CN102432906A - 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 PDF

Info

Publication number
CN102432906A
CN102432906A CN2011102553782A CN201110255378A CN102432906A CN 102432906 A CN102432906 A CN 102432906A CN 2011102553782 A CN2011102553782 A CN 2011102553782A CN 201110255378 A CN201110255378 A CN 201110255378A CN 102432906 A CN102432906 A CN 102432906A
Authority
CN
China
Prior art keywords
preferable
woven fabrics
monomer
chain
graft
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.)
Granted
Application number
CN2011102553782A
Other languages
Chinese (zh)
Other versions
CN102432906B (en
Inventor
李景烨
李林繁
邓波
虞鸣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shilong Science-Technology Co., Ltd., Shanghai
Original Assignee
Shanghai Institute of Applied Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Applied Physics of CAS filed Critical Shanghai Institute of Applied Physics of CAS
Priority to CN2011102553782A priority Critical patent/CN102432906B/en
Publication of CN102432906A publication Critical patent/CN102432906A/en
Application granted granted Critical
Publication of CN102432906B publication Critical patent/CN102432906B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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

The graft modification macromolecular material
Technical field
The present invention relates to a kind of graft modification macromolecular material.
Background technology
Lithium ion battery has the WV height, and energy density is big, and operating temperature range is wide, and self-discharge is little, and it is long to recycle the life-span, does not have plurality of advantages such as environmental pollution, has become the focus that secondary cell is researched and developed and used in the world today 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 made up of positive pole, negative pole, electrolytic solution and barrier film.Wherein battery diaphragm is an important integral part, and main effect is to separate positive and negative electrode, prevents the positive and negative electrode short circuit, and necessary lithium ion passage is provided simultaneously, accomplishes charge and discharge process.Polyolefine material has cheap, the characteristics that mechanics, chemistry and stable electrochemical property property are good, so MIcroporous polyolefin films such as Vilaterm, Vestolen PP 7052 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 still mainly is a MIcroporous polyolefin film.Lithium battery diaphragm generally is to be processed by Vilaterm or microporous polypropylene membrane in the market.Recently, 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 two parts in crystalline region and pars amorpha.The crystalline region is that barrier film provides necessary mechanical strength and thermostability, and pars amorpha then Electolyte-absorptive becomes gel phase, and lithium ion conduction is mainly accomplished through the electrolytic solution of possessing in microporous membrane non-crystalline region gel phase and the micropore.Therefore, the structure direct relation of microporous membrane the quality of lithium ion conduction performance.
But the percent crystallinity of the polyalkene diaphragm that mainly uses at present is too high and polarity is little; In use, though membranous mechanical property is good, because electrolytic solution commonly used all is 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 that is adsorbed in the barrier film hole to realize.But because barrier film and electrolytic solution affinity are bad, most electrolytic solution can be only be present in the hole with the form of liquid state, leak easily, and barrier film maintenance electrolytic solution ability (guarantor's liquid rate) is bad, and understanding directly influence battery circulation life-time service performance.
Document 1 (2005, Journal of Power Sources, 235 pages to 241 pages of 139 volumes) has reported that with the PE non-woven fabrics be matrix, in the above coated polymer PVDF.The PE base material provides favorable mechanical performance and the self-closing security of high temperature, and the PVDF that applies has improved the affinity between barrier film and the electrolytic solution mutually.Document 2 (2004, Science Bulletin, 2290 pages to 2293 pages of 22 volumes) is immersed in PVDF-HFP/SiO with non-woven fabrics 2In the mixed solution of/butanone/butanols/softening agent, vacuum-drying is removed softening agent and is made the composite diaphragm that the porous non-woven fabrics supports.The result shows that this composite diaphragm has certain mechanical strength and good electrochemical.The nanometer SiO that among the CN 1547270A surface arrangement is had chemical group 2Filler and T 46155 or pvdf are dissolved in and form colloidal sol shape mixture in the solvent; To be immersed in the above-mentioned mixture gel as the membranous polyalkene diaphragm of matrix; Take out behind the certain hour; Use the molecular sieve adsorption solvent, obtain after the 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 membranous performance, this kind barrier film use properties of battery after repeated charge descends less stable to some extent.
Summary of the invention
It is bad with ester class electrolytic solution affinity commonly used that technical problem to be solved by this invention has been to overcome the polyalkene diaphragm that uses in the existing lithium ion battery; And polyalkene diaphragm percent crystallinity is too high; Thereby the electrolytic solution that is difficult to be caused this barrier film to absorb by the electrolytic solution swell gelization is limited, protect that the liquid rate is not high, electrolytic solution is prone to leak, and influences the conductive performance and the life-time service performance of lithium ion; In addition; Improve the affinity of MIcroporous polyolefin film through on polyalkene diaphragm, applying affinity groups in the prior art; But this kind barrier film use properties of battery after repeated charge descends to some extent, and less stable equally also influences the defectives such as use properties of battery.The invention provides a kind of new graft modification macromolecular material and preparation method thereof; This kind macromolecular material is specially adapted to use as lithium ion battery separator; Can reduce the percent crystallinity of polyalkene diaphragm; And ester class organic electrolyte had good affinity, can improve effectively electrolytic solution absorbed dose, protect liquid rate and conductivity of lithium ions can, the use properties that prolongs battery.Preparing method of the present invention is the domestic method in the industry, and is easy to operate, is easy to promote.
