CN1280149A - Polymer solid electrolyte and its preparing method and use - Google Patents
Polymer solid electrolyte and its preparing method and use Download PDFInfo
- Publication number
- CN1280149A CN1280149A CN99109568A CN99109568A CN1280149A CN 1280149 A CN1280149 A CN 1280149A CN 99109568 A CN99109568 A CN 99109568A CN 99109568 A CN99109568 A CN 99109568A CN 1280149 A CN1280149 A CN 1280149A
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- Prior art keywords
- solid electrolyte
- copolymer solid
- polymer
- chain
- polyoxyethylene
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 31
- 229920000642 polymer Polymers 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 14
- -1 polyoxyethylene Polymers 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 2
- 125000000524 functional group Chemical group 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 239000002001 electrolyte material Substances 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
-
- 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
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- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
本发明的一种聚合物固体电解质,是由交联网络聚合物和无机锂盐组成,将交联网络聚合物预聚物,交联剂和无机锂盐按重量份1∶0.2∶0.24～0.72进行混合,经无水THF溶解后,在催化剂二月桂酸二丁基锡作用下于75～95℃搅拌反应制得聚合物固体电解质。本发明的一种聚合物固体电解质可一次性成膜,具有高的离子传导率,可用于锂离子二次电池中的电解质材料。A polymer solid electrolyte of the present invention is composed of a cross-linked network polymer and an inorganic lithium salt, and the cross-linked network polymer prepolymer, the cross-linking agent and the inorganic lithium salt are prepared in parts by weight of 1:0.2:0.24-0.72 Mixing, dissolving in anhydrous THF, stirring and reacting at 75-95 DEG C under the action of dibutyltin dilaurate as a catalyst to prepare a polymer solid electrolyte. The polymer solid electrolyte of the invention can be formed into a film at one time, has high ion conductivity, and can be used as an electrolyte material in a lithium-ion secondary battery.
Description
The present invention relates to a kind of copolymer solid electrolyte and its production and use.Be particularly related to a kind of copolymer solid electrolyte, be mainly used in field of lithium ion secondary with internal plasticizer.
G.Schwab and MT.Lee delivered patent [U.S.Patent 4,792,508; U.S.Patent 4,830,939] reported a kind of polarity small molecules such as PC plastifying gel polymer solid electrolyte, it is to make line style PEO chain be cross-linked to form three-dimensional network with polyacrylic ester as linking agent to play the support frame effect, and the small molecules softening agent in the network is as conducting material.This ionogen has higher ionic conductance, but the polarity small molecules is easy to overflow from network, makes the system poor stability, has also reduced the security of lithium ion battery simultaneously; The people such as Watanabe of Japan methylate three official's degree polyalkylene glycol moieties, and remaining hydroxyl changes into acrylate, form cross-linked network copolymer solid electrolyte [J.Electrochem.Soc.1998, V.145,5,1521] through light initiation polymerization then.They have studied ionic conductance with the degree change rule that methylates, but the degree that methylates of this system is wayward, and ionic conductance is than the end (10
-6Scm
-1), this system preparation process complexity, technology is wayward, is unsuitable for scale operation.
The objective of the invention is to overcome the defective of above-mentioned system poor stability, made a kind of copolymer solid electrolyte and proposed softening agent is connected with network by chemical bond.Preparation method of the present invention is simple, is suitable for making on a large scale the production lithium-ion secondary cell.
The present invention has prepared a kind of New Polymer Solid Electrolytes with internal plasticizer.Wherein internal plasticizer be by the chemical bond grafting in three-dimensional network, avoided the unsettled defective of conventional gel ionogen; Internal plasticizer on the network can reduce the second-order transition temperature of whole system, makes the sub-chain motion aggravation, is beneficial to the ionic transmission.The passage of taking on simultaneously ion transport again.This polymer electrolyte film adopts a step solution casting method, and preparation is simple, can carry out scale operation, saves the manufacturing expense of lithium ion battery greatly.
Network-type copolymer solid electrolyte of the present invention is made up of cross-linked network polymkeric substance and two kinds of components of inorganic lithium salt ionogen.
In above-mentioned cross-linked network polymeric constituent, the cross-linked network polymkeric substance is the network polymer that generates by network polymer performed polymer and linking agent generation crosslinking reaction.
