The expression alkyl, X 1Expression halogen atom, alkoxyl or acyloxy, M representes Sn (tin atom), Si (silicon atom) or Ge (germanium atom), n1 is 2～4 integer.
In this general formula (1), as expression R 1Alkyl, can enumerate out carbon numbers such as methyl, butyl, hexyl, octyl group for example and be 1～12 alkyl, phenyl etc., be preferably methyl.
As expression X 1Halogen atom, can enumerate out chlorine atom, bromine atoms etc., be preferably the chlorine atom.
In addition, as expression X 1Alkoxyl, can enumerate out methoxyl group, ethyoxyl etc., be preferably methoxyl group.
In addition, as expression X 1Acyloxy, can enumerate out acetoxyl group, benzoyloxy etc., be preferably acetoxyl group.
The compound that contains the 14th family's element as shown in the general formula (1) is preferably X 1Be the compound of halogen atom, tin compound, the silane compound of halogen atom and the germanium compound of halogen atom of preferred particularly halogen atom, the germanium compound of the tin compound of preferred especially chloride atom, the silane compound of chloride atom, chloride atom.
As the tin compound of chloride atom, can enumerate out for example dichloride dibutyl tin, dichloride dihexyl tin, dichloride dioctyl tin, tri-chlorination phenyltin, tri-chlorination butyl tin, tri-chlorination tin octylate, butter of tin etc.
As the silane compound of chloride atom, can enumerate out for example diphenyl dichlorosilane, dihexyl dichlorosilane, dioctyl dichlorosilane, dibutyl dichlorosilane, dimethyldichlorosilane, dimethyldichlorosilane, phenyl trichlorosilane, hexyl trichlorosilane, octyl group trichlorosilane, butyl trichlorosilane, methyl trichlorosilane, silicon tetrachloride etc.
As the germanium compound of chloride atom, can enumerate out for example dichloride dibutyl germanium, dichloride diphenyl germanium, tri-chlorination butyl germanium, germanium tetrachloride etc.
In the general formula (2) of expression halogenated hydrocarbon compound, R 2Expression hydrogen atom or alkyl, X 2The expression halogen atom, n2 is 2～4 integer.
In this general formula (2), as expression R 2Alkyl, for example can enumerate out that carbon numbers such as methyl, ethyl, butyl are alkyl of 1～12 etc., be preferably methyl.
As expression X 2Halogen atom, can enumerate out chlorine atom, bromine atoms, iodine atom, fluorine atom etc., be preferably chlorine atom, bromine atoms and iodine atom.
As the halogenated hydrocarbon compound shown in the general formula (2), can enumerate out for example carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, chloroform, bromoform, iodoformum, carrene, methylene bromide, diiodomethane, trichloroethanes, dichloroethanes etc.
As the ester group compound that contains that in molecule, has two above ester bonds, can enumerate out for example aliphat polybasic ester compound, aromatic series polybasic ester compound and (methyl) acrylate polymer etc.
As aliphat polybasic ester compound; Can enumerate out for example diester malonate compounds such as dimethyl malenate, diethyl malonate, dibutyl malonate, malonic acid two (2-ethylhexyl) ester; Maleate compounds such as dimethyl maleate, diethyl maleate, maleic acid dipropyl, maleic acid dibutyl ester, maleic acid two (2-ethylhexyl) ester, di adipate compounds such as diethylene adipate etc.
As aromatic series polybasic ester compound, can enumerate out for example repefral, trihemellitic acid tributyl, pyromellitic acid four monooctyl esters, mellic acid six ethyl esters etc.
As (methyl) acrylate polymer, can enumerate out for example polymethyl methacrylate, polyethyl acrylate, polyacrylic acid isobutyl etc., its molecular weight is preferably 5,000～1,000,000.
As the oxidant compound that contains that in molecule, has two above epoxy radicals, for example can enumerate out glycidyl ether compound, glycidyl amines, epoxidised soybean oil of (gathering) alkylene glycol diglycidyl ether, polyalcohol etc.
As (gathering) alkylene glycol diglycidyl ether, can enumerate out ethylene glycol diglycidylether, neopentylglycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethyleneglycol diglycidylether etc.
As the glycidyl ether compound of polyalcohol, can enumerate out for example trimethylolpropane polyglycidyl ether, glycerine polyglycidyl ether, sorbitan polyglycidyl ether, bisphenol-A glycidol ether etc.
As the glycidyl amines, can enumerate out for example N, N-diglycidylaniline, N; N-diglycidyl toluidines, N, N-diglycidyl-3-glycidyloxyaniline, N, N-diglycidyl-2-glycidyloxyaniline, N; N; N ', N '-four glycidyl ether ADP methylmethane, N, N-diglycidyl butylamine, triglycidyl group chlorinated isocyanurates etc.
As the vinyl compound that contains that in molecule, has two above vinyl, can enumerate out the mixture of aromatic compound such as divinylbenzene, divinyl biphenyl, divinyl naphthalene for example and these aromatic compounds.
In the hydrogenating conjugate diene base polymer, the coupling rate is preferably 10～80%, and more preferably 20～80%.
When the coupling rate is too small, can't in the electrode layer that forms, obtain enough adaptations to collector body and solid electrolyte layer as the formation material of electrode is possibly.In addition, as the formation material of solid electrolyte layer, maybe be in the solid electrolyte layer that forms, can't obtain electrode specifically to enough adaptations of electrode layer.
Wherein, described " coupling rate " be since the polymer (polymer of modified-reaction is provided through coupling agent) that the coupled reaction agent effect of coupling agent is connected to form have a rate.
Coupling rate in the hydrogenating conjugate diene base polymer can be passed through gel permeation chromatography (GPC) and measure.
