CN102731707B - The purposes of vinylidene fluoride analog copolymer and this multipolymer - Google Patents

The purposes of vinylidene fluoride analog copolymer and this multipolymer Download PDF

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CN102731707B
CN102731707B CN201210098820.XA CN201210098820A CN102731707B CN 102731707 B CN102731707 B CN 102731707B CN 201210098820 A CN201210098820 A CN 201210098820A CN 102731707 B CN102731707 B CN 102731707B
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analog copolymer
vinylidene fluoride
electrode
structural unit
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CN102731707A (en
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佐藤圭介
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Kureha Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—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 a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides 1 of a kind of binding property excellence with base materials such as metals, 1-difluoroethylene analog copolymer, and a kind of the battery electrode tackiness agent and rechargeable nonaqueous electrolytic battery mixture, the electrode for nonaqueous electrolyte secondary battery using this mixture to obtain and the rechargeable nonaqueous electrolytic battery with this electrode that contain this vinylidene fluoride analog copolymer are provided.The structural unit that vinylidene fluoride analog copolymer of the present invention has structural unit that 80 ~ 99.95mol% general formula a represents, 0 ~ 19.99mol% general formula b represents and the structural unit that 0.01 ~ 20mol% general formula c represents.In general formula b, c, R cOOHfor the organic group containing carboxyl, R n, Sfor containing the heteroatomic organic group of at least one be selected from nitrogen and sulphur.

Description

The purposes of vinylidene fluoride analog copolymer and this multipolymer
Technical field
The present invention relates to the purposes of vinylidene fluoride analog copolymer and this multipolymer.Specifically, vinylidene fluoride analog copolymer, electrode battery tackiness agent, electrode for nonaqueous electrolyte secondary battery mixture, electrode for nonaqueous electrolyte secondary battery and rechargeable nonaqueous electrolytic battery is related to.
Background technology
As 1, poly-1 of the polymkeric substance of 1-difluoroethylene (being also denoted as VDF below), the excellence such as chemical proofing, weathering resistance, stain resistance of 1-difluoroethylene (being also denoted as PVDF below), can be used as the material for the manufacture of various film and products formed after melt molding.In addition, PVDF also can be used as coating or tackiness agent resin, but due to the bond strength of the base material such as PVDF and metal little, so expect improvement bond strength.
All the time, the fusible various method for improveing PVDF is disclosed.Disclosed method is many all the time realizes fusible improvement by importing carboxyl in PVDF.
As the PVDF being imported with carboxyl, existing following report: by VDF and maleic anhydride, hydrolyzed acid anhydride, what obtain thus contains carboxyl vinylidene fluoride analog copolymer (for example, see patent documentation 1); By the monoesters copolymerization of the unsaturated dibasic acid such as VDF and monomethyl maleate, what obtain thus contains carboxyl vinylidene fluoride analog copolymer (for example, see patent documentation 2).
But, even if be above-mentioned polymkeric substance, also still insufficient with the binding property of the base materials such as metal.
Patent documentation 1: Japanese Unexamined Patent Publication 2-604 publication
Patent documentation 2: Japanese Unexamined Patent Publication 6-172452 publication
Summary of the invention
The present invention in view of exist in above-mentioned prior art problem complete, object be to provide a kind of compared with all the time known PVDF being imported with carboxyl, with the novel vinylidene fluoride analog copolymer of the binding property excellence of the base material such as metal.
In addition, the object of the present invention is to provide a kind of containing this vinylidene fluoride analog copolymer, battery electrode tackiness agent and rechargeable nonaqueous electrolytic battery mixture, the electrode for nonaqueous electrolyte secondary battery using this mixture to obtain and the rechargeable nonaqueous electrolytic battery with this electrode.
The present inventor etc. further investigate to achieve these goals and repeatedly, found that the binding property of the base materials such as the PVDF that is imported with containing the heteroatomic organic group being selected from nitrogen and sulphur and metal is excellent, thus complete the present invention.
Namely, of the present invention 1, the structural unit that 1-difluoroethylene analog copolymer has structural unit that 80 ~ 99.95mol% following general formula a represents, 0 ~ 19.99mol% following general formula b represents and the structural unit (structural unit that wherein, general formula a, b and c represents adds up to 100mol%) that the following general formula c of 0.01 ~ 20mol% represents.
(in above-mentioned general formula b, R cOOHfor the organic group containing carboxyl, R 1, R 2, R 3be the alkyl of hydrogen atom, halogen atom, carboxyl or derivatives thereof or carbonatoms 1 ~ 5 independently of one another,
In above-mentioned general formula c, R n, Sfor containing being selected from the heteroatomic organic group of at least one in nitrogen and sulphur, R 4, R 5, R 6be the alkyl of hydrogen atom, halogen atom, carboxyl or derivatives thereof or carbonatoms 1 ~ 5 independently of one another.)
In above-mentioned general formula c, preferred R n, Sfor the organic group containing at least one group be selected from amine, thioether, thiocarbonyl and heterocycle, above-mentioned heterocycle is containing the heteroatomic heterocycle of at least one be selected from nitrogen and sulphur.
Of the present invention 1, 1-difluoroethylene analog copolymer is preferably by carboxylic 1, the binding groups forming reactions of 1-difluoroethylene analog copolymer (X) and following compound and obtaining, described carboxylic 1, 1-difluoroethylene analog copolymer (X) has the structural unit that the following general formula a of 80 ~ 99.95mol% represents, and the structural unit that the following general formula b ' of 0.05 ~ 20mol% represents (wherein, the structural unit that general formula a and b ' represents adds up to 100mol%), described compound has the group being formed binding groups by chemical reaction and carboxyl or derivatives thereof, and containing being selected from least one heteroatoms in nitrogen and sulphur.
(in above-mentioned general formula b ', R cOOHfor the organic group containing carboxyl,
In above-mentioned general formula b ', R 1, R 2, R 3be the alkyl of hydrogen atom, halogen atom, carboxyl or derivatives thereof or carbonatoms 1 ~ 5 independently of one another.)
For vinylidene fluoride analog copolymer of the present invention, preferred logarithmic viscosity number is 0.5 ~ 5.0dl/g.
Battery electrode tackiness agent of the present invention contains above-mentioned vinylidene fluoride analog copolymer and non-aqueous solvent.
Electrode for nonaqueous electrolyte secondary battery mixture of the present invention contains above-mentioned 1,1-difluoroethylene analog copolymer, electrode active material and non-aqueous solvent, anode for nonaqueous electrolyte secondary battery mixture of the present invention contains the vinylidene fluoride analog copolymer of above-mentioned record, negative electrode active material and non-aqueous solvent.
Electrode for nonaqueous electrolyte secondary battery of the present invention passes through be coated with by the electrode for nonaqueous electrolyte secondary battery mixture of above-mentioned record also dry on the current collector and obtain, and anode for nonaqueous electrolyte secondary battery of the present invention obtains by the anode for nonaqueous electrolyte secondary battery mixture of above-mentioned record is coated with on the current collector also drying.
Rechargeable nonaqueous electrolytic battery of the present invention has above-mentioned electrode for nonaqueous electrolyte secondary battery, preferably has anode for nonaqueous electrolyte secondary battery.
Compared with all the time known PVDF being imported with carboxyl, the binding property of the base materials such as vinylidene fluoride analog copolymer of the present invention and metal is excellent.