Wherein, have various internal plasticization segments and the terminal polyethylene oxide/polypropylene oxide segment (PEO-PPOH) that is hung with hydroxyl on the skeleton of network polymer performed polymer, two kinds of segmental mol ratios of internal plasticization chain and PEO-PPOH are 1: 1 ∽ 1: 7.This network polymer performed polymer skeleton comprises:
Polymethyl siloxane (PMS), its molecular structure is as follows:
Or cluster ethylene glycol (PLEG), its molecular structure is as follows:
R in above-mentioned molecular structure
1: polyethylene oxide/polypropylene oxide segment R
2: the internal plasticization chain
The above-mentioned internal plasticization chain that hangs on the network polymer performed polymer comprises:
Allyl methyl polyoxyethylene (APEOM, the PEO molecular weight is 150-1000, is preferably 350-750); Allyl methyl polyoxytrimethylene (APPOM); Allyl methyl polyoxyethylene sulfonic acid lithium (APEOSO
3Li, the PEO molecular weight is 150-350, is preferably 150); Allyl methyl polyoxyethylene Lithium Sulphate (APEOSO
4Li, the PEO molecular weight is 150-350, is preferably 150); Acrylate (R=CH
3, C
2H
5, C
3H
7, C
4H
9).
Above-mentioned linking agent (TMP-TDI) is a kind of isocyanic ester with trifunctional, and it is by TriMethylolPropane(TMP) and 2,4 toluene diisocyanate prepared in reaction, and its structural representation formula is as follows:
Above-mentioned inorganic lithium salt ionogen comprises LiClO
4, LiCF
3SO
3, LiN (CF
3SO
2)
2
Of the present invention have internal plasticizer network polymer method for preparing solid electrolyte in the following order step carry out: 1. do not have water treatment:
Solvent for use THF uses earlier anhydrous CaCl
2Backflow 12h, refluxing through sodium Metal 99.5 presents avy blue until the benzophenone indicator again, and distillation at last obtains anhydrous solvent; Inorganic lithium salt ionogen [LiClO
4, LiCF
3SO
3, LiN (CF
3SO
2)
2] all at 140 ℃ of vacuum-drying 24h, obtain the exsiccant white powder.2. the preparation that has internal plasticizer network polymer solid electrolyte:
1. network polymer performed polymer (the mol ratio PEO-PPOH: APEO that takes by weighing
350M=1: 1 ∽ 1: 7) 1 part, 0.2 part of linking agent (TMP-TDI), inorganic lithium salt 0.24-0.72 part joins and has prolong and N
2Mix in the 100ml there-necked flask of ingress pipe; 2. add THF, induction stirring makes it dissolving; 3. feed N
2Gas, and be warming up to 75-95 ℃, adding 0.5% (wt.) dibutyltin dilaurate catalyst behind the 15min, vigorous stirring 1.5h generates the viscous liquid that flows; 4. be cast to then in the tetrafluoroethylene mould, place 80 ℃ of baking ovens to solidify 48h, obtain conductive film; 5. conductive film is placed in 80 ℃ of vacuum drying ovens and extract solvent, carry out the ionic conduction property testing until constant weight.
The network polymer solid electrolyte of the present invention's preparation is obtained following invention effect:
1. an one-step film forming is easy to operate; 2. avoid softening agent to escape, improved stability greatly; 3. conductive film has high ionic conductance, σ=4.0 * 10
-4Scm
-1(25 ℃); 4. good film-forming property can be made into the large-area ultrathin film.This invention is mainly used in the polymer lithium ion secondary battery field, is suitable for making on a large scale production.
Embodiment one: PMS-APEO
350M/LiClO
4The network polymer solid electrolyte
1.0g PMS-APEO
350M[PEO-PPOH/APEO
350M=1: 7 (mol ratios)], 0.2gTMP-TDI and 0.24g LiClO
4(drying) joins and has prolong and N
2Mix in the 100ml there-necked flask of ingress pipe; Add THF, induction stirring makes it dissolving, feeds N
2Gas, and be warming up to 75 ℃, add 0.5% (wt.) dibutyltin dilaurate catalyst behind the 15min, vigorous stirring 1.5h generates the viscous liquid that flows, and is cast to then in the tetrafluoroethylene mould, place 80 ℃ of baking ovens to solidify 48h, obtain conductive film, conductive film is placed in 80 ℃ of vacuum drying ovens extract solvent, carry out the ionic conduction property testing until constant weight.
