CN104725544B - A kind of high-adhesion vinylidene fluoride copolymers - Google Patents
A kind of high-adhesion vinylidene fluoride copolymers Download PDFInfo
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Abstract
The invention provides a kind of high-adhesion vinylidene fluoride copolymers, vinylidene fluoride monomers and at least one modified acroleic acid esters comonomer form, be suitable as lithium ion battery binding agent.
Description
Technical field
The present invention relates to a kind of high-adhesion vinylidene fluoride copolymers, especially relate to a kind of high-adhesion vinylidene fluoride copolymers that can serve as lithium ion cell electrode binding agent.
Background technology
PVDF is a kind of polymer partially fluorinated, hemicrystalline, has the characteristics such as the chemical resistance of excellence, thermomechanically performance, weatherability, the most also has the solvent resistance of appropriateness equilibrium, good molding processibility, good toughness.Additionally there is good electrical property, be therefore widely used in the fields such as membrane material, coating, lithium electricity, tubing cable.
Lithium battery is the chargeable chemical cell that technology is the highest in the world at present, and the nearest more than ten years quickly grow, are mainly used in mobile phone, electronic product and electric tool.The active substance of lithium ion battery electrode assembly, conductive agent, use in being maintained at collector body by binding agent, and this binding agent being accomplished by using has enough adhesive properties.
Owing to the adhesive property of PVDF homopolymer is limited, it is difficult to meet the demand of high-capacity lithium battery, therefore need to be modified PVDF improving its adhesive property.Conventional polyvinylidene fluoride modified method has other method of modifying such as modification by copolymerization, blending and modifying and grafting, irradiation, modified with functional group.Prior art has a following report for modification by copolymerization:
The open adhesive property improving copolymer toward interpolation 1wt%2-glycidyl methacrylate (2M-GMA) in vinylidene of Japan Patent spy 2003-155313.The peel strength of the electrode that the electrode for binding agent of embodiment data display this copolymer of use is prepared compared with polyvinylidene fluoride homopolymer improves 5 times, and the peel strength after high temperature soaks 5 days in Allyl carbonate is high 14 times.In actual polymerisation process, owing to the activity of 2M-GMA differs relatively big with vinylidene, considerably reduce rate of polymerization after addition, it is impossible to take emulsion polymerisation process to prepare, and the easy homopolymerization of 2M-GMA, cause battery life-time service stability to reduce.
The flat 9-161804 of Japan Patent, flat 10-233217 and special 2001-22301 etc. disclose vinylidene and TFE and the copolymer of perfluorovinyl sulfide ethers monomer, and the ratio of vinylidene controls between 60-80%.TFE and the introducing of perfluorovinyl sulfide ethers monomer, improve molecule chain flexibility and cohesive force.But perfluorovinyl sulfide ethers monomer is expensive.
Japan Patent spy 2001-19896 discloses the copolymer of vinylidene and the monomethyl maleate (MMM) of 1wt%, the electrode using this copolymer to be binding agent relatively polyvinylidene fluoride homopolymer peel strength improves 4 times, after in the electrolyte of Allyl carbonate/glycol dimethyl ether=1/1, high temperature soaks one week, peel strength is high compared with homopolymer 5 times.When this copolymer is prepared with suspension polymerization, at 28 DEG C, need the response time of more than 40 hours；When preparing with emulsion polymerization, reaction rate is extremely slow, easily causes breakdown of emulsion.
Chinese patent CN1714465A discloses the copolymer of the monomers such as vinylidene and acrylate, maleic mono-ester, allyl glycidyl ether, uses safety with the bonding force and battery improving binding agent.
Chinese patent CN101188283A discloses the copolymer of vinylidene and HFP, jointly acts on other inorganic binder, suppression positive electrode and the side reaction of electrolyte.
Chinese patent CN101679563A discloses vinylidene and (methyl) acrylic monomers copolymerization, and ensures that the polar monomer of 40% is uniformly distributed, and in order to keep the mechanical performance of Kynoar, chemical stability, improves cohesive force simultaneously.
