CN102432906B - Grafting modified high polymer material, and preparation method and application thereof - Google Patents
Grafting modified high polymer material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN102432906B CN102432906B CN2011102553782A CN201110255378A CN102432906B CN 102432906 B CN102432906 B CN 102432906B CN 2011102553782 A CN2011102553782 A CN 2011102553782A CN 201110255378 A CN201110255378 A CN 201110255378A CN 102432906 B CN102432906 B CN 102432906B
- Authority
- CN
- China
- Prior art keywords
- polymer material
- grafting
- modified polymer
- monomer
- woven fabrics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Landscapes
- Cell Separators (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a grafting modified high polymer material which is a high polymer micro-porous membrane or a high polymer non-woven fabric with a graft chain, wherein the graft chain is a polymeric chain of more than one monomer; the polymeric chain is a homo-polymer chain formed by the same monomer or a random copolymer chain formed by different monomers; and the monomer is provided with at least one C=C double bond and at least one ether group or a group shown in the formula I. The invention overcomes the defect that the affinity of the polyolefin micro-porous membrane is improved by coating the affinity group, but the affinity group is easy to drop in the process of using the lithium ion battery, and provides the grafting modified polymer material and a preparation method thereof. The high polymer material is especially suitable for serving as the lithium ion battery separator, reduces the crystallinity of the polyolefin separator and has good affinity for the ester organic electrolyte, and at the same time, the polymer material is not easy to drop from the separator in the use process and can lengthen the use performance of the battery.
Description
Technical field
The present invention relates to a kind of graft modified polymer material and its preparation method and application.
Background technology
It is high that lithium ion battery has operating voltage, and energy density is large, and operating temperature range is wide, and self-discharge is little, and service life cycle is long, there is no the plurality of advantages such as environmental pollution, become the focus that in the world today, secondary cell is researched and developed and applied at present.It not only is widely used in mobile communication product and portable type electronic product, and the application on power vehicle also has prospect.
Lithium ion battery mainly is comprised of positive pole, negative pole, electrolytic solution and barrier film.Wherein battery diaphragm is an important integral part, and Main Function is to separate positive and negative electrode, prevents the positive and negative electrode short circuit, and necessary lithium ion passage is provided simultaneously, completes charge and discharge process.Polyolefine material has cheap, the characteristics that mechanics, chemistry and stable electrochemical property are good, so the microporous polyolefin film such as polyethylene, polypropylene just are used as lithium ion battery separator at the Study on Li-ion batteries using initial stage of development.Even to this day, commercial lithium ion battery separator is mainly still microporous polyolefin film.Lithium battery diaphragm is generally to be made by polyethylene or microporous polypropylene membrane in the market.Recently, polyvinylidene difluoride (PVDF) (PVDF) microporous membrane also day by day increases as the research of lithium ion battery separator.
The skeleton structure of microporous membrane can be divided into crystalline region and two of pars amorphas part.Crystalline region provides necessary mechanical strength and thermostability for barrier film, and pars amorpha Electolyte-absorptive becomes gel phase, and lithium ion conduction mainly completes by the electrolytic solution of possessing in microporous membrane non-crystalline region gel phase and micropore.Therefore, the structure direct relation of microporous membrane the quality of lithium ion conduction performance.
But the degree of crystallinity of the polyalkene diaphragm mainly used at present is too high and polarity is little, in use, although the mechanical property of barrier film is good, but because electrolytic solution commonly used is all ester class organic solvents, therefore the affinity of barrier film and electrolytic solution is bad, almost can not be by the electrolytic solution swelling, degree of gelation is low, and the conduction of lithium ion mainly relies on the organosilane ester electrolytic solution be adsorbed in the barrier film hole to realize.But due to barrier film and the electrolytic solution affinity bad, most electrolytic solution can only be present in hole with liquid form, easily leaks, barrier film keeps electrolytic solution ability (protecting the liquid rate) bad, can directly affect the circulating battery Long-Term Properties.
Document 1 (2005, Journal of Power Sources, 139 235 pages of volumes are to 241 pages) reported and take the PE non-woven fabrics as matrix, in the above coated polymer PVDF.The PE base material provides good mechanical property and the self-closing security of high temperature, and the PVDF applied has improved the affinity between barrier film and electrolytic solution mutually.Document 2 (2004, Science Bulletin, 22 2290 pages of volumes are to 2293 pages) non-woven fabrics is immersed in to PVDF-HFP/SiO
2in the mixed solution of/butanone/butanols/softening agent, the composite diaphragm that softening agent makes the non-woven fabrics support of porous is removed in vacuum-drying.Result shows that this composite diaphragm has certain physical strength and good chemical property.In CN 1547270A, surface arrangement is had to the nanometer SiO of chemical group
2filler and polyoxyethylene or polyvinylidene difluoride (PVDF) are dissolved in solvent and form colloidal sol shape mixture, to be immersed in as the polyalkene diaphragm of matrix barrier film in above-mentioned mixture gel, after certain hour, take out, use the molecular sieve adsorption solvent, obtain after drying that wetting property is good, specific conductivity is high, the composite diaphragm of good cycling stability.Although above-mentioned research makes moderate progress to the performance of barrier film, this kind of barrier film use properties of battery after repeated charge descends to some extent, less stable.
Summary of the invention
Technical problem to be solved by this invention be to overcome the polyalkene diaphragm that uses in existing lithium ion battery and ester class electrolytic solution affinity commonly used bad, and polyalkene diaphragm degree of crystallinity is too high, thereby the electrolytic solution that is difficult to be caused this barrier film to absorb by the electrolytic solution swell gel is limited, protect that the liquid rate is not high, electrolytic solution easily leaks, and affects conductive performance and the Long-Term Properties of lithium ion; In addition, improve the affinity of microporous polyolefin film in prior art by coating affinity groups on polyalkene diaphragm, but this kind of barrier film use properties of battery after repeated charge descends to some extent, less stable, equally also affect the defects such as use properties of battery.The invention provides a kind of new graft modified polymer material and preparation method thereof, this kind of macromolecular material is specially adapted to use as lithium ion battery separator, can reduce the degree of crystallinity of polyalkene diaphragm, and ester class organic electrolyte is had to good affinity, can effectively improve the conductivity of absorbed dose, guarantor's liquid rate and the lithium ion of electrolytic solution, the use properties that extends battery.Preparation method of the present invention is the common method in industry, easy to operate, is easy to promote.