Therefore, battery electrode tackiness agent of the present invention and electrode for nonaqueous electrolyte secondary battery mixture productivity can manufacture electrode for nonaqueous electrolyte secondary battery and rechargeable nonaqueous electrolytic battery well, and the stripping strength of the mixture layer of electrode for nonaqueous electrolyte secondary battery and current collector is excellent.
Accompanying drawing explanation
[Fig. 1] is the vinylidene fluoride analog copolymer (1) that obtains in embodiment 1 1hNMR composes.
[Fig. 2] is the vinylidene fluoride analog copolymer (2) that obtains in embodiment 2 1hNMR composes.
[Fig. 3] is the vinylidene fluoride analog copolymer (3) that obtains in embodiment 3 1hNMR composes.
Embodiment
Next, the present invention is illustrated.
(vinylidene fluoride analog copolymer)
Of the present invention 1, the structural unit that 1-difluoroethylene analog copolymer has structural unit that 80 ~ 99.95mol% following general formula a represents, 0 ~ 19.99mol% following general formula b represents and the structural unit (structural unit that wherein, general formula a, b and c represents adds up to 100mol%) that the following general formula c of 0.01 ~ 20mol% represents.
(in above-mentioned general formula b, R cOOHfor the organic group containing carboxyl, R 1, R 2, R 3be the alkyl of hydrogen atom, halogen atom, carboxyl or derivatives thereof or carbonatoms 1 ~ 5 independently of one another,
In above-mentioned general formula c, R n, Sfor containing being selected from the heteroatomic organic group of at least one in nitrogen and sulphur, R 4, R 5, R 6be the alkyl of hydrogen atom, halogen atom, carboxyl or derivatives thereof or carbonatoms 1 ~ 5 independently of one another.)
Of the present invention 1,1-difluoroethylene analog copolymer is polymkeric substance as described below: have structural unit that above-mentioned general formula a represents namely from 1, the structural unit that the structural unit of 1-difluoroethylene and above-mentioned general formula c represent, has the structural unit that above-mentioned general formula b represents usually.In addition, the structural unit from other monomers can also be had.
The R that the structural unit that above-mentioned general formula b represents has cOOHfor the organic group containing carboxyl, being preferably carboxyl, carboxyethyl base, carboxyl propyl ester base, carboxymethyl group, carboxy ethyl, carboxypropyl, is more preferably carboxyl, carboxyethyl base, carboxyl propyl ester base.In addition, above-mentioned R cOOHbe preferably the organic group of molecular weight less than 500.
The R that the structural unit that above-mentioned general formula b represents has 1, R 2, R 3be the alkyl of hydrogen atom, halogen atom, carboxyl or derivatives thereof or carbonatoms 1 ~ 5 independently of one another, being preferably hydrogen atom, fluorine atom, chlorine atom, methyl, ethyl, n-propyl, carboxyl, methoxycarbonyl, is more preferably hydrogen atom, fluorine atom, chlorine atom, methyl.
As the structural unit that above-mentioned general formula b represents, be preferably the structural unit from carboxyl group-containing monomer.As above-mentioned carboxyl group-containing monomer, vinylformic acid, methacrylic acid, monomethyl maleate, vinylformic acid-2-carboxyethyl, methacrylic acid-2-carboxyethyl, succsinic acid acryloyloxyethyl ester, succsinic acid methacryloyloxyethyl, acryloxy ethyl phthalate(DEP), methacryloxy ethyl phthalate(DEP), trifluoropropyl olefin(e) acid, trifluoromethyl acrylate etc. can be enumerated.It should be noted that, as carboxyl group-containing monomer, can be used alone one, also can use two or more.
The R that the structural unit that above-mentioned general formula c represents has n, Sfor containing being selected from the heteroatomic organic group of at least one in nitrogen and sulphur, be preferably the organic group containing at least one group be selected from amine, mercaptan, thioether, thiocarbonyl and heterocycle, be more preferably the organic group containing at least one group be selected from amine, thioether, thiocarbonyl and heterocycle, be particularly preferably the organic group containing at least one group be selected from thioether, pyridine, thiophene, imidazoles and triazole.In addition, above-mentioned R n, Sbe preferably the organic group of molecular weight less than 500.
It should be noted that, above-mentioned R n, Sfor containing being selected from the heteroatomic organic group of at least one in nitrogen and sulphur, when above-mentioned heteroatoms is three-dimensionally protected by bulky substituting group, likely can not get effect of the present invention, thus not preferred.Specifically, being preferably less than 180 degree with the substituent cone angle of above-mentioned heteroatoms bonding, is more preferably less than 160 degree.
The R that the structural unit that above-mentioned general formula c represents has 4, R 5, R 6be the alkyl of hydrogen atom, halogen atom, carboxyl or derivatives thereof or carbonatoms 1 ~ 5 independently of one another, being preferably hydrogen atom, fluorine atom, chlorine atom, methyl, ethyl, n-propyl, carboxyl, methoxycarbonyl, is more preferably hydrogen atom, fluorine atom, chlorine atom, methyl.It should be noted that, when vinylidene fluoride analog copolymer of the present invention adopts following method 1 to manufacture, the R that the structural unit that above-mentioned general formula c represents has 4, R 5, R 6the R that the structural unit represented with above-mentioned general formula b respectively has 1, R 2, R 3identical.
As the structural unit that above-mentioned general formula c represents, it can be the structural unit from the monomer containing organic group, described organic group contains at least one heteroatoms be selected from nitrogen and sulphur, usual preferred following structural unit: by the carboxyl that has from the structural unit of carboxyl group-containing monomer and following compound generation binding groups forming reactions and the structural unit obtained, described compound have by chemical reaction and carboxyl or derivatives thereof formed binding groups group and containing at least one heteroatoms be selected from nitrogen and sulphur.It should be noted that, the binding groups forming reactions of carboxyl and above-claimed cpd can be undertaken by single step reaction, also can be undertaken by polystep reaction.It should be noted that, as binding groups, ester group (-COO-), carbonyl, alkyl, alkenyl, acid amides, ether etc. can be enumerated, be preferably ester group, carbonyl, acid amides, more preferably ester group.In addition, as chemical reaction, esterification, functional group's substitution reaction, Wittig reaction, amidate action etc. can be enumerated, preferred esterification, amidate action, more preferably esterification.
As the group forming binding groups above by chemical reaction and carboxyl or derivatives thereof, the group of ester is formed preferably by chemical reaction and carboxyl or derivatives thereof, more preferably for being selected from least one group in hydroxyl, chloro, bromo, particularly preferably hydroxyl.
The group of binding groups is formed and the concrete example containing the heteroatomic compound of at least one be selected from nitrogen and sulphur by chemical reaction and carboxyl or derivatives thereof as having, 3-pyridone, 2-(2-thienyl) ethanol, 2-(methylthio group) ethanol, 4-pyridone, Zyloric, 4-oxyindole, 4-hydroxyquinazoline, 2-hydroxybenzimidazole, hydroxy imidazole etc. can be enumerated, wherein, preferred 3-pyridone, 2-(2-thienyl) ethanol, 2-(methylthio group) ethanol, 4-pyridone, hydroxy imidazole.It should be noted that, above-claimed cpd has the group being formed ester by chemical reaction and carboxyl or derivatives thereof, and containing at least one heteroatoms be selected from nitrogen and sulphur, be equivalent to there is hydroxyl and containing the heteroatomic compound of at least one be selected from nitrogen and sulphur.