PCT Patent Application WO01//57095 disclose a kind of method of fluoroolefin and non-fluorine polar monomer copolymerization, wherein fluoroolefin includes that tetrafluoroethene, CTFE, trifluoro-ethylene, fluorothene and vinylidene, non-fluorine polar monomer include vinyl alcohol, acrylic acid, acrylate, methacrylate.Supercritical polymerization process (carbon dioxide makees reaction medium) is used to prepare copolymer.
In sum, making vinylidene and polar monomer copolymerization is a more difficult job, owing to two kinds of monomer has different response features and poor compatibility, cause the overwhelming majority polar monomer can not be with vinylidene copolymerization, fraction polar monomer can be with vinylidene copolymerization, but rate of polymerization relatively vinylidene homopolymerization significantly declines.
Summary of the invention
It is an object of the invention to provide a kind of vinylidene fluoride copolymers, it has higher mean molecule quantity, moderate molecular weight distribution, higher fusing point, preferable thermodynamic property and high-adhesion energy, and this vinylidene fluoride copolymers can be dissolved completely in the solvent of conventional Kynoar.
For reaching goal of the invention the technical solution used in the present invention it is:
A kind of high-adhesion vinylidene fluoride copolymers, is formed by vinylidene fluoride monomers and at least one modified acroleic acid esters comonomer represented selected from following general structural formula (I):
Wherein:
R1、R2And R3Independently selected from F, H, C1-C8Alkyl, the C replaced by least one atom in F, O, S and N1-C8Alkyl；
R4Selected from C1-C8Alkyl, the C replaced by least one atom in F, O, S and N1-C8Alkyl；
Described modified acroleic acid esters comonomer content in the copolymer is 0.1～10wt%.
Carrying out combined polymerization owing to acrylic ester monomer is more difficult with vinylidene, the present invention is by being modified acrylic ester monomer so that it is structure and polymerization activity are similar with vinylidene, it is possible to be easier to carry out combined polymerization with vinylidene.
As preferred mode, said structure leads in the modified acroleic acid esters comonomer that formula (I) represents, substituent group: R1、R2And R3Independently selected from F, H, C1-C3Alkyl, the C replaced by least one F atom1-C3. alkyl, more preferably R1、R2And R3Independently selected from F, H, methyl, ethyl, the methyl replaced by least one F atom or ethyl；R4Selected from C1-C3Alkyl, the C replaced by least one F atom1-C3Alkyl, more preferably R4Selected from methyl, ethyl, the methyl replaced by least one F atom or ethyl.The modified acroleic acid esters comonomer that described general structure (I) represents be particularly preferably 2-trifluoroethyl methacrylate, 2-methacrylic acid trifluoro methyl ester, 1,1-bis-fluoro-2-methyl methacrylate, 2-trifluoromethyl acrylate methyl ester, structural formula is as follows:
The consumption of the modified acroleic acid esters comonomer that described general structure (I) represents, being preferably content in the copolymer is 1～5wt%.
High-adhesion vinylidene fluoride copolymers of the present invention, can further contain the 3rd comonomer, described 3rd comonomer preferably is selected from the one in fluorothene, trifluoro-ethylene, tetrafluoroethene, CTFE, tetrafluoroethene, tetrafluoropropene, pentafluoropropene, hexafluoropropene, perfluoro methyl vinyl ether and perfluoro propyl vinyl ether, two or three combination of the above, more preferably hexafluoropropene.Described 3rd comonomer content in the copolymer is preferably 0.1～50wt%, and more preferably the 3rd comonomer content in the copolymer is 1～10%.
