CN114050314A - Epoxy resin-based ionic gel electrolyte and preparation method thereof - Google Patents
Epoxy resin-based ionic gel electrolyte and preparation method thereof Download PDFInfo
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- CN114050314A CN114050314A CN202111336717.XA CN202111336717A CN114050314A CN 114050314 A CN114050314 A CN 114050314A CN 202111336717 A CN202111336717 A CN 202111336717A CN 114050314 A CN114050314 A CN 114050314A
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- gel electrolyte
- based ionic
- epoxy resin
- epoxy
- ionic liquid
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- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 42
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 30
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 239000002608 ionic liquid Substances 0.000 claims description 33
- 229910003002 lithium salt Inorganic materials 0.000 claims description 20
- 159000000002 lithium salts Chemical class 0.000 claims description 20
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 7
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000003990 capacitor Substances 0.000 claims description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229960001231 choline Drugs 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 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 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 12
- 239000003999 initiator Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 8
- 239000004809 Teflon Substances 0.000 description 7
- 229920006362 Teflon® Polymers 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 7
- 239000013557 residual solvent Substances 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- DMAYBPBPEUFIHJ-UHFFFAOYSA-N 4-bromobut-1-ene Chemical compound BrCCC=C DMAYBPBPEUFIHJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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 Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
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Abstract
The invention discloses an epoxy resin-based ionic gel electrolyte and a preparation method thereof, belonging to the technical field of lithium batteries. The method is simple to operate, does not contain an initiator, is environment-friendly, and the prepared electrolyte has higher ionic conductivity at room temperature, thereby being beneficial to large-scale preparation and widening application in electrochemical energy storage devices.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to an epoxy resin-based ionic gel electrolyte and a preparation method thereof.
Background
In recent years, lithium batteries have been storing energy due to their higher energy densityAnd electric vehicles, etc. However, the use of the conventional organic electrolyte often causes safety accidents such as leakage, combustion, explosion and the like. In this regard, attention has been turned to the development of solid electrolytes, and devices made using these materials generally have high safety performance, but unfortunately, the ionic conductivity of these materials at room temperature is generally only 10-5-10-6S cm-1And seriously hamper their use in practical production.
The ionic gel electrolyte is a novel electrolyte developed in recent years and is composed of a solid matrix, an ionic liquid and other additives. Which combines the characteristics of solid and liquid electrolytes and is capable of increasing the conductivity to 10-2-10-3S cm-1. The solid matrix is typically a linear or cross-linked polymer such as polyethylene oxide (PEO), polytetrafluoroethylene (ptfe), and the like. In addition, the ionic liquid is a low-temperature molten salt which is completely composed of ions and has an extremely low vapor pressure, so that the improvement of the electrical conductivity is ensured, and the ionic liquid has the advantages of being difficult to burn and promoting the dissolution of lithium salt, and is widely concerned by scientists.
Currently, the one-step method for preparing the ionic gel electrolyte is considered to be the most suitable method for mass production due to its simple operation. The electrolyte membrane is prepared by a free radical initiation mode by preparing a precursor solution by using acrylate containing PEO soft segments, a cross-linking agent, an initiator, an ionic liquid and other additives. However, the films produced generally contain a number of highly reactive by-products resulting from free radical initiation and residual free radical monomers, which have a strong corrosive effect on lithium metal and are detrimental to its further use. Therefore, it is an urgent technical problem to develop a method for preparing ionic gel without initiator and by one-step method.
Disclosure of Invention
The invention aims to provide a method for preparing an ionic gel electrolyte by using an initiator-free one-step method and the prepared ionic gel electrolyte.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides an epoxy resin-based ionic gel electrolyte, which comprises the following components in percentage by weight: 20-60% of epoxy resin monomer, curing agent and vinylidene fluoride-hexafluoropropylene copolymer, 5-30% of lithium salt, and the balance of ionic liquid.
Further, the lithium salt includes at least one of lithium perchlorate, lithium dioxalate borate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bistrifluoromethylsulfonyl imide, or lithium trifluoromethanesulfonate.