As mentioned above, of the present invention 1, 1-difluoroethylene analog copolymer has the structural unit that the above-mentioned general formula a of 80 ~ 99.95mol% represents, the structural unit that the above-mentioned general formula b of 0 ~ 19.99mol% represents, and the structural unit that the above-mentioned general formula c of 0.01 ~ 20mol% represents (wherein, general formula a, the structural unit that b and c represents adds up to 100mol%), preferably there is the structural unit that the above-mentioned general formula a of 85 ~ 99.9mol% represents, the structural unit that the above-mentioned general formula b of 0 ~ 14.99mol% represents, and the structural unit that the above-mentioned general formula c of 0.01 ~ 15mol% represents, more preferably there is the structural unit that the above-mentioned general formula a of 90 ~ 99.5mol% represents, the structural unit that the above-mentioned general formula b of 0 ~ 9.99mol% represents, and the structural unit that the above-mentioned general formula c of 0.01 ~ 10mol% represents.For vinylidene fluoride analog copolymer of the present invention, have each structural unit in above-mentioned scope time, owing to not destroying each physical property of poly-vinylidene fluoride excellence, the function that functional group brings can be given, therefore preferably.It should be noted that, the amount of each structural unit can use 1h NMR obtains.
In addition, as other monomers above-mentioned, such as can enumerate can with the fluorine class monomer of vinylidene fluoride copolymerization or the hydrocarbon monomer such as ethene, propylene and can with the monomer of above-mentioned carboxyl group-containing monomer copolymerization.As can with the monomer of above-mentioned carboxyl group-containing monomer copolymerization, (methyl) methyl acrylate can be enumerated, (methyl) acrylic acid alkyl ester compound etc. that (methyl) ethyl propenoate is representative.It should be noted that, other monomers above-mentioned can be used alone a kind, also can use two or more.
Of the present invention 1, when 1-difluoroethylene analog copolymer has the structural unit from other monomers above-mentioned, when structural unit from the total monomer forming this multipolymer is 100 % by mole, preferably there is the structural unit from other monomers above-mentioned of less than 10 % by mole, more preferably there is 0.01 ~ 10 % by mole of structural unit from other monomers above-mentioned.
As manufacture of the present invention 1, the method of 1-difluoroethylene analog copolymer, be not particularly limited, such as can enumerate following manufacture method: by 1, 1-difluoroethylene, the carboxyl group-containing monomer of the structural unit that general formula b represents is formed by polymerization, and other monomer copolymerizations above-mentioned as required, manufacture thus containing carboxyl 1, 1-difluoroethylene analog copolymer (X), then by carrying out this containing carboxyl 1, the binding groups forming reactions of 1-difluoroethylene analog copolymer (X) and following compound, manufacture of the present invention 1, the method (method 1) of 1-difluoroethylene analog copolymer, described compound has the group being formed binding groups by chemical reaction and carboxyl or derivatives thereof, and containing the heteroatomic compound of at least one be selected from nitrogen and sulphur, by 1,1-difluoroethylene, to be formed by polymerization the structural unit that general formula c represents containing being selected from the heteroatomic monomer of at least one in nitrogen and sulphur, the carboxyl group-containing monomer of the arbitrarily used structural unit represented by polymerization formation general formula b and other monomer copolymerizations above-mentioned as required, manufacture the method (method 2) of vinylidene fluoride analog copolymer of the present invention thus, by 1,1-difluoroethylene, containing epoxy based monomers, other monomer copolymerizations as required, manufacture 1 containing epoxy group(ing) thus, 1-difluoroethylene analog copolymer, then, by this being contained 1 of epoxy group(ing) with following compound, the modification of 1-difluoroethylene analog copolymer, manufacture of the present invention 1 thus, the method (method 3) of 1-difluoroethylene analog copolymer, described compound have by chemical reaction and epoxy group(ing) or derivatives thereof formed binding groups group and containing at least one heteroatoms be selected from nitrogen and sulphur.
In aforesaid method, easy from the viewpoint of synthesis, preferred using method 1 manufactures vinylidene fluoride analog copolymer of the present invention.
Illustrate in greater detail aforesaid method 1.In aforesaid method 1, first by vinylidene fluoride, the carboxyl group-containing monomer being formed the structural unit that general formula b represents by polymerization and other monomer copolymerizations above-mentioned as required, manufacture carboxylic vinylidene fluoride analog copolymer (X) thus.It should be noted that, above-mentioned carboxylic 1,1-difluoroethylene analog copolymer (X) has structural unit that 80 ~ 99.95mol% following general formula a represents and the structural unit (structural unit that wherein, general formula a and b ' represents adds up to 100mol%) that the following general formula b ' of 0.05 ~ 20mol% represents.
(in above-mentioned general formula b ', R cOOHfor the organic group containing carboxyl,
In above-mentioned general formula b ', R 1, R 2, R 3be the alkyl of hydrogen atom, halogen atom, carboxyl or derivatives thereof or carbonatoms 1 ~ 5 independently of one another.)
It should be noted that, the R in above-mentioned general formula b ' cOOH, R 1, R 2, R 3respectively with the R in general formula b cOOH, R 1, R 2, R 3identical.
As mentioned above, above-mentioned carboxylic 1, 1-difluoroethylene analog copolymer (X) has the structural unit that the above-mentioned general formula a of 80 ~ 99.95mol% represents, and the structural unit that the above-mentioned general formula b ' of 0.05 ~ 20mol% represents (wherein, the structural unit that general formula a and b ' represents adds up to 100mol%), preferably there is the structural unit that the above-mentioned general formula a of 85 ~ 99.9mol% represents, and the structural unit that the above-mentioned general formula b ' of 0.01 ~ 15mol% represents, more preferably there is the structural unit that the above-mentioned general formula a of 90 ~ 99.5mol% represents, and the structural unit that the above-mentioned general formula b ' of 0.5 ~ 10mol% represents.For above-mentioned carboxylic 1,1-difluoroethylene analog copolymer (X), have each structural unit in above-mentioned scope time, due to carboxylic 1,1-difluoroethylene analog copolymer (X) is the optimal dose expressing effect of the present invention with the binding groups forming reactions of following compound, therefore preferably, described compound have by chemical reaction and carboxyl or derivatives thereof formed binding groups group and containing at least one heteroatoms be selected from nitrogen and sulphur.
In addition, when using other monomers above-mentioned carboxylic vinylidene fluoride analog copolymer (X) to be polymerized, carboxylic vinylidene fluoride analog copolymer (X) has the structural unit from other monomers above-mentioned.When structural unit from the total monomer forming this multipolymer is 100 % by mole, preferably there are less than the 10 % by mole structural units from other monomers above-mentioned, more preferably there is 0.01 ~ 10 % by mole of structural unit from other monomers above-mentioned.
As by by above-mentioned method of carrying out manufacturing containing carboxyl vinylidene fluoride analog copolymer (X), be not particularly limited, usually use the methods such as suspension polymerization, letex polymerization, solution polymerization to carry out.From the viewpoint of the easiness etc. of aftertreatment, the suspension polymerization of preferred water system, letex polymerization, the particularly preferably suspension polymerization of water system.
Using water as in the suspension polymerization of dispersion medium, relative to the total monomer (1 used in copolymerization, 1-difluoroethylene and carboxyl group-containing monomer, carry out other monomers of copolymerization as required) 100 mass parts, add the suspension agent such as methylcellulose gum, methoxylation methylcellulose gum, propoxylated methyl Mierocrystalline cellulose, Natvosol, hydroxypropylcellulose, polyvinyl alcohol, polyethylene oxide, gelatin in the scope of 0.005 ~ 1.0 mass parts, preferably 0.01 ~ 0.4 mass parts, use.