The high-adhesion vinylidene fluoride copolymers that the present invention provides, its fusing point is 160～172 DEG C, thermal weight loss (400 DEG C) be < 1%(is according to its weightlessness of standing in TGA analyzes of ISO11358 standard), intrinsic viscosity 0.7～4dl/g, weight average molecular weight is 30～1,200,000 grams/mol, molecular weight distribution index is 1.6～5, molecular weight distribution curve is Unimodal Distribution, melt flow rate (MFR) is 0.02-10 gram/10 minutes (reference GB/T3682-2000, 230 DEG C, bear a heavy burden 5 kilograms), adhesion strength is 1～10N/m(to measure polymer preparation by ISO4624 standard (adhesion pull-off test) and become the adhesion strength after electrode), wherein adhesion strength is further preferably 5～10N/m.
The high-adhesion vinylidene fluoride copolymers of this offer, property indices illustrates, it is especially suitable for use as lithium ion battery binding agent.
High-adhesion vinylidene fluoride copolymers of the present invention can be prepared by emulsion polymerization or suspension polymerization.
When using emulsion polymerization, common preparation process is as follows:
A () provides vinylidene and one or more selected comonomers dispersion in water, described dispersion optionally contains surfactant；
B () adds a certain amount of water and dispersant to polymerization reaction kettle, add a certain amount of vinylidene fluoride monomers to polymeric kettle, be warming up to assigned temperature, add chain-transferring agent and organic initiators with initiated polymerization after closing still；
C () adds organic initiators further, add vinylidene fluoride monomers when reacting kettle inner pressure is less than specified pressure；
D () adds the dispersion of the comonomer selected to reactor when vinylidene fluoride monomers addition arrives certain value；
E () arrives designated value when vinylidene addition, and when reacting kettle inner pressure is less than designated value, stop adding organic initiators；
F () carries out post processing to products therefrom emulsion, obtain vinylidene fluoride copolymers.
When using emulsion polymerization way, in order to improve the stability of monomer dispersion liquid, in dispersion liquid, the most optionally add stabilizer.In a preferable example of the present invention, use paraffin as the stabilizer of dispersion liquid.The addition of stabilizer is without particular limitation, mainly can stable dispersions.
When using emulsion polymerization way, it is applicable to the monomer feed mode of the inventive method and is vinylidene fluoride monomers and comonomer segmentation joins in polymerization reaction kettle, when in still, pressure adds vinylidene fluoride monomers to specified pressure when being less than 5.5～6.0MPa, when vinylidene fluoride monomers addition to certain value, at intervals comonomer dispersion is added to wherein by pressure measurement pump, until polyreaction terminates.Reaction pressure is maintained at above vinylidene fluoride monomers critical pressure generally.
When using suspension polymerization, common preparation process is as follows:
A () provides vinylidene and one or more selected comonomers；
B () adds a certain amount of water and dispersant to polymerization reaction kettle, close after still the disposable vinylidene fluoride monomers adding specified amount to after in polymeric kettle, and by pressure measurement pump, comonomer is added to reactor, being warming up to assigned temperature, the disposable pressure measurement pump that passes through adds chain-transferring agent and organic initiators with initiated polymerization；
(c) when reacted between arrive certain value, and reacting kettle inner pressure less than designated value time, stopped reaction；
D () carries out post processing to products therefrom, obtain vinylidene fluoride copolymers.
In suspension polymerization, in order to improve monomer dispersibility in water, optionally add dispersant to dispersion.The addition of dispersant is without particular limitation, mainly can improve the dispersibility of monomer and will not have adverse effect on the polymer of polyreaction subsequently or formation.The type of same dispersant is the most without particular limitation, as long as it can improve the dispersibility of monomer and will not have a negative impact the polymer of polyreaction subsequently or formation.In a preferable example of the present invention, described dispersant typically uses fluorine-containing surfactant or cellulose, and its not limiting example has: XCnF2nCOOM, wherein X is fluorine atom or hydrogen atom, and n is the integer of 4～12, and M is hydrogen atom or alkali metal ion or ammonium ion or substituted ammonium ion or polyether segment, such as C7F15COOH.In a preferable example of the present invention, based on 100 weight parts monomers raw materials, dispersant addition is 0.01～1 weight portion.
