CN1479399A - Manufacturing process electrolyte membrane special for solid lithium ion battery - Google Patents
Manufacturing process electrolyte membrane special for solid lithium ion battery Download PDFInfo
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- CN1479399A CN1479399A CNA021382042A CN02138204A CN1479399A CN 1479399 A CN1479399 A CN 1479399A CN A021382042 A CNA021382042 A CN A021382042A CN 02138204 A CN02138204 A CN 02138204A CN 1479399 A CN1479399 A CN 1479399A
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- film
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The electrolyte membrane is made from polyvinylidene fluoride, grafting ethenylbenzene and sulfonic acid. In grafting phase, 10-18% polyvinylidene fluoride, 40-70% N methyl pyrrolidone are heated to 100 deg.C, then 12-50% ethenylbenzene and slight initiator is added at 90 deg.C. The mixture is heated at 100deg.C for 2 hr. rinsing by using trichloromethane obtains solid of polymer. In phase of making diaphragm, diaphragm is coated by solution containing proper portions of mixed round polymer solid, acetone and butyl alcohol. The coated diaphragm is dipped in trichloromethane for 1 hr. The solid electrolyte diaphragm is obtained after procedures of washing, heating diaphragm in sulfonic acid at 100 deg.C, rinsing and drying. The advantages of the diaphragm are good charging and discharging performances, low cost and high-qualified rate.
Description
Affiliated technical field
The present invention relates to a kind of preparation method of solid polymer lithium ion battery electrolyte, specifically is a kind of solid polymer lithium ion battery manufacturing process electrolyte membrane special.
Background technology
Some general inorganic electrolytes are restricted in lithium battery applications because of there being various defectives at present, seek the key problem in technology that suitable solid electrolyte becomes current development high power lithium battery.Polymer solid electrolyte is a class new function material that develops rapidly the eighties, has higher ionic conductivity, plasticity is strong, viscoplasticity is good, process film forming easily, the change in volume that can adapt to electrode in the battery charge and discharge process has better chemical and electrochemical stability simultaneously, therefore demonstrates very big superiority in the application of pond and electric electrochemical element in all solid state high energy lithium.
Have the polymer solid electrolyte of actual application value to mainly contain two classes at present: the one, with the colloid macromolecule electron solutions matter that aprotic solvent such as high polymers such as Pioloform, polyvinyl acetal and propene carbonate are compounded to form, cost is higher in industrial production; The 2nd, the solvent-free polymer solid electrolyte that is compounded to form with poly(ethylene oxide) (PEO) or PPOX polyethers such as (PPO) and alkali metal salt.
Because PEO and alkali metal salt complex compound have higher conductivity, so the research of present polyethers solid electrolyte mainly concentrates on the PEO, the degree of crystallinity of line style very high (75%) causes the room-temperature conductivity very low (10 of PEO alkali metal salt complex compound
-8Scm
-1), limited its scope of application.Widely used in the world at present is U.S. Bellcore technology, uses colloid that electrolyte solution carries out plasticising formation to the copolymer of vinylidene and hexafluoropropylene as electrolyte, and this method cost in industrial production is higher.Another kind of use is more is colloidal electrolyte based on Kynoar PVDF, still need use some organic solvents in this electrolyte, therefore flatulence in the battery use, unavoidably occur, influence battery life, reduce the qualification rate of battery, thereby increased the production cost of battery.
The objective of the invention is poly(ethylene oxide) (PE0) is carried out modification,, obtain more stable electrolyte to improve electrolyte room temperature conductivity.
Production technology of the present invention is added by polymer poly vinylidene (PVDF) graft phenylethene respectively that sulfonic acid lithium and system film oven dry two stages realize.
