CN106229547A - A kind of boracic solid polymer electrolyte and its preparation method and application - Google Patents
A kind of boracic solid polymer electrolyte and its preparation method and application Download PDFInfo
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- CN106229547A CN106229547A CN201610832940.6A CN201610832940A CN106229547A CN 106229547 A CN106229547 A CN 106229547A CN 201610832940 A CN201610832940 A CN 201610832940A CN 106229547 A CN106229547 A CN 106229547A
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 47
- 239000007787 solid Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 230000032050 esterification Effects 0.000 claims abstract description 15
- 238000005886 esterification reaction Methods 0.000 claims abstract description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 vinyl compound Chemical class 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 239000000446 fuel Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 5
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003990 capacitor Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000012719 thermal polymerization Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- UVSSPWOKVSKHCU-UHFFFAOYSA-N [2-(trifluoromethyl)phenoxy]boronic acid Chemical compound OB(O)OC1=CC=CC=C1C(F)(F)F UVSSPWOKVSKHCU-UHFFFAOYSA-N 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 3
- 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 claims description 2
- QHFAXRHEKNHTDH-UHFFFAOYSA-N (2-ethenylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1C=C QHFAXRHEKNHTDH-UHFFFAOYSA-N 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 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-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
- 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 description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 238000013467 fragmentation Methods 0.000 claims description 2
- 238000006062 fragmentation reaction Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical group 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229960002645 boric acid Drugs 0.000 claims 3
- 235000010338 boric acid Nutrition 0.000 claims 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 150000002009 diols Chemical group 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- BCYWDUVHAPHGIP-UHFFFAOYSA-N (6-bromopyridin-3-yl)boronic acid Chemical compound OB(O)C1=CC=C(Br)N=C1 BCYWDUVHAPHGIP-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- CICPLSUBCGMYNR-UHFFFAOYSA-N [B].FC(C=1C=CC=CC1)(F)F Chemical compound [B].FC(C=1C=CC=CC1)(F)F CICPLSUBCGMYNR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012711 chain transfer polymerization Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect 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
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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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
- 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
- Y02E60/13—Energy storage using capacitors
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention belongs to electrolyte technical field, be specially a kind of boracic solid polymer electrolyte and preparation method and application.The polymer dielectric of the present invention includes high molecular polymer matrix and the electrolytic salt of boracic heterocycle, its preparation method comprises the steps: boronic acid containing compound and the vinyl monomer having the vinyl compound of diol structure and obtaining through esterification boracic heterocycle, by itself and the uniformly rear radical polymerization of initiator, electrolytic salt and organic solvent dispersion, gained mixture the most i.e. obtains boracic solid polymer electrolyte.This boracic solid polymer electrolyte has the electrode/electrolyte interface effect of high ionic conductivity, high-cation transport number, good mechanical property and excellence, can be applicable to the fields such as ultracapacitor, lithium ion battery, hybrid super capacitor and fuel cell.The ultracapacitor that this polymer dielectric assembles has wide electrochemical window, long cycle life and high safety performance.
Description
Technical field
The invention belongs to electrolyte technical field, be specifically related to boracic solid polymer electrolyte and preparation method thereof
With application.
Background technology
In recent years, lightweight, miniaturization new forms of energy equipment more and more universal, battery is in notebook computer, mobile phone, charging
Treasured, electric motor car, the application in the fields such as unmanned plane gets growing concern for.Electrolyte be energy storage device such as ultracapacitor,
One of important component part in lithium ion battery, its Main Function is to provide the ion that can transmit or as ion transmission
Passage.Traditional electrolyte is mainly organic electrolyte system, and in liquid conditions, the electrical conductivity of ion is the highest, but
Organic system exists that high temperature is inflammable and explosive, the defect of easy-to-leak liquid.Gel polymer electrolyte is compared with tradition organic system, permissible
Efficiently solve leakage problem, but because system still contains substantial amounts of organic electrolyte, be therefore still unavoidable from high temperature and draw
Rise expansion, combustion problem.In 20 years of past, solid polymer electrolyte is used can effectively to solve lithium ion battery
Safety problem, and be easy to be processed into miniaturization and variously-shaped, improve energy density.Simultaneously because solve conventional batteries
Leakage and bad inflammable, the explosive problem of safety, solid polymer electrolyte has had very on lithium rechargeable battery
Good application, but conventional polymer dielectric ion transmission performance is poor, mechanical property, and processing characteristics cannot be the most satisfied.