Particularly, based on whole peak areas (S0) of the hydrogenating conjugate diene base polymer that obtains through gel permeation chromatography with and do not receive the area (S1) at the coupling agent modified corresponding peak of part, use following mathematical expression (1) to calculate.
Mathematical expression (1)
Figure BPA00001577547800131
In addition, in the hydrogenating conjugate diene base polymer, the modification that has or not coupling agent be except can confirming the coupling rate through said method, for example can also in molecular structure, produce the molecule expansion that branch causes through measuring coupling agent modified and confirm.
Particularly, the modification that coupling agent produces, the molecule expansion that the modified-reaction (coupling reaction) that just produces through coupling agent causes can be tried to achieve from the degree of branching of the branch dendritic of coupling reaction generation.This degree of branching is to measure weight average molecular weight (MwL) of not carrying out coupling agent modified hydrogenating conjugate diene base polymer and the weight average molecular weight (MwL) of carrying out coupling agent modified polymer through GPC-light scattering method (GPC-LALLS method), tries to achieve based on the molecular weight increase of the coupling reaction of calculating like this.
Wherein, described " GPC-light scattering method " is to the solution irradiates light, based on the solute of this solution, measures the method for the fluctuating of light scattering (scattered light).And the principle through GPC-light scattering determining molecular weight is: this fluctuating is that the heat operation of solute molecule causes, and utilizes the high more fluctuating of molecular weight of solute molecule big more, based on the fluctuating quantity in the thin solution, measures bulk of molecule (molecular weight).Through this GPC-light scattering method, can with molecular size determining molecular weight irrespectively.
In addition; Carry out in the coupling agent modified hydrogenating conjugate diene base polymer, the generation ratio of the branch dendritic that coupling reaction forms can be tried to achieve with the ratio (MwL/MwR) of the weight average molecular weight (MwR) of GPC-differential refraction rate method mensuration from the weight average molecular weight (MwL) of GPC-light scattering determining.(MwL/MwR) expresses following relation through this ratio: this value is big more, divides the generation ratio of dendritic big more.
The weight average molecular weight (Mw) that converts according to the polystyrene standard of hydrogenating conjugate diene base polymer of the present invention is preferably 50,000～1,700,000, and more preferably 100,000～1,000,000, be preferably 200,000～600,000 especially.
When the weight average molecular weight of hydrogenating conjugate diene base polymer is excessive; Formation material as electrode; The fully solid battery electrode that is formed by fully solid adhesive for cell composition and electrode active material obviously increases with the viscosity of slurry, possibly can't obtain enough operation property in the electrode forming process.In addition; Formation material as solid electrolyte layer; Also and to form the situation of material as electrode same; The viscosity that contains the slurry of fully solid adhesive for cell composition and solid electrolyte obviously increases, so in the process that forms solid electrolyte layer, possibly can't obtain enough operation property.On the other hand, when the weight average molecular weight of hydrogenating conjugate diene base polymer is too small,, in the electrode layer that forms, possibly can't obtain enough adaptations to collector body and solid electrolyte layer as the formation material of electrode.In addition, as the formation material of solid electrolyte layer, in the solid electrolyte layer that forms, possibly can't obtain enough adaptations to electrode layer specifically to electrode.
In addition, in hydrogenating conjugate diene base polymer of the present invention, the weight average molecular weight (Mw) that converts through polystyrene standard is preferably below 5 with the molecular weight distribution (Mw/Mn) that the ratio of the number-average molecular weight (Mn) of polystyrene standard conversion is represented.
In addition, the glass transition temperature of hydrogenating conjugate diene base polymer of the present invention (Tg) is preferably-90 ℃～0 ℃, more preferably-80 ℃～-40 ℃, be preferably-70～-50 ℃ especially.
Glass transition temperature (Tg) is through in above-mentioned scope, and as the formation material of electrode, the electrode layer that can form has higher closing force to collector body and solid electrolyte layer.In addition, as the formation material of solid electrolyte layer, the solid electrolyte layer of formation has higher closing force to electrode layer specifically to electrode.
This hydrogenating conjugate diene base polymer for example can in the presence of polymerization initiator, carry out polymerization reaction with monomer in hydrocarbon solvent, particularly, obtain polymer through being carried out polymerization reaction by the monomer that conjugated diene compound constitutes; Perhaps will be and be used to obtain the monomer that other compounds of other construction units constitutes as required and carry out polymerization reaction by conjugated diene compound, aromatic ethenyl compound; Obtain polymer, afterwards, the polymer that polymerization reaction is obtained is under this state; Form specific conjugated diolefine polymer; Perhaps carry out modification through coupling agent as required, the material that obtains is formed specific conjugated diolefine polymer, this specific conjugated diolefine polymer hydrogenation is made.
Polymerization reaction as being used for obtaining specific conjugated diolefine polymer is used hydrocarbon solvent, can share for example pentane, hexane, heptane, methyl cyclopentane, cyclohexane, benzene,toluene,xylene etc.Among them, preferred cyclohexane, heptane.
The total concentration of the preferred conjugated diene compound of the consumption of hydrocarbon solvent, aromatic ethenyl compound and other compound is the amount of 5～30 quality %, more preferably the amount of 7～20 quality %.
In addition, as polymerization initiator, be fit to use organic alkali metal or organic base earth metal.
Particularly, can enumerate out for example lithium alkylides such as n-BuLi, s-butyl lithium, tert-butyl lithium; 1, alkylidene two lithiums such as 4-two lithium butane; Phenyl lithium, stilbene lithium, naphthalene lithium, naphthalene sodium, naphthalene potassium, normal-butyl magnesium, n-hexyl magnesium, barium ethoxide, barium isopropoxide, ethyl sulfydryl barium, tert-butoxy barium, phenoxy group barium, diethylamino barium, barium stearate etc.
