CN105680093A - Gel polymer electrolyte with self-crosslinking characteristic for lithium ion battery - Google Patents
Gel polymer electrolyte with self-crosslinking characteristic for lithium ion battery Download PDFInfo
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- CN105680093A CN105680093A CN201610055337.1A CN201610055337A CN105680093A CN 105680093 A CN105680093 A CN 105680093A CN 201610055337 A CN201610055337 A CN 201610055337A CN 105680093 A CN105680093 A CN 105680093A
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 32
- 238000004132 cross linking Methods 0.000 title claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 17
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 2
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 32
- 229920000570 polyether Polymers 0.000 abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052744 lithium Inorganic materials 0.000 abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- 229920006037 cross link polymer Polymers 0.000 abstract 1
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 abstract 1
- -1 phosphate ester Chemical class 0.000 description 18
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 16
- 239000011245 gel electrolyte Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 229920002678 cellulose Polymers 0.000 description 11
- 239000001913 cellulose Substances 0.000 description 11
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000010382 chemical cross-linking Methods 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 229910013188 LiBOB Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- AEDFPTMUSGKDJC-UHFFFAOYSA-N C(C=1C(O)=CC=CC1)(=O)O.C(C=1C(O)=CC=CC1)(=O)O.[Li] Chemical compound C(C=1C(O)=CC=CC1)(=O)O.C(C=1C(O)=CC=CC1)(=O)O.[Li] AEDFPTMUSGKDJC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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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- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to novel polymer electrolyte for a lithium ion battery and a preparation method for the novel polymer electrolyte. A silicon-methoxy-terminated polyether low polymer is taken as a substrate polymer; a boric acid lithium salt can be used as a lithium source and also can catalyze the substrate polymer to realize in situ crosslinking so as to obtain the end group crosslinked polymer electrolyte. The polymer electrolyte has high strength and self-supporting property, high flexibility and relatively wide electrochemical steady window (4.7V); a relatively ideal ionic conductivity (10<-3>Scm<-1>) can be reached by matching with a certain amount of solvent; and in addition, the gel polymer electrolyte is applicable to a power lithium battery and a flexible lithium battery for wearable equipment.
Description
Technical field
The invention belongs to lithium ion battery polymer electrolyte field, relate to a kind of polymer dielectric with self-crosslinking characteristic and preparation method thereof.
Background technology
Polymer dielectric substitutes traditional liquid electrolyte, lithium secondary battery development is had to the meaning of the property changed, because its safety is high, profile is plastic, is one of the perfect electrolyte of wearable electronic flexible battery.
Polymer dielectric includes full solid state polymer electrolyte and gel polymer electrolyte. But with polyethylene oxide polymer electrolyte be representative all solid state electrolyte because the too low ionic conductivity of room temperature and narrower electrochemical stability window, so far cannot extensive use. Conventional physical cross-linking type gel polymer electrolyte is usually and is formed by after linear polymer Electolyte-absorptive, although there is higher ionic conductivity but mechanical strength and dimensional stability (especially high temperature dimensional stability) being too poor, the needs of flexible battery still cannot be met. The chemical crosslinking of appropriateness is one of best approach solving conventional gel polymer dielectric mechanical strength and ionic conductivity contradiction. Chemical crosslinking is usually in raw material and electrolyte and adds initiator or the cross-linking agent effect polymerized in-situ by heating or photoirradiation, prepare and have chemical crosslinking structural polymer gel electrolyte, thus improve mechanical strength and thermo mechanical stability.
Patent CN102064342A provides urethane acrylate system monomer and by light trigger under the action of uv light, is forming gel-form solid polymer electrolyte film, and obtaining good chemical property. Patent CN103772607A provides and discloses a kind of phosphorous cross-linked gel polymer dielectric and on-the-spot thermal polymerization preparation method, application, in case of heating the phosphate ester monomer containing double bond and electrolyte are solidified by cross-linking agent and initiator, form gel electrolyte. The common ground of the typical chemical crosslinking mode of both is to add the additive such as cross-linking agent or initiator in polymerization at the scene, and this results in and inevitably introduces impurity in gel electrolyte, and the stability of gel electrolyte is adversely affected. Although also having been reported that and utilizing the direct irradiation polymerization thing monomer polymerization of gamma-rays, without any initiator, but people's cognition is damaged by gamma-ray high radioactivity, and the requirement of equipment is very high, really implements extremely difficult.
