CN106432608A - Boron-containing gel polymer electrolyte and preparation method and application thereof - Google Patents
Boron-containing gel polymer electrolyte and preparation method and application thereof Download PDFInfo
- Publication number
- CN106432608A CN106432608A CN201610832793.2A CN201610832793A CN106432608A CN 106432608 A CN106432608 A CN 106432608A CN 201610832793 A CN201610832793 A CN 201610832793A CN 106432608 A CN106432608 A CN 106432608A
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- Prior art keywords
- polymer electrolyte
- boracic
- gel polymer
- boron
- compound
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 title abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 25
- -1 alkene compound Chemical class 0.000 claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 230000032050 esterification Effects 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 12
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 244000028419 Styrax benzoin Species 0.000 claims description 6
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 6
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 6
- 229960002130 benzoin Drugs 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 235000019382 gum benzoic Nutrition 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 150000002835 noble gases Chemical class 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- UFXXGUUBTPZQIL-UHFFFAOYSA-N OBO.FC(F)(F)C1=CC=CC=C1 Chemical compound OBO.FC(F)(F)C1=CC=CC=C1 UFXXGUUBTPZQIL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 229960002645 boric acid Drugs 0.000 claims description 2
- 235000010338 boric acid Nutrition 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 claims 1
- SMUBDXBCXZNRAU-UHFFFAOYSA-N C1(=CC=CC=C1)OB(O)O.[F] Chemical compound C1(=CC=CC=C1)OB(O)O.[F] SMUBDXBCXZNRAU-UHFFFAOYSA-N 0.000 claims 1
- IAMOBKCZIPGZDM-UHFFFAOYSA-N [2-(trifluoromethoxy)phenoxy]boronic acid Chemical compound OB(O)OC1=CC=CC=C1OC(F)(F)F IAMOBKCZIPGZDM-UHFFFAOYSA-N 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 4
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 3
- 159000000002 lithium salts Chemical class 0.000 abstract description 3
- 239000011244 liquid electrolyte Substances 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 2
- 125000005619 boric acid group Chemical group 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 150000002009 diols Chemical group 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 21
- 210000004027 cell Anatomy 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 1
- YIADFIBQAFEBDO-UHFFFAOYSA-N 4,5-dihydroxy-2-methylidenepentanoic acid Chemical compound OCC(O)CC(=C)C(O)=O YIADFIBQAFEBDO-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- 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
- 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
Abstract
The invention belongs to the technical field of polymer electrolytes, and particularly relates to a boron-containing gel polymer electrolyte and a preparation method and application thereof. The gel polymer electrolyte is prepared from lithium salt, an organic solvent, a photoinitiator, boron-containing heterocyclic photosensitive monomers and acrylate monomers in a copolymerization mode. The preparation method of the gel polymer electrolyte includes the steps that a compound containing boric acid groups and an alkene compound with a diol structure are esterified to obtain boron-containing heterocyclic alkene monomers, and the boron-containing heterocyclic alkene monomers, the acrylate monomers, the photoinitiator, the lithium salt and the organic solvent are uniformly dispersed; a mould containing the mixed solution is irradiated by an LED lamp for surface photo-initiated polymerization, and the boron-containing gel polymer electrolyte is obtained. The boron-containing gel polymer electrolyte has high ionic conductivity and a high cationic transference number, effectively solves the problems of liquid leakage, corrosion, poor mechanical performance and the like of a liquid electrolyte in traditional lithium-ion batteries and can be applied to preparation of supercapacitors, lithium-ion batteries, hybrid supercapacitors and the like.
Description
Technical field
The invention belongs to polymer dielectric technical field is and in particular to a kind of boracic gel polymer electrolyte and its system
Preparation Method and application.
Background technology
Traditional energy storage device as in lithium ion battery liquid electrolyte due to exist leakage, inflammable and explosive the shortcomings of be difficult to full
The routine use of sufficient people.With scientific and technological continuous progress, lightweight, the new forms of energy equipment of miniaturization more and more enter big
Many visuals field, in notebook computer, mobile phone, charger baby, electric motor car, the application in the field such as unmanned plane is more and more general for polymer battery
And.Electrolyte is energy storage device as one of important component part in ultracapacitor, lithium ion battery, and its Main Function is to carry
Passage for the ion that can transmit or as ion transmission.Traditional electrolyte is mainly organic electrolyte system, in liquid
Under concrete conditions in the establishment of a specific crime, the electrical conductivity of ion is especially high, but organic system exists, and high temperature is inflammable and explosive, easy-to-leak liquid defect.Gel gathers
Polymer electrolyte is compared with traditional organic system, and is easy to be processed into miniaturization and prepares flexible battery, improves energy density.