In addition, as polymerization initiator, can also use the product of organic alkali metal and amines.As this organic alkali metal, preferably use organo-lithium compound, more preferably use n-BuLi, s-butyl lithium.In addition, as the organic alkali metal of polymerization initiator use and the product of amines, can be the lithium amide compound, also can be other compound.
At the polymerization reaction system that is used for obtaining specific conjugated diolefine polymer; Through using organic alkali metal or organic base earth metal as polymerization initiator; Can control in the polymer that obtains from 1 in the construction unit of conjugated diene compound; The content of 2-vinyl bonds, and can be through coupling agent modified material with the polymer that obtains.
With respect to the total amount 1g of conjugated diene compound, aromatic ethenyl compound and other compound, the consumption of polymerization initiator converts with alkali metal atom or alkaline-earth metal raw material, is preferably 0.002～0.1mmol, more preferably 0.005～0.03mmol.
In addition, in the polymerization reaction that is used for obtaining specific conjugated diolefine polymer,, can control in the polymer that obtains from 1 in the construction unit of conjugated diene compound, the amount of 2-vinyl bonds through in this reaction system, adding the vinyl controlling agent.
As the vinyl controlling agent; Can use for example ether compounds such as oxolane, Anaesthetie Ether, dimethoxy benzene, dimethoxy-ethane, ethylene glycol bisthioglycolate butyl ether particularly, triethylamine, pyridine, N, N; N ', the tertiary amine compound of N '-tetramethylethylenediamine, two piperidines-1-base ethane etc.
Through coupling agent modified method, can use known method as the polymer that polymerization reaction is obtained.
Alkali-metal every 1g atom equivalent of relative polymerization initiator, the consumption of coupling agent is preferably 0.005～1mol, more preferably 0.01～0.5mol.
As the method that is used for specific conjugated diolefine polymer hydrogenation, can use known method, for example specific conjugated diolefine polymer is dissolved in the appropriate solvent, in the presence of hydrogenation catalyst, handle hydrogen and carry out.
The condition that is used to handle hydrogen does not have special qualification, normally under 20～150 ℃, and the pressurized with hydrogen of 0.1～10MPa.
In addition, hydrogen interpolation rate can change arbitrarily through changing conditions such as catalytic amount, Hydrogen Vapor Pressure, reaction time.
As solvent, the hydrocarbon solvent that can use the polymerization reaction that for example is used for obtaining specific conjugated diolefine polymer to use.
As hydrogenation catalyst, for example use the compound that contains Ti atom, V atom, Co atom, Ni atom, Zr atom, Ru atom, Rh atom, Pd atom, Hf atom, Re atom, Pt atom.
Particularly, can enumerate out the Metallocenic compound of Ti, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, Pt etc.; Metals such as Pd, Ni, Pt, Rh, Ru are carried the inhomogeneous type of catalyst that on carriers such as carbon, silica, aluminium oxide, diatomite, forms; The organic salt of metallic elements such as combination Co, Ni or the even type of Ziegler-type catalyst that reducing agents such as acetylacetonate and organo-aluminium form; Organo-metallic compound such as Ru, Rh or complex compound; Receive fullerene or CNT of hydrogen etc.
Among them; From can be (particularly at inert organic solvents; Hydrocarbon solvents such as alkane, cycloalkane, toluene, xylenes for example, MEK, ethyl acetate, ether, oxolane isopolarity solvent) in, in homogeneous system, carry out hydrogenation to set out; The preferred Metallocenic compound that uses Ti, Co, Ni, Zr, Hf; More preferably use the Metallocenic compound of Ti, Zr, Hf,, especially preferably use the catalyst of two cyclopentadiene titanium compounds and lithium alkylide prepared in reaction because cheapness and industry are upward useful.
Wherein, As the catalyst of two cyclopentadiene titanium compounds and lithium alkylide prepared in reaction, can enumerate out the catalyst of record in japanese kokai publication hei 1-275605 communique, japanese kokai publication hei 5-271326 communique, japanese kokai publication hei 5-271325 communique, japanese kokai publication hei 5-222115 communique, japanese kokai publication hei 11-292924 communique, TOHKEMY 2000-37632 communique, japanese kokai publication sho 59-133203 communique, the special public clear 63-5401 communique of Japan, japanese kokai publication sho 62-218403 communique, japanese kokai publication hei 7-90017 communique, the special public clear 43-19960 communique of Japan, the special public clear 47-40473 communique of Japan etc.In addition, these catalyst can use separately, also can make up two or more uses.
(nonpolar aqueous organic solvent)
The nonpolar liquid medium that constitutes fully solid adhesive for cell composition of the present invention does not have special qualification, can use for example varsols such as hexane, heptane, octane, silane, dodecane; Aromatic hydrocarbon solvents such as toluene, xylenes, mesitylene, cumene; Ketones solvent such as methyl hexyl ketone, dipropyl ketone; Esters solvent such as butyl acetate, methyl butyrate; Ether solvent such as dibutyl ethers, oxolane etc.These solvents can two or more alone or in combination uses.
With respect to 100 mass parts adhesive resins, the content of nonpolar liquid organic media is preferably 100～10,000 mass parts, more preferably 500～2,000 mass parts.
Proportional when too small in containing of nonpolar liquid organic media, as the formation material of electrode, when preparation fully solid battery electrode was used slurry, the Combination of electrode active material and adhesive resin possibly obviously reduce.In addition, in the formation material of solid electrolyte, when preparation contained the slurry of solid electrolyte and fully solid adhesive for cell composition, the Combination of solid electrolyte and adhesive resin maybe be obviously low.