Further, the ionic liquid is low-temperature molten salt which is completely composed of anions/cations and has no volatility.
Further, the cationic liquid comprises at least one of imidazole ionic liquid, pyrrolidone ionic liquid, choline ionic liquid, pyridine ionic liquid or piperidine ionic liquid.
Furthermore, the imidazole cation is preferably EMIM+、BMIM+、EEIM+One of (1); the pyrrolidone cation is preferably PyR13 +、PyR14 +、PyR16 +One of (1); the choline cation is preferably DMEA+、C4choline+、C6choline+、C8choline+One of (1); the pyridine cation is preferably C4Py+、C4PyM+、N1Py+One of (1); the piperidine cation is preferably N1N1Pd+、C2MPd+、C4MPd+One kind of (1).
Further, the anion comprises BF4 -、PF6 -、TFSI-Or Tf2N-One kind of (1).
Further, the epoxy resin monomer comprises at least one of DGEBA, DGEBF, DGEBS, PEGDGE and epoxy modified ionic liquid (ionic liquid monomer containing diepoxy group).
Further, the curing agent comprises at least one of polyether amine type curing agents D230 and D400, aliphatic polyamine type curing agent Ethylenediamine (EDA), Diethylenetriamine (DETA) or alicyclic polyamine type curing agent diaminodiphenylmethane (MDA) and N-aminoethyl piperazine (AEP).
The invention provides a preparation method of an epoxy resin-based ionic gel electrolyte, which comprises the following steps: dissolving lithium salt in ionic liquid to obtain ionic liquid dissolved with lithium salt, mixing epoxy resin monomer and curing agent, adding the ionic liquid dissolved with lithium salt and Dimethylformamide (DMF) solution containing a small amount of vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HPF) to prepare viscous precursor solution, coating the precursor solution on a polytetrafluoroethylene template, curing in a next step under a thermal initiation condition, and finally removing redundant solvent through vacuum to obtain the epoxy resin-based ionic gel electrolyte.
According to the invention, the lithium salt, the ionic liquid and the polymer are sequentially added into the DMF solvent, so that the better dispersion of each component is facilitated.
Further, the mass ratio of the epoxy resin monomer to the curing agent to the vinylidene fluoride-hexafluoropropylene copolymer is (4-6): (1-4): (1-2).
The invention also provides application of the epoxy resin-based ionic gel electrolyte in preparation of batteries or capacitors.
Further, the epoxy resin-based ionic gel electrolyte is used for preparing a lithium metal battery, and the loading amount of the ionic gel electrolyte on a positive electrode is 1-4 mg-cm-2The lithium metal was used as a negative electrode, and the charge/discharge current density was 0.5C (1C 170mAh g)-1)。
Further, the service temperature range of the lithium metal battery is 20-120 ℃.
The invention discloses the following technical effects:
the amine curing of the epoxy resin belongs to ionic polymerization, other initiators are not needed, the method for preparing the ionic gel electrolyte by the one-step method without the initiators is provided, the prepared ionic gel electrolyte is favorable for reducing the conductivity of the interface resistance of the ionic liquid gel electrolyte and other battery materials, and the ionic gel electrolyte can be used for preparing batteries or capacitors.
The preparation method disclosed by the invention is simple to operate, does not contain an initiator, is environment-friendly, and the prepared electrolyte has higher ionic conductivity at room temperature, so that the large-scale preparation of the electrolyte is facilitated, and the application of the electrolyte in electrochemical energy storage devices is widened.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a physical representation of an epoxy-based ionic gel electrolyte prepared in example 1;
fig. 2 is a graph of the cycle performance of a lithium ion battery prepared from the epoxy resin-based ionic gel electrolyte prepared in example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
The conductivity of the ionic gel electrolyte based on the epoxy resin is measured by adopting an alternating current impedance method.