When using suspension polymerisation mode, the monomer feed mode being applicable to the inventive method is similarly vinylidene fluoride monomers segmentation addition to reactor, comonomer vinylidene fluoride monomers add after, in still pressure less than 5.5～6.0MPa time, at intervals comonomer dispersion is joined reactor by pressure measurement pump.Reaction pressure is maintained at above vinylidene fluoride monomers critical pressure generally.In emulsion polymerization and suspension polymerization, the organic initiators of use is not particularly limited, and it can be polymerization initiator commonly used in the art.Described initiator is generally organic peroxide, and its example includes: di-isopropyl peroxydicarbonate, peroxy dicarbonate diisobutyl ester, peroxy dicarbonate diethylester.In emulsion polymerization, general distribution adds organic initiators, based on 100 weight portion vinylidene fluoride monomers or copolymerization mix monomer, the consumption (i.e. the addition of initiator in step (b)) for the initiator of initial initiated polymerization can be 0.05～0.5 weight portion.In suspension polymerization, the most disposably add organic initiators.
In emulsion polymerization and suspension polymerization, also need to add chain-transferring agent, it is adaptable to the chain-transferring agent of the present invention can be any compound that can continue vinylidene fluoride polymerization reaction, including: alcohols, such as isopropanol, n-butyl alcohol；Ketone, such as acetone, butanone；Esters, such as ethyl acetate, diethyl carbonate, dimethyl carbonate；Containing halogenated hydrocarbons, such as chloroform, dichloromethane；Aliphatic alkane, such as normal hexane.Based on 100 weight portion vinylidenes or copolymerization mix monomer, the consumption of chain-transferring agent is 0.01～0.2 weight portion.
Vinylidene fluoride copolymers of the present invention can be dissolved completely in the solvent of conventional Kynoar, and the example of described solvent has N, N-dimethyl pyrrolidone (NMP), dimethyl acetylamide (DMAc), DMF (DMF) etc., preferably NMP.
High-adhesion vinylidene fluoride copolymers various performance parameters method of testing of the present invention is as follows:
(1) measure polymer preparation by ISO4624 standard (adhesion pull-off test) and become the adhesion strength after electrode, carry out under 25 DEG C and 50% relative humidity；
(2) GB/T3682-2000 standard test melt flow rate (MFR) (MFR) is pressed.Test temperature is 230 DEG C, and loading is 5 kilograms；
(3) by ISO11358 standard, sample is carried out TGA analysis.In a nitrogen atmosphere, carrying out in a dynamic mode, record the temperature needed for the weightlessness to the polymer obtaining respectively 0.5%, 0.75% and 1%wt, these temperature are the highest, and the heat stability of polymer is the highest；
(4) ASTM D4591 standard test melting enthalpy is pressed.Heating schedule is: be warming up to 190 DEG C with the programming rates of 10 DEG C/min by 80 DEG C, it is incubated 10 minutes at 190 DEG C, it is cooled to 80 DEG C with the cooling rates of 80 DEG C/min by 190 DEG C, in 80 DEG C, is incubated 2 minutes, is warming up to 190 DEG C with the programming rates of 10 DEG C/min by 80 DEG C.DSC spectrogram when record second time is melted；
(5) solubility experiment uses NMP to be solvent.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these detailed description of the invention.One skilled in the art would recognize that all alternatives, improvement project and the equivalents potentially included in present invention encompasses Claims scope.
