CN103588921B - A kind of high viscosity self-crosslinking vinylidene fluoride copolymers, its preparation method and application - Google Patents
A kind of high viscosity self-crosslinking vinylidene fluoride copolymers, its preparation method and application Download PDFInfo
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- CN103588921B CN103588921B CN201210286993.4A CN201210286993A CN103588921B CN 103588921 B CN103588921 B CN 103588921B CN 201210286993 A CN201210286993 A CN 201210286993A CN 103588921 B CN103588921 B CN 103588921B
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- 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
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- Y02E60/10—Energy storage using batteries
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses the novel vinylidene fluoride copolymers of a kind of high viscosity self-crosslinking, containing vinylidene fluoride monomers and at least one modification connection alkene ether compounds (structural formula is shown in specification sheets).The novel vinylidene fluoride copolymers of high viscosity self-crosslinking provided by the invention, adhesive property comparatively prior art significantly improves, and is suitable as lithium ion binding agent.
Description
Technical field
The present invention relates to a kind of novel vinylidene fluoride copolymers.
Background technology
PVDF is a kind of partially fluorinated, hemicrystalline polymkeric substance, has the excellent characteristic such as chemical resistant properties, thermomechanically performance, weathering resistance, also has solvent resistance, good molding processibility, good toughness that appropriateness is balanced simultaneously.There is good electrical property in addition, be therefore widely used in the fields such as mould material, coating, lithium electricity, tubing cable.
Lithium cell is the chargeable chemical cell that technology is the highest in the world at present, and nearest more than ten years development rapidly, is mainly used in mobile phone, electronic product and power tool.For the lithium-ions battery positive and negative electrode of the meeting of volume in charge and discharge process dilation, require that binding agent can play certain shock absorption, the requirement that therefore must meet as lithium ion battery binding agent is: (1) has enough cohesive strengths, prevent active substance from coming off from current collector, or cracking in battery assembling process; (2) binding agent can not be dissolved in for as in the organic solvent of electrolytic solution, but can be dissolved in the solvent making current collector top coat; (3) at operating voltage range, binding agent can not be oxidated or reduced.
Because the adhesive property of PVDF homopolymer is limited, be difficult to the needs meeting high-capacity lithium battery, therefore need to carry out modification to improve its adhesive property to PVDF.Functional modification can be realized by the surface-functionalized acquisition graft copolymer of PVDF material, namely by producing free radical and carry out graft polymerization reaction acquisition on PVDF molecular chain, but some uncontrolled side reactions can be there are in this process, even molecular chain ruptures, and causes the mechanical property of PVDF to decline to a great extent.Another kind of method of modifying is modification by copolymerization, has following report in prior art:
Japanese Patent Te Open 2003-155313 for comonomer, guarantees that binding agent has good solvent resistant resistance toheat with (methyl) vinylformic acid shrink ester, promotes the bounding force of binding agent, improves stripping strength.In VDF, such as add 1wt%2-glycidyl methacrylate (2M-GMA), suspension copolymerization, this multipolymer is that the stripping strength of the electrode that the electrode of binding agent is prepared compared with PVDF homopolymer improves 5 times, and in propylene carbonate, to soak the stripping strength after 5 days high 14 times for high temperature.
Japanese Patent Te Open 2001-19896 with maleic mono-ester class for comonomer.The monomethyl maleate (MMM) of 1wt% is added in VDF, suspension copolymerization, this multipolymer be binding agent electrode comparatively PVDF homopolymer stripping strength improve 4 times, after in the electrolytic solution of propylene carbonate/glycol dimethyl ether=1/1, high temperature soaks one week, stripping strength is high 5 times.
Great Jin is in the many sections of patents such as the flat 9-161804 of Japanese Patent, flat 10-233217, special Open 2001-223011, and the copolymerization of research VDF and TFE and perfluorovinyl sulfide ethers monomer, the ratio control of VDF is between 60-80%.
The method of VDF and the monomer copolymerization containing hydroxyl and carboxyl is refer in Wu Yu Chinese patent CN1714465A, list the monomers such as acrylate, maleic mono-ester, glycidyl allyl ether, main purpose is for improving the bounding force of binding agent and battery use safety.
The comonomer mentioned in great Jin Chinese patent CN1240053A and its monomer mentioned in the open patent 2001-223011 of Japanese publication basically identical, adding of TFE improves swelling resistance performance, and adding of Third monomer, in order to promote cohesive force.