The invention provides a kind of graft modified polymer material, it is with the porous membranes of grafted chain or polymer non-woven fabrics;
formula I
Wherein, the polymeric chain that described grafted chain is more than one monomers, described polymeric chain can be the homopolymer chain formed by monomer of the same race, can be also the random copolymers chain formed by different monomers; Described monomer has the two keys of at least one C=C, and at least one ether or at least one is suc as formula the group shown in I.
In the present invention, described porous membranes is optional to be used in and commonly in the lithium ion battery field to can be used as all kinds of porous membranes that diaphragm material is used, and is preferably polyolefins, polysulfones or cellulose family microporous membrane.Described polyolefin microporous film is preferably polyethylene, polypropylene, tetrafluoroethylene, polyvinylidene difluoride (PVDF) or polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer microporous membrane, and better is polyvinylidene fluoride microporous film or polyethene microporous membrane; Described polysulfones microporous membrane is preferably polyethersulfone or polysulfones microporous membrane; Described cellulose family microporous membrane is preferably the cellulose acetate microporous membrane.The number-average molecular weight of described porous membranes can be selected according to this area general knowledge, is preferably 50,000～2,000,000, and better is 20～700,000.The thickness of described porous membranes can be selected according to the thickness of diaphragm material common in lithium ion battery, is preferably 1～200 micron, and better is 10～150 microns, and best is 40～110 microns.The mean pore size of described porous membranes is preferably 0.01～10 micron, and better is 0.1～5 micron, and especially better is 0.4～3 micron, and best is 0.4～2 micron.
In the present invention, described polymer non-woven fabrics is polymeric staple fiber dimension or long filament to be carried out to orientation or random arrangement form after reticulated structure the material that adopts the method reinforcing such as mechanical, hot sticky or chemical to form, it is optional is used in and commonly in the lithium ion battery field can be used as each family macromolecule non-woven fabrics that diaphragm material is used, be preferably polyethylene, polypropylene, nylon, polyethylene terephthalate, polyacrylonitrile or polyvinyl chloride non-woven fabrics, better is polyethylene non-woven fabrics or polypropylene non-woven fabric.The number-average molecular weight of described polymer non-woven fabrics can be selected according to this area general knowledge, is preferably 50,000～2,000,000, and better is 20～700,000.The thickness of described polymer non-woven fabrics can be selected according to the thickness of diaphragm material common in lithium ion battery, is preferably 1～200 micron, and better is 10～150 microns, and best is 40～110 microns.The mean pore size of described polymer non-woven fabrics is preferably 0.01～10 micron, and better is 0.1～5 micron, is especially preferably 0.4～3 micron, and best is 0.4～2 micron.
In the present invention, described monomer preferably there are a C=C two key and ethers or there are the two keys of a C=C and one suc as formula the group shown in I.Wherein, the vinyl ethers compound that the described monomer with the two keys of a C=C and an ether is preferably 3-6 for carbonatoms, one or more that better is in methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE and divinyl ether.Described have the two keys of a C=C and a monomer suc as formula group shown in I is preferably acrylic ester compound and/or the vinyl acetate of carbonatoms 4-11.Wherein, described acrylic ester compound be preferably in methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, vinylformic acid isopentyl ester, Isooctyl acrylate monomer, β-dimethyl-aminoethylmethacrylate, glycidyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate and glycolmethacrylate one or more.
In the present invention one preferably in embodiment,
The thickness of described porous membranes or polymer non-woven fabrics is preferably 40～110 microns, and aperture is preferably 0.4～3 micron, and better is 0.4～2 micron;
When described porous membranes is polyvinylidene fluoride microporous film, the homopolymer chain that described grafted chain is β-dimethyl-aminoethylmethacrylate, n-butyl acrylate, vinyl acetate, divinyl ether, methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether or IVE, the random copolymers chain of vinyl acetate and propyl acrylate or the random copolymers chain of divinyl ether and vinyl acetate;
When described porous membranes is polyethene microporous membrane, the homopolymer chain that described grafted chain is β-dimethyl-aminoethylmethacrylate or methyl acrylate, or the random copolymers chain of methylvinylether and n-butyl acrylate;
When described polymer non-woven fabrics is the polyethylene non-woven fabrics, the homopolymer chain that described grafted chain is vinyl acetate, divinyl ether, methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether or IVE;
When described polymer non-woven fabrics is polypropylene non-woven fabric, the homopolymer chain that described grafted chain is ethyl propenoate.
In the present invention, in described graft modified polymer material, the content of described monomer is so that the percentage of grafting of monomer reaches 1%～200% for good, and for realizing better electronic conduction performance, better is 10%～100%, and best is 10～50%.
The present invention also provides the preparation method of described graft modified polymer material, and it comprises the steps: described porous membranes or polymer non-woven fabrics and described monomer generation graft polymerization reaction are got final product; Described graft polymerization reaction is radiation grafting copolymerization reaction or chemical grafting polymerization reaction.
Wherein, technique and the optimum condition of described radiation grafting copolymerization reaction can be selected according to this area general knowledge, the preferred preradiation grafting reaction of the present invention or mutual radiation graft polymerization reaction.
In the present invention; technique and the optimum condition of described preradiation grafting reaction can be selected according to this area general knowledge; concrete operation step is: in solution system or emulsion system; under protection of inert gas, through the porous membranes of pre-irradiation or polymer non-woven fabrics and described monomer, carry out graft polymerization reaction.Wherein, described pre-irradiation preferably adopts gamma-rays or electron beam as irradiation source.
In the present invention; the technique of described mutual radiation Graft Method and optimum condition can be selected according to this area general knowledge; concrete operation step is: in solution system or emulsion system; under vacuum or protection of inert gas; to described porous membranes or polymer non-woven fabrics, and described monomer carries out common irradiation generation graft polymerization reaction.Wherein, described mutual radiation preferably adopts cobalt or electron beam as irradiation source.
In described pre-irradiation grafting or mutual radiation graft polymerization reaction, described irradiation dose can be selected according to this area general knowledge, is preferably 1～100kGy, and that better is 5～50kGy; The temperature of described preradiation grafting reaction can be selected according to this area general knowledge, is preferably 40～100 ℃, and better is 50～80 ℃.The time of described preradiation grafting reaction is preferably 0.1～20 hour till reaching default percentage of grafting with described macromolecular material, and better is 3～8 hours.The time of described mutual radiation graft polymerization reaction so that irradiation dose reaches above-mentioned dosage require till.
