CN113823831A - Sulfonic acid functionalized polyethyleneimine polymer solid electrolyte - Google Patents
Sulfonic acid functionalized polyethyleneimine polymer solid electrolyte Download PDFInfo
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- CN113823831A CN113823831A CN202010561563.3A CN202010561563A CN113823831A CN 113823831 A CN113823831 A CN 113823831A CN 202010561563 A CN202010561563 A CN 202010561563A CN 113823831 A CN113823831 A CN 113823831A
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- sulfonic acid
- polyethyleneimine
- acid functionalized
- solid electrolyte
- polymer solid
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- 229920002873 Polyethylenimine Polymers 0.000 title claims abstract description 118
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 63
- 229920000642 polymer Polymers 0.000 title claims abstract description 57
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 36
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 20
- -1 sulfonic acid compound Chemical class 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 10
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 239000004014 plasticizer Substances 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- NEKSMZUJCUEYAR-UHFFFAOYSA-M lithium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Li+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C NEKSMZUJCUEYAR-UHFFFAOYSA-M 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 238000012983 electrochemical energy storage Methods 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 229920001002 functional polymer Polymers 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 15
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical group [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 239000011244 liquid electrolyte Substances 0.000 description 8
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 229960001484 edetic acid Drugs 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- OHGICEXGYYWLRO-UHFFFAOYSA-N lithium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound [Li].OS(=O)(=O)CC(C)(C)NC(=O)C=C OHGICEXGYYWLRO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005554 polynitrile Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000348 solid-phase epitaxy Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction 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
- 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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
-
- 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
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention discloses a sulfonic acid functionalized polyethyleneimine polymer electrolyte matrix material and a sulfonic acid functionalized polyethyleneimine polymer solid electrolyte thereof, wherein polyethyleneimine is subjected to functional modification through Michael addition reaction between polyethyleneimine and a sulfonic acid compound containing double bonds, and the sulfonic acid functionalized polyethyleneimine polymer solid electrolyte or polymer gel electrolyte is prepared by taking the polyethyleneimine as a matrix.
Description
The technical field is as follows:
the invention relates to the technical field of polymer electrolytes, in particular to a sulfonic acid functionalized polyethyleneimine polymer solid electrolyte.
Background art:
currently, most commercial lithium ion batteries use a liquid electrolyte consisting of an organic carbonate solvent and a free lithium salt dissolved therein. The flammability of these organic liquid electrolytes poses a serious safety problem that must be addressed before they can be used in high energy density lithium ion batteries for future personal electronics and electric vehicles. Therefore, there is a high expectation for safe and high-voltage-resistant electrolyte materials to meet the new era of energy storage devices. Polymer solid Electrolytes (SPEs) having sufficient mechanical properties and good electrochemical compatibility, compared to liquid Electrolytes, can effectively solve the above problems. The replacement of liquid electrolytes with polymer solid electrolytes offers bright prospects for solving the safety problems of lithium ion batteries, but the practical application of solid electrolytes is limited by low ionic conductivity and high solid-solid interface resistance. Under such circumstances, Polymer Gel Electrolytes (Gel Polymer Electrolytes, GPEs) have the advantages of both liquid Electrolytes and solid Electrolytes, have the advantages of acceptable ionic conductivity, good interfacial contact and wettability with electrodes, and can inhibit organic solvent leakage, and thus have received wide attention.
With respect to the application of polymer electrolyte materials, such as lithium-based batteries, a great deal of scientific literature has focused on the research of polyether-based materials, particularly typical Polyethylene oxides (also known as Polyethylene oxide, PEO). In addition, a number of alternative polymers have been discovered in recent years, including polycarbonates, polyesters, polynitriles, polyols and polyamines, among others. They differ fundamentally from polyethers in their properties and may therefore be able to solve key problems limiting the inability of polymer electrolytes to fully exploit their potential, for example in terms of ionic conductivity, chemical or electrochemical stability and temperature sensitivity.