Replace conventional organic solution liquid system with novel polymer electrolyte and prepare the polymer Li-ion electricity of high security
Pond, is lithium ion battery or an important directions of ultracapacitor development.A kind of Novel boron heterocycle solid-state prepared by the present invention
Polymer dielectric, has broken the conventional solid-state polymer dielectric (polyethylene oxide base PEO) biography by ion transition mode
Defeated mechanism, high molecular polymer side chain bora ring electron withdraw group complexation anion prepared by the present invention, promote electrolytic salt
Height dissociate, fixing anion makes cation can realize free transmission, it is achieved thereby that this polymer dielectric height
There is under temperature high ionic conductivity, high-cation transport number and high-energy-density, simultaneously this polymer dielectric can stretching,
Good mechanical stability energy, thermal property and chemical property is still kept under the conditions of bending, folding and high/low temperature etc..Therefore
Boracic solid polymer electrolyte prepared by the present invention can be applied to new energy field especially lithium ion battery or lithium from
Sub-ultracapacitor aspect.
Summary of the invention
It is an object of the invention to provide one and there is high ionic conductivity, high-cation transport number and high-energy-density, and
And stretching, bend, fold and still keep good mechanical stability energy, thermal property and electrochemistry under the conditions of high/low temperature etc.
Boracic solid polymer electrolyte of performance and preparation method and application.
The preparation method of the boracic solid polymer electrolyte that the present invention provides, specifically comprises the following steps that
S1. boronic acid containing group compound and alkenes diol compound are obtained through esterification the vinyl monomer of boracic heterocycle；
S2. by uniform with the solution containing initiator, electrolytic salt and organic solvent for the bora ring vinyl monomer of step S1 gained
After mixing, water and cast from the mould with regular shape；
S3. solution is carried out thermal polymerization, cool down the most at room temperature, obtain the polymer dielectric with a small amount of solvent；
S4. the polymer dielectric of step S3 gained room temperature under inert gas shielding is volatilized or through low temperature cold lyophilizing
Dry process, obtains boracic solid polymer electrolyte.
Wherein " alkenes glycol " compound refers to that containing " carbon-carbon double bond " and pendant group be the compound of o-dihydroxy.
Described boronic acid containing group compound is boric acid, phenylboric acid, trifluoromethylbenzene boronic acid, double (trifluoromethyl) benzene boron
One in acid, trifluoromethoxy phenylboric acid, pentafluorophenyl boric acid, vinylphenylboronic acid, or the mixing that above two is formed above
Thing.
Described alkenes diol compound be 3-allyloxy-1,2-propylene glycol, 2,3-dihydroxypropyl acrylate, 2,
One in 3-bishydroxymethyl propyl acrylate, or the mixture that above two is formed above.
Esterification described in step S1 can be room temperature esterification or the esterification of high temperature azeotropic water removing, particularly as follows:
S11. room temperature esterification, preferably rubs boric acid base group compound with alkenes diol compound 1:0.8-1:1.5(in molar ratio
That ratio is 1:1) it is scattered in the anhydrous methylene chloride containing 4 molecular sieves, lower esterification is stirred at room temperature, obtains the alkenes of boracic heterocycle
Monomer；
S12. high temperature azeotropic water removing esterification, by boric acid base group compound and alkenes diol compound 1:0.8-1:1.5 in molar ratio
(preferred molar ratio is 1:1) is dissolved in dry toluene, 130～145 DEG C of Toluene azeotropic water removing esterifications, obtains boracic heterocycle
Vinyl monomer.
Initiator described in step S2 can be dibenzoyl peroxide (BPO), the tradition of azodiisobutyronitrile (AIBN)
Radical polymerization initiator.
Electrolytic salt described in step S2 is lithium salts or sodium salt, potassium salt.
Organic solvent described in step S2 is N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or PC/EC/
DEC/DMC mixed solvent or ionic liquid.
Thermal polymerization method described in step S3 is traditional free radical thermal polymerization, or Controlled/Living Radical Polymerization, should
Controlled/Living Radical Polymerization is atom transfer radical polymerization (ATRP), reversible addion-fragmentation chain transfer polymerization
(RAFT).
The weight average molecular weight of the polymer described in step S3 is 4 × 103～6 × 106, or number-average molecular weight is 2 × 103～6
×106。
Noble gas described in step S4 is 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 double (trifluoromethyl) phenylboric acid (BPBA)
With 3-allyloxy-1,2-PD as a example by raw material (see subsequent embodiment 1), its polymerisation routes is as follows:
The present invention also provides for the boracic heterocycle solid polymer electrolyte according to above-mentioned preparation method gained.