Simultaneously because solving conventional batteries leakage and safety issue, gel polymer electrolyte obtains on lithium rechargeable battery
Extensive application
The polymer Li-ion battery that conventional organic solution liquid system prepares high security is replaced with novel polymer electrolyte, is
Lithium ion battery or important directions of ultracapacitor development.A kind of Novel boron heterocycle gelatin polymer of present invention preparation
Electrolyte, has broken conventional polymer electrolyte（Polyethylene oxide base PEO）By the transporting mechanism of ion transition mode, this
The high molecular polymer side chain bora ring electron withdraw group complexation anion of bright preparation, promotes the height dissociation of electrolytic salt,
Fixing anion makes cation can realize free transmission, it is achieved thereby that this polymer dielectric have under high/low temperature high from
Electron conductivity, high-cation transport number and high-energy-density, this polymer dielectric film can be in stretching, bending, folding simultaneously
And still keep good mechanical stability energy, thermal property and chemical property under the conditions of high/low temperature etc..System therefore of the present invention
Standby boracic gel polymer electrolyte film can be applied to new energy field especially lithium ion battery or lithium ion super
Capacitor aspect.
Content of the invention
It is an object of the invention to provide one kind has high ionic conductivity, high-cation transport number and high-energy-density, and
And still keep good mechanical stability energy, thermal property and electrochemistry under the conditions of stretching, bending, folding and high/low temperature etc.
Boracic gel polymer electrolyte of performance and its preparation method and application.
The boracic method for preparing gel polymer electrolyte that the present invention provides, using LED light elicitation technique, concrete steps
For：
S1. boracic acid compound and alkenes diol compound are obtained the vinyl monomer of boracic heterocycle through esterification；
S2. the bora ring vinyl monomer of step S1 gained with containing acrylic ester monomer, light trigger, electrolytic salt and have
The solution of machine solvent uniformly mixes, and pours and casts from the mould with regular shape；
S3. under inert gas shielding, irradiate, with LED, the mould having mixed solution and carry out photopolymerization, obtain boracic gel and gather
Polymer electrolyte membrane.
Wherein " alkenes glycol " compound refers to containing " carbon-carbon double bond " and pendant group is the compound of o-dihydroxy.
In the present invention：
Described boronic acid containing group compound is phenylboric acid, trifluoromethylbenzene boronic acid, double（Trifluoromethyl）Phenylboric acid, trifluoro methoxy
Base phenylboric acid or pentafluorophenyl boric acid, or the mixture that above two is formed above.
Described alkenes diol compound is 2,3- bishydroxymethyl propyl acrylate or 2,3- dihydroxypropyl acrylic acid
Ester, or the mixture that above two is formed.
Esterification described in step S1 can be room temperature esterification or the esterification of high temperature azeotropic water removing, specially：
S11. room temperature esterification, by boronic acid containing group compound and alkenes diol compound in molar ratio 1:0.8-1:1.5（Preferably
Mol ratio is 1:1）It is scattered in the anhydrous methylene chloride containing 4 molecular sieves, lower esterification is stirred at room temperature, obtain the alkene of boracic heterocycle
Class monomer；
S12. high temperature azeotropic water removing esterification, by boronic acid containing group compound and alkenes diol compound in molar ratio 1:0.8-1:
1.5（Preferred molar ratio is 1:1）It is dissolved in dry toluene, 130～145 DEG C of Toluene azeotropic water removing esterifications, obtain containing bora
The vinyl monomer of ring.
Acrylic ester monomer described in step S2 is methoxypolyethylene glycol methacrylate, Glycidyl methacrylate
Glyceride etc..
Light trigger described in step S2 is benzoin dimethylether, 1- hydroxycyclohexyl phenyl ketone, or both press one
Determine in mass ratio mixing addition system.
Electrolytic salt described in step S2 is the lithium salts such as lithium perchlorate or hexafluoro phosphorus lithium.
Organic solvent described in step S2 is N,N-dimethylformamide（DMF）Or dimethyl sulfoxide（DMSO）, or
PC/EC/DEC/DMC mixed solvent or ionic liquid.