The invention provides a kind of graft modification macromolecular material, it is high molecule micropore film or the polymer non-woven fabrics that has grafted chain;
Figure BSA00000566135700031
formula I
Wherein, described grafted chain is more than one monomeric polymeric chains, and described polymeric chain can be the homopolymer chain that is formed by monomer of the same race, also can be the random copolymers chain that is 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 the I.
Among the present invention, said high molecule micropore film is optional to be used in and commonly in the lithium ion battery field to can be used as all kinds of high molecule micropore films that diaphragm material uses, and preferable is polyolefins, polysulfones or cellulose family microporous membrane.What said polyolefin microporous film was preferable is Vilaterm, Vestolen PP 7052, tetrafluoroethylene, pvdf or pvdf-hexafluoropropylene copolymer microporous membrane, and better is polyvinylidene fluoride microporous film or polyethene microporous membrane; What said polysulfones microporous membrane was preferable is polyethersulfone or polysulfones microporous membrane; What said cellulose family microporous membrane was preferable is the FM microporous membrane.The number-average molecular weight of said high molecule micropore film can be selected according to this area general knowledge, and preferable is 50,000～2,000,000, and better is 20～700,000.The thickness of said high molecule micropore film can be selected according to the thickness of diaphragm material common in the lithium ion battery, and preferable is 1～200 micron, and better is 10～150 microns, and best is 40～110 microns.What the mean pore size of said high molecule micropore film was preferable is 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.
Among the present invention; Said polymer non-woven fabrics be with polymeric staple fiber dimension or long filament carry out adopting machinery after orientation or random arrangement form reticulated structure, heat is sticking or method such as chemistry is reinforced the material that forms; It is optional to be used in and commonly in the lithium ion battery field to can be used as each family macromolecule non-woven fabrics that diaphragm material uses; Preferable is Vilaterm, Vestolen PP 7052, nylon, polyethylene terephthalate, polyacrylonitrile or SE non-woven fabrics, and better is Vilaterm non-woven fabrics or polypropylene non-woven fabric.The number-average molecular weight of said polymer non-woven fabrics can be selected according to this area general knowledge, and preferable is 50,000～2,000,000, and better is 20～700,000.The thickness of said polymer non-woven fabrics can be selected according to the thickness of diaphragm material common in the lithium ion battery, and preferable is 1～200 micron, and better is 10～150 microns, and best is 40～110 microns.What the mean pore size of said polymer non-woven fabrics was preferable is 0.01～10 micron, and better is 0.1～5 micron, and especially preferable is 0.4～3 micron, and best is 0.4～2 micron.
Among the present invention, said monomer is preferable have a C=C two key and ethers or have the two keys of a C=C and one suc as formula the group shown in the I.Wherein, Described monomer with the two keys of a C=C and an ether preferable for carbonatoms is the vinyl ethers compound of 3-6, 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 the divinyl ether.Described have the two keys of a C=C and one suc as formula the monomer of group shown in the I preferable be acrylic ester compound and/or the vinyl acetate of carbonatoms 4-11.Wherein, described acrylic ester compound is preferable be in methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, NSC 20949, tert-butyl acrylate, vinylformic acid isopentyl ester, Isooctyl acrylate monomer, Jia Jibingxisuanyizhi, SY-Monomer G, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate and the glycolmethacrylate one or more.
In the present invention's one preferred implementation,
What the thickness of described high molecule micropore film or polymer non-woven fabrics was preferable is 40～110 microns, and what the aperture was preferable is 0.4～3 micron, and better is 0.4～2 micron;
When said high molecule micropore film is polyvinylidene fluoride microporous film; Described grafted chain is the homopolymer chain of Jia Jibingxisuanyizhi, 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 said high molecule micropore film was polyethene microporous membrane, described grafted chain was the homopolymer chain of Jia Jibingxisuanyizhi or methyl acrylate, or the random copolymers chain of methylvinylether and n-butyl acrylate;
When said polymer non-woven fabrics was the Vilaterm non-woven fabrics, described grafted chain was the homopolymer chain of vinyl acetate, divinyl ether, methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether or IVE;
When said polymer non-woven fabrics was polypropylene non-woven fabric, described grafted chain was the homopolymer chain of ethyl propenoate.
Among the present invention, in the described graft modification macromolecular material, said monomeric content is so that monomeric percentage of grafting 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 said graft modification macromolecular material, and it comprises the steps: said high molecule micropore film or polymer non-woven fabrics and said monomer generation graft polymerization reaction are got final product; Described graft polymerization reaction is irradiation grafting polyreaction or chemical graft polyreaction.
