CN1133686C - Gel polymer solid electrolyte and preparation process and use thereof - Google Patents
Gel polymer solid electrolyte and preparation process and use thereof Download PDFInfo
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- CN1133686C CN1133686C CNB991115902A CN99111590A CN1133686C CN 1133686 C CN1133686 C CN 1133686C CN B991115902 A CNB991115902 A CN B991115902A CN 99111590 A CN99111590 A CN 99111590A CN 1133686 C CN1133686 C CN 1133686C
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- solid electrolyte
- polymer solid
- gel polymer
- chain
- softening agent
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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
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Abstract
The present invention relates to a gel polymer solid electrolyte which is composed of three-dimensional network polymer with internal plasticization chains, inorganic lithium salt and polar small molecule plasticizer. The three-dimensional network polymer, cross-linking agents, the inorganic lithium salt and the polar small molecule plasticizer are mixed by the weight portion of 1:0.2:0.24 to 0.72:0.5 to 2.0; the mixture is stirred at 75 to 95 DEG C under the action of a catalyst namely dibutyltin dilaurate after being dissolved by anhydrous THF, and then, the polymer solid electrolyte is prepared. The gel polymer solid electrolyte of the present invention is capable of forming films once, have high room temperature ion conductance, and is used as electrolyte materials in secondary lithium ion batteries.
Description
The present invention relates to a kind of copolymer solid electrolyte, particularly a kind of gel polymer solid electrolyte and its production and use.
In environmental protection and energy problem increasingly serious today, the research and development of copolymer solid electrolyte has great economic benefit and social benefit.J.Electrochem.Soc.1998, V.145,5,1521 have reported a kind of copolymer solid electrolyte, the polyalkylene glycol moiety that will have three hydroxyls methylates, and then remaining hydroxyl is changed into acrylate group, forms the cross-linked network copolymer solid electrolyte through light initiation polymerization.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 lower by (10
-6Scm
-1); Patent WO 9621953 has reported a kind of gel polymer solid electrolyte, its polymeric matrix is the polysiloxane with side chain, and side chain is that end has single ionic fluoro polyoxygenated alkane alkene, and softening agent comprises linear carbonic ether, glycol dimethyl ether, and/or ring-type ethers.But this system poor dimensional stability, softening agent escapes easily, causes freeze thaw stability to reduce, and also can cause electrode and electrolyte interface instability simultaneously.
It is lower to the objective of the invention is to overcome in the above-mentioned prior art electrolyte system ionic conductance, poor dimensional stability, softening agent escapes, the unsettled defective of electrode and electrolyte interface, and a kind of gel polymer solid electrolyte has been proposed, the preparation method who adopts an one-step film forming is provided simultaneously.
The present invention has prepared a kind of gel polymer solid electrolyte system, and it is formed, made through the single step reaction film forming by " the three-dimensional network polymer/inorganic lithium salts/polarity small molecules softening agent with internal plasticization chain " three components.The three-dimensional network polymkeric substance serves as the effect of support frame on the one hand, guarantees that electrolyte has good three-dimensional dimension stability and processing characteristics; Simple plasticizer in the network has reduced the second-order transition temperature of whole electrolyte system, simultaneously except and three-dimensional network between exist interact, softening agent also and exist intensive to interact between the internal plasticization chain that hangs on the network, therefore alleviate escaping of simple plasticizer, improved the stability of gelling system greatly.The room-temperature ion conductivity of gel polymer solid electrolyte of the present invention is up to 10
-3Scm
-1
Gel polymer solid electrolyte of the present invention is made up of the three-dimensional network polymkeric substance with internal plasticization chain, inorganic lithium salt and polarity small molecules softening agent three components.
Wherein said three-dimensional network polymkeric substance with internal plasticization chain is the network polymer that is generated by network polymer performed polymer and linking agent generation crosslinking reaction.Have internal plasticization segment and the terminal polyethylene oxide/polypropylene oxide segment (PEO-PPOH) that is hung with hydroxyl on the skeleton of above-mentioned network polymer performed polymer, two kinds of segmental mol ratios of internal plasticization chain and PEO-PPOH are 1: 1 to 1: 7.This network polymer performed polymer is polymethyl siloxane (PMS), and its chemical structural formula is as follows:
M+n=100, m=10 or 20 or cluster ethylene glycol (PLEG), its chemical structural formula is as follows:
N=4 to 13
In above-mentioned chemical structural formula, R
1Represent the polyethylene oxide/polypropylene oxide segment; R
2Represent the internal plasticization chain.