Example 1
0.15g of vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HPF) was dissolved in 3g of Dimethylformamide (DMF), and 2.4g of 0.8M PYR was added14The TFSI lithium salt solution, 0.5g polyethylene glycol diglycidyl ether (PEGDGE) and 0.2g D400 were stirred under an argon atmosphere for 3 h. After removing air bubbles under vacuum, the solution was smeared on a teflon plate with a razor blade and then heated at 80 ℃ for 12h and 120 ℃ for 24 h. Finally, vacuum drying is carried out at 100 ℃ for 24h to remove residual solvent, so as to obtain the epoxy resin-based ionic gel electrolyte with the film thickness of about 200 μm.
A physical diagram of the epoxy-based ionic gel electrolyte prepared in example 1 is shown in fig. 1, and the prepared ionic gel electrolyte is a yellow transparent film about 200um thick. Through testing, the ionic gel electrolyte electric conductance based on the epoxy resin prepared in the embodimentThe rate is 1.69mS · cm at 25 DEG C-1The conductivity is beneficial to reducing the interface resistance of the ionic liquid gel electrolyte and other battery materials.
Example 2
The preparation method of the 1, 3-bis (3-butenyl) imidazole bistrifluoromethanesulfonimide comprises the following steps: 15g of imidazole were dissolved in 125mL of acetonitrile containing 18.5g of sodium bicarbonate, 62.5g of 4-bromo-1-butene were added, refluxed at 82 ℃ for 18h, cooled, filtered and rotary evaporated to remove the solvent, and the crude product was dissolved in 100mL of CH2Cl2In (1), sodium bicarbonate precipitate is generated, and anhydrous magnesium sulfate is added to the suspension to make CH2Cl2Drying the phases to promote salt precipitation. Removal of CH in vacuo2Cl2And washed, then with 66.4g of LiTf2N ion exchange, the mixture was stirred for 3h, then the aqueous phase was removed, the product was extracted into 500mL ethyl acetate, washed twice with 75mL 1M HCl solution, twice with 75mL 1M deionized water, the organic phase was washed twice with 75mL saturated sodium bicarbonate solution, and then with 75mL deionized water until AgNO was added to the combined aqueous phases3No white precipitate was produced. The organic phase was collected over anhydrous MgSO4Dry on charcoal, stir for 3h, filter through a small plug of basic alumina to remove solvent, dry at room temperature for 24h under 20 μm Hg vacuum to yield 84.59g of a clear pale yellow viscous oil with a yield of 84%.
The preparation method of the 1, 3-bis (2-oxiranylethyl) imidazole bistrifluoromethanesulfonimide comprises the following steps: adding 130mL of CH3CN was added to 30g of 1, 3-bis (3-butenyl) imidazole bistrifluoromethanesulfonimide prepared in example 1, and the mixture was stirred in a 500mL flask. 59.6g of m-CPBA (I) was then added to the flask<77 wt%). After the reaction suspension was stirred at room temperature for 37 hours, the reaction solution was filtered, and CH was removed by rotary evaporation at room temperature3And (C) CN. Then using Et2The flask was quenched and placed in a-4 ℃ freezer for 12 h. Using 200mL Et2O washes three times. Removal of residual Et by rotary evaporation2O, then under vacuum at room temperature for 24h to give 25g of a yellowish, transparent oily liquid in 78% yield.
0.15g of PVDF-HPF was dissolved in 3g of DMF, and 2.8g of EMITFSI (1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt), 0.7g of 1, 3-bis (2-oxiranylethyl) imidazolium bistrifluoromethanesulfonimide prepared in example 2 and 0.2g D400 g were added, respectively, and stirred under an argon atmosphere for 3 hours. After removing air bubbles under vacuum, the solution was smeared on a teflon plate with a razor blade and then heated at 80 ℃ for 12h and 120 ℃ for 24 h. Finally, the sample was dried under vacuum at 100 ℃ for 24h to remove residual solvent. An epoxy resin-based ionic gel electrolyte was prepared with a film thickness of about 200 μm.
The electrolyte prepared in this example was tested to have a conductivity of 1.29mS cm at 25 deg.C-1The conductivity is beneficial to reducing the interface resistance of the ionic liquid gel electrolyte and other battery materials.