On the other hand; Proportional when excessive in containing of nonpolar liquid organic media; As the formation material of electrode, when the preparation electrode, possibly produce and to be coated with the problem of fully solid battery electrode with slurry; Perhaps in the dried after coating, electrode active material or adhesive resin possibly produce problems such as concentration gradient.In addition; Formation material as solid electrolyte; When making solid electrolyte layer; Possibly produce the problem that can't be coated with the slurry that contains solid electrolyte and fully solid adhesive for cell composition, perhaps in the dried after coating, electrode active material or adhesive resin possibly produce problems such as concentration gradient.
Through above this fully solid adhesive for cell composition of the present invention; Owing to use specific hydrogenating conjugate diene base polymer as adhesive resin; So when high operation property ground forms electrode layer and solid electrolyte layer,, can form the electrode layer that collector body and solid electrolyte layer is obtained high adaptation as the formation material of electrode; And; As the formation material of solid electrolyte layer, can form electrode, specifically electrode layer is obtained the solid electrolyte layer of high adaptation.
Its reason can be thought: because specific hydrogenating conjugate diene base polymer has high crystallinity; So when the formation material as electrode uses; Electrode active material is shown cohesive force, perhaps collector body and solid electrolyte layer are shown high cohesive force, and when the formation material as solid electrolyte layer uses; Also solid electrolyte is shown cohesive force, perhaps to electrode, specifically be that electrode layer is shown high cohesive force.
In fully solid adhesive for cell composition of the present invention; As adhesive resin; Through using coupling agent modified hydrogenating conjugate diene base polymer; The electrode layer that collector body and solid electrolyte layer is obtained higher adaptation can be formed as the formation material of electrode,, the solid electrolyte layer that to electrode, specifically electrode layer is obtained higher adaptation can be formed perhaps as the formation material of solid electrolyte layer.
Its reason can be thought: owing to be the specific hydrogenating conjugate diene base polymer material through coupling agent modified formation; Can polymer form be formed object type; The result is when the formation material as electrode uses and the cohesive force of electrode active material improves, and increases through the coupling agent modified molecular weight that causes; So the cohesive force to collector body and solid electrolyte layer improves; And when using as the formation material of solid electrolyte layer and the cohesive force of solid electrolyte improve, to electrode, specifically be that cohesive force to electrode layer improves.
< the fully solid battery electrode is used slurry >
Fully solid battery electrode of the present invention comprises the fully solid adhesive for cell composition and the electrode active material of the invention described above with slurry, just comprises the adhesive resin that is formed by specific hydrogenating conjugate diene base polymer, nonpolar liquid organic media and electrode active material.
Fully solid battery electrode of the present invention also can be used as any electrode of anodal and negative pole with slurry formation material uses.
Use electrode active material as positive pole, can use for example MnO 2, MoO 3, V 2O 5, V 6O 13, Fe 2O 3, Fe 3O 4, Li (1-x)CoO 2, Li (1-x)NiO 2, Li xCo ySn zO 2, Li (1-x)Co (1-y)Ni yO 2, TiS 2, TiS 3, MoS 3, FeS 2, CuF 2, NiF 2In inorganic compound; Material with carbon elements such as fluorocarbons, graphite, gas-phase growth of carbon fibre and/or its crushed material, PAN based carbon fiber and/or its crushed material, pitch-based carbon fiber and/or its crushed material; Electroconductive polymer such as polyacetylene, poly etc.
Use electrode active material as negative pole, can use for example material with carbon elements such as fluorocarbons, graphite, gas-phase growth of carbon fibre and/or its crushed material, PAN based carbon fiber and/or its crushed material, pitch-based carbon fiber and/or its crushed material; Electroconductive polymer such as polyacetylene, poly; Amorphous compound that forms by compounds such as stannic acid compound or fluorine etc.
With respect to the adhesive resin of 100 mass parts fully solid adhesive for cell compositions, electrode active material contain proportional 100～50,000 mass parts that is preferably, more preferably 1,000～20,000 mass parts.
Containing of electrode active material is proportional when too small, and the surface of adhesive resin coated electrode active material possibly cause inside battery resistance to increase or main performance reduction etc., so improper.
On the other hand, proportional when excessive in containing of electrode active material, possibly can't obtain enough adhesivenesss, form electrode layer and become fragile, thereby cause electrode active material to come off.
Fully solid battery electrode of the present invention with slurry in, can in the nonpolar liquid organic solvent that constitutes fully solid adhesive for cell composition, contain soluble viscosity adjustment as required with additives such as conductive carbon such as polymer, graphite, metal dusts.
In addition, the viewpoint of the compatibility of the solid electrolyte layer from the electrode layer of attempting to improve and form, fully solid battery electrode of the present invention with slurry in, can contain solid electrolyte.
As above; In the electrode layer that forms by the slurry that contains solid electrolyte; Since adhesive resin electrode active material and solid electrolyte arbitrarily between can both obtain enough caking property; Do not become fragile so can not produce electrode layer itself, cause coming off or producing slight crack etc. of electrode active material or solid electrolyte.
The fully solid battery electrode of the present invention of this structure for example can be mixed with through for example ball milling, ribbon blender (リ ボ Application ミ キ サ one), rod-type mixer (ピ Application ミ キ サ one) etc. through adhesive resin, electrode active material, nonpolar liquid organic media that will be made up of specific hydrogenating conjugate diene base polymer and the additive that uses as required with slurry; Preferably preparing adhesive resin in advance is dissolved into the solution that forms in the nonpolar liquid organic media; Fully solid adhesive for cell composition just of the present invention, dispersive electrode active material in this solution and preparing.