Polyethyleneimine (PEI) is a polymer with a structure highly similar to that of Polyethylene oxide, oxygen (O) in Polyethylene oxide is replaced by Nitrogen (NH), coordination of lithium ions and Nitrogen (NH) in polyethyleneimine is similar to that of lithium ions and oxygen (O) in Polyethylene oxide, and NH groups in polyethyleneimine also have a hydrogen bonding capability, and can interact with anions through hydrogen bonding, which makes polyethyleneimine a very potential polymer electrolyte matrix material. However, the pure polyethyleneimine-based polymer solid electrolyte has low room-temperature ionic conductivity (about 10-7S · cm-1), and cannot be practically applied, so that the functionalized grafting modification of polyethyleneimine is performed to prepare a novel polymer electrolyte matrix material with better electrochemical performance, and the method has great significance for developing a next-generation safe and efficient lithium ion battery system.
The invention content is as follows:
the invention aims to provide sulfonic acid functionalized polyethyleneimine and a sulfonic acid functionalized polyethyleneimine polymer solid electrolyte, wherein the sulfonic acid functionalized polyethyleneimine is obtained by performing functional modification on polyethyleneimine through Michael addition reaction between the polyethyleneimine and a sulfonic acid compound containing double bonds, and is used as a matrix to prepare the sulfonic acid functionalized polyethyleneimine polymer solid electrolyte or polymer gel electrolyte.
The invention is realized by the following technical scheme:
sulfonic acid functionalized polyethyleneimine polymer electrolyte matrix material, wherein the sulfonic acid functionalized polyethyleneimine polymer electrolyte matrix material is a functional polymer obtained by performing functional modification on polyethyleneimine through Michael addition reaction between the polyethyleneimine and a sulfonic acid compound containing double bonds; the double-bond-containing sulfonic acid compound is selected from more than one of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) and lithium 2-acrylamido-2-methylpropanesulfonate (AMPS-Li); the molar ratio of the repeating unit of the polyethyleneimine to the double-bond-containing sulfonic acid compound is 1: 0.01-1: 11; the number average molecular weight Mn of the polyethyleneimine is 5000-100000.
A sulfonic acid functionalized polyethyleneimine polymer solid electrolyte is formed by heating and crosslinking reaction of sulfonic acid functionalized polyethyleneimine, a crosslinking agent and a plasticizer; the sulfonic acid functionalized polyethyleneimine is a functional polymer obtained by performing functional modification on polyethyleneimine through Michael addition reaction between the polyethyleneimine and a sulfonic acid compound containing double bonds; the double-bond-containing sulfonic acid compound is selected from more than one of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) and lithium 2-acrylamido-2-methylpropanesulfonate (AMPS-Li); the molar ratio of the repeating unit of the polyethyleneimine to the double-bond-containing sulfonic acid compound is 1: 0.01-1: 11; the number average molecular weight Mn of the polyethyleneimine is 5000-100000.
Preferably, in the Michael addition reaction between the polyethyleneimine and the double-bond sulfonic acid compound, the concentration of the double-bond sulfonic acid compound aqueous solution is 0.1-2 mol/L, the reaction temperature is 30-80 ℃, and the reaction time is 5-120 h.
The cross-linking agent is one or more of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and ethylenediamine tetraacetic acid; the cross-linking agent accounts for 1-20% of the total mass of the sulfonic acid functionalized polyethyleneimine, the cross-linking agent and the plasticizer.
The plasticizer is more than one of lithium hexafluorophosphate (LiPF6), lithium bistrifluoromethylalkanesulfonimide (LiTFSI), montmorillonite, Ethylene Carbonate (EC), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC) and diethyl carbonate (DEC).
Preferably, the plasticizer accounts for 1-90% of the total mass of the sulfonic acid functionalized polyethyleneimine, the cross-linking agent and the plasticizer.
Preferably, the sulfonic acid functionalized polyethyleneimine polymer solid electrolyte is further soaked in a plasticizer solution for a certain time, and after a certain amount of the plasticizer solution is absorbed, the sulfonic acid functionalized polyethyleneimine polymer gel electrolyte is prepared.
The invention also protects the application of the sulfonic acid functionalized polyethyleneimine polymer solid electrolyte or the sulfonic acid functionalized polyethyleneimine polymer gel electrolyte, and is characterized by being applied to an electrochemical energy storage device.