Based on above technical background, the present invention, from polymer molecular structure, selects the polyether oligomers of silicon methoxy group as matrix polymer, and silicon methoxyl group is by this oligomer reactivity of imparting, the lithium ion part that polyether backbone is well recognized as.By adding lithium borate salt electrolyte so as to curing cross-linked. It can be seen that only include polymeric matrix and lithium salts in this system, without any initiator or cross-linking agent, the cross-linking reaction of system occurs completely voluntarily, and what thus thoroughly avoid the additive such as initiator or cross-linking agent is likely to residual or other side reactions caused.
The innovation and practicality of the present invention is in that:
1, silicon methoxyl group polyether oligomers is selected, appropriate design, utilize the catalytic action of system mesoboric acid lithium salts itself, original position self-crosslinking prepares gel polymer electrolyte, this electrolyte is while maintaining excellent electrochemical performance, fundamentally avoid impurity there is a possibility that, make gel electrolyte more stable.
2, the method that the present invention relates to all carries out under normal pressure non high temperature, and step is simple, it is simple to preparation in macroscopic quantity.
Summary of the invention
It is an object of the invention to provide a kind of gel polymer electrolyte with self-crosslinking characteristic, this electrolyte has the advantage that intensity is good, electrical conductivity is high.
For achieving the above object, the technical solution used in the present invention is:
A kind of lithium ion battery gel polymer electrolyte with self-crosslinking characteristic, initiation material is the mixture of the oligo-ether of the silicon methoxy group of viscous state and lithium borate salt electrolyte, it is 21-32.4% that the oligo-ether of the silicon methoxy group of wherein said viscous state accounts for the mass fraction of mixture, and it is 67.6-79% that lithium borate salt electrolyte accounts for the mass fraction of mixture; Being further characterized in that: it is 25-42.6% that the oligo-ether of silicon methoxy group accounts for the mass fraction of the gel polymer electrolyte of curing cross-linked, it is 58.4%-75% that lithium borate salt electrolyte accounts for the mass fraction of the gel polymer electrolyte of curing cross-linked.
The oligo-ether viscosity of described silicon methoxy group is at 5000-8000 centipoise, and structure is as follows:
Wherein: X1 is O-CaH2a+1, X2 is H, CbH2b+1, O-CbH2b+1And O-CbHbFb+1In one, X3 is CcH2c+1, a, b, c takes the integer of 1-5; P takes the integer of 0-5, and q is 0 or 1, and is 0 during p and q difference.
Described lithium borate salt structure is the one in following structure:
,,,,,,,
N is the integer of 1-10, and wherein X is the one of following group:
,,,,,,,,,
Solvent is one or more in Allyl carbonate, ethylene carbonate, butylene, sulfurous acid diethyl ester, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate; The concentration of lithium borate salt electrolyte is 0.1-2molL-1。
A kind of method for preparing gel polymer electrolyte for lithium ion battery with self-crosslinking characteristic, it is characterised in that comprise the following steps: lithium borate salt and solvent are configured to lithium borate salt electrolyte, and stir; The oligo-ether of the silicon methoxy group taking the viscous state of respective quality mark is mixed and stirred for uniformly with lithium borate salt electrolyte, point two ways film forming:
1) the gel polymer electrolyte mixed liquor stirred is directly injected in the mould with perforated membrane, heats 5-20 hour at 40-60oC, gel polymer electrolyte mixed liquor crosslinking curing film forming voluntarily;
2) being first 5000 centipoises by stirring under gel polymer electrolyte mixed liquor 30-40oC to viscosity, then blade coating is to pole piece, continues to keep 30-40oC to heat 5-20 hour, namely obtains self-crosslinking cured film.