In addition, prepare this fully solid battery electrode and can under reduced pressure carry out, can prevent thus in the electrode layer that obtains, to produce bubble with slurry.
Use slurry through this fully solid battery electrode of the present invention, for example can be applied to the surface of collector body, carry out dried, filming of obtaining extruded processing, can be formed on the electrode of structure of the surperficial range upon range of electrode layer of this collector body.
As collector body; Can use the material that forms by metal forming, etching metal paper tinsel, wire netting etc.; As the material that constitutes collector body, can from metal materials such as aluminium, copper, nickel, tantalum, stainless steel, titanium, suitably select to use according to the kind of the energy device of target.
In addition, the thickness of collector body when constituting the electrode of secondary lithium batteries, is 5～30 μ m for example, is preferably 8～25 μ m.
As the mechanism of coating fully solid battery electrode, can utilize scraping blade method, reverse roll rubbing method, comma cutter type rubbing method, gravure processes, air knife method etc. with slurry.
In addition, be that treatment temperature is preferably 20～250 ℃ as the fully solid battery electrode with the condition of the dried of the coated film of slurry, more preferably 50～150 ℃, the processing time is preferably 1～120 minute, more preferably 5～60 minutes.
In addition, as extrusion process mechanism, can utilize superhigh pressure extruder, soft press-polishing machine, 1 ton of extruder etc.The condition of extrusion process is suitably set according to the processing machine that uses.
The electrode layer that on collector body, forms so for example thickness is 40～100 μ m, and density is 1.3～2.0g/cm 2
And; The electrode that forms electrode layer with slurry through fully solid battery electrode of the present invention is suitable as the electrode in the fully solid battery of the structure that solid electrolyte layer is set between pair of electrodes, the positive pole and/or the negative pole that are suitable as secondary lithium batteries particularly use.
Do not have special qualification as solid electrolyte layer, can use existing known solid electrolyte layer.
As a concrete example, can enumerate out the tellite of the solid electrolytes such as inorganic powder body that for example will contain lithium-ion-conducting and fire the dielectric substrate of formation.As the inorganic powder of lithium-ion-conducting, can use the glass ceramics of this lithium-ion-conducting of putting down in writing in the TOHKEMY 2007-134305 communique is pulverized the powder that forms.
Embodiment
Below, embodiments of the invention are explained particularly, but the present invention does not receive the qualification of these embodiment.
Among the following embodiment and comparative example, the assay method of various physics values is as follows.
(1) as aromatic ethenyl compound from containing of cinnamic construction unit proportional (below, be called " ST content "):
Use heavy chloroform as solvent, from 500MHz, 1The H-NMR wave spectrum is calculated.
(2) from 1 in the construction unit of conjugated diene compound, the content of 2-ethylenic linkage (below, be called " ethylenic linkage content "):
Use infrared analysis, try to achieve by the Hampton method.
(3) weight average molecular weight (Mw), number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn):
Under 50 ℃ of temperature conditions; (GPC, post: trade name " GMHHR-H ", eastern ソ one Co., Ltd. makes) measures by gel permeation chromatography; Try to achieve the weight average molecular weight (Mw) and the number-average molecular weight (Mn) of polystyrene conversion, and try to achieve molecular weight distribution (Mw/Mn) from these values.
(4) coupling rate:
Under 50 ℃ of temperature conditions, whole peak areas (S0) of the polymer that obtains through gel permeation chromatography (GPC) with and do not receive the area (S1) at the coupling agent modified corresponding peak of part, use above-mentioned mathematical expression (1) to calculate.
(5) hydrogenation ratio:
Use carbon tetrachloride as solvent, from 500MHz, 1The H-NMR wave spectrum is calculated.
(6) glass transition temperature (Tg):
According to ASTM D3418, (DSC) measures through the differential scanning calorimetry.
(hydrogenating conjugate diene base polymer synthetic routine 1)
In the reaction vessel of the internal capacity 50L of nitrogen replacement; Add 25kg as the cyclohexane of hydrocarbon solvent, 50g as the oxolane of vinyl controlling agent, 1.76g as the n-BuLi of the polymerization initiator (addition of monomer relatively; Being scaled alkali metal atom is 27.4mmol) and 2500g as 1 of monomer; The 3-butadiene carries out adiabatic polymerisation under the condition of 50 ℃ of polymerization initiation temperatures, obtain conjugated diolefine polymer.
In this reaction system, the consumption of hydrocarbon solvent is that to make the concentration as the 1,3-butadiene of monomer be the amount of 9 quality %, and the consumption of polymerization initiator is with respect to the 1g monomer, and being scaled alkali metal atom is 0.01mmol.
Afterwards, in this reaction vessel, add the silicon tetrachloride of 0.83g (addition of monomer is 5mmol relatively) as coupling agent; Under the condition of 80 ℃ of temperature, carried out 60 minutes; Through coupling agent conjugated diolefine polymer is carried out modified-reaction, then, in reaction vessel with the pressure supply of hydrogen of 0.4MPa-Gauge; Stir after 20 minutes, unreacted lithium and the H-H reaction terminal through conjugated diolefine polymer stop modified-reaction.
In this reaction system, the consumption of coupling agent is 26mmol with respect to the alkali metal atom in every 1g polymerization initiator.
Modified conjugated diene base polymer to obtaining confirms 1, and the content of 2-ethylenic linkage is 42mol%.In addition, the coupling rate of this modified conjugated diene base polymer is 62%.