The above-mentioned internal plasticization chain R that hangs on the network polymer performed polymer
2Comprise: 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).
Above-mentioned linking agent (TMP-TDI) is a kind of material with three isocyanate functional groups, and it is that its structural formula is as follows by TriMethylolPropane(TMP) and 2,4 toluene diisocyanate prepared in reaction:
Described inorganic lithium salt ionogen comprises LiClO
4, LiPF
6, LiCF
3SO
3, LiN (CF
3SO
2)
2
Described polarity small molecules softening agent comprises: vinyl carbonate (EC), divinyl carbonic ether (DEC), propylene carbonate (PC), butyrolactone (γ-BL), N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), glycol dimethyl ether (DME) etc. and their mixture.
" the three-dimensional network polymer/inorganic carp salt/polarity small molecules softening agent with internal plasticization chain " of the present invention gel polymer solid electrolyte adopts the single stage method film forming, and its preparation follows these steps to carry out:
1. there is not water treatment:
(1) solvent for use THF refluxes through sodium Metal 99.5 and is blue until the indication of benzophenone indicator;
(2) used inorganic lithium salt [LiClO
4, LiPF
6, LiCF
3SO
3, LiN (CF
3SO
2)
2] all under vacuum 140 ℃ handled 12 hours;
(3) used polarity small molecules softening agent is purified through underpressure distillation in advance, uses 1 week of 4A molecular sieve drying then;
(4) used network polymer performed polymer is through the high-temperature vacuum drying treatment.
2. the preparation of gel polymer solid electrolyte film:
1. take by weighing above-mentioned exsiccant network polymer performed polymer PMS (mol ratio PEO-PPOH: APEO
350M=1: 1 ∽ 1: 7) 1 part, 0.2 part of linking agent (TMP-TDI), inorganic lithium salt 0.24-0.72 part, polarity small molecules softening agent 0.6-2.4 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 place after 12 hours, obtain specimen.
The polymer dielectric of the present invention's preparation has been obtained following invention effect: 1. single stage method preparation, and easy to operation; 2. conductive film has the macroion conductivity; 3. good stability.The gel polymer solid electrolyte room-temperature ion conductivity data of the present invention's preparation see Table 1.The present invention can be applied in the electronic devices and components especially field of lithium ion secondary.
Table 1. gel polymer solid electrolyte room-temperature ion conductivity (Scm
-1)
| Embodiment 1 | Softening agent and content (wt%) | PC％＝50 | PC％＝100 | PC％＝150 | ?PC％＝200 |
| Room-temperature ion conductivity (Scm -1) | 3.36×10 -5 | 2.45×10 -4 | 7.70×10 -4 | ?1.01×10 -3 | |
| Embodiment 2 | Softening agent and content (wt%) | PC％＝50 | PC％＝100 | PC％＝150 | ?PC％＝200 |
| Room-temperature ion conductivity (Scm -1) | 8.60×10 -5 | 7.54×10 -4 | 2.10×10 -3 | ?3.36×10 -3 | |
| Embodiment 3 | Softening agent and content (wt%) | EC％＝50 | EC％＝100 | EC％＝150 | ?EC％＝200 |
| Room-temperature ion conductivity (Scm -1) | 5.57×10 -5 | 4.40×10 -4 | 9.80×10 -4 | ?2.36×10 -3 | |
| Embodiment 4 | Softening agent and content (wt%) | γ-BL％＝50 | γ-BL％＝100 | γ-BL％＝150 | ?γ-BL％＝200 |
| Room-temperature ion conductivity (Scm -1) | 1.70×10 -5 | 8.80×10 -5 | 3.30×10 -4 | ?7.40×10 -4 | |
| Embodiment 5 | Softening agent and content (wt%) | EC/PC％＝50 | EC/PC％＝100 | EC/PC％＝150 | ?EC/PC％＝200 |
| Room-temperature ion conductivity (Scm -1) | 9.42×10 -5 | 8.36×10 -4 | 1.20×10 -3 | ?3.31×10 -3 |
Embodiment 1:PMS-APEO
350M/LiClO
4/ PC gel polymer solid electrolyte
1.0g PMS-APEO
350M[PEO-PPOH/APEO
350M=1: 5 (mol ratios)], O.20gTMP-TDI and 0.24gLiCO
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, adds 0.6g (50%), or 1.2g (100%), or 1.8g (150%), or 2.4g (200%) PC, 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 the 80C vacuum drying oven placed 12 hours, obtain specimen.