Embodiment 1
It is the paraffin of about 60 DEG C in adding 2500 grams of deionized waters, 5 grams of perfluorooctanoic acids and homologous mixture thereof and 1 gram of melting range in 5 liters of vertical polymerization reaction kettles.Merging reactor, evacuation is also replaced with nitrogen, until oxygen content is less than 5ppm in reactor, adds a certain amount of vinylidene fluoride monomers and makes in still pressure to 2.0MPa.Then start to be stirred with the speed of 500rpm, reactor temperature is risen to 65 DEG C, continue to supplement vinylidene fluoride monomers and reach 6.0MPa to reacting kettle inner pressure.Add 0.5 gram of dibenzoyl peroxide (BPO), start polyreaction.Make reacting kettle inner pressure maintain 5.5～6.0MPa by adding vinylidene fluoride monomers, add BPO with the speed of 0.1 gram/15 minutes, when in the vinylidene fluoride monomers of total amount 1000g adds complete and still, reaction pressure stops adding BPO when being down to below 3.0MPa；Comonomer 2-trifluoroethyl methacrylate feeds intake and ethyl acetate 0.5g in the ratio of the 1% of vinylidene weight portion, and when vinylidene fluoride monomers charged material weight reaches the 30% of predetermined value, 45%, 60%, 70%, 80%, 95%, average segmentation joins polymeric kettle.Reaction collects emulsion after terminating, and filters, breakdown of emulsion, and washing is dried, obtains vinylidene fluoride copolymers toner.
The adhesion strength after polymer preparation becomes electrode is measured by ISO4624 standard (adhesion pull-off test).The preparation process of electrode is as described below: under room temperature state, is dissolved in 50gNMP by aforementioned for the 1g vinylidene fluoride copolymers resin prepared under mechanical stirring.2g conductive black and 30g cobalt acid lithium (LiCoO is added when stirring2), it is sufficiently mixed guarantee homogeneity.Then mixture deaerated under vacuo and spread on aluminium foil with scraper, finally the aluminium foil sprawling upper electrode material mixture being positioned over vacuum drying oven and is warming up to 60 DEG C dry 12 hours, finally prepare electrode slice.Puller system measuring instrument is used to measure the adhesion strength of electrode slice upper electrode material.Each value at least takes the mensuration meansigma methods of 5 electrode slices, and test data are shown in Table 1.
Embodiment 2
2500 grams of deionized waters, 5 grams of methylcellulose are added in 5 liters of vertical polymerization reaction kettles.Merging reactor, evacuation is also replaced with nitrogen, until oxygen content is less than 5ppm in reactor, adds the vinylidene fluoride monomers of 1500g, 5g2-trifluoroethyl methacrylate, 2g ethyl acetate.Then start to be stirred with the speed of 500rpm, reactor temperature is risen to 28 DEG C, add 2.5 grams of dibenzoyl peroxides (BPO), start polyreaction.After reacting 12 hours, pressure is down to 3.0MPa, stops polyreaction.Reaction terminates rear collection material, washing, is dried, obtains vinylidene fluoride copolymers toner.
After tested, the intrinsic viscosity of the vinylidene fluoride copolymers toner prepared is 1.8dl/g.According to the method described in embodiment 1, the vinylidene fluoride copolymers toner restrained 1 prepare electrode slice, test data are shown in Table 1.
Embodiment 3
2500 grams of deionized waters, 5 grams of methylcellulose are added in 5 liters of vertical polymerization reaction kettles.Merging reactor, evacuation is also replaced with nitrogen, until oxygen content is less than 5ppm in reactor, adds the vinylidene fluoride monomers of 1500g, 5g1,1-bis-fluoro-2-methyl methacrylate, 2g ethyl acetate.Then start to be stirred with the speed of 500rpm, reactor temperature is risen to 28 DEG C, add 2.5 grams of dibenzoyl peroxides (BPO), start polyreaction.After reacting 12 hours, pressure is down to 3.0MPa, stops polyreaction.Reaction terminates rear collection material, washing, is dried, obtains vinylidene fluoride copolymers toner.
After tested, the intrinsic viscosity of the vinylidene fluoride copolymers toner prepared is 1.9dl/g.According to the method described in embodiment 1, the vinylidene fluoride copolymers toner restrained 1 prepare electrode slice, test data are shown in Table 1.