Example 3
0.3g PVDF-HPF was dissolved in 6g DMF, 3.4g 0.8M IMITFSI lithium salt solution, 0.7g1, 3-bis (2-oxiranylethyl) imidazole bistrifluoromethanesulfonimide and 1g D2000 were added, respectively, stirred under argon atmosphere for 3h, after removal of air bubbles under vacuum, the solution was smeared on a Teflon plate with a razor blade, then heated at 90 ℃ for 12h and at 110 ℃ for 24 h. Finally, the sample was dried under vacuum at 100 ℃ for 24h to remove residual solvent. The thickness of the film obtained was about 300. mu.m.
The electrolyte prepared in this example was tested to have a conductivity of 1.21mS cm at 25 deg.C-1。
Example 4
0.15g PVDF-HPF was dissolved in 3g DMF, 2g of 0.8M IMITFSI lithium salt solution, 0.7g DGEBA and 0.35g D400 were added respectively, stirred under argon atmosphere for 3h, after removal of air bubbles under vacuum, the solution was smeared on a Teflon plate with a razor blade, then heated at 80 ℃ for 12h, and at 120 ℃ for 24 h. Finally, the sample was dried under vacuum at 110 ℃ for 24h to remove residual solvent. The thickness of the film obtained was about 200. mu.m.
The electrolyte prepared in this example was tested to have a conductivity of 0.21mS cm at 25 deg.C-1。
Example 5
0.15g PVDF-HPF was dissolved in 3g DMF, 3g of 0.8M IMITFSI lithium salt solution, 0.7g DGEBA and 0.35g D230 were added, respectively, stirred under argon atmosphere for 3h, after removal of air bubbles under vacuum, the solution was smeared on a Teflon plate with a razor blade, then heated at 80 ℃ for 12h, and at 120 ℃ for 24 h. Finally, the sample was dried under vacuum at 110 ℃ for 24h to remove residual solvent. The thickness of the film obtained was about 200. mu.m.
The electrolyte prepared in this example was tested to have a conductivity of 0.89mS cm at 25 deg.C-1。
Example 6
0.15g PVDF-HPF was dissolved in 3g DMF, 4g 0.8M IMITFSI lithium salt solution, 0.7g DGEBA and 0.35g D400 were added respectively, stirred under argon atmosphere for 3h, after removal of air bubbles under vacuum, the solution was smeared on a Teflon plate with a razor blade, then heated at 80 ℃ for 12h, and at 120 ℃ for 24 h. Finally, the sample was dried under vacuum at 110 ℃ for 24h to remove residual solvent. The thickness of the film obtained was about 200. mu.m.
The electrolyte prepared in this example was tested to have a conductivity of 1.18mS cm at 25 deg.C-1。
Example 7
0.3g PVDF-HPF was dissolved in 6g DMF, 4.2g 0.8M IMITFSI lithium salt solution, 0.7g DGEBA and 1.4g D-2000 were added separately, stirred under argon atmosphere for 3h, after removal of air bubbles under vacuum, the solution was smeared on a Teflon plate with a razor blade, then heated at 90 ℃ for 12h and at 110 ℃ for 24 h. Finally, the sample was dried under vacuum at 120 ℃ for 24h to remove residual solvent. The thickness of the film obtained was about 250. mu.m.
The electrolyte prepared in this example was tested to have a conductivity of 1.64mS cm at 25 deg.C-1。
In the technical solutions described in the present invention, the epoxy resin-based ionic gel electrolyte obtained by randomly combining the polymer species, the lithium salt species and the ionic liquid species, or the epoxy resin-based ionic gel electrolyte obtained by changing the relationship between the amounts of the polymer, the lithium salt and the ionic liquid, is changed, as long as the effects of the epoxy resin-based ionic gel electrolyte obtained in the technical solutions described in the present invention are similar to those of the epoxy resin-based ionic gel electrolytes obtained in examples 1 to 7, and there is no significant difference.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. The ionic gel electrolyte based on the epoxy resin is characterized by comprising the following raw materials in percentage by weight: 20-60% of epoxy resin monomer, curing agent and vinylidene fluoride-hexafluoropropylene copolymer, 5-30% of lithium salt, and the balance of ionic liquid.