Wherein, the technology of described irradiation grafting polyreaction and optimum condition can be selected according to this area general knowledge, preferred pre-irradiation grafting polyreaction of the present invention or mutual radiation graft polymerization reaction.
Among the present invention; The technology of described pre-irradiation grafting polyreaction and optimum condition can be selected according to this area general knowledge; The concrete operations step is: in solution system or emulsion system; Under protection of inert gas, carry out graft polymerization reaction through the high molecule micropore film of pre-irradiation or polymer non-woven fabrics and said monomer.Wherein, described pre-irradiation preferably adopts gamma-rays or electron beam as irradiation source.
Among the present invention; The technology of described mutual radiation grafting method and optimum condition can be selected according to this area general knowledge; The concrete operations step is: in solution system or emulsion system; Under vacuum or protection of inert gas, to said high molecule micropore film or polymer non-woven fabrics, and said monomer carries out common irradiation generation graft polymerization reaction.Wherein, described mutual radiation preferably adopts cobalt or electron beam as irradiation source.
In said pre-irradiation grafting or mutual radiation graft polymerization reaction, described irradiation dose can be selected according to this area general knowledge, and that preferable is 1～100kGy, and that better is 5～50kGy; The temperature of said pre-irradiation grafting polyreaction can be selected according to this area general knowledge, and preferable is 40～100 ℃, and better is 50～80 ℃.The time of described pre-irradiation grafting polyreaction reaches till the preset percentage of grafting with said macromolecular material, and preferable is 0.1～20 hour, and better is 3～8 hours.The time of said mutual radiation graft polymerization reaction so that irradiation dose reaches above-mentioned dosage require till.
In said pre-irradiation grafting or mutual radiation graft polymerization reaction; Described high molecule micropore film or polymer non-woven fabrics and said monomeric mass ratio can be selected according to said percentage of grafting on the basis of this area general knowledge; Preferable is 10: 1～1: 10, and better is 1: 10～2: 1.
In said pre-irradiation grafting or mutual radiation graft polymerization reaction, said solution system is by said monomer and solvent composition.Described solvent can be selected the conventional all kinds of SOLVENTS that uses in this type of reaction of this area for use; As long as it can dissolve said monomer and does not react with high molecule micropore film or polymer non-woven fabrics, one or more that preferable is in ETHYLE ACETATE, methyl alcohol and the ethanol.The consumption of said solvent can be selected according to this area general knowledge, and preferable is 50%～99% of said solution system quality, and better is 80～95%.
In said pre-irradiation grafting or mutual radiation graft polymerization reaction, said emulsion system is made up of said monomer, water and emulsifying agent.Said monomeric consumption can be selected according to this area general knowledge, and preferable is 1～40% of said emulsion system quality, and better is 5～25%, and best is 15～25%.Said emulsifying agent can be selected according to this area general knowledge, and preferable is the oil-in-water-type tensio-active agent, and better is polysorbas20.The consumption of said emulsifying agent can be selected according to this area general knowledge, and preferable is 0.1～10% of said 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, and preferable is 50%～95% of said emulsion system quality, and better is 75～80%.
Among the present invention, described rare gas element can be selected rare gas element commonly used in the irradiation grafting field, this area for use, and preferable is nitrogen or argon gas.
Among the present invention; The technology of described chemical graft polyreaction and condition can be carried out according to the ordinary method of this area; The concrete operations step is: in solution system or emulsion system; Under protection of inert gas, under action of evocating, said high molecule micropore film or polymer non-woven fabrics and said monomer generation graft polymerization reaction.
Wherein, described initiator is this type of reaction of this area all kinds of initiators commonly used, like organic peroxide initiator and/or azo-initiator.Described initiator is preferable is in Lucidol (BPO), Potassium Persulphate, ammonium persulphate, Sodium Persulfate, Diisopropyl azodicarboxylate (AIBN), azo-bis-isobutyrate hydrochloride (V-50), peroxidized t-butyl perbenzoate (TBPB), Di Cumyl Peroxide 99 (DCP), ABVN and the peroxy dicarbonate ethylhexyl one or more, one or more that better is in Lucidol, Di Cumyl Peroxide 99 and the Diisopropyl azodicarboxylate.The consumption of described initiator can be selected according to this area general knowledge, and preferable is 0.1%～5% of said emulsion or solution system quality.Wherein, the temperature of described chemical graft polyreaction can be selected according to this area general knowledge, and preferable is 40～100 ℃, and better is 50～80 ℃.The time of described chemical graft polyreaction reaches till the preset percentage of grafting with said macromolecular material, and preferable is 0.1～20 hour, and better is 3～8 hours.
Among the present invention; In said chemical graft polyreaction; Described high molecule micropore film or polymer non-woven fabrics and said monomeric amount ratio can be selected according to said percentage of grafting on the base material of this area general knowledge, and preferable is 10: 1～1: 10, and better is 1: 10～2: 1.