Adopt the multipolymer of VDF and HFP in Samsung SDI Chinese patent CN101188283A, with other mineral binder bond acting in conjunction, suppress the side reaction of positive electrode material and electrolytic solution.
Mention VDF and the copolymerization of (methyl) Acrylic Acid Monomer in Su Wei Chinese patent CN101679563A, and ensure that the polar monomer of 40% is uniformly distributed, in order to keep mechanical property, the chemical stability of PVDF, improve cohesive force simultaneously.
Summary of the invention
The PVDF material of the present inventor to high Binder Properties is studied, find because connection alkene ether compounds has unique continuous double bond structure, after carrying out copolymerization with VDF, there is the double bond that can continue to react in the polymerisate of gained, can be used as the basis of next step crosslinking reaction.Further by after the light-initiated double bond radical polymerization of ultraviolet lamp, realize being cross-linked between copolymer molecule, form the crosslinked with high bond strength.
The invention provides the novel vinylidene fluoride copolymers of a kind of high viscosity self-crosslinking, containing vinylidene fluoride monomers and at least one modification connection alkene ether compounds, described modification connection alkene ether compounds has following structural formula (I):
（I）
Wherein:
R
1, R
2, R
3and R
4independently selected from hydrogen atom, halogen, C
1-C
8the C that alkyl, at least one hydrogen atom are optionally substituted by halogen
1-C
8alkyl or the C replaced containing optional at least one atom in O, S and N
1-C
8alkyl;
Described modification connection alkene ether compounds accounts for the quality proportioning of total comonomer for being greater than 0 ~ 10%, and namely in vinylidene fluoride copolymers, the content of modification connection alkene ether compounds is greater than 0, but is less than or equal to 10% simultaneously.
As preferred mode, above-mentioned
1, R
2, R
3and R
4independently selected from hydrogen atom, fluorine atom, C
1-C
4the C that alkyl, at least one hydrogen atom replaced by fluorine
1-C
4alkyl or the C replaced containing O atom
1-C
4alkyl; More preferably, R
1, R
2, R
3and R
4independently selected from hydrogen atom or methyl.
As preferred mode, the quality proportion optimization that above-mentioned modification connection alkene ether compounds accounts for total comonomer is 0.1 ~ 2%.
Vinylidene fluoride copolymers provided by the invention, can also further containing the 3rd comonomer, described 3rd comonomer be selected from vinyl fluoride, trifluoro-ethylene, tetrafluoroethylene, trifluorochloroethylene, tetrafluoroethylene, tetrafluoeopropene, five fluorine propylene, R 1216, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether and other can combine with the one in the Fluorine containing olefine of vinylidene copolymerization, more than two or three, the quality proportioning that described 3rd comonomer accounts for total comonomer is 0.1 ~ 50%.
Vinylidene fluoride copolymers of the present invention, performance perameter is preferably: weight-average molecular weight is 20 ~ 1,500,000 grams/mol, and molecular weight distribution index is 1.6 ~ 5, and molecular weight distribution curve is unimodal distribution, melt flow rate (MFR) is 0.02 ~ 20 gram/10 minutes, and limiting viscosity is 0.5 ~ 5.0 × 10
2dl/g, fusing point is greater than 160 DEG C, at higher than the temperature of 400 DEG C, stand the weightlessness being less than 1%wt.
Vinylidene fluoride copolymers of the present invention, is preferably in vinylidene fluoride copolymers the double bond existing and can proceed to react.
Be applicable to polymerization process of the present invention without particular limitation, in a better example of the present invention, described polymerization process is selected from letex polymerization, suspension polymerization and solution polymerization, more preferably letex polymerization and suspension polymerization.
The reaction pressure being applicable to the inventive method in whole operating process remains on the value being greater than vinylidene fluoride monomers emergent pressure generally.For used organic initiators, polyreaction of the present invention can adopt the polymerization temperature of the relative broad range being greater than vinylidene fluoride monomers critical temperature.
A method for the novel vinylidene fluoride copolymers of high viscosity self-crosslinking is prepared in letex polymerization, comprises the following steps:
(1) dispersion of compound monomer shown in part at least one structural formula (I) in water and vinylidene fluoride monomers is provided to reactor;
(2) emulsifying agent, chain-transfer agent and initiator is added to reactor, initiated polymerization at 70 DEG C ~ 120 DEG C temperature and 2.0 ~ 5.0MPa pressure;
(3) adopt the mode that feeds intake of segmentation to add the dispersion of compound monomer shown in remaining at least one structural formula (I) in water and vinylidene fluoride monomers, control polymerization pressure is 3.0 ~ 5.0MPa, and adds initiator;
(4) when polymerization pressure drops to 2.0 ~ 3.0MPa, stop adding initiator, until reaction terminates;
In reaction process, the shown compound monomer total amount of the structural formula (I) controlling to add accounts for the quality proportioning of total comonomer for being greater than 0 ~ 10%.