The electrochemical energy storage device comprises a lithium ion battery, a super capacitor, a lithium sulfur battery and a solar battery.
The invention has the following beneficial effects:
the invention carries out functional modification on polyethyleneimine through Michael addition reaction between the polyethyleneimine and a sulfonic acid compound containing double bonds, and takes the polyethyleneimine as a matrix to prepare the sulfonic acid functionalized polyethyleneimine polymer solid electrolyte or polymer gel electrolyte, which has higher ionic conductivity, thermal stability, lithium ion migration number and electrochemical window, better flexibility and mechanical strength, and can be widely applied to electrochemical energy storage devices such as lithium ion batteries, super capacitors, lithium sulfur batteries or solar batteries.
Description of the drawings:
FIG. 1 shows NMR spectra of sulfonic acid functionalized polyethyleneimines (PEI-AMPS-1, PEI-AMPS-2, PEI-AMPS-4) and Polyethyleneimine (PEI) of examples 1, 2, 3.
FIG. 2 is a NMR spectrum of sulfonic acid functionalized polyethyleneimines (PEI-AMPS-Li-1, PEI-AMPS-Li-2, PEI-AMPS-Li-4, PEI-AMPS-Li-8) and Polyethyleneimines (PEI) of examples 4, 5, 6, 7.
FIG. 3 is a true stress-strain curve of the PEI-AMPS-Li-1 polymer solid-state electrolyte in example 8 at room temperature.
FIG. 4 is a Linear Sweep Voltammetry (LSV) curve at room temperature for a PEI-AMPS-Li-1 polymer solid electrolyte in example 8.
Fig. 5 is a Linear Sweep Voltammetry (LSV) curve at room temperature for a conventional organic liquid electrolyte in examples 8 and 9.
FIG. 6 is an optical photograph of PEI-AMPS-Li-1 polymer gel electrolyte in example 9.
FIG. 7 is a Scanning Electron Microscope (SEM) photograph of a PEI-AMPS-Li-1 polymer gel electrolyte in example 9.
FIG. 8 is a true stress-strain curve of the PEI-AMPS-Li-1 polymer gel electrolyte in example 9 at room temperature.
FIG. 9 is a Chronoamperometric (CA) curve of the PEI-AMPS-Li-1 polymer gel electrolyte in example 9 at room temperature and Electrochemical Impedance Spectroscopy (EIS) spectra before and after polarization.
FIG. 10 is a Linear Sweep Voltammetry (LSV) curve at room temperature for a PEI-AMPS-Li-1 polymer gel electrolyte in example 9.
FIG. 11 is a true stress-strain curve of the PEI-AMPS-1 polymer solid electrolyte in example 10 at room temperature.
FIG. 12 is a stress-strain curve of the CN-PEI polymer solid-state electrolyte in comparative example 1 at room temperature.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1: specific preparation of sulfonic acid functionalized polyethyleneimine
The method comprises the following steps:
(1) weighing 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), stirring and dissolving in solvent deionized water to obtain a 1 mol/L2-acrylamide-2-methylpropanesulfonic Acid (AMPS) aqueous solution.
(2) Weighing branched polyethyleneimine (Mn is 100000) and deionized water, placing the branched polyethyleneimine and the deionized water into a three-neck flask connected with a condenser, a thermometer and a dropping funnel, stirring the mixture evenly at room temperature under the argon atmosphere, slowly dropwise adding a 1mol/L aqueous solution of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) by using the dropping funnel while stirring, controlling the molar ratio of a repeating unit of the polyethyleneimine to the added 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) to be 1:1, heating the mixture to 50 ℃ after the dropwise addition is finished, and continuously stirring the mixture for reaction for 72 hours to obtain a sulfonic acid functionalized polyethyleneimine (PEI-AMPS-1) aqueous solution.
(3) And (3) slowly dripping a certain amount of good solvent methanol into the sulfonic acid functionalized polyethyleneimine (PEI-AMPS-1) aqueous solution obtained in the step (2) by stirring, and then slowly dripping poor solvent diethyl ether by stirring until a product is recrystallized and separated out to obtain the purified sulfonic acid functionalized polyethyleneimine (PEI-AMPS-1). And (3) carrying out nuclear magnetic resonance hydrogen spectrum detection on the obtained sulfonic acid functionalized polyethyleneimine (PEI-AMPS-1), wherein the deuterated reagent is deuterium oxide, and the detected nuclear magnetic resonance hydrogen spectrum is shown in figure 1.