Afterwards; Making hydrogen supply pressure is 0.7MPa-Gauge, and reaction solution is 90 ℃, is the hydrogenation catalyst of main body through adding with the titanocene dichloride; Cause hydrogenation; The absorption of the hydrogen in the modified conjugated diene base polymer reaches the time point of the cumulant of target hydrogenation ratio, through with nitrogen replacement in the reaction vessel, obtains containing the polymer solution of hydrogenating conjugate diene base polymer.In this polymer solution, add 2, the 6-BHT afterwards, is carried desolventizing through gas, and is dry through the hot-rolling of temperature adjustment to 110 ℃, obtains elastomeric hydrogenating conjugate diene base polymer (below, be called " polymer (A) ").
Polymer (A) to obtaining is confirmed hydrogenation ratio, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn) and glass transition temperature (Tg).The result representes in table 1.
(hydrogenating conjugate diene base polymer synthetic routine 2～10)
Except the hydrogenating conjugate diene base polymer synthetic routine 1 in; Beyond carrying out according to the prescription of table 1; Through with synthetic routine 1 of this hydrogenating conjugate diene base polymer same method, obtain rubber-like hydrogenating conjugate diene base polymer (below, be called " polymer (B) "～" polymer (J) ").
Polymer (B)～polymer (J) to obtaining is confirmed ST content, ethylenic linkage content, hydrogenation ratio, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn) and glass transition temperature (Tg) respectively.The result representes in table 1.
Wherein, polymer (B), polymer (C) and polymer (F)～(I) are homopolymers, and in addition, polymer (D), polymer (E) and polymer (J) are random copolymers.
(hydrogenating conjugate diene base polymer synthetic routine 11)
In the reaction vessel of the internal capacity 50L of nitrogen replacement; Add 25kg as the cyclohexane of hydrocarbon solvent, 200g as the oxolane of vinyl controlling agent, 2.76g as the n-BuLi of polymerization initiator and 500g as the styrene of monomer, under the condition of 50 ℃ of polymerization initiation temperatures, carry out adiabatic polymerisation.After confirming that polymerisation conversion reaches 100%, in reactant liquor, add the 1,3-butadiene of 2000g, carry out adiabatic polymerisation, thereby obtain the copolymer (block copolymer) that forms by conjugated diene compound and aromatic ethenyl compound.
Afterwards, in this reaction vessel, add the dimethyldichlorosilane of 1.95g, under the condition of 80 ℃ of temperature, carried out 60 minutes as coupling agent; Through coupling agent block copolymer is carried out modified-reaction; Then, in reaction vessel,, stir after 20 minutes with the pressure supply of hydrogen of 0.4MPa-Gauge; Make block copolymer terminal unreacted lithium and H-H reaction, stop modified-reaction.
To the modified block copolymer that obtains, confirm that the content of 2-ethylenic linkage is 56mol% from 1 in the construction unit of conjugated diene compound.In addition, the coupling rate of this modified block copolymer is 67%, and ST content is 20 quality %.
Afterwards; Making hydrogen supply pressure is 0.7MPa-Gauge, and reaction solution is 90 ℃, is the hydrogenation catalyst of main body through adding with the titanocene dichloride; Cause hydrogenation; The absorption of the hydrogen in the block copolymer of modification reaches the time point of the cumulant of target hydrogenation ratio, through with nitrogen replacement in the reaction vessel, obtains containing the polymer solution of the block copolymer of hydrogenation.In this polymer solution, add 2, the 6-BHT afterwards, is carried desolventizing through gas, and is dry through the hot-rolling of temperature adjustment to 110 ℃, obtains elastomeric hydrogenated block copolymer (below, be called " polymer (K) ").
Polymer (K) to obtaining is confirmed hydrogenation ratio, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn) and glass transition temperature (Tg).The result representes in table 1.
In addition, polymer (K) observes two glass transition temperatures (Tg).
(hydrogenating conjugate diene base polymer synthetic routine 12)
In the reaction vessel of the internal capacity 50L of nitrogen replacement; Add 25kg as the cyclohexane of hydrocarbon solvent, 1.2g as the oxolane of vinyl controlling agent, 2.35g as the n-BuLi of polymerization initiator and 750g as 1 of monomer; The 3-butadiene; Under the condition of 50 ℃ of polymerization initiation temperatures, carry out adiabatic polymerisation, obtain polymer.After confirming that polymerisation conversion reaches 100%, extract a spot of reactant liquor (polymeric solution) out, put in the methanol solution, confirm that the content of 2-ethylenic linkage is 15mol% from 1 in the construction unit of conjugated diene compound from reaction vessel.
Afterwards, the 1,3-butadiene and the 35g oxolane that in reaction vessel, further add 1750g carry out polymerization, thereby obtain having the conjugated diolefine polymer (below, be also referred to as " conjugated diene kind block polymer ") of block structure.
Afterwards, in this reaction vessel, add the dimethyldichlorosilane of 2.37g, under the condition of 80 ℃ of temperature, carried out 60 minutes as coupling agent; Through coupling agent the conjugated diene kind block polymer is carried out modified-reaction; Then, in reaction vessel,, stir after 20 minutes with the pressure supply of hydrogen of 0.4MPa-Gauge; Make conjugated diene kind block polymer terminal unreacted lithium and H-H reaction, stop modified-reaction.
To the modified conjugated diene kind block polymer that obtains, confirm that the content of 2-ethylenic linkage is 28mol% from 1 in the construction unit of conjugated diene compound.In addition, the coupling rate of this modified conjugated diene kind block polymer is 64%.