In described pre-irradiation grafting or mutual radiation graft polymerization reaction, the mass ratio of described porous membranes or polymer non-woven fabrics and described monomer can be selected according to described percentage of grafting on the basis of this area general knowledge, be preferably 10: 1～1: 10, better is 1: 10～2: 1.
In described pre-irradiation grafting or mutual radiation graft polymerization reaction, described solution system is by described monomer and solvent composition.Described solvent can be selected the conventional all kinds of SOLVENTS used in this type of reaction of this area, as long as it can dissolve described monomer and not react with porous membranes or polymer non-woven fabrics, be preferably one or more in ethyl acetate, methyl alcohol and ethanol.The consumption of described solvent can be selected according to this area general knowledge, is preferably 50%～99% of described solution system quality, and better is 80～95%.
In described pre-irradiation grafting or mutual radiation graft polymerization reaction, described emulsion system is comprised of described monomer, water and emulsifying agent.The consumption of described monomer can be selected according to this area general knowledge, is preferably 1～40% of described emulsion system quality, and better is 5～25%, and best is 15～25%.Described emulsifying agent can be selected according to this area general knowledge, is preferably the oil-in-water-type tensio-active agent, and better is polysorbas20.The consumption of described emulsifying agent can be selected according to this area general knowledge, is preferably 0.1～10% of described emulsion system quality, and better is 1～5%, and best is 1.5～2.5%.The consumption of described water can be selected according to this area general knowledge, is preferably 50%～95% of described emulsion system quality, and better is 75～80%.
In the present invention, described rare gas element can be selected rare gas element commonly used in irradiation grafting field, this area, is preferably nitrogen or argon gas.
In the present invention; the technology and condition of described chemical grafting polymerization reaction can carry out according to the ordinary method of this area; concrete operation step is: in solution system or emulsion system; under protection of inert gas; under the effect of initiator, described porous membranes or polymer non-woven fabrics and described monomer generation graft polymerization reaction.
Wherein, described initiator is this type of reaction of this area all kinds of initiators commonly used, as organic peroxide initiator and/or azo-initiator.Described initiator is preferably one or more in benzoyl peroxide (BPO), Potassium Persulphate, ammonium persulphate, Sodium Persulfate, Diisopropyl azodicarboxylate (AIBN), azo-bis-isobutyrate hydrochloride (V-50), peroxidized t-butyl perbenzoate (TBPB), dicumyl peroxide (DCP), 2,2'-Azobis(2,4-dimethylvaleronitrile) and peroxy dicarbonate ethylhexyl, and better is one or more in benzoyl peroxide, dicumyl peroxide and Diisopropyl azodicarboxylate.The consumption of described initiator can be selected according to this area general knowledge, is preferably 0.1%～5% of described emulsion or solution system quality.Wherein, the temperature of described chemical grafting polymerization reaction can be selected according to this area general knowledge, is preferably 40～100 ℃, and better is 50～80 ℃.The time of described chemical grafting polymerization reaction is preferably 0.1～20 hour till reaching default percentage of grafting with described macromolecular material, and better is 3～8 hours.
In the present invention, in described chemical grafting polymerization reaction, the amount ratio of described porous membranes or polymer non-woven fabrics and described monomer can be selected according to described percentage of grafting on the base material of this area general knowledge, is preferably 10: 1～1: 10, and better is 1: 10～2: 1.
In the present invention, in described chemical grafting polymerization reaction, described solution system is by described monomer and solvent composition.Described solvent can be selected the conventional all kinds of SOLVENTS used in this type of reaction of this area, as long as it can dissolve described monomer and not react with porous membranes or polymer non-woven fabrics, be preferably one or more in ethyl acetate, methyl alcohol and ethanol.The consumption of described solvent can be selected according to this area general knowledge, is preferably 50%～99% of described solution system quality, and better is 80～95%.
In the present invention, in described chemical grafting polymerization reaction, described emulsion system is comprised of monomer, water and emulsifying agent.The consumption of described monomer can be selected according to this area general knowledge, is preferably 1～40% of described emulsion system quality, and better is 5～25%, and best is 15～25%.Described emulsifying agent can be selected according to this area general knowledge, is preferably the oil-in-water-type tensio-active agent, and better is polysorbas20.The consumption of described emulsifying agent can be selected according to this area general knowledge, is preferably 0.1～10% of described emulsion system quality, and better is 1～5%, and best is 1.5～2.5%.The consumption of described water can be selected according to this area general knowledge, is preferably 50%～95% of described emulsion system quality, and better is 75～80%.
After finishing, graft polymerization reaction of the present invention preferably can adopt the method for this area routine to carry out aftertreatment.The present invention preferably soaks, rinses with solvent extraction or hot solvent, with the homopolymer except producing in dereaction.
Graft modified polymer material of the present invention is particularly suitable as the barrier film in lithium ion battery, and it not only has good affinity with electrolytic solution, and, easily by gelation, Electolyte-absorptives, protect liquid rate and specific conductivity thereby have very high electrolytic solution in a large number.Therefore the present invention also provides the application of described graft modified polymer material as lithium ion battery separator.
The present invention's reagent used is commercially available obtaining all.
In the present invention, but above-mentioned optimum condition arbitrary combination on the basis that meets this area general knowledge obtains the preferred embodiments of the invention.
Positive progressive effect of the present invention is:
1. the present invention utilizes conventional grafting copolymerization process that the special groups monomer is incorporated on macromolecular material, reduce the degree of crystallinity of polymer itself, improved the affinity of barrier film and ester class electrolytic solution commonly used, can effectively improve the systemic electrolytic solution of film, become large in the pars amorpha degree of gelation, increase the zone of lithium ion conduction, thereby improve the lithium ion conductivity of barrier film.
2. barrier film of the present invention and organosilane ester electrolytic solution have better affinity, further improve guarantor's liquid rate of barrier film, avoid electrolytic solution seepage to occur, and the Long-Term Properties of battery is also increased.
3. barrier film of the present invention has very large repeatedly cycle performance for lithium ion battery the time.
The accompanying drawing explanation
Fig. 1 is PE-g-PVAc non-woven infrared spectrogram after grafted polyethylene non-woven fabrics and grafting not in embodiment 1.
Fig. 2 is the repeatedly charge and discharge cycles test pattern of the barrier film in effect embodiment 4.
Fig. 3 is the repeatedly charge and discharge cycles test pattern of the barrier film in effect embodiment 5.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further, but the present invention is not limited.