Example 2:
the specific operation process is as in example 1, except that: and (3) in the step (2), the molar ratio of the repeating unit of the polyethyleneimine to the added 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) is 1:2, so as to obtain sulfonic acid functionalized polyethyleneimine (PEI-AMPS-2). And (3) carrying out nuclear magnetic resonance hydrogen spectrum detection on the obtained sulfonic acid functionalized polyethyleneimine (PEI-AMPS-2), wherein the deuterated reagent is deuterium oxide, and the detected nuclear magnetic resonance hydrogen spectrum is shown in figure 1.
Example 3:
the specific operation process is as in example 1, except that: and (3) in the step (2), the molar ratio of the repeating unit of the polyethyleneimine to the added 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) is 1:4, so as to obtain sulfonic acid functionalized polyethyleneimine (PEI-AMPS-4), and performing nuclear magnetic resonance hydrogen spectrum detection on the obtained sulfonic acid functionalized polyethyleneimine (PEI-AMPS-4), wherein the deuterated reagent is deuterium oxide, and the detected nuclear magnetic resonance hydrogen spectrum is shown in figure 1.
Example 4: preparation of sulfonic acid functionalized polyethyleneimine
The method comprises the following steps:
(1) weighing 2-acrylamide-2-methyl propanesulfonic Acid (AMPS), stirring and dissolving in solvent deionized water to obtain 1mol/L AMPS aqueous solution, and weighing lithium hydroxide monohydrate (LiOH. H)2O) stirring and dissolving in solvent deionized water to obtain a LiOH aqueous solution with the concentration of 1 mol/L. And (2) putting the LiOH aqueous solution into a two-mouth bottle connected with a dropping funnel, uniformly stirring at room temperature in an argon atmosphere, then slowly dropping the AMPS aqueous solution into the bottle by using the dropping funnel while stirring under the condition of ice water bath, and continuously stirring until the reaction is complete after the dropping is finished to obtain the 1mol/L aqueous solution of 2-acrylamido-2-methylpropanesulfonic acid lithium (AMPS-Li).
(2) Weighing branched polyethyleneimine (Mn is 100000) and solvent deionized water, placing the branched polyethyleneimine and the solvent deionized water into a three-neck flask connected with a condenser, a thermometer and a dropping funnel, stirring uniformly at room temperature under argon atmosphere, slowly dropwise adding 1mol/L aqueous solution of 2-acrylamido-2-methylpropanesulfonic acid lithium (AMPS-Li) by using the dropping funnel while stirring, controlling the molar ratio of a repeating unit of the polyethyleneimine to the added 2-acrylamido-2-methylpropanesulfonic acid lithium (AMPS-Li) to be 1:1, after the dropwise addition is finished, heating to 50 ℃, and continuing stirring for reaction for 24 hours to obtain the sulfonic acid functionalized polyethyleneimine (PEI-AMPS-Li-1) aqueous solution.
(3) And (3) slowly dripping a certain amount of good solvent methanol into the sulfonic acid functionalized polyethyleneimine (PEI-AMPS-Li-1) aqueous solution obtained in the step (2) by stirring, and then slowly dripping poor solvent diethyl ether by stirring until a product is recrystallized and separated out, so as to obtain the purified sulfonic acid functionalized polyethyleneimine (PEI-AMPS-Li-1). And (3) carrying out nuclear magnetic resonance hydrogen spectrum detection on the obtained sulfonic acid functionalized polyethyleneimine (PEI-AMPS-Li-1), wherein the deuterated reagent is deuterium oxide, and the detected nuclear magnetic resonance hydrogen spectrum is shown in figure 2.
Example 5:
the specific operation process is as in example 4, except that: and (3) in the step (2), the molar ratio of the repeating unit of the polyethyleneimine to the added lithium 2-acrylamido-2-methylpropanesulfonate (AMPS-Li) is 1:2, so that the sulfonic acid functionalized polyethyleneimine (PEI-AMPS-Li-2) is obtained.