This ionogen conductive film (thickness is 0.1-0.3mm) is translucent, and has snappiness and high-flexibility.This embodiment system room-temperature ion conductivity reaches 5.1 * 10
-5Scm
-1Embodiment two: PMS-APEO
350M/LiN (CF
3SO
2)
2The network polymer solid electrolyte
1.0g PMS-APEO
350M[PEO-PPOH/APEO
350M=1: 7 (mol ratios)], 0.2g linking agent (TMP-TDI) and 0.50g (20%) LiN (CF
3SO
2)
2(drying) joins and has prolong and N
2Mix in the 100ml there-necked flask of ingress pipe; Add THF, induction stirring makes it dissolving, feeds N
2Gas, and be warming up to 80 ℃, adding 0.5% (wt.) dibutyltin dilaurate catalyst behind the 15min, vigorous stirring 2h generates the viscous liquid that flows, and is cast to then in the tetrafluoroethylene mould, places 85 ℃ of baking ovens until constant weight, carries out the ionic conduction property testing.
This system room-temperature ion conductivity is 1.0 * 10
-4Scm
-1, the intensity and the machining property of conductive film are good, are a kind of copolymer solid electrolytes with practical value.Embodiment three: PMS-APEO
550M/LiClO
4The network polymer solid electrolyte
1.0g PMS-APEO
550M[PEO-PPOH/APEO
550M=1: 7 (mol ratios)], 0.2g linking agent (TMP-TDI) and 0.24g (20%) LiClO
4(drying) joins and has prolong and N
2Mix in the 100ml there-necked flask of ingress pipe; Add THF, induction stirring makes it dissolving, feeds N
2Gas, and be warming up to 80 ℃, adding 0.5% (wt.) dibutyltin dilaurate catalyst behind the 15min, vigorous stirring 2h generates the viscous liquid that flows, and is cast to then in the tetrafluoroethylene mould, places 85 ℃ of baking ovens until constant weight, carries out the ionic conduction property testing.
Obtained conductive film is with respect to embodiment one, two,, its snappiness descends, and electric conductivity reduces (room temperature σ=2.4 * 10
-5Scm
-1), this mainly is because internal plasticization chain APEO
550There is crystalline polamer in M, has suppressed ion and must dissociate and transmit.Embodiment four: PMS-APEO
150SO
3Li/LiN (CF
3SO
2)
2The network polymer solid electrolyte
1.0g PMS-APEO
150SO
3Li[PEO-PPOH/APEO
350M=1: 7 (mol ratios)], 0.2g linking agent (TMP-TDI) and 0.50g (20%) LiN (CF
3SO
2)
2Dry) join and have prolong and N
2Mix in the 100ml there-necked flask of ingress pipe; Add THF, induction stirring makes it dissolving, feeds N
2Gas, and be warming up to 95 ℃, adding 0.5% (wt.) dibutyltin dilaurate catalyst behind the 25min, vigorous stirring 3h generates the viscous liquid that flows, and is cast to then in the tetrafluoroethylene mould, places 90 ℃ of baking ovens until constant weight, carries out the ionic conduction property testing.
This polymer electrolyte system good film-forming property, the physical strength height interacts owing to hang on to exist between organic ion on the network and the inorganic salt, has destroyed the inorganic salt crystalline network, impels dissociating of inorganic ion, and its room-temperature ion conductivity is up to 4.0 * 10
-4Scm
-1, its performance index have all satisfied requirement of actual application, are a kind of polymers of excellent properties solid electrolyte materials.
Claims (7)
1. copolymer solid electrolyte is characterized in that described copolymer solid electrolyte is made up of cross-linked network polymkeric substance and inorganic lithium salt that polymkeric substance performed polymer and linking agent generation crosslinking reaction generate, and the structural formula of described network polymer is:
Polymethyl siloxane (PMS), its molecular structure is as follows:
Or cluster ethylene glycol (PLEG), its molecular structure is as follows:
R in above-mentioned molecular structure
1Be the polyethylene oxide/polypropylene oxide segment; R
2Be the internal plasticization chain.1: 1 in molar ratio ∽ of R1: R2 1: 7; Described inorganic salt are LiClO
4Or LiN (CF
3SO
2)
2
2. a kind of copolymer solid electrolyte according to claim 1 is characterized in that described internal plasticization chain is allyl methyl polyoxyethylene or allyl group polyoxyethylene sulfonic acid lithium.