In embodiment 1-27, the formula of graft modified polymer material is in Table 1, and the preparation method is as follows:
Table 1
Embodiment 1
(number-average molecular weight is 200,000 as macromolecular material to select the 5g polyethylene non-woven fabrics that thickness is 50 microns, mean pore size is 1.7 microns), this polyethylene non-woven fabrics is immersed in the solution formed by 10g vinyl acetate and 40g ethyl acetate, the gamma-ray irradiation that utilizes the cobalt source to produce in nitrogen atmosphere is to 30kGy, ethyl acetate extracting 2 days are used in taking-up in apparatus,Soxhlet's, obtain percentage of grafting and be 90% modified PE-g-PVAc non-woven fabrics, i.e. required lithium-ion membrane.
Embodiment 2
(number-average molecular weight is 250,000 as macromolecular material to select the polypropylene non-woven fabric 20g that thickness is 100 microns, mean pore size is 2.5 microns), this non-woven fabrics is immersed in the solution formed by 10g ethyl propenoate and 90g ethyl acetate, the x ray irradiation x that utilizes electron beam to produce in nitrogen atmosphere is to 20kGy, acetone extracting 2 days are used in taking-up in apparatus,Soxhlet's, obtain the modification nonwoven cloth that the ethyl propenoate percentage of grafting is 30%, i.e. required lithium-ion membrane.
Embodiment 3
Select PVDF microporous membrane 10g that thickness is 40 microns as macromolecular material (number-average molecular weight is 550,000,2 microns of aperture average out to), in air, utilize the Co 60 gamma-ray source to carry out irradiation to it, irradiation dose is 20kGy.By the 20g β-dimethyl-aminoethylmethacrylate; the 2g polysorbas20 is made into emulsion in 78g water; PVDF microporous membrane after irradiation is submerged in this emulsion; under the nitrogen protection condition; be warming up to 60 ℃ of reactions 6 hours, take out, with acetone extracting 2 days; the modification PVDF-g-PEMA microporous membrane that to obtain percentage of grafting be 70%, i.e. required lithium-ion membrane.
Embodiment 4
Select polyethene microporous membrane 5g that thickness is 80 microns as macromolecular material (number-average molecular weight is 600,000,1.0 microns of aperture average out to), in air, utilize the Co 60 gamma-ray source to carry out irradiation to it, irradiation dose is 30kGy.By 10g β-dimethyl-aminoethylmethacrylate wiring solution-forming in 40g methyl alcohol; PE microporous membrane after irradiation is submerged in this solution; under the nitrogen protection condition; be warming up to 60 ℃ of reactions 8 hours; after taking-up is repeatedly soaked drip washing with hot acetone; obtain percentage of grafting and be 90% modified PE-g-PEMA microporous membrane, i.e. required lithium-ion membrane.
Embodiment 5
Select microporous membrane of polyethersulfone 25g that thickness is 60 microns as macromolecular material (number-average molecular weight is 50,000,0.5 micron of aperture average out to), in air, utilize electron beam to carry out irradiation to it, irradiation dose is 20kGy.By the 20g n-butyl acrylate; the 2g polysorbas20 is made into emulsion in 78g water; PVDF microporous membrane after irradiation is submerged in this emulsion; under the nitrogen protection condition; be warming up to 60 ℃ of reactions 4 hours; take out with methylene dichloride extracting 2 days the modified poly (ether-sulfone) microporous membrane that to obtain percentage of grafting be 30%, i.e. required lithium-ion membrane.
Embodiment 6
(number-average molecular weight is 300,000 as macromolecular material to select the PE microporous membrane 10g that thickness is 70 microns, 0.5 micron of aperture average out to), the PE microporous membrane is immersed in the ethyl acetate solution 100g that contains the 10g methyl acrylate, the benzoyl peroxide that adds 0.5g, be warmed up to 60 ℃ of reactions 3 hours after logical nitrogen excluding air, repeatedly after soaking flushing, remove methyl acrylate homopolymer and monomer with hot ethyl acetate after taking-up, obtain percentage of grafting and be 50% modified PE-g-PMA microporous membrane, i.e. required lithium-ion membrane.
Embodiment 7
(number-average molecular weight is 700,000 as macromolecular material to select the PVDF microporous membrane 20g that thickness is 40 microns, mean pore size is 0.45 micron), 20g vinyl acetate, 2g polysorbas20 are made into to emulsion in 78g water, this microporous membrane is immersed in this emulsion, the Potassium Persulphate that adds 0.5g, be warmed up to 80 ℃ of reactions 5 hours after logical nitrogen excluding air, ethyl acetate extracting 2 days are used in taking-up in apparatus,Soxhlet's, the modification PVDF microporous membrane that to obtain percentage of grafting be 75%, i.e. required lithium-ion membrane.
Embodiment 8
(number-average molecular weight is 700,000 as macromolecular material to select the PVDF microporous membrane 20g that thickness is 40 microns, mean pore size is 0.45 micron), 10g vinyl acetate, 10g propyl acrylate, 2g polysorbas20 are made into to emulsion in 78g water, this microporous membrane is immersed in this emulsion, the Potassium Persulphate that adds 0.5g, be warmed up to 80 ℃ of reactions 5 hours after logical nitrogen excluding air, repeatedly rinse immersion with hot acetone after taking-up and repeatedly remove monomer and homopolymer, the modification PVDF microporous membrane that to obtain percentage of grafting be 58%, i.e. required lithium-ion membrane.
Embodiment 9
Select PVDF microporous membrane 10g that thickness is 40 microns as macromolecular material (number-average molecular weight is 700,000, and mean pore size is 0.45 micron), in air, utilize the Co 60 gamma-ray source to carry out irradiation to it, irradiation dose is 30kGy.PVDF microporous membrane after irradiation is immersed in the ethanolic soln 100g that contains the 20g divinyl ether; under the nitrogen protection condition; be warming up to 60 ℃ of reactions 4 hours; toluene extracting 2 days are used in taking-up in apparatus,Soxhlet's; the modification PVDF microporous membrane that to obtain percentage of grafting be 50%, i.e. required lithium-ion membrane.
Embodiment 10-22
Adopt respectively macromolecular material and monomer in table 1, other raw material and reaction conditions all carry out according to embodiment 8.Wherein, the PVDF microporous membrane number-average molecular weight in embodiment 10-15 is 700,000; The number-average molecular weight of the polyethylene non-woven fabrics in embodiment 16-22 is 180,000.