When PC content was 200%, the room-temperature ion conductivity of this gelling system reached 1.01 * 10
-3Scm
-1Embodiment 2:PMS-APEO
350M/LiN (CF
3SO
2)
2/ PC gel polymer solid electrolyte
1.0g PMS-APEO
350M[PEO-PPOH/APEO
350M=1: 5 (mol ratios)], 0.20g 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, adds 0.6g (50%) then, or 1.2g (100%), or 1.8g (150%), or 2.4g (200%) PC, 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 to place 12 hours, carries out the ionic conductance test.
The maximum room-temperature ion conductivity of this system is 3.36 * 10
-3Scm
-1,, mainly be because the anion N (CF in the lithium salts than embodiment 1 height
3SO
2)
2 -Have due to the plasticization effect.Embodiment 3:PMS-APEO
550M/LiClO
4/ EC gel polymer solid electrolyte
1.0g PMS-APEO
550M[PEO-PPOH/APEO
550M=1: 5 (mol ratios)], 0.20g 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, adds 0.6g (50%) then, or 1.2g (100%), or 1.8g (150%), or 2.4g (200%) EC, feeds N
2Gas, and be warming up to 85 ℃, 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 80 ℃ of baking ovens to place 12 hours, carries out the ionic conductance test.The room-temperature ion conductivity of this system is high slightly than embodiment 1.Embodiment 4:PMS-APEO
550M/LiClO
4/ γ-BL gel lattice polymer solid electrolyte
1.0g PMS-APEO
550M[PEO-PPOH/APEO
550M=1: 5 (mol ratios)], 0.20g 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, adds 0.6g (50%) then, or 1.2g (100%), or 1.8g (150%), or 2.4g (200%) γ-BL, feeds N
2Gas, and be warming up to 80 ℃, add 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, place 85 ℃ of baking ovens to place 12 hours, carry out the ionic conductance test.
By the listed ionic conductance data of table 1 as can be known, γ-BL is the poorest small molecules softening agent of the plasticization effect of selected use.Embodiment 5:PMS-APEO
550M/LiClO
4/ EC/PC (3: 1v/v) gel polymer solid electrolyte
1.0g PMS-APEO
550M[PEO-PPOH/APEO
550M=1: 5 (mol ratios)], 0.20g 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, adds 0.6g (50%) then, or 1.2g (100%), or 1.8g (150%), or 2.4g (200%) EC/PC (3: 1v/v), feed N
2Gas, and be warming up to 80 ℃, add 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, place 85 ℃ of baking ovens to place 12 hours, carry out the ionic conductance test.
The room-temperature ion conductivity height of this gel electrolyte, film-forming properties and good stability have the favorable mechanical performance simultaneously.
In embodiment 1-5, when the micromolecular content of polarity increased to 100% gradually by 50%, the room-temperature ion conductivity is significantly increased trend, and increased at 200% o'clock by 100%, and the room-temperature ion conductivity increases slowly.Result of study shows, as plastic binder EC/PC (3: 1 v/v) when content is 200%, the room-temperature ion conductivity of embodiment 5 gelling systems reaches 3.31 * 10
3Scm
-1, reach actual application level, and the support membrane intensity and the good stability that obtain, be a kind of polymer dielectric with actual application prospect.