Embodiment 4
2500 grams of deionized waters, 5 grams of methylcellulose are added in 5 liters of vertical polymerization reaction kettles.Merging reactor, evacuation is also replaced with nitrogen, until oxygen content is less than 5ppm in reactor, adds the vinylidene fluoride monomers of 1500g, 5g2-trifluoromethyl acrylate methyl ester, 2g ethyl acetate.Then start to be stirred with the speed of 500rpm, reactor temperature is risen to 28 DEG C, add 2.5 grams of dibenzoyl peroxides (BPO), start polyreaction.After reacting 12 hours, pressure is down to 3.0MPa, stops polyreaction.Reaction terminates rear collection material, washing, is dried, obtains vinylidene fluoride copolymers toner.
After tested, the intrinsic viscosity of the vinylidene fluoride copolymers toner prepared is 1.9dl/g.According to the method described in embodiment 1, the vinylidene fluoride copolymers toner restrained 1 prepare electrode slice, test data are shown in Table 1.
Comparing embodiment 1
2500 grams of deionized waters, 5 grams of methylcellulose are added in 5 liters of vertical polymerization reaction kettles.Merging reactor, evacuation is also replaced with nitrogen, until oxygen content is less than 5ppm in reactor, adds the vinylidene fluoride monomers of 1500g, 5g ethyl acrylate, 2g ethyl acetate.Then start to be stirred with the speed of 500rpm, reactor temperature is risen to 28 DEG C, add 2.5 grams of dibenzoyl peroxides (BPO), start polyreaction.Treat that pressure is down to 3.0MPa, stop polyreaction.Reaction terminates rear collection material, washing, is dried, obtains vinylidene fluoride copolymers toner.
After tested, the intrinsic viscosity of the vinylidene fluoride copolymers toner prepared is 2.0dl/g.According to the method described in embodiment 1, the vinylidene fluoride copolymers toner restrained 1 prepare electrode slice, test data are shown in Table 1.
Comparing embodiment 2
According to the method described in embodiment 1, the KUREHA9200 vinylidene fluoride copolymers that the intrinsic viscosity of 1 gram is 1.8dl/g being prepared electrode slice, test data are shown in Table 1.
Comparing embodiment 3
According to the method described in embodiment 1, the SOLVAY5130 vinylidene fluoride copolymers that the intrinsic viscosity of 1 gram is 2.3dl/g being prepared electrode slice, test data are shown in Table 1.
Table 1
Vinylidene is understood by after the modified acroleic acid esters comonomer that represents with general structure (I) by the data of above-mentioned table 1, adhesive property can be obtained and have the polyvinylidene fluoride copolymer greatly improved, and polymerization time more non-fluorinated class polar monomer is greatly reduced.
Claims (10)
1. a high-adhesion vinylidene fluoride copolymers, it is characterised in that vinylidene fluoride copolymers is polymerized by following comonomer:
Vinylidene fluoride monomers and at least one modified acroleic acid esters comonomer represented selected from following general structural formula (I)；
Or, vinylidene fluoride copolymers is polymerized by following comonomer: vinylidene fluoride monomers, at least one is selected from following knot
Structure leads to modified acroleic acid esters comonomer and the 3rd comonomer that formula (I) represents；
Wherein:
R1、R2And R3Independently selected from F, H, C1-C3Alkyl, the C replaced by least one F atom1-C3Alkyl, R4Selected from C1-C3
Alkyl, the C replaced by least one F atom1-C3Alkyl, and R1、R2、R3And R4In to have at least one be F or quilt
The substituted C of at least one F atom1-C3Alkyl, modified acroleic acid esters comonomer content in the copolymer is 1～5wt%；
When there is three comonomers in comonomer, the 3rd comonomer content in the copolymer is 0.1～50wt%.