Embodiment 23
Select the PVDF microporous membrane 10g that thickness is 40 microns in air, to utilize the Co 60 gamma-ray source to carry out irradiation to it as macromolecular material (number-average molecular weight is 700,000, and mean pore size is 0.45 micron), irradiation dose is 30kGy.PVDF microporous membrane after irradiation is immersed in the ethanolic soln 100g that contains 10g divinyl ether, 10g vinyl acetate; under the nitrogen protection condition; be warming up to 60 ℃ of reactions 4 hours; toluene extracting 2 days are used in taking-up in apparatus,Soxhlet's; the modification PVDF microporous membrane that to obtain percentage of grafting be 62%, i.e. required lithium-ion membrane.
Embodiment 24
Select polyethene microporous membrane 15g that thickness is 80 microns as macromolecular material (number-average molecular weight is 1,000,000,1.0 microns of aperture average out to).This polyethene microporous membrane is immersed in the ethanolic soln 100g that contains 10g methylvinylether, 10g n-butyl acrylate, the benzoyl peroxide that adds 0.5g, be warmed up to 80 ℃ of reactions 4 hours after logical nitrogen excluding air, acetone extracting 2 days are used in taking-up in apparatus,Soxhlet's, the modified poly ethylene microporous membrane that to obtain percentage of grafting be 47%, i.e. required lithium-ion membrane.
Embodiment 25
(number-average molecular weight is 200,000 as macromolecular material to select the 10g polyethylene non-woven fabrics that thickness is 110 microns, mean pore size is 2.0 microns), this polyethylene non-woven fabrics is immersed in the solution formed by 10g vinyl acetate and 30g methyl alcohol, the gamma-ray irradiation that utilizes the cobalt source to produce in nitrogen atmosphere is to 10kGy, ethyl acetate extracting 2 days are used in taking-up in apparatus,Soxhlet's, obtain percentage of grafting and be 7% modified PE-g-PVAc non-woven fabrics, i.e. required lithium-ion membrane.
Embodiment 26
(number-average molecular weight is 200,000 as macromolecular material to select the 10g polyethylene non-woven fabrics that thickness is 110 microns, mean pore size is 2.0 microns), this polyethylene non-woven fabrics is immersed in the solution formed by 15g vinyl acetate and 25g methyl alcohol, the gamma-ray irradiation that utilizes the cobalt source to produce in nitrogen atmosphere is to 40kGy, ethyl acetate extracting 2 days are used in taking-up in apparatus,Soxhlet's, obtain percentage of grafting and be 31% modified PE-g-PVAc non-woven fabrics, i.e. required lithium-ion membrane.
Embodiment 27
(number-average molecular weight is 200,000 as macromolecular material to select the 10g polyethylene non-woven fabrics that thickness is 110 microns, mean pore size is 2.0 microns), this polyethylene non-woven fabrics is immersed in the solution formed by 25g vinyl acetate and 15g methyl alcohol, the gamma-ray irradiation that utilizes the cobalt source to produce in nitrogen atmosphere is to 40kGy, ethyl acetate extracting 2 days are used in taking-up in apparatus,Soxhlet's, obtain percentage of grafting and be 42% modified PE-g-PVAc non-woven fabrics, i.e. required lithium-ion membrane.
Effect embodiment 1
Get each 2g of modification nonwoven cloth that in embodiment 1, in unmodified polyethylene non-woven fabrics and embodiment 1, percentage of grafting is 90%, be immersed in respectively EC and DMC1: take out after 24 hours in the electrolyte solvent commonly used of 1 configuration, after with filter paper, surface solvent being wiped away, on electronic balance, weigh, the rate of body weight gain of unmodified polyethylene non-woven fabrics is 13.5%, and the rate of body weight gain of modification nonwoven cloth PE-g-PVAc is 78.8%.
Effect embodiment 2
Get in embodiment 3 each 5g of PVDF-g-PEMA modified micro-pore film of percentage of grafting 70% in unmodified polyvinylidene fluoride microporous film and embodiment 3, be immersed in respectively EC and DMC1: take out after 24 hours in the electrolyte solvent commonly used of 1 configuration, after with filter paper, surface solvent being wiped away, on electronic balance, weigh, the rate of body weight gain of unmodified polyvinylidene fluoride microporous film is 39.8%, and the rate of body weight gain of modification PVDF-g-PMMA is 65.0%.
Effect embodiment 3
Get each 5g of PVDF microporous membrane that in embodiment 9, in unmodified polyvinylidene fluoride microporous film and embodiment 9, the divinyl ether percentage of grafting is 50%, be immersed in respectively EC and DMC1: take out after 24 hours in the electrolyte solvent commonly used of 1 configuration, after with filter paper, surface solvent being wiped away, on electronic balance, weigh, the rate of body weight gain of unmodified polyvinylidene fluoride microporous film is 29.5%, and the rate of body weight gain of modification PVDF-g-PMMA is 47.4%.
Effect embodiment 4
Get unmodified polyethylene non-woven fabrics and embodiment 25 in embodiment 25, 26, in 27, percentage of grafting is 7%, the modification nonwoven cloth of 31% and 42% grafting vinyl acetate is cut into 19mm diameter disk as barrier film, cobalt acid lithium is as positive pole, negative pole adopts metal lithium sheet, electrolytic solution is that ionogen lithium hexafluoro phosphate (1.0mol/L) and volume ratio are 1: 1 NSC 11801 (EC)/dimethyl carbonate (DMC) forms, after being assembled into 2032 button cells, adopt the 1C multiplying power to carry out repeatedly the charge and discharge cycles test to battery, as Fig. 2, the battery of use graft modification metacneme repeatedly discharges and recharges rear specific storage, and obviously than using, the grafting barrier film is not high, battery performance is better.
Effect embodiment 5
The modification nonwoven cloth of getting the grafting vinyl acetate that in embodiment 26, in unmodified polyethylene non-woven fabrics and embodiment 26, percentage of grafting is 31% is cut into 19mm diameter disk as barrier film, cobalt acid lithium is as positive pole, negative pole adopts metal lithium sheet, electrolytic solution is that ionogen lithium hexafluoro phosphate (1.0mol/L) and volume ratio are 1: 1 NSC 11801 (EC)/dimethyl carbonate (DMC) forms, after being assembled into 2032 button cells, adopt respectively 0.1C, 0.3C, 0.5C, 1C and 3C multiplying power are carried out repeatedly the charge and discharge cycles test to battery, as Fig. 3, the battery that uses the graft modification metacneme when high rate charge-discharge is tested specific storage obviously than using, the grafting barrier film is not high, battery performance is better.