Afterwards; Making hydrogen supply pressure is 0.7MPa-Gauge, and reaction solution is 90 ℃, is the hydrogenation catalyst of main body through adding with the titanocene dichloride; Cause hydrogenation; The absorption of the hydrogen in the conjugated diene kind block polymer of modification reaches the time point of the cumulant of target hydrogenation ratio, through with nitrogen replacement in the reaction vessel, obtains containing the polymer solution of conjugated diolefine polymer of the modification of hydrogenation.In this polymer solution, add 2, the 6-BHT afterwards, is carried desolventizing through gas, and is dry through the hot-rolling of temperature adjustment to 110 ℃, obtains elastomeric hydrogenation modified conjugated diene kind block polymer (below, be called " polymer (L) ").
Polymer (L) to obtaining is confirmed hydrogenation ratio, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn) and glass transition temperature (Tg).The result representes in table 1.
In addition, polymer (L) observes two glass transition temperatures (Tg).
Figure BPA00001577547800271
In table 1, the consumption unit of polymerization initiator " mmol " expression alkali metal atom (lithium atom) is with respect to the conversion amount of the monomer total amount of using, and in addition, the consumption unit of coupling agent " mmol " expression is with respect to the amount of the monomer total amount of using.
[embodiment 1]
(the fully solid battery electrode is with the preparation example 1 of slurry)
To be dissolved into as the polymer (A) of adhesive resin the toluene solution that forms in the toluene as nonpolar liquid organic media (below, be called " fully solid adhesive for cell composition (1) ") with as anodal LiCoO with electrode active material 2Mix, fully mixing, form pulp-like, thereby obtain the fully solid battery electrode with slurry (below, be called " the fully solid battery electrode is with slurry (1) ").
Wherein, in fully solid adhesive for cell composition (1), with respect to 100 mass parts polymer (A), the consumption of toluene is 1,000 mass parts.
In addition, fully solid adhesive for cell composition (1) and LiCoO 2Mixing ratio be solid constituent and the LiCoO that constitutes the polymer (A) of fully solid adhesive for cell composition (1) 2Weight ratio is 4: 96.
(the manufacturing example 1 of electrode)
The fully solid battery electrode is applied on the aluminium foil through scraping the skill in using a kitchen knife in cookery with slurry (1), under 100 ℃ decompression, makes toluene evaporates, spend 3 hours dryings, thereby on the collector body that forms by aluminium foil, form the electrode layer of thickness 0.1mm, make electrode.
In the forming process of the electrode layer of this electrode, through following benchmark, evaluating operation property.The result representes in table 2.
" A ": Visual Confirmation forms in the front, surface of aluminium foil and films uniformly.
" B ": Visual Confirmation has the part of not filmed and covering on the surface of aluminium foil.
" C ": coating difficulty.
In addition, to the electrode layer that on the aluminium foil that obtains, forms, the adhesive tape of the wide 20mm that on electrode layer, fits, the peel strength when measuring it and under the condition of 90 ° of peel angle, peeling rate 50mm/min, peeling off.The result representes in table 2.
[embodiment 2～7, reference example 1 and comparative example 1～4]
Except in embodiment 1, using the adhesive resin shown in the table 2; Likewise obtain fully solid adhesive for cell composition with this embodiment 1; Form the fully solid battery electrode then with slurry and electrode; In the forming process of this electrode, evaluating operation property, determination of electrode peel strength simultaneously to obtaining.The result representes in table 2.
[table 2]
Figure BPA00001577547800291
From the result of table 2, confirm that the fully solid adhesive for cell composition of embodiment 1～embodiment 7 can have high operation property ground formation electrode layer, and in the electrode layer that forms, collector body is obtained high adaptation.
[embodiment 8]
(the fully solid battery electrode is with the preparation example of slurry)
With fully solid adhesive for cell composition (1), as anodal LiCoO with electrode active material 2And as the 0.01Li of lithium-ion-conducting inorganic solid electrolyte 3PO 4-0.63Li 2S-0.36SiS 2Mix, fully mixing, form pulp-like, obtain the fully solid battery electrode with slurry (below, be called " the fully solid battery electrode is with slurry (8) ").
Wherein, fully solid adhesive for cell composition (1) and 0.01Li 3PO 4-0.63Li 2S-0.36SiS 2, LiCoO 2Mixing ratio be solid constituent and the 0.01Li that constitutes the polymer (A) of fully solid adhesive for cell composition (1) 3PO 4-0.63Li 2S-0.36SiS 2, LiCoO 2Weight ratio be 2: 32: 66.
(the making example 8 of electrode)
The fully solid battery electrode is applied on the aluminium foil through scraping the skill in using a kitchen knife in cookery with slurry (8), under 100 ℃ decompression, makes toluene evaporates, spend 3 hours dryings, thereby on the collector body that forms by aluminium foil, form the electrode layer of thickness 0.1mm, make electrode.
In the forming process of the electrode layer of this electrode, through said reference, evaluating operation property.The result representes in table 3.
In addition, to the electrode layer that on the aluminium foil that obtains, forms, the adhesive tape of the wide 20mm that on electrode layer, fits, the peel strength when measuring it and under the condition of 90 ° of peel angle, peeling rate 50mm/min, peeling off.The result representes in table 3.
(evaluation of the electrical property of electrode layer)
The fully solid battery electrode is applied on the fluorocarbon resin sheet through scraping the skill in using a kitchen knife in cookery with slurry (8), under 100 ℃ decompression, makes toluene evaporates, spend 3 hours dryings, form the electrode layer of thickness 0.1mm.The electrode layer that will on this fluorocarbon resin sheet, form is peeled off from this fluorocarbon resin sheet, the size of cutting diameter 10mm, thus obtain electrode layer formed body (below, be also referred to as " electrode layer formed body (1) ").
Electrode layer formed body (1) to obtaining is confirmed electrochemical properties through AC impedence method.