Accompanying drawing explanation
Fig. 1 is with LiFePO4 for positive electrode in embodiment 1, the cycle performance of polymer dielectric half-cell.
Fig. 2 is with LiFePO4 for positive electrode in embodiment 1, the high rate performance of polymer dielectric half-cell.
Fig. 3 is with lithium ferric manganese phosphate for positive electrode in embodiment 4, the cycle performance of polymer dielectric half-cell.
Fig. 4 is with lithium ferric manganese phosphate for positive electrode in embodiment 4, the high rate performance of polymer dielectric half-cell.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in further detail, below in conjunction with embodiment, the present invention is further described, but do not limit the scope of the invention.
Embodiment 1
1.32g di-oxalate lithium borate salt (LiBOB) is dissolved in 5ml propene carbonate (PC) so that it is be completely dissolved. At room temperature, the poly(propylene oxide) adding 2g silicon methoxy group in the electrolyte of di-oxalate lithium borate salt and propene carbonate stirs (indicating viscosity number average molecular weight), then on polyfluortetraethylene plate, with cellulose membrane for support frame, two sides by the polymer dielectric blade coating that stirs to cellulose membrane, then, after heating 20h in the baking oven of 45 DEG C, polymer dielectric is film-forming voluntarily. After film-forming, crosslinked polyethers accounts for the mass fraction of gel electrolyte is except 25%(cellulose membrane).
Embodiment 2
0.88g bis-(salicylic acid) Lithium biborate (LBSB) is dissolved in 5ml propene carbonate (PC) and ethylene carbonate (EC) (v:v=1:1) so that it is be completely dissolved. At room temperature, the poly(ethylene oxide) adding 2g silicon methoxy group in the electrolyte of di-oxalate lithium borate salt and propene carbonate stirs, then on polyfluortetraethylene plate, with cellulose membrane for support frame, two sides by the polymer dielectric blade coating that stirs to cellulose membrane, then, after heating 18h in the baking oven of 45 DEG C, polymer dielectric is film-forming voluntarily. After film-forming, crosslinked polyethers accounts for the mass fraction of gel electrolyte is except 27%(cellulose membrane).
Embodiment 3
The dimalonic acid Lithium biborate (LiBMB) of 1.12g is dissolved in 5ml propene carbonate (PC) and ethylene carbonate (EC) (v:v=1:1) so that it is be completely dissolved. At room temperature, the poly(ethylene oxide) adding 3g silicon methoxy group in the electrolyte of di-oxalate lithium borate salt and propene carbonate stirs, then on polyfluortetraethylene plate, with polyimide porous membrane for support frame, two sides by the polymer dielectric blade coating that stirs to polyimide film, then, after heating 10h in the baking oven of 45 DEG C, polymer dielectric is film-forming voluntarily. After film-forming, crosslinked polyethers accounts for the mass fraction of gel electrolyte is except 38%(polyimide film).
Embodiment 4
0.82g di-oxalate lithium borate salt (LiBOB) is dissolved in 5ml propene carbonate (EC) and dimethyl carbonate (DMC) (v:v=1:1) so that it is be completely dissolved. At room temperature, the poly(propylene oxide) adding 2g silicon methoxy group in the electrolyte of di-oxalate lithium borate salt and propene carbonate stirs, then by polymer dielectric 40 DEG C heating to viscosity be 5000 centipoises, then blade coating is to pole piece, continue to keep 40 DEG C of heating 12h, polymer dielectric self-crosslinking film forming. After film-forming, crosslinked polyethers accounts for the mass fraction of gel electrolyte is 29%.