By effect embodiment 1-5, can be found out, the lithium ion battery separator made by the present invention and electrolytic solution affinity are good, soak after certain hour the imbibition rate of body weight gain much larger than the polymeric membrane of non-modified in electrolytic solution, carry out battery performance test and show that the button cell battery performance of battery diaphragm assembling after modification is better, reached the set goal.
Claims (24)
1. a graft modified polymer material is characterized in that: it is porous membranes or polymer non-woven fabrics with grafted chain; Described porous membranes is polyolefins, polysulfones or cellulose family microporous membrane; Described polyolefin microporous film is polyethylene, polypropylene, tetrafluoroethylene, polyvinylidene difluoride (PVDF) or polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer microporous membrane; Described polysulfones microporous membrane is polyethersulfone or polysulfones microporous membrane; Described cellulose family microporous membrane is the cellulose acetate microporous membrane; Described polymer non-woven fabrics is polyethylene, polypropylene, nylon, polyethylene terephthalate, polyacrylonitrile or polyvinyl chloride non-woven fabrics;
Wherein, the polymeric chain that described grafted chain is more than one monomers, described polymeric chain is the homopolymer chain formed by monomer of the same race, or the random copolymers chain formed by different monomers; Described monomer has the two keys of a C=C, and ether or one are suc as formula the group shown in I;
The vinyl ethers compound that the described monomer with the two keys of a C=C and an ether is carbonatoms 3-6, described have the two keys of a C=C and a monomer suc as formula group shown in I is vinyl acetate.
2. graft modified polymer material as claimed in claim 1, it is characterized in that: in described porous membranes or polymer non-woven fabrics, high molecular number-average molecular weight is 50,000～2,000,000; The thickness of described porous membranes or polymer non-woven fabrics is 1～200 micron; The mean pore size of described porous membranes or polymer non-woven fabrics is 0.01～10 micron.
3. graft modified polymer material as claimed in claim 2, it is characterized in that: in described porous membranes or polymer non-woven fabrics, high molecular number-average molecular weight is 20～700,000; The thickness of described porous membranes or polymer non-woven fabrics is 10～150 microns; The mean pore size of described porous membranes or polymer non-woven fabrics is 0.1～5 micron.
4. graft modified polymer material as claimed in claim 3, it is characterized in that: the thickness of described porous membranes or polymer non-woven fabrics is 40～110 microns; The mean pore size of described porous membranes or polymer non-woven fabrics is 0.4～3 micron.
5. graft modified polymer material as claimed in claim 4, it is characterized in that: the mean pore size of described porous membranes or polymer non-woven fabrics is 0.4～2 micron.
6. graft modified polymer material as described as any one in claim 1～5 is characterized in that: described monomer has the two keys of a C=C, and ether or one are suc as formula the group shown in I; The described monomer with the two keys of a C=C and an ether is one or more in methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE and divinyl ether.
7. graft modified polymer material as claimed in claim 1, it is characterized in that: the thickness of described porous membranes or polymer non-woven fabrics is 40～110 microns, aperture is 0.4～3 micron;
When described porous membranes is polyvinylidene fluoride microporous film, the homopolymer chain that described grafted chain is vinyl acetate, divinyl ether, methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether or IVE, or the random copolymers chain of divinyl ether and vinyl acetate;
When described polymer non-woven fabrics is the polyethylene non-woven fabrics, the homopolymer chain that described grafted chain is vinyl acetate, divinyl ether, methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether or IVE.
8. graft modified polymer material as claimed in claim 7, it is characterized in that: the aperture of described porous membranes or polymer non-woven fabrics is 0.4～2 micron.
9. graft modified polymer material as claimed in claim 1, it is characterized in that: in described graft modified polymer material, the percentage of grafting of described monomer is 1%～200%.
10. graft modified polymer material as claimed in claim 9, it is characterized in that: in described graft modified polymer material, the percentage of grafting of described monomer is 10%～100%.
11. graft modified polymer material as claimed in claim 10 is characterized in that: in described graft modified polymer material, the percentage of grafting of described monomer is 10%～50%.
12. graft modified polymer material as claimed in claim 2 is characterized in that: it is characterized in that: in described graft modified polymer material, the percentage of grafting of described monomer is 1%～200%.
13. graft modified polymer material as claimed in claim 6 is characterized in that: it is characterized in that: in described graft modified polymer material, the percentage of grafting of described monomer is 1%～200%.
14. graft modified polymer material as claimed in claim 7 is characterized in that: it is characterized in that: in described graft modified polymer material, the percentage of grafting of described monomer is 1%～200%.
15. the preparation method of the described graft modified polymer material of any one in claim 1～14 is characterized in that: it comprises the steps: described porous membranes or polymer non-woven fabrics and described monomer are carried out to graft polymerization reaction, gets final product; Described graft polymerization reaction is radiation grafting copolymerization reaction or chemical grafting polymerization reaction.
16. the preparation method of graft modified polymer material as claimed in claim 15 is characterized in that: described radiation grafting copolymerization reaction is preradiation grafting reaction or mutual radiation graft polymerization reaction.
17. the preparation method of graft modified polymer material as claimed in claim 16, it is characterized in that: the concrete operation step of described preradiation grafting reaction is: under protection of inert gas, through porous membranes and the described monomer of pre-irradiation, carry out graft polymerization reaction; The concrete operation step of described mutual radiation graft polymerization reaction is: under vacuum or protection of inert gas, to described porous membranes, and described monomer carries out common irradiation generation graft polymerization reaction; The concrete operation step of described chemical grafting polymerization reaction is: under protection of inert gas, and under the effect of initiator, described porous membranes and described monomer generation graft polymerization reaction.
18. the preparation method of graft modified polymer material as claimed in claim 17 is characterized in that: described pre-irradiation adopts gamma-rays or electron beam as irradiation source; Described mutual radiation adopts cobalt or electron beam as irradiation source.
19. the preparation method of graft modified polymer material as claimed in claim 17 is characterized in that: in described preradiation grafting reaction or mutual radiation graft polymerization reaction, the dosage of described irradiation is 1～100kGy.
20. the preparation method of graft modified polymer material as claimed in claim 19 is characterized in that: in described preradiation grafting reaction or mutual radiation graft polymerization reaction, the dosage of described irradiation is 5～50kGy.