Among the present invention, in said chemical graft polyreaction, described solution system is by said monomer and solvent composition.Said solvent can be selected the conventional all kinds of SOLVENTS that uses in this type of reaction of this area for use; As long as it can dissolve said monomer and does not react with high molecule micropore film or polymer non-woven fabrics, one or more that preferable is in ETHYLE ACETATE, methyl alcohol and the ethanol.The consumption of said solvent can be selected according to this area general knowledge, and preferable is 50%～99% of said solution system quality, and better is 80～95%.
Among the present invention, in said chemical graft polyreaction, described emulsion system is made up of monomer, water and emulsifying agent.Said monomeric consumption can be selected according to this area general knowledge, and preferable is 1～40% of said emulsion system quality, and better is 5～25%, and best is 15～25%.Said emulsifying agent can be selected according to this area general knowledge, and preferable is the oil-in-water-type tensio-active agent, and better is polysorbas20.The consumption of said emulsifying agent can be selected according to this area general knowledge, and preferable is 0.1～10% of said 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, and preferable is 50%～95% of said emulsion system quality, and better is 75～80%.
, preferably can adopt graft polymerization reaction of the present invention the conventional method in this area to carry out aftertreatment after finishing.The present invention preferably soaks, washes with solvent extraction or hot solvent, to remove the homopolymer that produces in the dereaction.
Graft modification macromolecular material of the present invention is particularly suitable for as the barrier film in the lithium ion battery, and it not only has good affinity with electrolytic solution, and is prone to by gelation, and Electolyte-absorptives are protected 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 modification macromolecular material as lithium ion battery separator.
All commercially available the getting of reagent that the present invention is used.
Among the present invention, but above-mentioned optimum condition arbitrary combination on the basis that meets this area general knowledge promptly gets each preferred embodiments of the present 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 the macromolecular material; Reduce the percent 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, degree of gelation becomes big in the pars amorpha; Increase the zone of lithium ion conduction, thereby improve membranous lithium ion conductivity.
2. barrier film of the present invention and organosilane ester electrolytic solution have better affinity, further improve membranous guarantor's liquid rate, avoid electrolytic solution seepage to occur, and the life-time service performance of battery is also increased.
3. barrier film of the present invention has very big repeatedly cycle performance when being used for lithium ion battery.
Description of drawings
Fig. 1 is a PE-g-PVAc non-woven fabrics infrared spectrogram after grafted polyethylene non-woven fabrics and the grafting not among the embodiment 1.
Fig. 2 is the membranous repeatedly charge and discharge cycles test pattern among the effect embodiment 4.
Fig. 3 is the membranous repeatedly charge and discharge cycles test pattern among the effect embodiment 5.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further specified, but the present invention is not limited.
The prescription of graft modification macromolecular material is seen table 1 among the embodiment 1-27, and the preparation method is following:
Table 1
Figure BSA00000566135700091
Figure BSA00000566135700101
Embodiment 1
Selecting thickness for use is that (number-average molecular weight is 200,000 as macromolecular material for 50 microns 5g Vilaterm non-woven fabrics; Mean pore size is 1.7 microns); This Vilaterm non-woven fabrics is immersed in the solution of being made up of 10g vinyl acetate and 40g ETHYLE ACETATE, and the gamma-ray irradiation that in nitrogen atmosphere, utilizes the generation of cobalt source takes out in apparatus,Soxhlet's with ETHYLE ACETATE extracting 2 days to 30kGy; Obtain percentage of grafting and be modified PE-g-PVAc non-woven fabrics of 90%, promptly required lithium-ion membrane.
Embodiment 2
Selecting thickness for use is that (number-average molecular weight is 250,000 as macromolecular material for 100 microns polypropylene non-woven fabric 20g; Mean pore size is 2.5 microns); This non-woven fabrics is immersed in the solution of being made up of 10g ethyl propenoate and 90g ETHYLE ACETATE, and the x ray irradiation x that in nitrogen atmosphere, utilizes the electron beam generation takes out in apparatus,Soxhlet's with acetone extracting 2 days to 20kGy; Obtain the ethyl propenoate percentage of grafting and be 30% modification nonwoven cloth, promptly required lithium-ion membrane.
Embodiment 3
Select for use thickness be 40 microns PVDF microporous membrane 10g as macromolecular material (number-average molecular weight is 550,000,2 microns of aperture average out to), in air, utilize cobalt 60 gamma-ray sources that it is carried out irradiation, irradiation dose is 20kGy.With the 20g Jia Jibingxisuanyizhi, the 2g polysorbas20 is made into emulsion in 78g water, and the PVDF microporous membrane behind the 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; Obtain percentage of grafting and be 70% modification PVDF-g-PEMA microporous membrane, promptly required lithium-ion membrane.
Embodiment 4
Select for use thickness be 80 microns polyethene microporous membrane 5g as macromolecular material (number-average molecular weight is 600,000,1.0 microns of aperture average out to), in air, utilize cobalt 60 gamma-ray sources that it is carried out irradiation, irradiation dose is 30kGy.With 10g Jia Jibingxisuanyizhi wiring solution-forming in 40g methyl alcohol; PE microporous membrane behind the 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 modified PE-g-PEMA microporous membrane of 90%, promptly required lithium-ion membrane.