Embodiment 5
1g fluoro di-oxalate lithium borate (LiBODF) is dissolved in 5ml propene carbonate (PC) so that it is be completely dissolved. At room temperature, the poly(ethylene oxide) adding 3.2g silicon methoxy group in the electrolyte of di-oxalate lithium borate salt and propene carbonate stirs, then by polymer dielectric 40 DEG C heating to viscosity be 5000 centipoises, then blade coating is to pole piece, continue to keep 40 DEG C of heating 18h, polymer dielectric self-crosslinking film forming.After film-forming, crosslinked polyethers accounts for the mass fraction of gel electrolyte is 42.6%.
Embodiment 6
(5th) of 0.26g number lithium salts is dissolved in 5ml propene carbonate (PC) so that it is be completely dissolved. At room temperature, the poly(propylene oxide) adding 2g silicon methoxy group in the electrolyte of di-oxalate lithium borate salt and propene carbonate stirs, then on polytetrafluoro plate, with cellulose membrane for matrix, two sides by the polymer dielectric blade coating that stirs to PET perforated membrane, then, after heating 8h in the baking oven of 35 DEG C, polymer dielectric is film-forming voluntarily. After film-forming, crosslinked polyethers accounts for the mass fraction of gel electrolyte is except 38%(PET film).
Embodiment 7
(7th) of 0.36g number lithium salts is dissolved in 5ml propene carbonate (PC) so that it is be completely dissolved. At room temperature, the poly(ethylene oxide) adding 2.9g silicon methoxy group in the electrolyte of di-oxalate lithium borate salt and propene carbonate stirs, then on polytetrafluoro plate, with cellulose membrane for matrix, two sides by the polymer dielectric blade coating that stirs to glass fiber membrane (copy paper method), then, after heating 20h in the baking oven of 40 DEG C, polymer dielectric is film-forming voluntarily. After film-forming, crosslinked polyethers accounts for the mass fraction of gel electrolyte is except 27%(glass fibre membrane).
Embodiment 8
The di-oxalate lithium borate salt (LiBOB) of 1.32g is dissolved in 5ml propene carbonate (PC) and ethylene carbonate (EC) (v:v=1:1) so that it is be completely dissolved. At room temperature, the poly(ethylene oxide) adding 2g silicon methoxy group in the electrolyte of di-oxalate lithium borate salt and propene carbonate stirs, then on polyfluortetraethylene plate, with cellulose membrane for matrix, two sides by the polymer dielectric blade coating that stirs to cellulose membrane, then, after heating 15h in the baking oven of 40 DEG C, polymer dielectric is film-forming voluntarily. After film-forming, crosslinked polyethers accounts for the mass fraction of gel electrolyte is except 28%(cellulose membrane).
The performance of gel polymer electrolyte in each embodiment of table 1.
Claims (4)
1. a lithium ion battery gel polymer electrolyte with self-crosslinking characteristic, it is characterized in that: initiation material is the mixture of the oligo-ether of the silicon methoxy group of viscous state and lithium borate salt electrolyte, it is 21-32.4% that the oligo-ether of the silicon methoxy group of wherein said viscous state accounts for the mass fraction of mixture, and it is 67.6-79% that lithium borate salt electrolyte accounts for the mass fraction of mixture; Being further characterized in that: it is 25-42.6% that the oligo-ether of silicon methoxy group accounts for the mass fraction of the gel polymer electrolyte of curing cross-linked, it is 58.4%-75% that lithium borate salt electrolyte accounts for the mass fraction of the gel polymer electrolyte of curing cross-linked.
2. a kind of lithium ion battery gel polymer electrolyte with self-crosslinking characteristic as claimed in claim 1, it is characterised in that the oligo-ether viscosity of silicon methoxy group is at 5000-8000 centipoise, and structure is as follows:
Wherein: X1 is O-CaH2a+1, X2 is H, CbH2b+1, O-CbH2b+1And O-CbHbFb+1In one, X3 is CcH2c+1, a, b, c takes the integer of 1-5; P takes the integer of 0-5, and q is 0 or 1, and is 0 during p and q difference.