21. the preparation method of graft modified polymer material as claimed in claim 15 is characterized in that: in described graft polymerization reaction, the mass ratio of described porous membranes or polymer non-woven fabrics and described monomer is 10:1～1:10;
The temperature of described pre-irradiation grafting or chemical grafting polymerization reaction is 40～100 ℃; The time of described pre-irradiation grafting or chemical grafting polymerization reaction is 0.1～20 hour;
Described graft polymerization reaction carries out in solution system or emulsion system; Described solution system is by described monomer and solvent composition; The consumption of described solvent is 50%～99% of described solution system quality;
Described emulsion system is comprised of described monomer, water and emulsifying agent; The consumption of described monomer is 1～40% of described emulsion system quality; The consumption of described emulsifying agent is 0.1～10% of described emulsion system quality; The consumption of described water is 50%～95% of described emulsion system quality;
Described initiator is organic peroxy class initiator and/or azo-initiator; The consumption of described initiator is 0.1%～5% of described emulsion system or solution system quality.
22. the preparation method of graft modified polymer material as claimed in claim 21 is characterized in that: in described graft polymerization reaction, the mass ratio of described porous membranes or polymer non-woven fabrics and described monomer is 1:10～2:1;
The temperature of described pre-irradiation grafting or chemical grafting polymerization reaction is 50～80 ℃; The time of described pre-irradiation grafting or chemical grafting polymerization reaction is 3～8 hours;
Described solvent is one or more in ethyl acetate, methyl alcohol and ethanol; The consumption of described solvent is 80～95% of described solution system quality;
Described emulsifying agent is polysorbas20; The consumption of described monomer is 5～25% of described emulsion system quality; The consumption of described emulsifying agent is 1～5% of described emulsion system quality; The consumption of described water is 75～80% of described emulsion system quality;
Described initiator is one or more in benzoyl peroxide, Potassium Persulphate, ammonium persulphate, Sodium Persulfate, Diisopropyl azodicarboxylate, azo-bis-isobutyrate hydrochloride, peroxidized t-butyl perbenzoate, dicumyl peroxide, 2,2'-Azobis(2,4-dimethylvaleronitrile) and peroxy dicarbonate ethylhexyl.
23. the preparation method of graft modified polymer material as claimed in claim 22 is characterized in that: the consumption of described monomer is 15～25% of described emulsion system quality; The consumption of described emulsifying agent is 0.5～2% of described emulsion system quality.
24. in claim 1～14, the described graft modified polymer material of any one is as the application of lithium ion battery separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102553782A CN102432906B (en) | 2010-08-20 | 2011-08-22 | Grafting modified high polymer material, and preparation method and application thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102602801A CN101948571A (en) | 2010-08-20 | 2010-08-20 | Grafting modified polymer material and preparation method and application thereof |
| CN201010260280.1 | 2010-08-20 | ||
| CN2011102553782A CN102432906B (en) | 2010-08-20 | 2011-08-22 | Grafting modified high polymer material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102432906A CN102432906A (en) | 2012-05-02 |
| CN102432906B true CN102432906B (en) | 2013-12-18 |
Family
ID=43452209
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102602801A Pending CN101948571A (en) | 2010-08-20 | 2010-08-20 | Grafting modified polymer material and preparation method and application thereof |
| CN2011102553782A Active CN102432906B (en) | 2010-08-20 | 2011-08-22 | Grafting modified high polymer material, and preparation method and application thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102602801A Pending CN101948571A (en) | 2010-08-20 | 2010-08-20 | Grafting modified polymer material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN101948571A (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108635B (en) * | 2011-01-25 | 2012-05-09 | 桂林正翰科技开发有限责任公司 | Method for preparing battery diaphragm material by irradiation grafting of acrylic acid |
| CN102926197B (en) * | 2012-11-15 | 2014-05-07 | 杭州水处理技术研究开发中心有限公司 | Manufacturing method of support cloth for preparation of ion exchange membrane |
| CN102983299A (en) * | 2012-12-17 | 2013-03-20 | 天津工业大学 | Preparation and product of battery membrane material with low electrolyte leakage |
| CN103147291B (en) * | 2013-01-18 | 2015-08-12 | 中国科学院上海应用物理研究所 | A kind of amino modified graft copolymer, preparation method and application thereof |
| CN104088154A (en) * | 2014-06-25 | 2014-10-08 | 中国第一汽车股份有限公司 | Composite modification method of non-woven fabric diaphragm |
| CN105199137B (en) * | 2015-09-08 | 2018-03-16 | 哈尔滨工业大学 | A kind of preparation method of porous composite polymer electrolyte membrane material |
| CN105206775B (en) * | 2015-09-11 | 2017-10-17 | 湖南中锂新材料有限公司 | A kind of method that polyethylene surface grafting polyethylene glycol adipate prepares lithium battery diaphragm |
| CN105098126B (en) * | 2015-09-14 | 2017-09-01 | 河南科高辐射化工科技有限公司 | Composite diaphragm for the square nickel-cadmium cell of exhaust and preparation method thereof |
| CN105098127B (en) * | 2015-09-14 | 2017-09-15 | 河南科高辐射化工科技有限公司 | Composite diaphragm for secondary alkaline zinc-manganese battery and preparation method thereof |
| CN105098128B (en) * | 2015-09-18 | 2018-02-27 | 河南科高辐射化工科技有限公司 | A kind of composite diaphragm for secondary nickel-zinc cell and preparation method thereof |
| US10707524B2 (en) * | 2016-10-19 | 2020-07-07 | Semiconductor Energy Laboratory Co., Ltd. | Graphene compound and manufacturing method thereof, electrolyte, and power storage device |
| CN107447512A (en) * | 2017-08-29 | 2017-12-08 | 苏州市苏真床垫有限公司 | It is a kind of suitable for composite polypropylene non-woven fabrics of fuel filter core and preparation method thereof |
| CN113226528A (en) * | 2018-12-27 | 2021-08-06 | 丸善石油化学株式会社 | Porous film made of polyvinylidene fluoride resin and method for producing same |
| CN109853233B (en) * | 2019-02-12 | 2020-05-15 | 中国科学技术大学 | Modified polyethylene nanofiber membrane and preparation method thereof |