The present invention also provides for above-mentioned boracic heterocycle solid polymer electrolyte, in ultracapacitor, lithium ion battery, mixing
Application in ultracapacitor or fuel cell.
Boracic heterocycle solid polymer electrolyte homogeneous transparent prepared by the present invention, bora ring on high molecular polymer side chain
Group can the anion of complexation electrolytic salt effectively, thus cation can be freely-movable, and the degree of dissociation of electrolytic salt is high.By
In complexing, polymer dielectric presents the feature of microcosmic porous, and this polymer dielectric has high lithium ion transference number
(0.7), with material with carbon element or other electrode material interface stabilities, electrochemical stability window width.This solid polymer electrolyte is 10
Electrical conductivity under ° C still can reach 0.4 mS cm-1, the most traditional solid polymer electrolyte performance (＜ 10- 6S·cm-1).The ultracapacitor assembled, also can work under low temperature, and has the cycle performance of excellence.Therefore, the present invention carries
The boracic solid polymer electrolyte of confession can be applied at ultracapacitor, lithium ion battery, hybrid super capacitor or fuel
The fields such as battery.
Accompanying drawing explanation
Fig. 1 is the AC impedance curve of the boracic solid polymer electrolyte using embodiment 4.
Fig. 2 is that the ultracapacitor of the boracic solid polymer electrolyte using embodiment 6 is in different voltage scan rate
Under Cyclic voltamogram curve (electrode be symmetrical redox graphene electrode).
Fig. 3 is that to use the ultracapacitor of boracic solid polymer electrolyte of embodiment 6 be 2A/g bar in electric current density
The loop test of 3000 times is carried out under part.
Detailed description of the invention
Describe the present invention in detail with specific embodiment below in conjunction with the accompanying drawings and prepare the preparation of boracic solid polymer electrolyte
Method.The preparation of polymeric film uses the method for solution-cast to carry out, and will prepare polymeric film volatile dry can use.Remove
Non-specifically illustrates, reagent, equipment and the method that the present invention uses is that conventional commercial reagent, equipment and the routine of the art makes
Method.
Boracic heterocycle solid polymer electrolyte prepared by the present invention can be applicable in ultracapacitor, this polymer electrolytic
Matter transparent and homogeneous, the degree of dissociation of electrolytic salt is high, and lithium ion transference number is high (0.7), with material with carbon element or other electrode material interfaces
Stable, electrochemical stability window width.This solid polymer electrolyte electrical conductivity at 10 DEG C still can reach 0.4 mS
cm-1, the most traditional solid polymer electrolyte performance (＜ 10-7S·cm-1).The ultracapacitor assembled, under low temperature
Also can work, and there is the cycle performance of excellence.Therefore, the boracic solid polymer electrolyte that the present invention provides can be applied
In fields such as ultracapacitor, lithium ion battery, hybrid super capacitor or fuel cells.
Embodiment 1
By double for 21.75 mmol (trifluoromethyl) phenylboric acids (BPBA), 21.75mmol 3-allyloxy-1,2-PD
(GAE), 20g 4 molecular sieve and 200 ml anhydrous methylene chlorides join in three mouthfuls of beakers of 500ml, are passed through indifferent gas
Body is protected, and constantly more than agitating solution 24h.By mixture through sucking filtration more than 3 times, then wash with neutral alumina column
Obtain the dichloromethane solution of pure alkenes boracic heterocyclic monomer (GAE-BPBA).Pure faint yellow list is obtained after being revolved steaming
Body (GAE-BPBA), its productivity approximates 1.
Taking above-mentioned monomer GAE-BPBA 2ml, initiator (BPO) content is 0.5%-1% and 20ml solvent N, N-dimethyl
Methanamide (DMF) joins in the there-necked flask of 50ml, under inert gas shielding, after 85 DEG C of radical reactions 6-8h, by institute
Obtain mixture dry oil ether to precipitate, obtain white powder, 40 DEG C of dry 24h of vacuum, obtain being dried pure polymer P
(GAE-BPBA).The molecular weight of polymer and molecular weight distribution are 105g·mol-1With 1.71.
Embodiment 2
By double for 21.75 mmol (trifluoromethyl) phenylboric acids (BPBA), 21.75mmol 3-allyloxy-1,2-PD (GAE)
And 100 ml dry toluene join equipped with in tri-mouthfuls of beakers of 200ml of condensing tube and azeotropic device, temperature be 130～
Azeotropic water removing 6-8h under the conditions of 145 DEG C.By mixture through sucking filtration more than 3 times, then obtain pure with neutral alumina column washing
The toluene solution of alkenes boracic heterocyclic monomer (GAE-BPBA).Pure faint yellow monomer (GAE-is obtained after being revolved steaming
BPBA), its productivity approximates 1.