As polymerization starter, the positive seven fluoropropyl esters of di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate two, di-isopropyl peroxydicarbonate, isobutyryl peroxide, two (chlorine fluorine acyl group) superoxide, two (perfluoro acidyl) superoxide, tert-Butyl peroxypivalate etc. can be used.When the total monomer that uses in copolymerization (vinylidene fluoride and carboxyl group-containing monomer, carry out other monomers of copolymerization as required) is 100 mass parts, its usage quantity is 0.1 ~ 5 mass parts, is preferably 0.2 ~ 2 mass parts.
In addition, also the chain-transfer agents such as ethyl acetate, methyl acetate, diethyl carbonate, acetone, ethanol, n-propyl alcohol, acetaldehyde, propionic aldehyde, ethyl propionate, tetracol phenixin can be added, regulate the polymerization degree of the carboxylic vinylidene fluoride analog copolymer (X) of gained.When the total monomer that uses in copolymerization (vinylidene fluoride and carboxyl group-containing monomer, carry out other monomers of copolymerization as required) is 100 mass parts, its usage quantity is generally 0.1 ~ 5 mass parts, is preferably 0.5 ~ 3 mass parts.
In addition, for the input amount of the total monomer used in copolymerization (vinylidene fluoride and carboxyl group-containing monomer, carry out other monomers of copolymerization as required), monomer amounts to: in the mass ratio of water, be generally 1: 1 ~ 1: 10, be preferably 1: 2 ~ 1: 5.Polymerization temperature T can according to 10 hr half-life temperature T of polymerization starter 10suitable selection, usually at T 10-25 DEG C≤T≤T 10select in the scope of+25 DEG C.Such as, the T of tert-Butyl peroxypivalate and di-isopropyl peroxydicarbonate 10be respectively 54.6 DEG C and 40.5 DEG C.Therefore, use tert-Butyl peroxypivalate and di-isopropyl peroxydicarbonate as in the polymerization of polymerization starter, their polymerization temperature T suitably selects respectively in the scope of 29.6 DEG C≤T≤79.6 DEG C and 15.5 DEG C≤T≤65.5 DEG C.Polymerization time is not particularly limited, but when considering productivity etc., is preferably less than 100 hours.Pressure during polymerization carries out usually under elevated pressure, is preferably 2.0 ~ 8.0MPa-G.
By carrying out the suspension polymerization of water system under these conditions, easily by vinylidene fluoride and carboxyl group-containing monomer, other monomer copolymerizations carrying out copolymerization as required, carboxylic vinylidene fluoride analog copolymer (X) can be obtained.
The logarithmic viscosity number of the carboxylic vinylidene fluoride analog copolymer (X) of gained is preferably 0.5 ~ 5.0dl/g, is more preferably 0.8 ~ 4.0dl/g.It should be noted that, the logarithmic viscosity number of carboxylic vinylidene fluoride analog copolymer (X) can use the method same with the logarithmic viscosity number of vinylidene fluoride analog copolymer of the present invention to measure.
In aforesaid method 1, by carrying out above-mentioned carboxylic 1, the binding groups forming reactions of 1-difluoroethylene analog copolymer (X) and following compound, obtain of the present invention 1,1-difluoroethylene analog copolymer, described compound have by chemical reaction and carboxyl or derivatives thereof formed binding groups group and containing at least one heteroatoms be selected from nitrogen and sulphur.Binding groups forming reactions can be undertaken by single step reaction, also can be undertaken by polystep reaction.In addition, as binding groups forming reactions, can enumerate esterification, functional group's substitution reaction, Wittig reaction, amidate action etc., being preferably esterification, amidate action, is more preferably esterification.
Of the present invention 1 is obtained by esterification, during 1-difluoroethylene analog copolymer, as have by chemical reaction and carboxyl or derivatives thereof formed binding groups group and containing the heteroatomic compound of at least one be selected from nitrogen and sulphur, use to have and forms the group of ester by chemical reaction and carboxyl or derivatives thereof and containing the heteroatomic compound of at least one be selected from nitrogen and sulphur, preferred use has hydroxyl and containing being selected from the heteroatomic compound of at least one in nitrogen and sulphur.
Esterification can be undertaken by single step reaction, also can be undertaken by polystep reaction.Esterification is such as carried out as follows: make above-mentioned carboxylic 1,1-difluoroethylene analog copolymer (X) reacts with thionyl chloride in the organic solvents such as N-Methyl pyrrolidone, obtaining converting carboxylate groups is at least partially the reactant of acid chloride groups, then, make this reactant and there is hydroxyl and react containing the heteroatomic compound of at least one be selected from nitrogen and sulphur.
As above-mentioned organic solvent, as long as dissolve above-mentioned carboxylic 1,1-difluoroethylene analog copolymer (X) and do not hinder the solvent of desired esterification, such as, can enumerate N-Methyl pyrrolidone, DMF, dimethyl sulfoxide (DMSO) etc.
It should be noted that, in aforesaid method 1, above-mentioned carboxylic 1, the carboxyl at least partially that 1-difluoroethylene analog copolymer (X) has and following compound bonding, form the structural unit that above-mentioned general formula c represents thus, described compound have by chemical reaction and carboxyl or derivatives thereof formed binding groups group and containing at least one heteroatoms be selected from nitrogen and sulphur.
As what use in binding groups forming reactions, be there is the group being formed binding groups by chemical reaction and carboxyl or derivatives thereof, and the amount containing the heteroatomic compound of at least one be selected from nitrogen and sulphur, as mentioned above, can suitably adjust, make gained 1, 1-difluoroethylene analog copolymer has the structural unit that the above-mentioned general formula a of 80 ~ 99.95mol% represents, the structural unit that the above-mentioned general formula b of 0 ~ 19.99mol% represents, and the structural unit that the above-mentioned general formula c of 0.01 ~ 20mol% represents (wherein, general formula a, the structural unit that b and c represents adds up to 100mol%).
As the binding groups forming reactions in aforesaid method 1, concrete example except esterification, such as can enumerate amidate action.Now, will there is hydroxyl and change to containing the heteroatomic compound of at least one be selected from nitrogen and sulphur and there is amino and containing the heteroatomic compound of at least one be selected from nitrogen and sulphur, in addition, use the method identical with esterification to carry out.
Be described for aforesaid method 2.In the method, with following ratio by 80 ~ 99.95mol%1,1-difluoroethylene, 0 ~ 19.99mol% by above-mentioned polymerization formed the carboxyl group-containing monomer of the structural unit that general formula b represents and 0.01 ~ 20mol% by above-mentioned polymerization formed the structural unit that general formula c represents, containing the heteroatomic monomer of at least one be selected from nitrogen and sulphur (structural unit that wherein, general formula a, b and c represents adds up to 100mol%) mixing and copolymerization carry out.For copolymerization, the method identical with carboxylic vinylidene fluoride analog copolymer (X) can be used to carry out.