Embodiment 5
Select for use thickness be 60 microns microporous membrane of polyethersulfone 25g as macromolecular material (number-average molecular weight is 50,000,0.5 micron of aperture average out to), in air, utilize electron beam that it is carried out irradiation, irradiation dose is 20kGy.With the 20g n-butyl acrylate; The 2g polysorbas20 is made into emulsion in 78g water, the PVDF microporous membrane behind the 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, obtain percentage of grafting and be 30% modified poly (ether-sulfone) microporous membrane, promptly required lithium-ion membrane.
Embodiment 6
Selecting thickness for use is that (number-average molecular weight is 300,000 as macromolecular material for 70 microns PE microporous membrane 10g; 0.5 micron of aperture average out to); The immersion of PE microporous membrane is contained among the ethyl acetate solution 100g of 10g methyl acrylate; The Lucidol that adds 0.5g is warmed up to 60 ℃ of reactions 3 hours behind the logical nitrogen excluding air, take out the back and remove methyl acrylate homopolymer and monomer after the soaking flushing repeatedly with hot ethyl acetate; Obtain percentage of grafting and be modified PE-g-PMA microporous membrane of 50%, promptly required lithium-ion membrane.
Embodiment 7
Select for use thickness be 40 microns PVDF microporous membrane 20g as macromolecular material (number-average molecular weight is 700,000, and mean pore size is 0.45 micron), 20g vinyl acetate, 2g polysorbas20 are made into emulsion in 78g water; This microporous membrane is immersed in this emulsion; The Potassium Persulphate that adds 0.5g is warmed up to 80 ℃ of reactions 5 hours behind the logical nitrogen excluding air, take out in apparatus,Soxhlet's with ETHYLE ACETATE extracting 2 days; Obtain percentage of grafting and be 75% modification PVDF microporous membrane, promptly required lithium-ion membrane.
Embodiment 8
Selecting thickness for use is that (number-average molecular weight is 700,000 as macromolecular material for 40 microns PVDF microporous membrane 20g; Mean pore size is 0.45 micron); 10g vinyl acetate, 10g propyl acrylate, 2g polysorbas20 are made into emulsion in 78g water, this microporous membrane is immersed in this emulsion, add the Potassium Persulphate of 0.5g; Be warmed up to 80 ℃ of reactions 5 hours behind the logical nitrogen excluding air; Take out the back and wash immersion repeatedly with hot acetone and repeatedly remove monomer and homopolymer, obtain percentage of grafting and be 58% modification PVDF microporous membrane, promptly required lithium-ion membrane.
Embodiment 9
Select for use thickness be 40 microns PVDF microporous membrane 10g as macromolecular material (number-average molecular weight is 700,000, and mean pore size is 0.45 micron), in air, utilize cobalt 60 gamma-ray sources that it is carried out irradiation, irradiation dose is 30kGy.PVDF microporous membrane behind the irradiation is immersed among the ethanolic soln 100g that contains the 20g divinyl ether; Under the nitrogen protection condition; Be warming up to 60 ℃ of reactions 4 hours; Taking-up with toluene extracting 2 days, obtains percentage of grafting and is 50% modification PVDF microporous membrane, promptly required lithium-ion membrane in apparatus,Soxhlet's.
Embodiment 10-22
Adopt macromolecular material and monomer in the table 1 respectively, other raw material and reaction conditions all carry out according to embodiment 8.Wherein, the PVDF microporous membrane number-average molecular weight among the embodiment 10-15 is 700,000; The number-average molecular weight of the Vilaterm non-woven fabrics among the embodiment 16-22 is 180,000.
Embodiment 23
Selecting thickness for use is that 40 microns PVDF microporous membrane 10g utilizes cobalt 60 gamma-ray sources that it is carried out irradiation in air as macromolecular material (number-average molecular weight is 700,000, and mean pore size is 0.45 micron), and irradiation dose is 30kGy.PVDF microporous membrane behind the irradiation is immersed among 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; Taking-up with toluene extracting 2 days, obtains percentage of grafting and is 62% modification PVDF microporous membrane, promptly required lithium-ion membrane in apparatus,Soxhlet's.
Embodiment 24
Selecting thickness for use is that 80 microns polyethene microporous membrane 15g is 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 among the ethanolic soln 100g that contains 10g methylvinylether, 10g n-butyl acrylate; The Lucidol that adds 0.5g; Be warmed up to 80 ℃ of reactions 4 hours behind the logical nitrogen excluding air; Taking-up with acetone extracting 2 days, obtains percentage of grafting and is 47% modified poly ethylene microporous membrane, promptly required lithium-ion membrane in apparatus,Soxhlet's.