Taking above-mentioned monomer GAE-BPBA 2ml, initiator (BPO) content is 0.5%-1% and 20ml solvent N, N-dimethyl
Methanamide (DMF) joins in the there-necked flask of 50ml, under inert gas shielding, after 85 DEG C of radical reactions 6-8h, by institute
Obtain mixture dry oil ether to precipitate, obtain white powder, 40 DEG C of dry 24h of vacuum, obtain being dried pure polymer P
(GAE-BPBA).The molecular weight of polymer and molecular weight distribution are 105g·mol-1With 1.71.
Embodiment 3
Precise boracic heterocycle vinyl monomer GAE-BPBA 2ml, electrolyte solution is 2M LiClO4DMF solution, high chlorine
Acid lithium addition is the 10% of monomer mass mark, and initiator (BPO) content is 0.5%-1%.After uniform (2-3h) is stirred at room temperature,
Mixed liquor is watered in the mould of the PTFE after casting from 0.5mm, be then placed in the drying baker of high pure nitrogen protection, at 85 DEG C
Reaction 6-8h.After being cooled to room temperature, the polymeric film of gained is placed in freezer dryer, at-80 DEG C, removes the organic of trace
Solvent time more than one week.Finally giving the solid polymer electrolyte of boracic, the thickness of film is in 150～200 μm.Electrostrictive polymer
The mensuration solving matter electrical conductivity uses sandwich structure to be i.e. contained according to rustless steel/polymer dielectric/rustless steel der group
In 2016 type button cells.The ac impedance spectroscopy of test polymer electrolyte, being calculated room-temperature conductivity is 0.3 mS cm-1。
Embodiment 4
Precise boracic heterocycle vinyl monomer GAE-BPBA 2ml, electrolyte solution is 2M LiClO4DMF solution, high chlorine
Acid lithium addition is the 20% of monomer mass mark, and initiator (BPO) content is 0.5%-1%.After uniform (2-3h) is stirred at room temperature,
Mixed liquor is watered in the mould of the PTFE after casting from 0.5mm, be then placed in the drying baker of high pure nitrogen protection, at 85 DEG C
Reaction 6-8h.After being cooled to room temperature, the polymeric film of gained is placed in freezer dryer, at-80 DEG C, removes the organic of trace
Solvent time more than one week.Finally giving the solid polymer electrolyte of boracic, the thickness of film is in 150～200 μm.Electrostrictive polymer
The mensuration solving matter electrical conductivity uses sandwich structure to be i.e. contained according to rustless steel/polymer dielectric/rustless steel der group
In 2016 type button cells.The ac impedance spectroscopy of test polymer electrolyte, as it is shown in figure 1, be calculated room-temperature conductivity be
0.5 mS·cm-1。
Embodiment 5
Precise boracic heterocycle vinyl monomer GAE-BPBA 2ml, electrolyte solution is 2M LiClO4DMF solution, high chlorine
Acid lithium addition is the 30% of monomer mass mark, and initiator (BPO) content is 0.5%-1%.After uniform (2-3h) is stirred at room temperature,
Mixed liquor is watered in the mould of the PTFE after casting from 0.5mm, be then placed in the drying baker of high pure nitrogen protection, at 85 DEG C
Reaction 6-8h.After being cooled to room temperature, the polymeric film of gained is placed in freezer dryer, at-80 DEG C, removes the organic of trace
Solvent time more than one week.Finally giving the solid polymer electrolyte of boracic, the thickness of film is in 150～200 μm.Electrostrictive polymer
The mensuration solving matter electrical conductivity uses sandwich structure to be i.e. contained according to rustless steel/polymer dielectric/rustless steel der group
In 2016 type button cells.The ac impedance spectroscopy of test polymer electrolyte, being calculated room-temperature conductivity is 0.25 mS
cm-1。
Embodiment 6
The electrochemical properties of symmetrical ultracapacitor is to be obtained by the 2032 type button cells signs being assembled into symmetry.Wherein
Two electrode materials are the redox graphenes (rGO) prepared by modified Hummers method.The preparation method of electrode material is as follows:
Stock quality than proportioning according to rGO: conductive black: binding agent PVDF=8:1:1 joins in methyl pyrrolidone (NMP), room
Temperature stirs 2-3 hour to uniform state.Then slurry is coated in the nickel foam being cut into diameter 14mm, in vacuum drying oven
110 DEG C of dry more than 12h.With infrared tablet machine, dry material is pressed into thin slice (0.15mm), and pressure is 3.0MPa.Two panels electricity
The gross mass of pole is about 10mg(3.25mg cm-1).The assembling of ultracapacitor is according to rGO electrode/polymer dielectric/rGO
The der group of electrode is contained in 2032 type button cells.The ultracapacitor of test boracic solid polymer electrolyte is at different electricity
Cyclic voltammetry curve under pressure sweep speed, as shown in Figure 2.The length of the ultracapacitor of test boracic solid polymer electrolyte
Cycle performance, charge and discharge cycles number of times is 3000 times, and electric current density is 2 A/g, and its performance is as shown in Figure 3.