A method for the novel vinylidene fluoride copolymers of high viscosity self-crosslinking is prepared in suspension polymerization, comprises the following steps:
(1) dispersion of compound monomer shown in part at least one structural formula (I) in water and vinylidene fluoride monomers is provided to reactor;
(2) dispersion agent, chain-transfer agent and initiator is added, initiated polymerization under the condition of 20 DEG C ~ 60 DEG C temperature and 3.0 ~ 12.0MPa pressure;
(3) adopt the mode that feeds intake of segmentation to add the dispersion of compound monomer shown in remaining at least one structural formula (I) in water and vinylidene fluoride monomers, control polymerization pressure is 3.0 ~ 5.0MPa;
(4) when polymerization pressure drops to 2.0 ~ 4.0MPa, stopped reaction;
In reaction process, the shown total amount of compound of the structural formula (I) controlling to add accounts for the quality proportioning of total comonomer for being greater than 0 ~ 10%.
A method for the novel vinylidene fluoride copolymers of high viscosity self-crosslinking is prepared in solution polymerization, comprises the following steps:
(1) compound monomer dichloromethane solution shown in dichloromethane solvent, part vinylidene fluoride monomers and at least one structural formula (I) is provided to reactor;
(2) chain-transfer agent and initiator is added, initiated polymerization under the condition of 20 DEG C ~ 60 DEG C temperature and 3.0 ~ 12.0MPa pressure;
(3) mode adopting segmentation to feed intake adds compound monomer dichloromethane solution shown in remaining vinylidene fluoride monomers and at least one structural formula (I), and control polymerization pressure is 3.0 ~ 5.0MPa;
(4) when polymerization pressure drops to 2.0 ~ 4.0MPa, stopped reaction;
In reaction process, the shown compound monomer total amount of the structural formula (I) controlling to add accounts for the quality proportioning of total comonomer for being greater than 0 ~ 10%.
As preferred mode, in above-mentioned three kinds of polymerization processs, the vinylidene fluoride monomers amount added in described step (1) accounts for 1 ~ 25% of total vinylidene fluoride monomers add-on.
In order to improve the dispersiveness of monomer in water, optionally add dispersion agent to dispersion system.The add-on of dispersion agent is without particular limitation, mainly can improve the dispersiveness of monomer and can not produce adverse influence to the polymkeric substance of polyreaction subsequently or formation.The type of same dispersion agent is also without particular limitation, as long as it can improve the dispersiveness of monomer and can not have a negative impact to the polymkeric substance of polyreaction subsequently or formation.In a good example of the present invention, described dispersion agent generally adopts fluorochemical surfactant or Mierocrystalline cellulose, and its not limiting example has: XC
nf
2ncOOM, wherein X is fluorine atom or hydrogen atom, and n is the integer of 4-12, and M is hydrogen atom or alkalimetal ion or ammonium ion or substituted ammonium ion or polyether segment, as C
7f
15cOOH.In a better example of the present invention, by 100 weight parts monomers raw materials, dispersion agent add-on is 0.01-1 weight part.
When adopting emulsion polymerization way, in order to improve the stability of monomer dispersion liquid, also optionally in dispersion liquid, add stablizer.In a better example of the present invention, use paraffin as the stablizer of dispersion liquid.The add-on of stablizer is without particular limitation, mainly can stable dispersions.Then without the need to adding stablizer when adopting suspension polymerization mode.
The organic initiators being applicable to the inventive method is without particular limitation, and it can be the polymerization starter that this area is commonly used.Described initiator is generally organo-peroxide, and its example comprises: di-isopropyl peroxydicarbonate, peroxy dicarbonate diisobutyl ester, peroxy dicarbonate diethyl ester.By 100 weight part vinylidene fluoride monomers or copolymerization mix monomer, the consumption (i.e. the add-on of the middle initiator of step (2)) for the initiator of initial initiated polymerization can be 0.05-0.5 weight part.