And (3) carrying out nuclear magnetic resonance hydrogen spectrum detection on the obtained sulfonic acid functionalized polyethyleneimine (PEI-AMPS-Li-2), wherein the deuterated reagent is deuterium oxide, and the detected nuclear magnetic resonance hydrogen spectrum is shown in figure 2.
Example 6:
the specific operation process is as in example 4, except that: and (3) in the step (2), the molar ratio of the repeating unit of the polyethyleneimine to the added lithium 2-acrylamido-2-methylpropanesulfonate (AMPS-Li) is 1:4, so that the sulfonic acid functionalized polyethyleneimine (PEI-AMPS-Li-4) is obtained. And (3) carrying out nuclear magnetic resonance hydrogen spectrum detection on the obtained sulfonic acid functionalized polyethyleneimine (PEI-AMPS-Li-4), wherein the deuterated reagent is deuterium oxide, and the detected nuclear magnetic resonance hydrogen spectrum is shown in figure 2.
Example 7:
the specific operation process is as in example 4, except that: and (3) in the step (2), the molar ratio of the repeating unit of the polyethyleneimine to the added lithium 2-acrylamido-2-methylpropanesulfonate (AMPS-Li) is 1:8, so that the sulfonic acid functionalized polyethyleneimine (PEI-AMPS-Li-8) is obtained. And (3) carrying out nuclear magnetic resonance hydrogen spectrum detection on the obtained sulfonic acid functionalized polyethyleneimine (PEI-AMPS-Li-8), wherein the deuterated reagent is deuterium oxide, and the detected nuclear magnetic resonance hydrogen spectrum is shown in figure 2.
Example 8: preparation of sulfonic acid functionalized polyethyleneimine polymer solid electrolyte
The method comprises the following steps:
sulfonic acid functionalized polyethyleneimine (PEI-AMPS-Li-1) prepared in example 4 is used as a matrix of a polymer solid electrolyte, and a cross-linking agent Ethylene Diamine Tetraacetic Acid (EDTA) is added in a molar ratio]：[NH]1:50) and plasticizer lithium bistrifluoromethylalkanesulfonimide (molar ratio [ LiTFSI ]]：[NH]1:100) is heated and crosslinked, then the PEI-AMPS-Li-1 polymer solid electrolyte with interpenetrating network type is prepared, the ionic conductivity is 1.53 multiplied by 10-5S·cm-1(65 ℃), the apparent activation energy of ionic conductance is Ea which is 0.73eV, the thermal decomposition temperature can reach 250 ℃, the elongation at break can reach more than 200% (figure 3), the transference number of lithium ions can reach 0.92, the electrochemical window can reach 5.5V (figure 4), and compared with the electrochemical window of 4.2V (figure 5) of the traditional organic liquid electrolyte, the PEI-AMPS-Li-1 polymer solid electrolyte has a wider electrochemical window and better electrochemical stability.
Example 9: preparation of sulfonic acid functionalized polyethyleneimine polymer gel electrolyte
The method comprises the following steps:
sulfonic acid functionalized polyethyleneimine (PEI-AMPS-Li-1) prepared in example 4 is used as a matrix of a polymer gel electrolyte, and a cross-linking agent Ethylene Diamine Tetraacetic Acid (EDTA) is added in a molar ratio]：[NH]1:50) and a plasticizer montmorillonite (mass fraction of 5%), performing a thermal crosslinking reaction, and absorbing a certain amount of a plasticizer solution (1mol/L LiPF6, EC: DMC: EMC: 1:1:1) in a glove box filled with argon atmosphere to prepare the PEI-AMPS-Li-1 polymer gel electrolyte (FIG. 6 and FIG. 7), wherein the ionic conductivity of the PEI-AMPS-Li-1 polymer gel electrolyte is 2.22 multiplied by 10-3S·cm-1(room temperature)) The elongation at break can reach more than 250 percent (figure 8), the transference number of lithium ions can reach 0.56 (figure 9), the electrochemical window can reach 4.5V (figure 10), and compared with the electrochemical window of 4.2V (figure 5) of the traditional organic liquid electrolyte, the PEI-AMPS-Li-1 polymer gel electrolyte has a wider electrochemical window and better electrochemical stability.