Contain Kynoar 10～18% in essence in the grafting stage, N methyl pyrrolidone 40～70% and styrene 12～50%, successively by poly-producing of following step:
Kynoar 10～18% adds N methyl pyrrolidone 40～70% and slowly is heated to 100 ℃ of off-bottoms, stir simultaneously, add styrene 12～50% and a small amount of initator benzoyl peroxide when waiting to be cooled to 90 ℃, being heated to 100 ℃ again kept 2 hours, clean 2 times with chloroform, the polymer solids that graft reaction generates is collected;
Contain grafting resulting polymers solid 5-15% in essence at system film baking stage, acetone 32～60%, butanols 5～15% and sulfonic acid lithium 10～58%, realize by the following step successively:
Above-mentioned grafting resulting polymers solid 5～15% is added acetone 32～60% and butanols 5～15%, be heated to and film after 100 ℃ stirring is dissolved it fully simultaneously, coating thickness remains on about 50 microns, treat wherein acetone volatile dry, carrying out sulfonation handles, it is in 80% the chloroform soln 3 hours that the film that coats is immersed in concentration, film is taken out, put into concentration after water cleans and be 50% sulfonic acid lithium solution and soak and be heated to 100 ℃ and kept 1 hour, with film take out clean several all over after put into 80 ℃ of vacuum and promptly made solid polymer lithium ion battery electrolyte membrane special in dry 2 hours.
Good effect of the present invention is owing to utilized Kynoar (PVDF) graft phenylethene+sulfonic acid lithium as electrolyte, anionic grafting is on the polymer molecule main chain, it is a kind of single ion conductor of lithium ion, can reduce the polarization of battery in charging process, thereby improve the charge-discharge performance of battery.Owing on the branch chain of polymer, deposited lithium ion, therefore in battery, no longer add lithium salts, reduced the cost of manufacture of battery.In addition, compare with the Bellcore technology, this electrolyte no longer is colloid but solid electrolyte membrane, makes battery flatulence phenomenon when charging obtain relaxing, and has improved lithium ion battery quality and qualification rate.
Embodiment
The invention will be further described with embodiment below:
Embodiment 1. Kynoar 110 grams add N methyl pyrrolidone 726 grams, being heated to 100 ℃ stirs simultaneously, treat to dissolve fully and be cooled to 90 ℃, add styrene 195 grams and initator benzoyl peroxide 2.2 grams, being heated to 100 ℃ again kept 2 hours, clean 2 times with chloroform soln, polymer solids is collected; Get above-mentioned polymer solids 110 grams and add acetone 660 grams, butanols 110 grams are heated to 100 ℃ and are stirred to dissolving fully simultaneously; With above-mentioned solution coating, coating thickness remains on about 50 microns, treats its acetone volatile dry after filming; Film is immersed in the chloroform soln 3 hours, takes out, clean with clear water; Film is soaked into is heated to 100 ℃ in 50% the sulfonic acid lithium solution and kept 1 hour; Taking out the film clear water washes several times; Film was put into 80 ℃ of vacuum dry 2 hours, and solid polymer lithium ion battery electrolyte membrane special completes, and through the AC bridge test, conductivity is 1.108 * 10
-3(S).
Embodiment 2. Kynoar 200 grams add N methyl pyrrolidone 1390 grams, are heated to 100 ℃ and are stirred to off-bottom simultaneously; Add styrene 356 grams and initator benzoyl peroxide 4 grams when waiting to be cooled to 90 ℃, be heated to 100 ℃, kept 2 hours, clean 2 times, the polymer solids that graft reaction generates is collected with chloroform; Above-mentioned polymer solids 200 grams are added acetone 1200 grams, butanols 200 grams, be heated to and film after 100 ℃ stirring is dissolved it fully simultaneously, coating thickness remains on about 50 microns, treated behind the acetone volatile dry film is immersed in concentration and be in 80% the chloroform soln 3 hours, take out the cleaning of film water, the sulfonic acid lithium solution of putting into concentration 50% soaks and is heated to 100 ℃ and kept 1 hour, takes out and puts into 80 ℃ of vacuum dry 2 hours after film cleans several times.Record the conductivity 1.20 * 10 of this film with AC bridge
-3(S).