When adopting emulsion polymerization way, except step (2) adds except part initiator, need to add organic initiators further in reaction process.In the methods of the invention, the object of the organic initiators added subsequently controls to generate the transient molecular amount of polymkeric substance and final molecular weight distribution, therefore needs the change controlling organic initiators concentration in reaction system.The method controlling organic initiators change in concentration in reaction system adds initiator according to initiator decomposition rate at a certain temperature by certain time interval.Then disposablely when adopting suspension polymerization mode add all initiators to reactor.
The chain-transfer agent being applicable to the inventive method can be any compound that can continue vinylidene fluoride polymerization reaction, and its example illustrated comprises: alcohols, as Virahol, propyl carbinol; Ketone, as acetone, butanone; Ester class, as ethyl acetate, diethyl carbonate, methylcarbonate; Containing halohydrocarbon, as chloroform, methylene dichloride; Aliphatic alkane, as normal hexane.By 100 weight part vinylidenes or copolymerization mix monomer, the consumption of chain-transfer agent is 0.01-0.2 weight part.
When adopting emulsion polymerization way, the monomer feed mode being applicable to the inventive method is that VDF monomer and polar monomer segmentation join in polymerization reaction kettle, add when still internal pressure is less than 4.0MPa VDF monomer enter in specified pressure, when polar monomer dispersion is added to wherein by pressure measurement pump to during certain value, until polyreaction terminates by VDF monomer add-on at intervals; When adopting suspension polymerization mode, the monomer feed mode being applicable to the inventive method is similarly the segmentation of VDF monomer and is added to reactor, polar monomer after VDF monomer adds, still internal pressure is when being less than 4.0MPa, at intervals polar monomer dispersion joined reactor by pressure measurement pump.
The novel vinylidene fluoride copolymers of high viscosity self-crosslinking of the present invention, its cohesive strength is greater than 50N/m, is suitable as lithium ion battery binding agent.
The present invention also provides a kind of composition forming electrode, comprises the novel vinylidene fluoride copolymers of high viscosity self-crosslinking, powdery electrode material and gives the additive of electrical conductivity.As preferred mode, each composition is by following quality proportioning composition:
(1) vinylidene fluoride copolymers 1% ~ 10%;
(2) as the carbon black of additive giving electrical conductivity, 2% ~ 10%;
(3) powdery electrode material 80% ~ 97%, for by general formula LiMY
2the complex metal compound of representative, the one, more than two or three that wherein M is selected from Co, Ni, Fe, Mn, Cr and V combines, and Y is O or S.
Vinylidene fluoride copolymers of the present invention, after being prepared into the composition of electrode, the double bond that can be caused by ultraviolet lamp in the vinylidene fluoride copolymers in the composition of electrode carries out radical crosslinking, forms crosslinking structure.
The composition of formation electrode of the present invention, is suitable as the electrode of lithium cell or electrical condenser.
Vinylidene fluoride copolymers of the present invention can be dissolved in the solvent of conventional polyvinylidene difluoride (PVDF) completely, and the example of described solvent has
n,
n-dimethyl pyrrolidone (NMP), N,N-DIMETHYLACETAMIDE (DMAc),
n,
n-dimethyl formamide (DMF) etc., preferred NMP.
Measure polymkeric substance preparation by ISO4624 standard (adhesive power pull-off test) and become the cohesive strength after electrode, carry out under 25 DEG C and 50% relative humidity.
By GB/T3682-2000 standard test melt flow rate (MFR) (MFR).Probe temperature is 230 DEG C, and loading is 5 kilograms.
By ISO11358 standard, TGA analysis is carried out to sample.In a nitrogen atmosphere, carry out in a dynamic mode, record to obtain be respectively 0.5%, 0.75% and 1%wt polymkeric substance weightlessness needed for temperature, these temperature are higher, and the thermostability of polymkeric substance is higher.
By ASTMD4591 standard test melting enthalpy.Heating schedule is: be warming up to 190 DEG C with the heat-up rate of 10 DEG C/min by 80 DEG C, 190 DEG C of insulations 10 minutes, be cooled to 80 DEG C with the cooling rate of 80 DEG C/min by 190 DEG C, in 80 DEG C, be incubated 2 minutes, be warming up to 190 DEG C with the heat-up rate of 10 DEG C/min by 80 DEG C.DSC spectrogram during the melting of record second time.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these embodiments.One skilled in the art would recognize that all alternativess, improvement project and the equivalents that present invention encompasses and may comprise in Claims scope.