Embodiment 25
Selecting thickness for use is that (number-average molecular weight is 200,000 as macromolecular material for 110 microns 10g Vilaterm non-woven fabrics; Mean pore size is 2.0 microns); This Vilaterm non-woven fabrics is immersed in the solution of being made up of 10g vinyl acetate and 30g methyl alcohol, and the gamma-ray irradiation that in nitrogen atmosphere, utilizes the generation of cobalt source takes out in apparatus,Soxhlet's with ETHYLE ACETATE extracting 2 days to 10kGy; Obtain percentage of grafting and be modified PE-g-PVAc non-woven fabrics of 7%, promptly required lithium-ion membrane.
Embodiment 26
Selecting thickness for use is that (number-average molecular weight is 200,000 as macromolecular material for 110 microns 10g Vilaterm non-woven fabrics; Mean pore size is 2.0 microns); This Vilaterm non-woven fabrics is immersed in the solution of being made up of 15g vinyl acetate and 25g methyl alcohol, and the gamma-ray irradiation that in nitrogen atmosphere, utilizes the generation of cobalt source takes out in apparatus,Soxhlet's with ETHYLE ACETATE extracting 2 days to 40kGy; Obtain percentage of grafting and be modified PE-g-PVAc non-woven fabrics of 31%, promptly required lithium-ion membrane.
Embodiment 27
Selecting thickness for use is that (number-average molecular weight is 200,000 as macromolecular material for 110 microns 10g Vilaterm non-woven fabrics; Mean pore size is 2.0 microns); This Vilaterm non-woven fabrics is immersed in the solution of being made up of 25g vinyl acetate and 15g methyl alcohol, and the gamma-ray irradiation that in nitrogen atmosphere, utilizes the generation of cobalt source takes out in apparatus,Soxhlet's with ETHYLE ACETATE extracting 2 days to 40kGy; Obtain percentage of grafting and be modified PE-g-PVAc non-woven fabrics of 42%, promptly required lithium-ion membrane.
Effect embodiment 1
Get among the embodiment 1 percentage of grafting in the unmodified Vilaterm non-woven fabrics and embodiment 1 and be each 2g of modification nonwoven cloth of 90%; Be immersed in EC and DMC1 respectively: 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 among the embodiment 3 each 5g of PVDF-g-PEMA modified micro-pore film of percentage of grafting 70% in the unmodified polyvinylidene fluoride microporous film and embodiment 3; Be immersed in EC and DMC1 respectively: 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 among the embodiment 9 divinyl ether percentage of grafting in the unmodified polyvinylidene fluoride microporous film and embodiment 9 and be each 5g of PVDF microporous membrane of 50%; Be immersed in EC and DMC1 respectively: 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
The modification nonwoven cloth of getting among the embodiment 25 percentage of grafting in the unmodified Vilaterm non-woven fabrics and embodiment 25,26,27 and be 7%, 31% and 42% grafting vinyl acetate is cut into 19mm diameter disk as barrier film; Cobalt acid lithium is as positive pole; It is that ionogen lithium hexafluoro phosphate (1.0mol/L) and volume ratio are NSC 11801 (EC)/dimethyl carbonate (DMC) composition of 1: 1 that negative pole adopts metal lithium sheet, electrolytic solution, be assembled into 2032 button cells after; Adopt the 1C multiplying power that battery is carried out repeatedly the charge and discharge cycles test; Like Fig. 2, use the battery of graft modification metacneme repeatedly to discharge and recharge the back specific storage obviously than using grafting barrier film height, battery performance is better.
Effect embodiment 5
The modification nonwoven cloth of getting among the embodiment 26 percentage of grafting in the unmodified Vilaterm non-woven fabrics and embodiment 26 and be 31% grafting vinyl acetate is cut into 19mm diameter disk as barrier film; Cobalt acid lithium is as positive pole, and negative pole adopts metal lithium sheet, and electrolytic solution is that ionogen lithium hexafluoro phosphate (1.0mol/L) and volume ratio are NSC 11801 (EC)/dimethyl carbonate (DMC) composition of 1: 1; After being assembled into 2032 button cells; Adopt 0.1C respectively, 0.3C, 0.5C; 1C and 3C multiplying power are carried out repeatedly the charge and discharge cycles test to battery; Like Fig. 3, specific storage is obviously than using grafting barrier film height when high rate charge-discharge is tested for the battery of use graft modification metacneme, and battery performance is better.
Can find out by effect embodiment 1-5; The lithium ion battery separator and the electrolytic solution affinity that are made by the present invention are good; In electrolytic solution, soak behind the certain hour imbibition rate of body weight gain much larger than the polymeric membrane of non-modified; Carry out battery performance test and show that the button cell battery performance of battery diaphragm assembling after the modification is better, reached the set goal.

Claims (10)

1. graft modification macromolecular material, it is characterized in that: it is high molecule micropore film or the polymer non-woven fabrics that has grafted chain;
formula I
Wherein, described grafted chain is more than one monomeric polymeric chains, and described polymeric chain is the homopolymer chain that is formed by monomer of the same race, or the random copolymers chain that is 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 the I.