Claims (7)
1. gel polymer solid electrolyte, it is characterized in that described gel polymer solid electrolyte is by the three-dimensional network polymkeric substance with internal plasticization chain, inorganic lithium salt and polarity small molecules softening agent are formed, the three-dimensional network polymkeric substance that wherein has the internal plasticization chain is to be made by network polymer performed polymer and the reaction of linking agent trifunctional isocyanates, the structural formula of described network polymer performed polymer is polymethyl siloxane PMS, and its molecular structural formula is as follows:
M+n=100, m=10 or 20 in above-mentioned molecular structural formula, R
1Be the polyethylene oxide/polypropylene oxide segment; R
2Be internal plasticization chain allyl group methyl polyoxyethylene; R
1With R
21: 1 in molar ratio to 1: 7; Described inorganic lithium salt is LiClO
4, LiPF
6Or LiN (CF
3SO
2)
2Described polarity small molecules softening agent is an annular lactone.
2. a kind of gel polymer 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 gel polymer solid electrolyte according to claim 1 is characterized in that described annular lactone polarity small molecules softening agent is vinyl carbonate EC, propylene carbonate PC or gamma-butyrolactone.
4. a kind of gel polymer solid electrolyte according to claim 2, the molecular weight that it is characterized in that described allyl methyl polyoxyethylene is 350 or 550.
5. according to the preparation method of the gel polymer solid electrolyte of claim 1, it is characterized in that step is carried out in the following order: 1. with mol ratio polyethylene oxide/polypropylene oxide chain R
1: internal plasticization chain allyl group methyl polyoxyethylene R
2=1: 1 to 1: 7 exsiccant polysiloxane, the linking agent that contains triisocyanate functional group, dry inorganic lithium salt and polarity small molecules softening agent 1: 0.2: 0.24 by weight to 0.72: 0.5 mix to 2.0, add anhydrous THF then and make it dissolving, 2. be warming up to 75 to 95 ℃, induction stirring, add the 0.5wt.% dibutyl tin laurate, vigorous stirring generates the viscous liquid that flows, 3. above-mentioned mobile viscous liquid is cured at 80 ℃, generates gel polymer solid electrolyte with interior external plasticizer.
6. according to the preparation method of the gel polymer solid electrolyte of claim 5, described lithium salts is LiClO
4, LiPF
6Or LiN (CF
3SO
2)
2
7. according to the purposes of the gel polymer solid electrolyte of claim 1, it is characterized in that being used to make the copolymer solid electrolyte film that lithium-ion secondary cell thickness is 100 to 300 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991115902A CN1133686C (en) | 1999-08-20 | 1999-08-20 | Gel polymer solid electrolyte and preparation process and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991115902A CN1133686C (en) | 1999-08-20 | 1999-08-20 | Gel polymer solid electrolyte and preparation process and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1285375A CN1285375A (en) | 2001-02-28 |
| CN1133686C true CN1133686C (en) | 2004-01-07 |
Family
ID=5275177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991115902A Expired - Fee Related CN1133686C (en) | 1999-08-20 | 1999-08-20 | Gel polymer solid electrolyte and preparation process and use thereof |
Country Status (1)
| Country | Link |
|---|---|
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372873C (en) * | 2005-06-13 | 2008-03-05 | 中国科学院化学研究所 | Gelatin type polymer solid electrolyte and its dedicated polymer and preparation method |
| JP2008308683A (en) * | 2007-05-17 | 2008-12-25 | Sumitomo Chemical Co Ltd | Crosslinked aromatic polymer, polymer electrolyte, catalyst ink, polymer electrolyte membrane, membrane-electrode assembly and fuel cell |
| CN106410270B (en) * | 2016-11-04 | 2018-12-21 | 中山大学 | It is a kind of using carbon dioxide-base polycarbonate as lithium single-ion conductor solid polymer electrolyte of main chain and preparation method thereof |
| CN106611874A (en) * | 2016-11-29 | 2017-05-03 | 德阳九鼎智远知识产权运营有限公司 | Gel polymer lithium-ion electrolyte and battery containing same |
| CN112436185A (en) * | 2020-10-30 | 2021-03-02 | 武汉瑞科美新能源有限责任公司 | Gel polymer electrolyte, preparation method and application thereof, and lithium ion battery containing gel polymer electrolyte |
-
1999
- 1999-08-20 CN CNB991115902A patent/CN1133686C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1285375A (en) | 2001-02-28 |
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