embodiment 1
Adding in 5 liters of vertical polymerization reaction kettles in 2500 grams of deionized waters, 5 grams of ammonium perfluorocaprylates and homologous mixture thereof and 1 gram of melting range is the paraffin of about 60 DEG C.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 10ppm in reactor, then adds a certain amount of vinylidene fluoride monomers and make still internal pressure to 2.0MPa.Then start to stir with the speed of 500rpm, reactor temperature is risen to 85 DEG C, continue to supplement vinylidene fluoride monomers and reach 4.5MPa to reacting kettle inner pressure.Add 0.5 gram of di-isopropyl peroxydicarbonate (IPP), start polyreaction.Making reacting kettle inner pressure maintain 4.5MPa by adding vinylidene fluoride monomers, adding IPP with the speed of 0.1 gram/15 minutes, when the vinylidene fluoride monomers of specified wt part add complete and in still, reaction pressure is down to below 3.0MPa time stop adding IPP; Polar monomer connection thiazolinyl methyl ether in vinylidene weight part 1% ratio feed intake, when vinylidene fluoride monomers charged material weight reaches 50%, 60%, 70%, 80% of preset value, average segmentation joins polymeric kettle.
Measure polymkeric substance preparation by ISO4624 standard (adhesive power pull-off test) and become the cohesive strength after electrode.The preparation process of electrode is as described below: under room temperature state, is dissolved in the NMP of 50g by the resin produced under mechanical stirring in 1g example 1.2g graphitized carbon black and 30g cobalt acid lithium (LiCoO is added under the state stirred
2), fully mixing ensures homogeneity.Then mixture is degassed under vacuo and spread on aluminium foil with scraper, finally the aluminium foil sprawling upper electrode material mixture is positioned over vacuum drying oven and is warming up to 60 DEG C of dryings 12 hours, finally prepare electrode slice.Puller system survey meter is used to measure the cohesive strength of electrode slice upper electrode material.Each value at least gets the mensuration mean value of 5 electrode slices, and Data Summary in Table 1.
embodiment 2
Adding in 5 liters of vertical polymerization reaction kettles in 2500 grams of deionized waters, 5 grams of ammonium perfluorocaprylates and homologous mixture thereof and 1 gram of melting range is the paraffin of about 60 DEG C.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 10ppm in reactor, then adds a certain amount of vinylidene fluoride monomers and make still internal pressure to 2.0MPa.Then start to stir with the speed of 500rpm, reactor temperature is risen to 85 DEG C, continue to supplement vinylidene fluoride monomers and reach 4.5MPa to reacting kettle inner pressure.Add 0.5 gram of di-isopropyl peroxydicarbonate (IPP), start polyreaction.Making reacting kettle inner pressure maintain 4.5MPa by adding vinylidene fluoride monomers, adding IPP with the speed of 0.1 gram/15 minutes, when the vinylidene fluoride monomers of specified wt part add complete and in still, reaction pressure is down to below 3.0MPa time stop adding IPP; Polar monomer connection thiazolinyl methyl ether in vinylidene weight part 10% ratio feed intake, when vinylidene fluoride monomers charged material weight reaches 50%, 60%, 70%, 80% of preset value, average segmentation joins polymeric kettle.
1 gram of multipolymer is used to prepare electrode slice.Cohesive strength measures to be summed up in Table 1.
embodiment 3
2500 grams of deionized waters, 5 grams of methylcellulose gum are added in 5 liters of vertical polymerization reaction kettles.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 10ppm in reactor, adding the vinylidene fluoride monomers of specified amount, then in vinylidene weight part 1% the ratio polar monomer that segmentation adds specified amount that feeds intake join thiazolinyl methyl ether.Then start to stir with the speed of 500rpm, reactor temperature is risen to 40 DEG C, add 2.5 grams of di-isopropyl peroxydicarbonates (IPP), start polyreaction.Question response stops polyreaction to during the fixed time.
1 gram of multipolymer is used to prepare electrode slice.Cohesive strength measures to be summed up in Table 1.
embodiment 4
2500 grams of deionized waters, 5 grams of methylcellulose gum are added in 5 liters of vertical polymerization reaction kettles.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 10ppm in reactor, adding the vinylidene fluoride monomers of specified amount, then in vinylidene weight part 1% the ratio polar monomer that segmentation adds specified amount that feeds intake join thiazolinyl propyl carbinol ether.Then start to stir with the speed of 500rpm, reactor temperature is risen to 40 DEG C, add 2.5 grams of di-isopropyl peroxydicarbonates (IPP), start polyreaction.Question response stops polyreaction to during the fixed time.