2. graft modification macromolecular material as claimed in claim 1 is characterized in that: said high molecule micropore film is polyolefins, polysulfones or cellulose family microporous membrane; What described polyolefin microporous film was preferable is Vilaterm, Vestolen PP 7052, tetrafluoroethylene, pvdf or pvdf-hexafluoropropylene copolymer microporous membrane; What described polysulfones microporous membrane was preferable is polyethersulfone or polysulfones microporous membrane; What described cellulose family microporous membrane was preferable is the FM microporous membrane;
Said polymer non-woven fabrics is Vilaterm, Vestolen PP 7052, nylon, polyethylene terephthalate, polyacrylonitrile or SE non-woven fabrics.
3. according to claim 1 or claim 2 graft modification macromolecular material, it is characterized in that: high molecular number-average molecular weight is 50,000～2,000,000 in said high molecule micropore film or the polymer non-woven fabrics, preferable is 20～700,000; The thickness of said high molecule micropore film or polymer non-woven fabrics is 1～200 micron, and preferable is 10～150 microns, and better is 40～110 microns; The mean pore size of said high molecule micropore film or polymer non-woven fabrics is 0.01～10 micron, and preferable is 0.1～5 micron, and better is 0.4～3 micron, and best is 0.4～2 micron.
4. like each described graft modification macromolecular material in the claim 1～3, it is characterized in that: said monomer has the two keys of a C=C, and ether or one are suc as formula the group shown in the I; Described monomer with the two keys of a C=C and an ether is preferable is the vinyl ethers compound of carbonatoms 3-6, 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 the divinyl ether; Described have the two keys of a C=C and one suc as formula the monomer of group shown in the I preferable be acrylic ester compound and/or the vinyl acetate of carbonatoms 4-11; Described acrylic ester compound is preferable be in methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, NSC 20949, tert-butyl acrylate, vinylformic acid isopentyl ester, Isooctyl acrylate monomer, Jia Jibingxisuanyizhi, SY-Monomer G, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate and the glycolmethacrylate one or more.
5. like each described graft modification macromolecular material in the claim 1～4, it is characterized in that: the thickness of described high molecule micropore film or polymer non-woven fabrics is 40～110 microns, and the aperture is 0.4～3 micron, and preferable is 0.4～2 micron;
When said high molecule micropore film is polyvinylidene fluoride microporous film; Described grafted chain is the homopolymer chain of Jia Jibingxisuanyizhi, 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 said high molecule micropore film was polyethene microporous membrane, described grafted chain was the homopolymer chain of Jia Jibingxisuanyizhi or methyl acrylate, or the random copolymers chain of methylvinylether and n-butyl acrylate;
When said polymer non-woven fabrics was the Vilaterm non-woven fabrics, described grafted chain was the homopolymer chain of vinyl acetate, divinyl ether, methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether or IVE;
When said polymer non-woven fabrics was polypropylene non-woven fabric, described grafted chain was the homopolymer chain of ethyl propenoate.
6. like each described graft modification macromolecular material in the claim 1～5, it is characterized in that: in the described graft modification macromolecular material, said monomeric percentage of grafting is 1%～200%, and preferable is 10%～100%, and better is 10～50%.
7. the preparation method of each described graft modification macromolecular material in the claim 1～6 is characterized in that: it comprises the steps: said high molecule micropore film or polymer non-woven fabrics and said monomer are carried out graft polymerization reaction, gets final product; Described graft polymerization reaction is irradiation grafting polyreaction or chemical graft polyreaction.
8. the preparation method of graft modification macromolecular material as claimed in claim 7 is characterized in that: said irradiation grafting polyreaction is pre-irradiation grafting polyreaction or mutual radiation graft polymerization reaction;
Preferable, the concrete operations step of said pre-irradiation grafting polyreaction is: under protection of inert gas, carry out graft polymerization reaction through the high molecule micropore film of pre-irradiation or polymer non-woven fabrics and said monomer; Wherein, said pre-irradiation preferably adopts gamma-rays or electron beam as irradiation source;
Preferable, the concrete operations step of said mutual radiation graft polymerization reaction is: under vacuum or protection of inert gas, to said high molecule micropore film or polymer non-woven fabrics, and said monomer carries out common irradiation generation graft polymerization reaction; Said mutual radiation preferably adopts cobalt or electron beam as irradiation source; In said pre-irradiation grafting polyreaction or mutual radiation graft polymerization reaction, that the dosage of said irradiation is preferable is 1～100kGy, and that better is 5～50kGy;
Preferable, the concrete operations step of said chemical graft polyreaction is: under protection of inert gas, and under action of evocating, said high molecule micropore film or polymer non-woven fabrics and said monomer generation graft polymerization reaction.