2. according to the high-adhesion vinylidene fluoride copolymers described in claim 1, it is characterised in that described modified acroleic acid esters copolymerization list
The R of body1、R2And R3Independently selected from F, H, methyl, ethyl, the methyl replaced by least one F atom or ethyl, R4Choosing
From methyl, ethyl, the methyl replaced by least one F atom or ethyl, and R1、R2、R3And R4In to have at least one be F
Or the C replaced by least one F atom1-C3Alkyl.
3. according to the high-adhesion vinylidene fluoride copolymers described in claim 2, it is characterised in that described modified acroleic acid esters copolymerization list
Body is 2-trifluoroethyl methacrylate, 2-methacrylic acid trifluoro methyl ester, 1,1-bis-fluoro-2-methyl methacrylate or 2-tri-
Methyl fluoride acrylic acid methyl ester..
4. according to the high-adhesion vinylidene fluoride copolymers described in claim 1, it is characterised in that described 3rd comonomer is selected from fluorine
Ethylene, trifluoro-ethylene, CTFE, tetrafluoroethene, tetrafluoropropene, pentafluoropropene, hexafluoropropene, perfluoromethylvinyl
One in base ether and perfluoro propyl vinyl ether, two or three combination of the above.
5. according to the high-adhesion vinylidene fluoride copolymers described in claim 4, it is characterised in that described 3rd comonomer is hexafluoro third
Alkene, described 3rd comonomer content in the copolymer is 1～10%.
6. according to the high-adhesion vinylidene fluoride copolymers described in claim 1, it is characterised in that described vinylidene fluoride copolymers is by emulsion
Prepared by polymerization or suspension polymerization.
7. according to the high-adhesion vinylidene fluoride copolymers described in claim 6, it is characterised in that vinylidene fluoride monomers and modified acroleic acid
Esters comonomer stagewise feeds, when in still, pressure adds residual monomer when being less than 5.5～6.0MPa；Dispersant is XCnF2nCOOM,
Wherein X is fluorine atom or hydrogen atom, and n is the integer of 4～12, M be hydrogen atom or alkali metal ion or ammonium ion or replace ammonium from
Son；Organic initiators is di-isopropyl peroxydicarbonate, peroxy dicarbonate diisobutyl ester or peroxy dicarbonate diethylester；
Chain-transferring agent be isopropanol, n-butyl alcohol, acetone, butanone, ethyl acetate, diethyl carbonate, dimethyl carbonate, chloroform, two
Chloromethanes or normal hexane.
8. according to the high-adhesion vinylidene fluoride copolymers one of claim 1-7 Suo Shu, it is characterised in that described vinylidene fluoride copolymers
Fusing point be 160～172 DEG C, adhesion strength thermal weight loss when being 1～10N/m, 400 DEG C < 1%, intrinsic viscosity 0.7～4dL/g,
Wherein, adhesion strength is to measure copolymer according to the adhesion pull-off test of ISO04624 under 25 DEG C and 50% relative humidity to prepare
Becoming the adhesion strength after electrode, thermal weight loss is to carry out thermogravimetic analysis (TGA) in a dynamic mode according to ISO11358.
9. according to the high-adhesion vinylidene fluoride copolymers described in claim 8, it is characterised in that the weight average of described vinylidene fluoride copolymers
Molecular weight is 30～1,200,000 grams/mol, molecular weight distribution index is 1.6～5, molecular weight distribution curve is Unimodal Distribution, molten
Body flow rate is 0.02～10 gram/10 minutes, adhesion strength is 5～10N/m, it is possible to be dissolved in N, N-dimethyl pyrrolidine
Ketone, dimethyl acetylamide or DMF, wherein, adhesion strength be under 25 DEG C and 50% relative humidity according to
The adhesion pull-off test of ISO04624 standard measures the adhesion strength after copolymer is prepared as electrode, melt flow rate (MFR) be according to
GB/T3682-2000 230 DEG C, 5Kg load under measure.
10. according to the high-adhesion vinylidene fluoride copolymers described in claim 8, it is characterised in that described vinylidene fluoride copolymers is used as
Lithium ion battery binding agent.
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