1 gram of multipolymer is used to prepare electrode slice.Cohesive strength measures to be summed up in Table 1.
embodiment 5
2500 grams of deionized waters, 5 grams of methylcellulose gum are added in 5 liters of vertical polymerization reaction kettles.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 10ppm in reactor, adding the vinylidene fluoride monomers of specified amount, then in vinylidene weight part 1% the ratio polar monomer that segmentation adds specified amount that feeds intake join thiazolinyl octyl ether.Then start to stir with the speed of 500rpm, reactor temperature is risen to 40 DEG C, add 3 grams of di-isopropyl peroxydicarbonates (IPP), start polyreaction.Question response stops polyreaction to during the fixed time.
1 gram of multipolymer is used to prepare electrode slice.Cohesive strength measures to be summed up in Table 1.
embodiment 6
Use by the electrode slice prepared by embodiment 1, the ultraviolet light utilizing wavelength to be 365nm in argon shield atmosphere irradiates, and takes out electrode slice after 12 hours.Use puller system survey meter to measure the cohesive strength of electrode slice upper electrode material, Data Summary in Table 1.
embodiment 7
Use by the electrode slice prepared by embodiment 2, the ultraviolet light utilizing wavelength to be 365nm in argon shield atmosphere irradiates, and takes out electrode slice after 12 hours.Use puller system survey meter to measure the cohesive strength of electrode slice upper electrode material, Data Summary in Table 1.
embodiment 8
Use by the electrode slice prepared by embodiment 3, the ultraviolet light utilizing wavelength to be 365nm in argon shield atmosphere irradiates, and takes out electrode slice after 12 hours.Use puller system survey meter to measure the cohesive strength of electrode slice upper electrode material, Data Summary in Table 1.
embodiment 9
Use by the electrode slice prepared by embodiment 4, the ultraviolet light utilizing wavelength to be 365nm in argon shield atmosphere irradiates, and takes out electrode slice after 12 hours.Use puller system survey meter to measure the cohesive strength of electrode slice upper electrode material, Data Summary in Table 1.
embodiment 10
Use by the electrode slice prepared by embodiment 4, the ultraviolet light utilizing wavelength to be 365nm in argon shield atmosphere irradiates, and takes out electrode slice after 12 hours.Use puller system survey meter to measure the cohesive strength of electrode slice upper electrode material, Data Summary in Table 1.
comparative example 11
The KUREHA9200 vinylidene fluoride copolymers that the limiting viscosity of 1 gram is 1.8dl/g is used to prepare electrode slice.Cohesive strength measures to be summed up in Table 1.
comparative example 12
The SOLVAY5130 vinylidene fluoride copolymers that the limiting viscosity of 1 gram is 2.3dl/g is used to prepare electrode slice.Cohesive strength measures to be summed up in Table 1.
Table 1
| Embodiment | Comonomer | Limiting viscosity | Melting index (g, 230 ° of C, 5kg/10min) | Fusing point (° C) | Cohesive strength (N/m) | Thermal weight loss (400 DEG C) | Solution appearance |
| Embodiment 1 | Connection thiazolinyl methyl ether (letex polymerization, 1%) | 1.4 | 0.47 | 170 | 103 | <1% | Clear |
| Embodiment 2 | Connection thiazolinyl methyl ether (letex polymerization, 10%) | 0.9 | 5.12 | 165 | 73 | <1% | Clear |
| Embodiment 3 | Connection thiazolinyl methyl ether (suspension polymerization, 1%) | 2.1 | 0.23 | 172 | 110 | <1% | Clear |
| Embodiment 4 | Connection thiazolinyl propyl carbinol ether (suspension polymerization, 1%) | 1.2 | 1.09 | 168 | 78 | <1% | Clear |
| Embodiment 5 | Connection thiazolinyl octyl ether (suspension polymerization, 1%) | 1.0 | 3.10 | 166 | 63 | <1% | Clear |
| Embodiment 6 | Sample 1 is through uv irradiating | - | - | - | 379 | - | - |
| Embodiment 7 | Sample 2 is through uv irradiating | - | - | - | 134 | - | - |
| Embodiment 8 | Sample 3 is through uv irradiating | - | - | - | 412 | - | - |
| Embodiment 9 | Sample 4 is through uv irradiating | - | - | - | 268 | - | - |
| Embodiment 10 | Sample 5 is through uv irradiating | - | - | - | 144 | - | - |
| Comparative example 11 | n.a | 1.8 | 0.56 | 171 | 23 | <1% | Clear |
| Comparative example 12 | n.a. | 2.3 | 0.12 | 166 | 56 | <1% | Clear |
Adhesive property can be obtained by the known VDF of the result of above-mentioned table 1 have by carrying out copolymerization with described polar monomer the PVDF multipolymer significantly improved, after simultaneously PVDF multipolymer and electro-conductive material are prepared and are become electrode slice, can crosslinking reaction be there is by ultra violet lamp, improve its cohesive strength as lithium cell binding agent further significantly.