Particularly; Use this determinator shown in Figure 1 with hollow sample mount 11 of PET system; In this hollow sample mount 11, solid electrolyte layer 16 and metallic lithium foil 15 that the lithium-ion-conducting solid electrolyte that stack gradually electrode layer formed body (1) 12, used at this electrode forming body of manufacturing at (1) 12 o'clock forms are to electrode layer formed body (1) 12 crimping lead terminal 13; To metallic lithium foil 15 crimping lead terminals 14; Thus, obtain measuring element with electrode layer formed body (1) 12, solid electrolyte layer 16 and metallic lithium foil 15 integral formings, with electrode layer formed body (1) 12 as the test utmost point, with metallic lithium foil 15 as to the utmost point; Through electric impedance analyzer this measuring element is applied the alternating voltage of 10mV, carry out AC impedance with the frequency range of 100kHz～1MHz and measure.The result representes in table 3.
[embodiment 9～14, reference example 2 and comparative example 5～8]
Except in embodiment 8, use beyond the adhesive resin shown in the table 3 and this embodiment 8 likewise; Obtain fully solid adhesive for cell composition; Then, form the fully solid battery electrode with slurry and electrode, evaluating operation property in the forming process of this electrode; Determination of electrode peel strength to obtaining is measured impedance then simultaneously.The result representes in table 3.
[table 3]
Figure BPA00001577547800311
Can confirm that from the result of table 3 the fully solid adhesive for cell composition of embodiment 8～embodiment 14 can have high operation property ground and form electrode layer, and in the electrode layer that forms, can obtain high adaptation collector body.
In addition, in embodiment 8～embodiment 14, can confirm to use slurry as the fully solid battery electrode; Use contains the material of electrode active material and solid electrolyte formation in fully solid adhesive for cell composition; Electrode layer for this slurry forms when measuring peel strength, can not produce electrode layer self and become fragile; Cause electrode active material or solid electrolyte to come off; Perhaps produce slight crack etc., adhesive resin electrode active material and solid electrolyte arbitrarily between can obtain enough adhesivenesss, therefore; The electrode layer that can infer the fully solid adhesive for cell composition formation of the application of the invention can obtain enough adaptations to solid electrolyte layer; And when using fully solid adhesive for cell composition of the present invention to form solid electrolyte layer, also can obtain high operation property, and can obtain enough adaptations to electrode layer in the solid electrolyte layer that forms.
Symbol description
Figure BPA00001577547800312

Claims (8)

1. fully solid adhesive for cell composition; This adhesive composition uses as the formation material in the fully solid battery; The structure that this fully solid battery is served as reasons and between pair of electrodes, solid electrolyte layer is set and forms; It is characterized in that: this adhesive composition comprises adhesive resin and the nonpolar liquid organic media that is formed by the hydrogenating conjugate diene base polymer; This hydrogenating conjugate diene base polymer is that the polymer hydrogenation that is selected from following polymer (a1) or following polymer (a2) is formed, and hydrogenation ratio is more than 70%
Polymer (a1) is the polymer that construction unit beyond the block polymer, an origin self-conjugate diolefin compound constitutes;
Polymer (a2) is a random copolymer; Comprise from the construction unit of conjugated diene compound and construction unit from aromatic ethenyl compound; From 1 in the construction unit of this conjugated diene compound; The content of 2-ethylenic linkage is below the 70mol%, and is proportional less than 40 quality % from containing of the construction unit of this aromatic ethenyl compound.
2. the fully solid adhesive for cell composition of putting down in writing according to claim 1; It is characterized in that: the hydrogenating conjugate diene base polymer that constitutes aforementioned adhesion agent resin is through from the compound shown in the formula (1); Compound shown in the formula (2); The compound that in molecule, has two above ester bonds; In molecule, have the compound of two above epoxy radicals and in molecule, have at least a kind of coupling agent modified material that obtains selecting in the compound of two above vinyl
General formula (1)
R 1 4-n1MX 1 n1
[in the formula, R 1The expression alkyl, M representes tin atom, silicon atom or germanium atom, X 1Expression halogen atom, alkoxyl or acyloxy, n1 is 2～4 integer ,]
General formula (2)
R 2 4-n2CX 2 n2
[in the formula, R 2Expression hydrogen atom or alkyl, X 2The expression halogen atom, n2 is 2～4 integer].
3. the fully solid adhesive for cell composition of putting down in writing according to claim 2 is characterized in that: the coupling rate in the aforementioned hydrogenating conjugate diene base polymer is 10～80%.
4. each fully solid adhesive for cell composition of being put down in writing according to claim 1～3 is characterized in that: the weight average molecular weight that constitutes the hydrogenating conjugate diene base polymer of aforementioned adhesion agent resin is 50,000～1,700,000.
5. each fully solid adhesive for cell composition of being put down in writing according to claim 1～4 is characterized in that: the construction unit from conjugated diene compound in aforementioned polymer (a1) and the aforementioned polymer (a2) is from the construction unit of butadiene or from the construction unit of isoprene.
6. each fully solid adhesive for cell composition of being put down in writing according to claim 1～5 is characterized in that: in the aforementioned polymer (a1) from 1 in the construction unit of conjugated diene compound, the content of 2-vinyl bonds is below the 70mol%.
7. each fully solid adhesive for cell composition of being put down in writing according to claim 1～6, it is characterized in that: the construction unit from aromatic ethenyl compound in the aforementioned polymer (a2) is from cinnamic construction unit.
8. a fully solid battery electrode is used slurry, it is characterized in that: comprise each fully solid adhesive for cell composition and electrode active material of being put down in writing of claim 1～7.
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