Be described for aforesaid method 3.First, except being changed to by carboxyl group-containing monomer containing except epoxy based monomers, by the method that the carboxylic vinylidene fluoride analog copolymer (X) with aforesaid method 1 is same, obtain the vinylidene fluoride analog copolymer containing epoxy group(ing).Afterwards, by making the vinylidene fluoride analog copolymer containing epoxy group(ing) form the group of binding groups by chemical reaction and epoxy group(ing) and react to carry out containing the heteroatomic compound of at least one be selected from nitrogen and sulphur with having.Formed the group of binding groups by chemical reaction and epoxy group(ing), such as, can enumerate hydroxyl.
Logarithmic viscosity number (the log viscosities of solution at 30 DEG C that 4g resin dissolves is obtained in the DMF of 1 liter of vinylidene fluoride analog copolymer of the present invention.Same below) be preferably value within the scope of 0.5 ~ 5.0dl/g, be more preferably the value within the scope of 1.0 ~ 4.0dl/g.If be the viscosity in above-mentioned scope, electrode for nonaqueous electrolyte secondary battery mixture can be suitable for.
Logarithmic viscosity number η icalculating can carry out as follows: 80mg vinylidene fluoride analog copolymer is dissolved in the DMF of 20ml, use Ubbelohde viscometer (Ubbelohde viscometer), in the thermostatic bath of 30 DEG C, utilize following formula to carry out.
η i＝(1/C)·ln(η/η 0)
Wherein, η is the viscosity of polymers soln, η 0for the viscosity that the DMF of solvent is independent, C is 0.4g/dl.
(battery electrode tackiness agent)
Battery electrode tackiness agent of the present invention contains vinylidene fluoride analog copolymer and the non-aqueous solvent of the invention described above.
As mentioned above, battery electrode tackiness agent of the present invention contains vinylidene fluoride analog copolymer and non-aqueous solvent, by adding electrode active material in this tackiness agent, can obtain following electrode for nonaqueous electrolyte secondary battery mixture.It should be noted that, when adding electrode active material in this tackiness agent, electrode active material can be added directly in tackiness agent, also electrode active material can be added non-aqueous solvent, add in tackiness agent after being uniformly mixed.
(non-aqueous solvent)
Battery electrode tackiness agent of the present invention contains non-aqueous solvent.As non-aqueous solvent, the non-aqueous solvent with the effect of dissolving above-mentioned vinylidene fluoride analog copolymer can be used, preferably use the solvent with polarity.As the concrete example of non-aqueous solvent, METHYLPYRROLIDONE, N can be enumerated, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, dioxane, tetrahydrofuran (THF), tetramethyl-urea, triethyl phosphate, trimethyl phosphate etc., be preferably METHYLPYRROLIDONE, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO).In addition, non-aqueous solvent can be used alone a kind, also can mix two or more and use.
For battery electrode tackiness agent of the present invention, when vinylidene fluoride analog copolymer is 100 mass parts, non-aqueous solvent is preferably 400 ~ 10000 mass parts, is more preferably 600 ~ 5000 mass parts.Time in above-mentioned scope, form the soltion viscosity of appropriateness, operability is excellent, therefore preferably.
(electrode for nonaqueous electrolyte secondary battery mixture)
Electrode for nonaqueous electrolyte secondary battery mixture of the present invention contains the vinylidene fluoride analog copolymer of the invention described above, electrode active material and non-aqueous solvent.In addition, the vinylidene fluoride analog copolymer of anode for nonaqueous electrolyte secondary battery mixture of the present invention usually containing the invention described above, negative electrode active material and non-aqueous solvent.Electrode for nonaqueous electrolyte secondary battery mixture of the present invention is due to containing above-mentioned 1,1-difluoroethylene analog copolymer, so the electrode for nonaqueous electrolyte secondary battery obtained by this mixture is coated with on the current collector also drying, the binding property of current collector and mixture layer is excellent.
For electrode for nonaqueous electrolyte secondary battery mixture of the present invention, by changing the kind etc. of electrode active material, mixture, i.e. the anode for nonaqueous electrolyte secondary battery mixture of negative pole can be used as, also can be used as mixture, i.e. the positive electrode for nonaqueous electrolyte secondary battery mixture of positive pole.When above-mentioned vinylidene fluoride base polymer is on positive pole, have the heteroatomic organic group such as nitrogen or sulphur oxidative degradation sometimes, therefore, electrode for nonaqueous electrolyte secondary battery mixture of the present invention is more preferably used as the mixture of negative pole.
(electrode active material)
As the electrode active material that electrode for nonaqueous electrolyte secondary battery mixture of the present invention contains, be not particularly limited, the electrode active material (being also denoted as negative electrode active material below) of existing known negative pole, the active substance (being also denoted as positive active material below) of positive pole can be used.
As negative electrode active material, such as, can enumerate carbon material, metal alloy compositions, metal oxide etc., wherein, preferred carbon material.
As above-mentioned carbon material, synthetic graphite, natural graphite, difficult graphitized carbon, easily graphitized carbon etc. can be used.In addition, above-mentioned carbon material can be used alone a kind, also can use two or more.
When using above-mentioned carbon material, the energy density of battery can be improved.
As above-mentioned synthetic graphite, such as can by by organic materials carbonization and then at high temperature heat-treat, carry out pulverizings also classification obtain.As synthetic graphite, MAG series (Hitachi changes into industry system), MCMB (Osaka gas system) etc. can be used.
As above-mentioned difficult graphitized carbon, such as, obtain by the material from petroleum pitch is burnt till at 1000 ~ 1500 DEG C.As difficult graphitized carbon, Carbotron P (Wu Yu system) etc. can be used.
The specific surface area of above-mentioned negative electrode active material is preferably 0.3 ~ 10m 2/ g is more preferably 0.6 ~ 6m 2/ g.Specific surface area is more than 10m 2during/g, the decomposition amount of electrolytic solution increases, and the irreversible capacity at initial stage increases, therefore not preferred.
As positive active material, the lithium class positive active material preferably at least containing lithium.As lithium class positive active material, such as, LiCoO can be enumerated 2, LiNi xco 1-xo 2general formula LiMY such as (0≤x≤1) 2(M is at least one of the transition metal such as Co, Ni, Fe, Mn, Cr, V; Y is the chalcogens such as O, S) the composition metal chalcogen compound, the LiMn that represent 2o 4deng the complex metal oxides, the LiFePO that form spinel structure 4deng olivine-type lithium compound etc.It should be noted that, as above-mentioned positive active material, can commercially available product be used.
The specific surface area of above-mentioned positive active material is preferably 0.05 ~ 50m 2/ g is more preferably 0.1 ~ 30m 2/ g.
It should be noted that, the specific surface area of electrode active material can use nitrogen adsorption method to obtain.
(non-aqueous solvent)
Electrode for nonaqueous electrolyte secondary battery mixture of the present invention contains non-aqueous solvent.As non-aqueous solvent, the material cited by non-aqueous solvent contained in above-mentioned battery electrode tackiness agent can be used as.In addition, non-aqueous solvent can be used alone a kind, also can mix two or more and use.
Electrode for nonaqueous electrolyte secondary battery mixture of the present invention contains above-mentioned vinylidene fluoride analog copolymer, electrode active material and non-aqueous solvent.
For electrode for nonaqueous electrolyte secondary battery mixture of the present invention, relative to 1,1-difluoroethylene analog copolymer and electrode active material amount to 100 mass parts, 1,1-difluoroethylene analog copolymer is preferably 0.5 ~ 15 mass parts, be more preferably 1 ~ 10 mass parts, active substance is preferably 85 ~ 99.5 mass parts, is more preferably 90 ~ 99 mass parts.In addition, when vinylidene fluoride analog copolymer and electrode active material add up to 100 mass parts, non-aqueous solvent is preferably 20 ~ 300 mass parts, is more preferably 50 ~ 200 mass parts.