Photopolymerization described in step S3 uses LED, its main peak 365nm, and power is more than 1750 mW/cm2, shadow surface
Long-pending 4 × 4 cm, 10～70 DEG C of atmosphere temperature, light application time 3-6min.
The weight average molecular weight of the high molecular polymer described in step S3 is 4 × 103～6 × 106, or number-average molecular weight be 2
×103～6 × 106.
Noble gases described in step S3 are high pure nitrogen, or high-purity argon gas, and the purity of above-mentioned high-purity gas is
99.99%-99.999%.
For the synthesis route of above-mentioned boracic solid polymer electrolyte, with phenylboric acid（PBA）With 2,3- dihydroxy
Propyl methacrylate（GMMA）And glycidyl methacrylate（GMA）As a example raw material（See subsequent embodiment 1）,
Its polymerisation routes is as follows：
.
The present invention also provides the boracic gel polymer electrolyte according to above-mentioned preparation method gained.
The present invention also provide above-mentioned boracic heterocycle gel polymer electrolyte prepare ultracapacitor, lithium ion a battery,
Application in hybrid super capacitor or fuel cell.
The boracic heterocycle gel polymer electrolyte film mechanical performance of present invention preparation is high, bora ring group on polymer lateral chain
Group can complexation electrolytic salt effectively anion, thus cation can be freely-movable, the degree of dissociation of electrolytic salt is high.This coagulates
Electrical conductivity under xanthan polymer electrolyte room temperature can reach 5 × 10-3S·cm-1, significantly larger than traditional polymer dielectric
Performance（10-4S·cm-1）, cryogenic property is good.Therefore, the gel polymer electrolyte film that the present invention provides can be applied
The fields such as lithium ion battery, ultracapacitor, hybrid super capacitor or fuel cell.
Brief description
Fig. 1 is the AC impedance curve of the boracic gel polymer electrolyte film using embodiment 1.
Fig. 2 is the ultracapacitor of the boracic gel polymer electrolyte using embodiment 5 in different voltage scan rate
Under Cyclic voltamogram curve（Electrode is symmetrical carbon electrode）.
Specific embodiment
Describe the preparation that the present invention prepares boracic gel polymer electrolyte with specific embodiment in detail below in conjunction with the accompanying drawings
Method.The preparation of polymeric film is carried out using the method for solution-cast.Unless stated otherwise, the reagent of present invention employing, equipment
It is the conventional commercial reagent of the art, equipment and conventional use of method with method.
The boracic heterocycle gel polymer electrolyte film of present invention preparation can be applicable in ultracapacitor, this electrostrictive polymer
Solution plasma membrane mechanical performance is high, and the degree of dissociation of electrolytic salt is high, and lithium ion transference number is high, with material with carbon element or other electrode material interfaces
Stable, electrochemical stability window width（2.5V）.Electrical conductivity under this gel polymer electrolyte room temperature can reach 5 × 10-3
S·cm-1, significantly larger than traditional polymer dielectric performance（10-4cm-1）, under low temperature, chemical property is good.Therefore, originally
Invention provide gel polymer electrolyte film can apply lithium ion battery, ultracapacitor, hybrid super capacitor or
The fields such as fuel cell.
Embodiment 1
By 50 mmol phenylboric acids（PBA）, 50 mmol 2,3- bishydroxymethyl propyl acrylate（GMMA）, 50g 4 molecular sieve
And 300 ml anhydrous methylene chloride be added in three mouthfuls of beakers of 500ml, be passed through noble gases and protected, and constantly stir
Mix more than solution 24h.By mixture through sucking filtration more than 3 times, then washed with neutral alumina column and obtain pure alkenes boracic
Heterocyclic monomer（GMMA-PBA）Dichloromethane solution.Pure yellowish chromophoric monomer will be obtained after its revolving（GMMA-PBA）, its product
Rate approximates 1.
Take above-mentioned monomer GMMA-PBA 2ml, light trigger（Benzoin dimethylether）Content is 1%-5%, and methacrylic acid contracts
Water glyceride（GMA, content is the 10% of GMMA-PBA）And the DMF LiClO of 1ml 2M4Stir in the beaker being added to 5 ml
Mix uniformly, then pour and cast from the thick PTFE mould of 0.5mm；Under inert gas shielding, LED irradiates mould about 6 minutes,
Obtain copolymer p ((GMMA-PBA)-GMA).The thickness of film is at 150～200 μm.The mensure of polymer dielectric electrical conductivity
2016 type button cells are assembled according to rustless steel/polymer dielectric film/rustless steel order using sandwich structure
In.The ac impedance spectroscopy of test polymer dielectric film, being calculated room-temperature conductivity is 5 × 10-3S·cm-1.Fig. 1 be containing
The AC impedance curve of boron gel polymer electrolyte film.