3. a kind of lithium ion battery gel polymer electrolyte with self-crosslinking characteristic as claimed in claim 1, it is characterised in that lithium borate salt structure is the one in following structure:
,,,,,,,
N is the integer of 1-10, and wherein X is the one of following group:
,,,,,,,,,
Solvent is one or more in Allyl carbonate, ethylene carbonate, butylene, sulfurous acid diethyl ester, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate;The concentration of lithium borate salt electrolyte is 0.1-2molL-1。
4. a method for preparing gel polymer electrolyte for lithium ion battery as claimed in claim 1 with self-crosslinking characteristic, it is characterised in that comprise the following steps: lithium borate salt and solvent are configured to lithium borate salt electrolyte, and stir; The oligo-ether of the silicon methoxy group taking the viscous state of respective quality mark is mixed and stirred for uniformly with lithium borate salt electrolyte, point two ways film forming:
1) the gel polymer electrolyte mixed liquor stirred is directly injected in the mould with perforated membrane, heats 5-20 hour at 40-60oC, gel polymer electrolyte mixed liquor crosslinking curing film forming voluntarily;
2) being first 5000 centipoises by stirring under gel polymer electrolyte mixed liquor 30-40oC to viscosity, then blade coating is to pole piece, continues to keep 30-40oC to heat 5-20 hour, namely obtains self-crosslinking cured film.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106785032A (en) * | 2017-03-17 | 2017-05-31 | 北京工业大学 | A kind of lithium ion battery polymer dielectric and preparation method |
| CN108736062A (en) * | 2018-04-28 | 2018-11-02 | 浙江天能能源科技股份有限公司 | A kind of lithium ion battery composite solid electrolyte and preparation method thereof |
| CN108878964A (en) * | 2018-06-04 | 2018-11-23 | 南京工业大学 | A kind of composite gel polymer electrolyte, preparation method and its purposes in lithium-air battery |
| CN109873208A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of gel polymer electrolyte secondary cell and its preparation |
| CN113410516A (en) * | 2021-08-02 | 2021-09-17 | 清远萨菲安新材料有限公司 | Organic silicon electrolyte and preparation method and application thereof |
| CN113437359A (en) * | 2021-05-18 | 2021-09-24 | 长沙矿冶研究院有限责任公司 | Preparation method of polypropylene oxide polymer solid electrolyte film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112687948A (en) * | 2020-12-22 | 2021-04-20 | 双登集团股份有限公司 | Solid-state battery with improved interface performance and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0420253A2 (en) * | 1989-09-28 | 1991-04-03 | Dow Corning Toray Silicone Company, Limited | Ionically conductive material |
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| CN106785032A (en) * | 2017-03-17 | 2017-05-31 | 北京工业大学 | A kind of lithium ion battery polymer dielectric and preparation method |
| CN106785032B (en) * | 2017-03-17 | 2019-08-09 | 北京工业大学 | A kind of lithium ion battery polymer dielectric and preparation method |
| CN109873208A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of gel polymer electrolyte secondary cell and its preparation |
| CN109873208B (en) * | 2017-12-01 | 2021-10-29 | 中国科学院大连化学物理研究所 | Gel polymer electrolyte secondary battery and preparation thereof |
| CN108736062A (en) * | 2018-04-28 | 2018-11-02 | 浙江天能能源科技股份有限公司 | A kind of lithium ion battery composite solid electrolyte and preparation method thereof |
| CN108878964A (en) * | 2018-06-04 | 2018-11-23 | 南京工业大学 | A kind of composite gel polymer electrolyte, preparation method and its purposes in lithium-air battery |
| CN113437359A (en) * | 2021-05-18 | 2021-09-24 | 长沙矿冶研究院有限责任公司 | Preparation method of polypropylene oxide polymer solid electrolyte film |
| CN113410516A (en) * | 2021-08-02 | 2021-09-17 | 清远萨菲安新材料有限公司 | Organic silicon electrolyte and preparation method and application thereof |
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| CN105680093B (en) | 2018-06-19 |
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