Embodiment 3. Kynoar 150 gram adds N methyl pyrrolidones 1050 grams, is heated to 100 ℃ and be stirred to dissolving fully; Be cooled to 90 ℃, add styrene 294 grams and initator benzoyl peroxide 3.3 grams, be heated to 100 ℃ again, kept 2 hours, clean 2 times, the polymer solids that graft reaction generates is collected with chloroform; Get above-mentioned polymer solids 150 grams, add acetone 900 grams, butanols 150 grams, be heated to and film after 100 ℃ stirring is dissolved it fully simultaneously, coating thickness remains on about 50 microns, treated film to be immersed in behind the acetone volatile dry in the chloroform soln of concentration 80% 3 hours, and took out the film water and clean, the sulfonic acid lithium solution of putting into concentration 50% soaks and is heated to 100 ℃ and kept 1 hour; Take out and put into 80 ℃ of vacuum dry 2 hours after film cleans several times.Record the conductance 1.105 * 10 of this dielectric film with AC bridge
-3(S).
Claims (1)
1. a solid polymer lithium ion battery manufacturing process electrolyte membrane special was finished by polymer graft and system film two stages of oven dry, it is characterized in that:
Contain Kynoar 10-18% in essence in the grafting stage, N methyl pyrrolidone 40～70% and styrene 12～50%, produce by following technology successively:
Kynoar 10～18% adding methyl pyrrolidones 40～70% slowly are heated to 100 ℃ and are stirred to off-bottom simultaneously, add styrene 12～50% and a small amount of initator benzoyl peroxide when waiting to be cooled to 90 ℃, heat again to 100 ℃ of maintenances 2 hours, clean 2 times with chloroform, the polymer solids that graft reaction generates is collected;
Contain grafting resulting polymers solid 5～15% in essence at system film baking stage, acetone 32～60%, butanols 5～15%, sulfonic acid lithium 10～58%, produce by following technology successively:
Grafting resulting polymers solid 5～15% is added acetone 32～60% and butanols 5～15% to be heated to 100 ℃ and to stir simultaneously and film after it is dissolved fully, coating thickness remains on about 50 microns, treated film to be immersed in behind the acetone volatile dry in the chloroform soln of 80% concentration 3 hours, take out film, put into the immersion of 10～58% sulfonic acid lithium solution after water cleans and be heated to 100 ℃ of maintenances 1 hour; Take out and put into 80 ℃ of vacuum dry 2 hours after film cleans several times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021382042A CN1479399A (en) | 2002-08-29 | 2002-08-29 | Manufacturing process electrolyte membrane special for solid lithium ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021382042A CN1479399A (en) | 2002-08-29 | 2002-08-29 | Manufacturing process electrolyte membrane special for solid lithium ion battery |
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|---|---|
| CN1479399A true CN1479399A (en) | 2004-03-03 |
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ID=34147170
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA021382042A Pending CN1479399A (en) | 2002-08-29 | 2002-08-29 | Manufacturing process electrolyte membrane special for solid lithium ion battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341168C (en) * | 2005-01-27 | 2007-10-03 | 河南环宇集团有限公司 | Polymer membrane for polymer lithium ion battery and method for making same |
| CN100412116C (en) * | 2005-02-07 | 2008-08-20 | 财团法人工业技术研究院 | Proton conducting membrane and production |
| CN102097653A (en) * | 2011-01-18 | 2011-06-15 | 中国人民解放军国防科学技术大学 | Electrolyte used for Li-S battery, Li-S battery and method for preparing electrolyte membrane contained in same |
| CN101136498B (en) * | 2006-08-31 | 2012-07-11 | 精工爱普生株式会社 | Method for manufacturing a secondary battery |
-
2002
- 2002-08-29 CN CNA021382042A patent/CN1479399A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341168C (en) * | 2005-01-27 | 2007-10-03 | 河南环宇集团有限公司 | Polymer membrane for polymer lithium ion battery and method for making same |
| CN100412116C (en) * | 2005-02-07 | 2008-08-20 | 财团法人工业技术研究院 | Proton conducting membrane and production |
| CN101136498B (en) * | 2006-08-31 | 2012-07-11 | 精工爱普生株式会社 | Method for manufacturing a secondary battery |
| CN102097653A (en) * | 2011-01-18 | 2011-06-15 | 中国人民解放军国防科学技术大学 | Electrolyte used for Li-S battery, Li-S battery and method for preparing electrolyte membrane contained in same |
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