Claims (17)
1. a self-crosslinking vinylidene fluoride copolymers, is characterized in that described vinylidene fluoride copolymers contains compound shown in vinylidene fluoride monomers and at least one structural formula (I):
Wherein:
R
1, R
2, R
3and R
4independently selected from hydrogen atom, halogen, C
1-C
8the C that alkyl, at least one hydrogen atom are optionally substituted by halogen
1-C
8alkyl or the C replaced containing optional at least one atom in O, S and N
1-C
8alkyl;
Shown in described structural formula (I), compound accounts for the quality proportioning of total comonomer for being greater than 0 ~ 10%.
2., according to self-crosslinking vinylidene fluoride copolymers according to claim 1, it is characterized in that described R
1, R
2, R
3and R
4independently selected from hydrogen atom, fluorine atom, C
1-C
4the C that alkyl, at least one hydrogen atom replaced by fluorine
1-C
4alkyl or the C replaced containing O atom
1-C
4alkyl.
3., according to self-crosslinking vinylidene fluoride copolymers according to claim 2, it is characterized in that described R
1, R
2, R
3and R
4independently selected from hydrogen atom or methyl.
4., according to self-crosslinking vinylidene fluoride copolymers according to claim 1, it is characterized in that the quality proportioning that the shown compound of described structural formula (I) accounts for total comonomer is 0.1 ~ 2%.
5. according to self-crosslinking vinylidene fluoride copolymers according to claim 1, it is characterized in that described vinylidene fluoride copolymers contains the 3rd comonomer, described 3rd comonomer be selected from vinyl fluoride, trifluoro-ethylene, trifluorochloroethylene, tetrafluoroethylene, tetrafluoeopropene, five fluorine propylene, R 1216, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether and other can combine with the one in the Fluorine containing olefine of vinylidene copolymerization, more than two or three, the quality proportioning that described 3rd comonomer accounts for total comonomer is 0.1 ~ 50%.
6. according to self-crosslinking vinylidene fluoride copolymers according to claim 1, it is characterized in that the weight-average molecular weight of described vinylidene fluoride copolymers is 20 ~ 1,500,000 grams/mol, molecular weight distribution index is 1.6 ~ 5, molecular weight distribution curve is unimodal distribution, melt flow rate (MFR) is 0.02 ~ 20 gram/10 minutes, and limiting viscosity is 0.5 ~ 5.0 × 10
2dl/g, fusing point is greater than 160 DEG C, at higher than the temperature of 400 DEG C, stand the weightlessness being less than 1%wt.
7., according to self-crosslinking vinylidene fluoride copolymers according to claim 6, it is characterized in that in described vinylidene fluoride copolymers, there is the double bond that can proceed to react.
8., according to a self-crosslinking vinylidene fluoride copolymers according to claim 1, it is characterized in that adopting letex polymerization, comprise the following steps:
(1) dispersion of compound shown in part at least one structural formula (I) in water and vinylidene fluoride monomers is provided to reactor;
(2) emulsifying agent, chain-transfer agent and initiator is added to reactor, initiated polymerization at 70 DEG C ~ 120 DEG C temperature and 2.0 ~ 5.0MPa pressure;
(3) adopt the mode that feeds intake of segmentation to add the dispersion of compound shown in remaining at least one structural formula (I) in water and vinylidene fluoride monomers, control polymerization pressure is 3.0 ~ 5.0MPa, and adds initiator;
(4) when polymerization pressure drops to 2.0 ~ 3.0MPa, stop adding initiator, until reaction terminates;
In reaction process, the shown total amount of compound of the structural formula (I) controlling to add accounts for the quality proportioning of total comonomer for being greater than 0 ~ 10%.