Time in above-mentioned scope containing each composition, use electrode for nonaqueous electrolyte secondary battery mixture of the present invention, productivity can manufacture electrode for nonaqueous electrolyte secondary battery well, when manufacturing electrode for nonaqueous electrolyte secondary battery, the stripping strength of mixture layer and current collector is excellent.
In addition, electrode for nonaqueous electrolyte secondary battery mixture of the present invention can containing other compositions except above-mentioned vinylidene fluoride analog copolymer, electrode active material and non-aqueous solvent.As other compositions, can containing bonding auxiliarys etc. such as the pigment dispersing agent such as conductive auxiliary agent or polyvinylpyrrolidone, polyacrylic acid, the polymethyl acrylic acid such as carbon black.As other compositions above-mentioned, can containing other polymkeric substance except above-mentioned vinylidene fluoride analog copolymer.As other polymkeric substance above-mentioned, such as can enumerate poly-1,1-difluoroethylene, 1,1-difluoroethylene-hexafluoropropylene copolymer, 1,1-fluoride-trifluoro-ethylene multipolymer, 1, the vinylidene fluoride base polymers such as 1-difluoroethylene-chlorotrifluoroethylcopolymer copolymer, vinylidene fluoride-perfluoro methyl vinyl ether multipolymer.Time in electrode for nonaqueous electrolyte secondary battery mixture of the present invention containing other polymkeric substance, usually relative to above-mentioned vinylidene fluoride analog copolymer 100 mass parts, contain with the amount below 25 mass parts.
Electrode for nonaqueous electrolyte secondary battery mixture of the present invention uses E type viscometer, at 25 DEG C, velocity of shear 2s -1under viscosity when measuring be generally 2000 ~ 50000mPas, be preferably 5000 ~ 30000mPas.
As the manufacture method of electrode for nonaqueous electrolyte secondary battery mixture of the present invention, above-mentioned 1 can be mixed, 1-difluoroethylene analog copolymer, electrode active material and non-aqueous solvent make it form uniform slurry, order during mixing is not particularly limited, such as can enumerate following method: by above-mentioned 1,1-difluoroethylene analog copolymer is dissolved in a part of non-aqueous solvent, obtain binder solution, electrode active material and remaining non-aqueous solvent is added in this binder solution, be uniformly mixed, obtain electrode for nonaqueous electrolyte secondary battery mixture.
(electrode for nonaqueous electrolyte secondary battery)
Electrode for nonaqueous electrolyte secondary battery of the present invention obtains by being coated with by above-mentioned electrode for nonaqueous electrolyte secondary battery mixture also dry on the current collector.The layer that electrode for nonaqueous electrolyte secondary battery of the present invention has current collector and formed by electrode for nonaqueous electrolyte secondary battery mixture.It should be noted that, as above-mentioned electrode for nonaqueous electrolyte secondary battery mixture, when using anode for nonaqueous electrolyte secondary battery mixture, obtain anode for nonaqueous electrolyte secondary battery, as above-mentioned electrode for nonaqueous electrolyte secondary battery mixture, when using positive electrode for nonaqueous electrolyte secondary battery mixture, obtain positive electrode for nonaqueous electrolyte secondary battery.When vinylidene fluoride base polymer is on positive pole, have the heteroatomic organic group such as nitrogen or sulphur oxidative degradation sometimes, therefore, electrode for nonaqueous electrolyte secondary battery of the present invention is more preferably used as anode for nonaqueous electrolyte secondary battery.
It should be noted that, in the present invention, by by by the coating of electrode for nonaqueous electrolyte secondary battery mixture on the current collector and dry and formed, the layer that formed by electrode for nonaqueous electrolyte secondary battery mixture is denoted as mixture layer.
As the current collector used in the present invention, in order to obtain anode for nonaqueous electrolyte secondary battery, such as, can enumerate copper, as its shape, such as, can enumerate tinsel or wire netting etc.In order to obtain anode for nonaqueous electrolyte secondary battery, preferably use Copper Foil as current collector.
As the current collector used in the present invention, in order to obtain positive electrode for nonaqueous electrolyte secondary battery, such as, can enumerate aluminium, as its shape, such as, can enumerate tinsel or wire netting etc.In order to obtain positive electrode for nonaqueous electrolyte secondary battery, preferably use aluminium foil as current collector.
The thickness of current collector is generally 5 ~ 100 μm, is preferably 5 ~ 20 μm.
The thickness of mixture layer is generally 20 ~ 250 μm, is preferably 20 ~ 150 μm.In addition, the weight per unit area of mixture layer is generally 20 ~ 700g/m 2, be preferably 30 ~ 500g/m 2.
When manufacturing electrode for nonaqueous electrolyte secondary battery of the present invention, above-mentioned electrode for nonaqueous electrolyte secondary battery mixture is coated at least one side, the preferably two sides of above-mentioned current collector.As method during coating, be not particularly limited, can enumerate and carry out the method such as being coated with bar coater, die coater, comma coater.
In addition, as the drying carried out after coating, usually at the temperature of 50 ~ 150 DEG C, 1 ~ 300 minute is carried out.In addition, pressure time dry is not particularly limited, and usually under atmospheric pressure or under decompression carries out.
And then, after carrying out drying, can heat-treat.When heat-treating, usually at the temperature of 100 ~ 250 DEG C, carry out 1 ~ 300 minute.It should be noted that, heat treated temperature and above-mentioned drying have repetition, and above-mentioned operation can, for the operation of carrying out respectively, also can be the operation of carrying out continuously.
In addition, pressure treatment can also be carried out.When carrying out pressure treatment, usually carry out under 1 ~ 200MP-G.When carrying out pressure treatment, can electrode density be improved, therefore preferably.
Use above method, electrode for nonaqueous electrolyte secondary battery of the present invention can be manufactured.It should be noted that, as the Rotating fields of electrode for nonaqueous electrolyte secondary battery, time in one side electrode for nonaqueous electrolyte secondary battery mixture being coated on current collector, for the two-layer structure of mixture layer/current collector, time on two sides electrode for nonaqueous electrolyte secondary battery mixture being coated on current collector, it is the three-decker of mixture layer/current collector/mixture layer.
For electrode for nonaqueous electrolyte secondary battery of the present invention, by using above-mentioned electrode for nonaqueous electrolyte secondary battery mixture, and the stripping strength of current collector and mixture layer is excellent, therefore, pressurizeing, cut, in the operation such as winding, electrode not easily cracks and peels off, productivity improves, therefore preferably.
For electrode for nonaqueous electrolyte secondary battery of the present invention, as mentioned above, the stripping strength of current collector and mixture layer is excellent, specifically, of the present invention 1 is replaced with using known carboxylic vinylidene fluoride analog copolymer all the time, when the electrode that 1-difluoroethylene analog copolymer obtains is compared, be generally more than 4.5 times according to JIS K6854, the stripping strength of being undertaken measuring by 180 degree of stripping tests, be preferably more than 5 times, be more preferably more than 5.5 times.In addition, less than 30 times are generally.
(rechargeable nonaqueous electrolytic battery)
The feature of rechargeable nonaqueous electrolytic battery of the present invention is, has above-mentioned electrode for nonaqueous electrolyte secondary battery.