| CN110957524A (en) * | 2019-12-23 | 2020-04-03 | 中南大学 | High-capacity lithium ion battery and preparation method thereof |
| CN111211277B (en) * | 2020-02-19 | 2023-04-07 | 重庆恩捷纽米科技股份有限公司 | Preparation method of PMMA gel coating diaphragm |
| CN111888800B (en) * | 2020-07-15 | 2022-04-15 | 深圳大学 | Grafting modified cotton material and preparation method and application thereof |
| CN112126113A (en) * | 2020-09-24 | 2020-12-25 | 湖南省凯纳方科技有限公司 | Surface grafting modifier for mh-ni battery diaphragm |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287275A (en) * | 1979-01-26 | 1981-09-01 | Sac Membrane Products Corporation | Alkaline cell with graft polymer separator |
| CN1970605A (en) * | 2006-11-09 | 2007-05-30 | 上海大学 | Method for preparing polyethylene ion chelating membrane by radiation graft method |
| CN101388441A (en) * | 2007-09-11 | 2009-03-18 | 松下电器产业株式会社 | Electrolyte film and porous substrate and preparation thereof, lithium ion secondary battery |
| CN101439265A (en) * | 2008-11-25 | 2009-05-27 | 浙江大学 | Hydrophilic modification method of polymer microporous film |
-
2010
- 2010-08-20 CN CN2010102602801A patent/CN101948571A/en active Pending
-
2011
- 2011-08-22 CN CN2011102553782A patent/CN102432906B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287275A (en) * | 1979-01-26 | 1981-09-01 | Sac Membrane Products Corporation | Alkaline cell with graft polymer separator |
| CN1970605A (en) * | 2006-11-09 | 2007-05-30 | 上海大学 | Method for preparing polyethylene ion chelating membrane by radiation graft method |
| CN101388441A (en) * | 2007-09-11 | 2009-03-18 | 松下电器产业株式会社 | Electrolyte film and porous substrate and preparation thereof, lithium ion secondary battery |
| CN101439265A (en) * | 2008-11-25 | 2009-05-27 | 浙江大学 | Hydrophilic modification method of polymer microporous film |
Non-Patent Citations (4)
| Title |
|---|
| Antifouling microfiltration membranes prepared from acrylic acid or methacrylic acid grafted poly(vinylidene fluoride) powder synthesized via pre-irradiation induced graft polymerization;Bo Deng et al.;《Journal of Membrane Science》;20100107;第350卷;第252–258页 * |
| Bo Deng et al..Antifouling microfiltration membranes prepared from acrylic acid or methacrylic acid grafted poly(vinylidene fluoride) powder synthesized via pre-irradiation induced graft polymerization.《Journal of Membrane Science》.2010,第350卷第252–258页. |
| Ming Yu et al..Preirradiation-Induced Emulsion Graft Polymerization of Glycidyl Methacrylate onto Poly(vinylidene fluoride) Powder.《Journal of Applied Polymer Science》.2010,第117卷全文. |
| Preirradiation-Induced Emulsion Graft Polymerization of Glycidyl Methacrylate onto Poly(vinylidene fluoride) Powder;Ming Yu et al.;《Journal of Applied Polymer Science》;20100512;第117卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102432906A (en) | 2012-05-02 |
| CN101948571A (en) | 2011-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102432906B (en) | Grafting modified high polymer material, and preparation method and application thereof | |
| CN109509857B (en) | Porous lithium ion battery diaphragm with interpenetrating network structure and application thereof | |
| TWI608023B (en) | Acrylonitrile Copolymer Adhesive and Its Application in Lithium Ion Battery | |
| CN102888016B (en) | Preparation method of lithium-ion secondary battery diaphragm with crosslinking composite layer | |
| CN105098233B (en) | The preparation method of semi-interpenetrating network polymer gel electrolyte membrane | |
| CN109473609B (en) | Organic/inorganic crosslinked composite lithium ion battery diaphragm and preparation method and application thereof | |
| US8389587B2 (en) | Microporous polymer separators for lithium ion batteries and method for producing the same | |
| CN109119574B (en) | Porous lithium ion battery diaphragm based on cross-linked and linear polymer and preparation method and application thereof | |
| CN107474270B (en) | Preparation method of polymer electrolyte membrane | |
| WO2011035689A1 (en) | Porous polymer membrane, battery comprising porous polymer membrane and method of preparing the same | |
| SG175878A1 (en) | Interpenetrating network of anion-exchange polymers, production method thereof and use of same | |
| CN110911612B (en) | Cellulose acetate-based cross-linked composite lithium ion battery diaphragm and preparation method and application thereof | |
| Ma et al. | Compliant gel polymer electrolyte based on poly (methyl acrylate-co-acrylonitrile)/poly (vinyl alcohol) for flexible lithium-ion batteries | |
| CN100467504C (en) | Preparing method and application of polymer gel electrolyte for lithium ion cell | |
| CN102074735A (en) | Diene/ether copolymer-based lithium ion gel electrolyte membrane and preparation method thereof | |
| KR20150059621A (en) | Composition for coating separator, separator formed by using the composition, and battery using the separator | |
| CN101381429B (en) | Self-supporting lithium ionic cell gel polymer electrolyte, special polymer and preparation method and application thereof | |
| CN111933864B (en) | Energy storage device | |
| CN114388795A (en) | Silicon-carbon cathode binder of lithium ion battery and preparation method thereof | |
| CN112909252B (en) | Polymer binder, its preparation and use | |
| CN115411454B (en) | Lithium battery diaphragm and preparation method thereof | |
| CN111682262A (en) | Three-dimensional cross-linked network gel polymer electrolyte membrane and preparation method and application thereof | |
| CN116845194A (en) | Polythiophene coated porous carbon composite material and preparation method and application thereof | |
| CN113563531A (en) | Graft copolymer aqueous adhesive, preparation method and application in silicon-carbon negative electrode | |
| JP2015099653A (en) | Secondary battery electrode composition, secondary battery electrode and secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHILONG SCIENCE-TECHNOLOGY CO., LTD., SHANGHAI Free format text: FORMER OWNER: SHANGHAI INST. OF APPLIED PHYSICS CHINESE ACADEMY OF SCIENCES Effective date: 20140625 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20140625 Address after: 201800 No. 1411, Yecheng Road, Jiading Industrial Zone, Shanghai, Jiading District Patentee after: Shilong Science-Technology Co., Ltd., Shanghai Address before: 201800 Shanghai city Jiading District Baojia Highway No. 2019 Patentee before: Shanghai Inst. of Applied Physics Chinese Academy of Sciences |