9., according to a self-crosslinking vinylidene fluoride copolymers according to claim 1, it is characterized in that adopting suspension polymerization, comprise the following steps:
(1) dispersion of compound shown in part at least one structural formula (I) in water and vinylidene fluoride monomers is provided to reactor;
(2) dispersion agent, chain-transfer agent and initiator is added, initiated polymerization under the condition of 20 DEG C ~ 60 DEG C temperature and 3.0 ~ 12.0MPa pressure;
(3) adopt the mode that feeds intake of segmentation to add the dispersion of compound shown in remaining at least one structural formula (I) in water and vinylidene fluoride monomers, control polymerization pressure is 3.0 ~ 5.0MPa;
(4) when polymerization pressure drops to 2.0 ~ 4.0MPa, stopped reaction;
In reaction process, the shown total amount of compound of the structural formula (I) controlling to add accounts for the quality proportioning of total comonomer for being greater than 0 ~ 10%.
10., according to a self-crosslinking vinylidene fluoride copolymers according to claim 1, it is characterized in that adopting solution polymerization, comprise the following steps:
(1) dichloromethane solution of compound shown in dichloromethane solvent, part vinylidene fluoride monomers and at least one structural formula (I) is provided to reactor;
(2) chain-transfer agent and initiator is added, initiated polymerization under the condition of 20 DEG C ~ 60 DEG C temperature and 3.0 ~ 12.0MPa pressure;
(3) mode adopting segmentation to feed intake adds the dichloromethane solution of compound shown in remaining vinylidene fluoride monomers and at least one structural formula (I), and control polymerization pressure is 3.0 ~ 5.0MPa;
(4) when polymerization pressure drops to 2.0 ~ 4.0MPa, stopped reaction;
In reaction process, the shown total amount of compound of the structural formula (I) controlling to add accounts for the quality proportioning of total comonomer for being greater than 0 ~ 10%.
11. according to the self-crosslinking vinylidene fluoride copolymers one of claim 8 to 10 Suo Shu, it is characterized in that the vinylidene fluoride monomers amount added in described step (1) accounts for 1 ~ 25% of total vinylidene fluoride monomers add-on.
12. according to the self-crosslinking vinylidene fluoride copolymers one of claim 8 to 10 Suo Shu, it is characterized in that adding vinylidene fluoride monomers when reactor pressure is less than 4.0MPa in described step (3).
13. according to the self-crosslinking vinylidene fluoride copolymers one of claim 1 to 10 Suo Shu, it is characterized in that the cohesive strength of described vinylidene fluoride copolymers is greater than 50N/m, as lithium ion battery binding agent.
14. 1 kinds of compositions forming electrode, is characterized in that comprising according to the vinylidene fluoride copolymers described in claim 13, powdery electrode material and the additive giving electrical conductivity.
15. according to the composition of formation electrode according to claim 14, and after it is characterized in that the composition of described electrode is formed, the double bond caused by ultraviolet lamp in the vinylidene fluoride copolymers in the composition of electrode carries out radical crosslinking, forms crosslinking structure.
16., according to the composition of formation electrode according to claim 14, is characterized in that in described composition, each composition forms by following quality proportioning:
(1) vinylidene fluoride copolymers 1% ~ 10%;
(2) as the carbon black of additive giving electrical conductivity, 2% ~ 10%;
(3) powdery electrode material 80% ~ 97%, for by general formula LiMY
2the complex metal compound of representative, the one, more than two or three that wherein M is selected from Co, Ni, Fe, Mn, Cr and V combines, and Y is O or S.
17. according to the composition of formation electrode according to claim 14, it is characterized in that the electrode being used as lithium cell or electrical condenser.
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| CN108011076B (en) * | 2017-11-27 | 2020-08-28 | 欣旺达电子股份有限公司 | Lithium ion battery, battery pole piece and preparation method thereof |
| KR102260002B1 (en) * | 2018-05-31 | 2021-06-02 | 가부시끼가이샤 구레하 | Adhesive composition, separator structure, electrode structure, nonaqueous electrolyte secondary battery, and manufacturing method thereof |
| CN112234209B (en) * | 2019-06-03 | 2021-11-23 | 宁德新能源科技有限公司 | Electrochemical device |
| CN111342048B (en) * | 2020-03-03 | 2021-08-24 | 珠海冠宇电池股份有限公司 | Adhesive, preparation method and application thereof |
| CN114685705B (en) * | 2020-12-30 | 2023-09-26 | 中化蓝天氟材料有限公司 | Application of low-swelling vinylidene fluoride copolymer as lithium electricity binder |
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| CN101906182A (en) * | 2009-06-08 | 2010-12-08 | 浙江蓝天环保高科技股份有限公司 | Emulsion polymerization method for VDF homopolymer or copolymer |
| CN101944595A (en) * | 2009-07-06 | 2011-01-12 | 索尼公司 | Electrode and battery with this electrode |
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