3. a kind of copolymer solid electrolyte according to claim 2 is characterized in that described internal plasticization chain is the allyl methyl polyoxyethylene, and wherein the molecular weight of polyoxyethylene is 350 or 550.
4. a kind of copolymer solid electrolyte according to claim 2 is characterized in that described internal plasticization chain is the yellow sulfonic acid lithium of allyl group polyoxyethylene, and wherein the molecular weight of polyoxyethylene is 150.
5. a kind of preparation of polymer solid electrolyte according to claim 1 is characterized in that step is carried out in the following order:
1. with mol ratio R
1: R
21: 7 polysiloxane of=1: 1 ∽ contains the linking agent of triisocyanate functional group, and 1: 0.2: 0.24 by weight ∽ 0.72 of dry inorganic lithium salt mixes, and add THF then and make it dissolving,
2. be warming up to 95 ℃ of 75 ∽, induction stirring adds 0.5% (wt.) dibutyl tin laurate, and vigorous stirring generates the viscous liquid that flows,
3. above-mentioned mobile viscous liquid is cured at 80 ℃, generates copolymer solid electrolyte with internal plasticization chain.
6. a kind of preparation of polymer solid electrolyte according to claim 5, described lithium salts are LiClO
4Or LiN (CF
3SO
2)
2
7. the purposes of a kind of copolymer solid electrolyte according to claim 1 is characterized in that being used to make the copolymer solid electrolyte film that lithium-ion secondary cell thickness is 0.1 ∽ 0.3mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991095685A CN1133685C (en) | 1999-07-09 | 1999-07-09 | Polymer solid electrolyte and its preparing method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991095685A CN1133685C (en) | 1999-07-09 | 1999-07-09 | Polymer solid electrolyte and its preparing method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1280149A true CN1280149A (en) | 2001-01-17 |
| CN1133685C CN1133685C (en) | 2004-01-07 |
Family
ID=5273984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991095685A Expired - Fee Related CN1133685C (en) | 1999-07-09 | 1999-07-09 | Polymer solid electrolyte and its preparing method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1133685C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319204C (en) * | 2002-04-15 | 2007-05-30 | 日立麦克赛尔株式会社 | Ion-conductive electrolyte and cell employing the same |
| CN100372873C (en) * | 2005-06-13 | 2008-03-05 | 中国科学院化学研究所 | Gel type polymer solid electrolyte, special polymer and preparation method thereof |
| CN106030721A (en) * | 2014-02-17 | 2016-10-12 | 富士胶片株式会社 | Solid electrolyte composition, battery electrode sheet and all-solid secondary battery using the same, and their manufacturing method |
| CN108878959A (en) * | 2018-06-14 | 2018-11-23 | 北京工业大学 | A kind of preparation and its application of organo-mineral complexing solid electrolyte |
| US10490848B2 (en) | 2013-10-18 | 2019-11-26 | Cornell University | Solid polymer electrolyte composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2046866B1 (en) * | 2006-08-02 | 2010-11-10 | Honeywell International Inc. | Siloxane polymers and uses thereof |
-
1999
- 1999-07-09 CN CNB991095685A patent/CN1133685C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319204C (en) * | 2002-04-15 | 2007-05-30 | 日立麦克赛尔株式会社 | Ion-conductive electrolyte and cell employing the same |
| CN100372873C (en) * | 2005-06-13 | 2008-03-05 | 中国科学院化学研究所 | Gel type polymer solid electrolyte, special polymer and preparation method thereof |
| US10490848B2 (en) | 2013-10-18 | 2019-11-26 | Cornell University | Solid polymer electrolyte composition |
| CN106030721A (en) * | 2014-02-17 | 2016-10-12 | 富士胶片株式会社 | Solid electrolyte composition, battery electrode sheet and all-solid secondary battery using the same, and their manufacturing method |
| US10535896B2 (en) | 2014-02-17 | 2020-01-14 | Fujifilm Corporation | Solid electrolyte composition containing nonspherical polymer particles, dispersion medium and inorganic solid electrolyte |
| CN108878959A (en) * | 2018-06-14 | 2018-11-23 | 北京工业大学 | A kind of preparation and its application of organo-mineral complexing solid electrolyte |
| CN108878959B (en) * | 2018-06-14 | 2020-09-25 | 北京工业大学 | Preparation and application of organic-inorganic composite solid electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1133685C (en) | 2004-01-07 |
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