9. the preparation method of graft modification macromolecular material as claimed in claim 8; It is characterized in that: in said graft polymerization reaction; Said high molecule micropore film or polymer non-woven fabrics and said monomeric mass ratio are 10: 1～1: 10, and preferable is 1: 10～2: 1;
The temperature of said pre-irradiation grafting or chemical graft polyreaction is 40～100 ℃, and preferable is 50～80 ℃; The time of said pre-irradiation grafting or chemical graft polyreaction is 0.1～20 hour, and preferable is 3～8 hours;
Said graft polymerization reaction carries out in solution system or emulsion system; Said solution system is by said monomer and solvent composition; Described preferred solvents be in ETHYLE ACETATE, methyl alcohol and the ethanol one or more; The consumption of said solvent is 50%～99% of a said solution system quality, and preferable is 80～95%;
Said emulsion system is made up of said monomer, water and emulsifying agent; What said emulsifying agent was preferable is polysorbas20; Said monomeric consumption is 1～40% of a said emulsion system quality, and preferable is 5～25%, and better is 15～25%; The consumption of said emulsifying agent is 0.1～10% of a said emulsion system quality, and preferable is 1～5%, and better is 0.5～2%; The consumption of said water is 50%～95% of a said emulsion system quality, and preferable is 75～80%;
Described initiator is organic peroxy class initiator and/or azo-initiator, one or more that preferable is in Lucidol, Potassium Persulphate, ammonium persulphate, Sodium Persulfate, Diisopropyl azodicarboxylate, azo-bis-isobutyrate hydrochloride, peroxidized t-butyl perbenzoate, Di Cumyl Peroxide 99, ABVN and the peroxy dicarbonate ethylhexyl; The consumption of described initiator is 0.1%～5% of said emulsion system or a solution system quality.
In the claim 1～6 each described graft modification macromolecular material as the application of lithium ion battery separator.
CN2011102553782A 2010-08-20 2011-08-22 Grafting modified high polymer material, and preparation method and application thereof Active CN102432906B (en)

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 true CN102432906A (en) 2012-05-02
CN102432906B 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)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105098126A (en) * 2015-09-14 2015-11-25 河南科高辐射化工科技有限公司 Composite membrane for exhaust-type square nickel-cadmium battery and preparation method of composite membrane
CN105098127A (en) * 2015-09-14 2015-11-25 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
CN105098128A (en) * 2015-09-18 2015-11-25 河南科高辐射化工科技有限公司 Composite membrane for secondary nickel-zinc cell and preparation method of composite membrane
CN109853233A (en) * 2019-02-12 2019-06-07 中国科学技术大学 A kind of modified poly ethylene nano fibrous 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

Families Citing this family (13)

* Cited by examiner, † Cited by third party
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
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
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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 (2)

* Cited by examiner, † Cited by third party
Title
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》 *
MING YU ET AL.: "Preirradiation-Induced Emulsion Graft Polymerization of Glycidyl Methacrylate onto Poly(vinylidene fluoride) Powder", 《JOURNAL OF APPLIED POLYMER SCIENCE》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105098126A (en) * 2015-09-14 2015-11-25 河南科高辐射化工科技有限公司 Composite membrane for exhaust-type square nickel-cadmium battery and preparation method of composite membrane
CN105098127A (en) * 2015-09-14 2015-11-25 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
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
CN105098128A (en) * 2015-09-18 2015-11-25 河南科高辐射化工科技有限公司 Composite membrane for secondary nickel-zinc cell and preparation method of composite membrane
CN109853233A (en) * 2019-02-12 2019-06-07 中国科学技术大学 A kind of modified poly ethylene nano fibrous 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

Also Published As

Publication number Publication date
CN102432906B (en) 2013-12-18
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
CN102888016B (en) Preparation method of lithium-ion secondary battery diaphragm with crosslinking composite layer
TWI608023B (en) Acrylonitrile Copolymer Adhesive and Its Application in Lithium Ion Battery
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
CN111635478B (en) Low-impedance binder and preparation method and application thereof
CN105098233A (en) Preparation method of semi-interpenetrating network polymer gel electrolyte membrane
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
CN107845812A (en) Anode pole piece and preparation method thereof and secondary cell
KR20160043768A (en) Organic/inorganic composite separator, method for manufacturing the same and electrochemical device containing the same
CN109428080B (en) Negative electrode binder, negative electrode plate and lithium ion secondary battery
CN111933864B (en) Energy storage device
CN1967906A (en) Method for preparing gelatin membrane by radiation grafting method
CN114388795A (en) Silicon-carbon cathode binder of lithium ion battery and preparation method thereof
CN116144290B (en) Terpolymer adhesive, preparation method thereof and application thereof in silicon-based lithium ion battery
CN104852004A (en) Secondary battery composite membrane, preparation method thereof and secondary battery
CN115411454B (en) Lithium battery diaphragm and preparation method thereof
CN113563531A (en) Graft copolymer aqueous adhesive, preparation method and application in silicon-carbon negative electrode
CN107170944B (en) Self-supporting polymer film material for lithium ion secondary battery and preparation method thereof
CN114243022B (en) Three-dimensional network water system binder for lithium ion battery, preparation and application thereof
CN113912898B (en) All-organic porous protective film for ultrahigh-rate high-capacity lithium metal negative electrode and preparation method and application thereof

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