As rechargeable nonaqueous electrolytic battery of the present invention, except there is above-mentioned electrode for nonaqueous electrolyte secondary battery, be not particularly limited.As rechargeable nonaqueous electrolytic battery, have above-mentioned electrode for nonaqueous electrolyte secondary battery, preferably have anode for nonaqueous electrolyte secondary battery, the component beyond electrode for nonaqueous electrolyte secondary battery, such as barrier film etc. can use existing known material.
[embodiment]
Below, provide embodiment, in further detail the present invention is described, but the present invention is not limited to these embodiments.
(comparative example 1)
(manufacture of carboxylic vinylidene fluoride analog copolymer (X1))
900g ion exchanged water, 0.4gMETOLOSE 90SH-100,0.2g carboxyethyl acrylate (being also denoted as CEA below), 2g 50wt% tert-Butyl peroxypivalate-Fron 225cb solution, 396g 1 is dropped in the autoclave of inner capacities 2 liters, 1-difluoroethylene, was warming up to 50 DEG C with 2 hours.
Afterwards, maintaining 50 DEG C, is the CEA aqueous solution that certain speed slowly adds 30g/l with polymerization pressure.Comprise the amount of initial stage interpolation, add total amount 5.92gCEA.
Be aggregated at the end of the CEA aqueous solution adds and stop simultaneously, from intensification, total carries out 13.1 hours.
Polymerization terminate after, at 95 DEG C, by polymer paste thermal treatment after 60 minutes, dewater and wash, so at 80 DEG C drying 20 hours, obtain polymer powder (carboxylic vinylidene fluoride analog copolymer (X1)).Percent polymerization is 25%, and the logarithmic viscosity number of the carboxylic vinylidene fluoride analog copolymer (X1) of gained is 2.65dl/g.
By 1h NMR composes and calculates the ratio of components of carboxylic vinylidene fluoride analog copolymer (X1), result with molar ratio computing, VDF/CEA=97.28/2.72.
It should be noted that, carboxylic vinylidene fluoride analog copolymer (X1) 1hNMR spectrum is obtained under the following conditions.
Device: Bruker Inc. AVANCE AC 400FT NMR spectrometer
Condition determination
Frequency: 400MHz
Measure solvent: DMSO-d 6
Measure temperature: 25 DEG C
For the amount of the amount of the structural unit from vinylidene fluoride of polymkeric substance and the structural unit from carboxyethyl acrylate, use 1h NMR composes, and calculates based on the integrated intensity at the main signal observed from the 4.19ppm place of carboxyethyl acrylate and the signal observed at main 2.24ppm and the 2.87ppm place from vinylidene fluoride.
In addition, the fusing point (Tm) of carboxylic vinylidene fluoride analog copolymer (X1) is 163 DEG C.
It should be noted that, the fusing point (Tm) of carboxylic vinylidene fluoride analog copolymer (X1) is measured by dsc (DSC).DSC working sample is made as follows: use pressure forming machine (Co., Ltd. god rattan metal industry AYSR-5), by carboxylic 1 at 210 DEG C, after 1-difluoroethylene analog copolymer (X1) preheated for 30 seconds, keep 1 minute under moulding pressure 0.5MPa, make presspahn (press sheet), cut about 10mg from this presspahn.The mensuration of DSC is carried out under the following conditions, obtains Tm by the endotherm peak temperature in temperature-rise period.
Device: METTLER DSC30
Specimen holder: Aluminum standard 40 μ l
Measure temperature range: 30-220 DEG C
Heat-up rate: 10 DEG C/min
Nitrogen flow: 50ml/min
(mensuration of stripping strength)
Make 94 mass parts synthetic graphites (Hitachi Chemical Industries (Ltd.) system " MAG-D20 "), 6 mass parts above-mentioned carboxylic 1,1-difluoroethylene analog copolymer (X1) is dispersed in N-Methyl pyrrolidone (being also denoted as NMP below), and preparation solid component concentration is the electrode slurry of 41 quality %.
Use bar coater to be coated on the Cu paper tinsel of thick 10 μm by above-mentioned electrode slurry, drying 30 minutes at 110 DEG C, making one side weight per unit area is 150g/m 2single spreading electrode.
Be 150g/m by above-mentioned one side weight per unit area 2single spreading electrode be cut into long 50mm, wide 20mm, at room temperature, moulding pressure 0.8t/cm 2under carry out plane compacting, make test film.
Continuous pressing device for stereo-pattern on the coating electrode face of test film, using Cu paper tinsel as " flexible adhesion material ", according to JISK-6854, use tensile testing machine (ORIENTEC Inc. " STA-1150UNIVERSAL TESTING MACHINE "), carry out 180 degree of stripping tests under speed 200mm/ minute at bar head (head), measure stripping strength.
(embodiment 1)
(manufacture of vinylidene fluoride analog copolymer (1))
In the 500ml three-necked bottle with enlightening nurse rood cooling tube, dropping funnel and magnetic stir bar, add the carboxylic vinylidene fluoride analog copolymer (X1) and 150ml N-Methyl pyrrolidone (NMP) of making in 10.1g comparative example 1 and dissolve.
At room temperature, in gained solution, instill 5.30g (0.0445mol) thionyl chloride, after instillation terminates, heated and stirred 1.5 hours at 80 DEG C.
After heated and stirred terminates, let cool to room temperature, add the 3-pyridone of 4.34g (0.0456mol), further 90 times heated and stirred 1.5 hours.
After heated and stirred terminates, by reclaiming polymkeric substance using water/methanol mixed solvent as the operation of the redeposition of lean solvent.
The logarithmic viscosity number of gained vinylidene fluoride analog copolymer (1) is 2.07dl/g.
In addition, by measure under the condition same with comparative example 1 1h NMR spectrum confirm, in the carboxyl in the carboxylic vinylidene fluoride analog copolymer (X1) of making in comparative example 1 45 % by mole esterified.It should be noted that, vinylidene fluoride analog copolymer (1) 1h NMR spectrum is shown in Fig. 1.The confirmation of above-mentioned esterification yield, by the peak of two hydrogen atoms from pyridine ring observed near 7.5ppm integrated intensity 0.75 and observe near 4.2ppm from-C (O) O-CH 2the integrated intensity 1.66 at the peak of the methylene radical of-structure calculates.
In addition, measure the fusing point (Tm) of vinylidene fluoride analog copolymer (1) by the method same with comparative example 1, result Tm is 164 DEG C.
(mensuration of stripping strength)
Change to except above-mentioned vinylidene fluoride analog copolymer (1) except by above-mentioned carboxylic vinylidene fluoride analog copolymer (X1), carry out in the same manner as comparative example 1, measure stripping strength.
(embodiment 2)
(manufacture of vinylidene fluoride analog copolymer (2))
Except the 3-pyridone of embodiment 1 being changed to except 2-(2-thienyl) ethanol, with method synthesis similarly to Example 1.
The logarithmic viscosity number of gained vinylidene fluoride analog copolymer (2) is 2.11dl/g.
In addition, by measure under the condition same with comparative example 1 1h NMR spectrum confirm, in the carboxyl in the carboxylic vinylidene fluoride analog copolymer (X1) of making in comparative example 1 74 % by mole esterified.It should be noted that, vinylidene fluoride analog copolymer (2) 1h NMR spectrum is shown in Fig. 2.The confirmation of above-mentioned esterification yield, by the peak of three hydrogen atoms from thiphene ring observed near 6.5 ~ 7.5ppm integrated intensity 1.84 and observe near 4.2ppm from-C (O) O-CH 2the integrated intensity 2.89 at the peak of the methylene radical of-structure calculates.