Claims (10)
1. the preparation method of a boracic solid polymer electrolyte, it is characterised in that specifically comprise the following steps that
S1. boronic acid containing group compound and alkenes diol compound are obtained through esterification the vinyl monomer of boracic heterocycle；
S2. by uniform with the solution containing initiator, electrolytic salt and organic solvent for the bora ring vinyl monomer of step S1 gained
After mixing, water and cast from the mould with regular shape；
S3. solution is carried out thermal polymerization, cool down the most at room temperature, obtain the polymer dielectric with a small amount of solvent；
S4. the polymer dielectric of step S3 gained room temperature under inert gas shielding is volatilized or through low temperature cold lyophilizing
Dry process, obtains boracic solid polymer electrolyte；
Wherein " alkenes glycol " compound refers to that containing " carbon-carbon double bond " and pendant group be the compound of o-dihydroxy.
The preparation method of boracic solid polymer electrolyte the most according to claim 1, it is characterised in that described boracic
Acid groups compound be boric acid, phenylboric acid, trifluoromethylbenzene boronic acid, double (trifluoromethyl) phenylboric acid, trifluoromethoxy phenylboric acid,
One in pentafluorophenyl boric acid, vinylphenylboronic acid, or the mixture that above two is formed above.
The preparation method of boracic solid polymer electrolyte the most according to claim 1 and 2, it is characterised in that described
Alkenes diol compound is 3-allyloxy-1,2-propylene glycol, 2,3-dihydroxypropyl acrylate, 2,3-bishydroxymethyl third
One in olefin(e) acid propyl ester, or the mixture that above two is formed above.
The preparation method of boracic solid polymer electrolyte the most according to claim 3, 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, particularly as follows:
Room temperature is esterified, and is scattered in containing 4 points with alkenes diol compound 1:0.8-1:1.5 in molar ratio by boric acid base group compound
In the anhydrous methylene chloride of son sieve, lower esterification is stirred at room temperature, obtains the vinyl monomer of boracic heterocycle；
High temperature azeotropic water removing is esterified, and is dissolved with alkenes diol compound 1:0.8-1:1.5 in molar ratio by boric acid base group compound
In dry toluene, 130～145 DEG C of Toluene azeotropic water removing esterifications, obtain the vinyl monomer of boracic heterocycle.
5. according to the preparation method of the boracic solid polymer electrolyte described in claim 1,2 or 4, it is characterised in that step
Initiator described in S2 is dibenzoyl peroxide or azodiisobutyronitrile；Described electrolytic salt is lithium salts, sodium salt or potassium
Salt；Described organic solvent is N,N-dimethylformamide, dimethyl sulfoxide or PC/EC/DEC/DMC mixed solvent or ion
Liquid.
The preparation method of boracic solid polymer electrolyte the most according to claim 5, it is characterised in that institute in step S3
The thermal polymerization method stated is free radical thermal polymerization, or Controlled/Living Radical Polymerization, this Controlled/Living Radical Polymerization
It is polymerized for atom transfer radical polymerization or reversible addion-fragmentation chain transfer.
7. according to the preparation method of the boracic solid polymer electrolyte described in claim 1,2,4 or 6, it is characterised in that step
The weight average molecular weight of the polymer described in rapid S3 is 4 × 103～6 × 106, or number-average molecular weight is 2 × 103～6 × 106。
The preparation method of boracic solid polymer electrolyte the most according to claim 7, it is characterised in that institute in step S4
The noble gas stated is high pure nitrogen, or high-purity argon gas, and the purity of above-mentioned high-purity gas is 99.99%-99.999%.
9. one kind by the boracic solid polymer electrolyte of the preparation method gained one of claim 1-8 Suo Shu.
10. polymer dielectric is preparing ultracapacitor, lithium ion battery, hybrid super capacitor as claimed in claim 9
Or the application in fuel cell.
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