Embodiment 2
By 50 mmol phenylboric acids（PBA）, 50 mmol 2,3- bishydroxymethyl propyl acrylate（GMMA）, 100 ml no water beetle
Benzene is added to equipped with tri- mouthfuls of beakers of 200ml of condensing tube and azeotropic device, and under the conditions of temperature is 130～145 DEG C, azeotropic removes
Water 6-8h.By mixture through sucking filtration more than 3 times, then washed with neutral alumina column and obtain pure alkenes boracic heterocyclic monomer
（GMMA-PBA）Toluene solution.Pure yellowish chromophoric monomer will be obtained after its revolving（GMMA-PBA）, its yield approximates 1.
Take above-mentioned monomer GMMA-PBA 2ml, light trigger（Benzoin dimethylether）Content is 1%-5%, and methacrylic acid contracts
Water glyceride（GMA, content is the 10% of GMMA-PBA）And the DMF LiClO of 1ml 2M4Stir in the beaker being added to 5 ml
Mix uniformly, then pour and cast from the thick PTFE mould of 0.5mm；Under inert gas shielding, LED irradiates mould about 6 minutes,
Obtain copolymer p ((GMMA-PBA)-GMA).The thickness of film is at 150～200 μm.The mensure of polymer dielectric electrical conductivity
2016 type button cells are assembled according to rustless steel/polymer dielectric film/rustless steel order using sandwich structure
In.The ac impedance spectroscopy of test polymer dielectric film, being calculated room-temperature conductivity is 5 × 10-3S·cm-1.Fig. 1 be containing
The AC impedance curve of boron gel polymer electrolyte film.
Embodiment 3
Precise boracic heterocycle vinyl monomer GMMA-PBA 2ml, light trigger（Benzoin dimethylether）Content is 1%-5%, first
Base glycidyl acrylate（GMA, content is the 20% of GMMA-PBA）And the DMF LiClO of 1ml 2M4It is added to 5 ml
Beaker in stir, then pour and cast from the thick PTFE mould of 0.5mm；Under inert gas shielding, LED irradiates mould
Tool about 6 minutes, that is, obtain copolymer p ((GMMA-PBA)-GMA).The thickness of film is at 150～200 μm.Polymer dielectric electricity
The mensure of conductance is assembled in 2016 according to rustless steel/polymer dielectric film/rustless steel order using sandwich structure
In type button cell.The ac impedance spectroscopy of test polymer dielectric film, being calculated room-temperature conductivity is 1.5 × 10-3S·
cm-1.
Embodiment 4
Precise boracic heterocycle vinyl monomer GMMA-PBA 2ml, light trigger（Benzoin dimethylether）Content is 1%-5%, first
Base glycidyl acrylate（GMA, content is the 10% of GMMA-PBA）And the DMF LiClO of 1ml 2M4It is added to 5 ml
Beaker in stir, then pour and cast from the thick PTFE mould of 0.5mm；Under inert gas shielding, LED irradiates mould
Tool about 10 minutes, that is, obtain copolymer p ((GMMA-PBA)-GMA).The thickness of film is at 150～200 μm.Polymer dielectric electricity
The mensure of conductance is assembled in 2016 according to rustless steel/polymer dielectric film/rustless steel order using sandwich structure
In type button cell.The ac impedance spectroscopy of test polymer dielectric film, being calculated room-temperature conductivity is 0.6 × 10-3S·
cm-1.
Embodiment 5
The electrochemical properties of symmetrical ultracapacitor are to be obtained by being assembled into 2032 symmetrical type button cells signs.Wherein
Two electrode materials are the redox graphenes with modified Hummers method preparation（rGO）.The preparation method of electrode material is as follows：
Stock quality is than proportioning according to rGO:Conductive black：Binding agent PVDF=8:1:1 is added to methyl pyrrolidone（NMP）In, room
Temperature stirring 2-3 hour is to uniform state.Then slurry is coated in the nickel foam being cut into diameter 14 mm, in vacuum drying oven
In 110 DEG C 12h more than is dried.The material being dried is pressed into thin slice with infrared tablet machine（0.15 mm）, pressure is 3.0 MPa.Two
The gross mass of plate electrode is about 10 mg（3.25 mg·cm-1）.The assembling of ultracapacitor is according to rGO electrode/polymer electrolytic
The order of plasma membrane/rGO electrode is assembled in 2032 type button cells.The ultracapacitor of test boracic gel polymer electrolyte
Cyclic voltammetry curve under different voltage scan rate, as shown in Figure 2.