2. The epoxy-based ionic gel electrolyte of claim 1, wherein the lithium salt comprises at least one of lithium perchlorate, lithium dioxalate borate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bistrifluoromethylsulfonyl imide, or lithium triflate.
3. The epoxy-based ionic gel electrolyte of claim 1, wherein the ionic liquid is a low temperature molten salt consisting entirely of anions/cations and having no volatility.
4. The epoxy-based ionic gel electrolyte of claim 3, wherein the cationic liquid comprises at least one of an imidazole-based ionic liquid, a pyrrolidone-based ionic liquid, a choline-based ionic liquid, a pyridine-based ionic liquid, or a piperidine-based ionic liquid.
5. The epoxy-based ionic gel electrolyte of claim 3, wherein the anion comprises BF4 -、PF6 -、TFSI-Or Tf2N-One kind of (1).
6. The epoxy-based ionic gel electrolyte of claim 1, wherein the epoxy monomer comprises at least one of DGEBA, DGEBF, DGEBS, PEGDGE, and epoxy-modified ionic liquids.
7. The epoxy-based ionic gel electrolyte of claim 1, wherein the curing agent comprises at least one of a polyetheramine-type curing agent, an aliphatic polyamine-type curing agent, or an alicyclic polyamine-type curing agent.
8. A method for preparing the epoxy resin-based ionic gel electrolyte according to any one of claims 1 to 7, comprising the steps of: dissolving lithium salt in ionic liquid to obtain ionic liquid dissolved with lithium salt, mixing epoxy resin monomer and curing agent, adding the ionic liquid dissolved with lithium salt and dimethylformamide solution containing vinylidene fluoride-hexafluoropropylene copolymer to prepare precursor solution, then coating the precursor solution on a polytetrafluoroethylene template, curing in one step under the condition of thermal initiation, and finally drying in vacuum to obtain the epoxy resin-based ionic gel electrolyte.
9. The preparation method according to claim 8, wherein the mass ratio of the epoxy resin monomer, the curing agent and the vinylidene fluoride-hexafluoropropylene copolymer is (4-6): (1-4): (1-2).
10. Use of the epoxy resin based ionic gel electrolyte of any one of claims 1 to 7 in the manufacture of a battery or capacitor.
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| KR20030014497A (en) * | 2001-08-11 | 2003-02-19 | 삼성에스디아이 주식회사 | Polymeric electrolytes with improved adhesion and lithium battery employing the same |
| CN102197066A (en) * | 2008-10-02 | 2011-09-21 | Ifp新能源公司 | Chemically gelled curable composition based on epoxy-amine resins and on ionic liquids |
| CN103181016A (en) * | 2010-09-13 | 2013-06-26 | 加利福尼亚大学董事会 | Ionic gel electrolyte, energy storage devices, and methods of manufacture thereof |
| CN111816916A (en) * | 2020-07-22 | 2020-10-23 | 珠海冠宇电池股份有限公司 | Composite solid electrolyte membrane, preparation method thereof and lithium ion battery |
| CN112421104A (en) * | 2020-11-17 | 2021-02-26 | 北京化工大学 | Elastomer epoxy resin-based all-solid-state electrolyte and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030014497A (en) * | 2001-08-11 | 2003-02-19 | 삼성에스디아이 주식회사 | Polymeric electrolytes with improved adhesion and lithium battery employing the same |
| CN102197066A (en) * | 2008-10-02 | 2011-09-21 | Ifp新能源公司 | Chemically gelled curable composition based on epoxy-amine resins and on ionic liquids |
| CN103181016A (en) * | 2010-09-13 | 2013-06-26 | 加利福尼亚大学董事会 | Ionic gel electrolyte, energy storage devices, and methods of manufacture thereof |
| CN111816916A (en) * | 2020-07-22 | 2020-10-23 | 珠海冠宇电池股份有限公司 | Composite solid electrolyte membrane, preparation method thereof and lithium ion battery |
| CN112421104A (en) * | 2020-11-17 | 2021-02-26 | 北京化工大学 | Elastomer epoxy resin-based all-solid-state electrolyte and preparation method and application thereof |
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