In addition, measure the fusing point (Tm) of vinylidene fluoride analog copolymer (2) by the method same with comparative example 1, result Tm is 164 DEG C.
(mensuration of stripping strength)
Change to except above-mentioned vinylidene fluoride analog copolymer (2) except by above-mentioned carboxylic vinylidene fluoride analog copolymer (X1), carry out in the same manner as comparative example 1, measure stripping strength.
(embodiment 3)
(manufacture of vinylidene fluoride analog copolymer (3))
Change to except 2-(methylthio group) ethanol except by the 3-pyridone of embodiment 1, with method synthesis similarly to Example 1.
The logarithmic viscosity number of gained vinylidene fluoride analog copolymer (3) is 2.04dl/g.
In addition, by measure under the condition same with comparative example 1 1h NMR spectrum confirm, in the carboxyl in the carboxylic vinylidene fluoride analog copolymer (X1) of making in comparative example 1 79 % by mole esterified.It should be noted that, vinylidene fluoride analog copolymer (3) 1h NMR spectrum is shown in Fig. 3.The confirmation of above-mentioned esterification yield, by observe near 2.1ppm from-S-CH 3the integrated intensity 1.88 at the peak of the methyl of structure and observe near 4.2ppm from-C (O) O-CH 2the integrated intensity 2.84 at the peak of the methylene radical of-structure calculates.
In addition, measure the fusing point (Tm) of vinylidene fluoride analog copolymer (3) by the method same with comparative example 1, result Tm is 164 DEG C.
(mensuration of stripping strength)
Change to except above-mentioned vinylidene fluoride analog copolymer (3) except by above-mentioned carboxylic vinylidene fluoride analog copolymer (X1), carry out in the same manner as comparative example 1, measure stripping strength.
(comparative example 2)
(mensuration of stripping strength)
When preparing electrode slurry, when carboxyl contained in carboxylic vinylidene fluoride analog copolymer (X1) is 100 % by mole, uses the 3-pyridone of 45 % by mole of amounts further, in addition, carry out in the same manner as comparative example 1, prepare electrode slurry.
Except this electrode slurry of use, carry out in the same manner as comparative example 1, measure stripping strength.
(comparative example 3)
(mensuration of stripping strength)
When preparing electrode slurry, when carboxyl contained in carboxylic vinylidene fluoride analog copolymer (X1) is 100 % by mole, 2-(2-thienyl) ethanol of further use 74 % by mole amount, in addition, carry out in the same manner as comparative example 1, prepare electrode slurry.
Except this electrode slurry of use, carry out in the same manner as comparative example 1, measure stripping strength.
(comparative example 4)
(mensuration of stripping strength)
When preparing electrode slurry, when carboxyl contained in carboxylic vinylidene fluoride analog copolymer (X1) is 100 % by mole, 2-(methylthio group) ethanol of further use 79 % by mole amount, in addition, carry out in the same manner as comparative example 1, prepare electrode slurry.
Except this electrode slurry of use, carry out in the same manner as comparative example 1, measure stripping strength.
The stripping strength measured in each embodiment and comparative example is shown in table 1.
[table 1]
Table 1
Stripping strength [gfmm -1]
Embodiment 1 4.55
Embodiment 2 8.79
Embodiment 3 6.83
Comparative example 1 0.51
Comparative example 2 0.54
Comparative example 3 0.51
Comparative example 4 0.50
From above-mentioned table 1, use of the present invention have containing the heteroatomic organic group of at least one be selected from nitrogen and sulphur 1, the electrode that 1-difluoroethylene analog copolymer manufactures, with use, not there is carboxylic 1 of this organic group, the electrode (comparative example 1) that 1-difluoroethylene analog copolymer manufactures is compared, and stripping strength is excellent.
In addition, in system, prepare electrode slurry having under the compound existent condition containing the heteroatomic organic group of at least one be selected from nitrogen and sulphur, even if the electrode (comparative example 2 ~ 4) for using this electrode slurry to manufacture, stripping strength and comparative example 1 are also same degree.
That is, only exist in system containing the heteroatomic organic group of at least one be selected from nitrogen and sulphur, can not improve the stripping strength of the electrode obtained, vinylidene fluoride analog copolymer needs to have this organic group.

Claims (9)

1. a 1-difluoroethylene analog copolymer, have: the structural unit that the structural unit that 80 ~ 99.95mol% following general formula a represents, 0 ~ 19.99mol% following general formula b represent and the structural unit that the following general formula c of 0.01 ~ 20mol% represents, wherein, the structural unit that general formula a, b and c represents adds up to 100mol%;
Described vinylidene fluoride analog copolymer is obtained by the binding groups forming reactions of carboxylic vinylidene fluoride analog copolymer (X) with following compound,
Described compound has to form the group of binding groups and the compound containing sulphur by chemical reaction and carboxyl or derivatives thereof,
Described carboxylic 1,1-difluoroethylene analog copolymer (X) has structural unit that 80 ~ 99.95mol% following general formula a represents and the structural unit that the following general formula b ' of 0.05 ~ 20mol% represents, wherein, the structural unit that general formula a and b ' represents adds up to 100mol%
In described general formula b, R cOOHfor the organic group containing carboxyl, R 1, R 2, R 3be the alkyl of hydrogen atom, halogen atom, carboxyl or derivatives thereof or carbonatoms 1 ~ 5 independently of one another,
In described general formula c, R n, Sfor the organic group containing at least one group be selected from thioether, thiocarbonyl and heterocycle, described heterocycle is the heterocycle containing sulphur, R 4, R 5, R 6be the alkyl of hydrogen atom, halogen atom, carboxyl or derivatives thereof or carbonatoms 1 ~ 5 independently of one another,
In described general formula b ', R cOOHfor the organic group containing carboxyl,
In described general formula b ', R 1, R 2, R 3be the alkyl of hydrogen atom, halogen atom, carboxyl or derivatives thereof or carbonatoms 1 ~ 5 independently of one another.
2. vinylidene fluoride analog copolymer as claimed in claim 1, wherein, logarithmic viscosity number is 0.5 ~ 5.0dl/g.
3. a battery electrode tackiness agent, containing the vinylidene fluoride analog copolymer described in claim 1 or 2 and non-aqueous solvent.
4. an electrode for nonaqueous electrolyte secondary battery mixture, containing vinylidene fluoride analog copolymer, electrode active material and non-aqueous solvent described in claim 1 or 2.
5. an anode for nonaqueous electrolyte secondary battery mixture, containing vinylidene fluoride analog copolymer, negative electrode active material and non-aqueous solvent described in claim 1 or 2.
6. an electrode for nonaqueous electrolyte secondary battery, obtains by being coated with by electrode for nonaqueous electrolyte secondary battery mixture according to claim 4 also dry on the current collector.
7. an anode for nonaqueous electrolyte secondary battery, obtains by being coated with by anode for nonaqueous electrolyte secondary battery mixture according to claim 5 also dry on the current collector.
8. a rechargeable nonaqueous electrolytic battery, has electrode for nonaqueous electrolyte secondary battery according to claim 6.
9. a rechargeable nonaqueous electrolytic battery, has anode for nonaqueous electrolyte secondary battery according to claim 7.
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