Claims (10)
1. a kind of boracic method for preparing gel polymer electrolyte, it is characterised in that adopting LED light elicitation technique, specifically walks
Suddenly it is：
S1. boracic acid compound and alkenes diol compound are obtained the vinyl monomer of boracic heterocycle through esterification；
S2. the bora ring vinyl monomer of step S1 gained with containing acrylic ester monomer, light trigger, electrolytic salt and have
The solution of machine solvent uniformly mixes, and pours and casts from the mould with regular shape；
S3. under inert gas shielding, irradiate, with LED, the mould having mixed solution and carry out photopolymerization, obtain boracic gel and gather
Polymer electrolyte membrane；
Wherein " alkenes glycol " compound refers to containing " carbon-carbon double bond " and pendant group is the compound of o-dihydroxy.
2. boracic method for preparing gel polymer electrolyte according to claim 1 is it is characterised in that described boracic
Acid groups compound is phenylboric acid, trifluoromethylbenzene boronic acid, double（Trifluoromethyl）Phenylboric acid, trifluoromethoxy phenylboric acid or five fluorine
Phenylboric acid, or the mixture that above two is formed above.
3. boracic method for preparing gel polymer electrolyte according to claim 1 and 2 is it is characterised in that described
Alkenes diol compound is 2,3- bishydroxymethyl propyl acrylate or 2,3- dihydroxypropyl acrylate, or above two shape
The mixture becoming.
4. boracic method for preparing gel polymer electrolyte according to claim 3 is it is characterised in that institute in step S1
The esterification stated is room temperature esterification or the esterification of high temperature azeotropic water removing, wherein：
Room temperature is esterified, by boronic acid containing group compound and alkenes diol compound in molar ratio 1:0.8-1:1.5 are scattered in containing 4
In the anhydrous methylene chloride of molecular sieve, lower esterification is stirred at room temperature, obtains the vinyl monomer of boracic heterocycle；
High temperature azeotropic water removing is esterified, by boronic acid containing group compound and alkenes diol compound in molar ratio 1:0.8-1:1.5 it is molten
In dry toluene, 130～145 DEG C of Toluene azeotropic water removings are esterified solution, obtain the vinyl monomer of boracic heterocycle.
5. the boracic method for preparing gel polymer electrolyte according to claim 1,2 or 4 is it is characterised in that step
Acrylic ester monomer described in S2 is methoxypolyethylene glycol methacrylate, glycidyl methacrylate.
6. boracic method for preparing gel polymer electrolyte according to claim 5 is it is characterised in that in step S2
Described light trigger is benzoin dimethylether, 1- hydroxycyclohexyl phenyl ketone, or both mixture；Described organic solvent
For DMF or dimethyl sulfoxide, or PC/EC/DEC/DMC mixed solvent or ionic liquid；Described electrolysis
Matter salt is lithium perchlorate or hexafluoro phosphorus lithium.
7. the boracic method for preparing gel polymer electrolyte according to claim 1,2,4 or 6 is it is characterised in that walk
Photopolymerization described in rapid S3 uses LED, its main peak 365nm, and power is more than 1750 mW/cm2, irradiated area 4 × 4 cm,
10～70 DEG C of atmosphere temperature, light application time 3-6min.
8. boracic method for preparing gel polymer electrolyte according to claim 8 is it is characterised in that institute in step S3
The weight average molecular weight of the high molecular polymer stated is 4 × 103～6 × 106, or number-average molecular weight be 2 × 103～6 × 106；Described
Noble gases be high pure nitrogen, or high-purity argon gas, the purity of above-mentioned high-purity gas is 99.99%-99.999%.
9. the boracic gel polymer electrolyte obtained by a kind of preparation method described in one of claim 1-8.
10. as boracic gel polymer electrolyte according to claim 9 prepare ultracapacitor, lithium ion battery,
Application in hybrid super capacitor or fuel cell.
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