Example 10: preparation of sulfonic acid functionalized polyethyleneimine polymer solid electrolyte
The method comprises the following steps:
sulfonic acid functionalized polyethyleneimine (PEI-AMPS-1) prepared in example 1 is used as a matrix of a polymer solid electrolyte, and a cross-linking agent Ethylene Diamine Tetraacetic Acid (EDTA) is added in a molar ratio]：[NH]1:50) and plasticizer lithium bistrifluoroamino-methylsulphonimide (molar ratio [ LiTFSI ]]：[NH]1:100) is heated and crosslinked, then the PEI-AMPS-1 polymer solid electrolyte with interpenetrating network type is prepared, the ionic conductivity is 9.91 multiplied by 10-6S·cm-1(65 ℃), the thermal decomposition temperature can reach 250 ℃, and the elongation at break can reach more than 200% (figure 11).
Comparative example 1:
referring to example 10, the difference is that sulfonic acid functionalized polyethyleneimine (PEI-AMPS-1) is replaced by acrylonitrile modified polyethyleneimine (CN-PEI), so as to prepare an interpenetrating network type CN-PEI polymer solid electrolyte, the elongation at break is only 4.5% (fig. 12), while the elongation at break of PEI-AMPS-Li-1 polymer solid electrolyte can reach more than 200%, and the flexibility and mechanical strength are much better than those of CN-PEI polymer solid electrolyte.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, simplifications, etc., which are made without departing from the spirit and principle of the present invention, should be regarded as being equivalent to the replacement of the above embodiments, and are included in the scope of the present invention.
Claims (8)
1. A sulfonic acid functionalized polyethyleneimine polymer electrolyte matrix material is characterized in that polyethyleneimine is functionally modified by Michael addition reaction between the polyethyleneimine and a sulfonic acid compound containing double bonds to obtain a functional polymer; the double-bond-containing sulfonic acid compound is selected from more than one of 2-acrylamido-2-methylpropanesulfonic acid and lithium 2-acrylamido-2-methylpropanesulfonate; the molar ratio of the repeating unit of the polyethyleneimine to the double-bond-containing sulfonic acid compound is 1: 0.01-1: 11; the number average molecular weight Mn of the polyethyleneimine is 5000-100000.
2. A sulfonic acid functionalized polyethyleneimine polymer solid electrolyte is characterized in that sulfonic acid functionalized polyethyleneimine, a cross-linking agent and a plasticizer are subjected to heating cross-linking reaction to form an interpenetrating network type material polymer solid electrolyte; the sulfonic acid functionalized polyethyleneimine is a functional polymer obtained by performing functional modification on polyethyleneimine through Michael addition reaction between the polyethyleneimine and a sulfonic acid compound containing double bonds; the double-bond-containing sulfonic acid compound is selected from more than one of 2-acrylamido-2-methylpropanesulfonic acid and lithium 2-acrylamido-2-methylpropanesulfonate; the molar ratio of the repeating unit of the polyethyleneimine to the double-bond-containing sulfonic acid compound is 1: 0.01-1: 11; the number average molecular weight Mn of the polyethyleneimine is 5000-100000.
3. The sulfonic acid functionalized polyethyleneimine-based polymer solid electrolyte according to claim 2, wherein the crosslinking agent is one or more of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, ethylenediaminetetraacetic acid; the cross-linking agent accounts for 1-20% of the total mass of the sulfonic acid functionalized polyethyleneimine, the cross-linking agent and the plasticizer.
4. The sulfonic acid-functionalized polyethyleneimine-based polymer solid electrolyte according to claim 2, wherein the plasticizer is at least one selected from lithium hexafluorophosphate, lithium bistrifluoromethylalkanesulfonimide, montmorillonite, ethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, and diethyl carbonate.
5. The sulfonic acid-functionalized polyethyleneimine-based polymer solid electrolyte according to claim 2, wherein the plasticizer accounts for 1% to 90% of the total mass of the sulfonic acid-functionalized polyethyleneimine, the crosslinking agent and the plasticizer.
6. The sulfonic acid functionalized polyethyleneimine polymer gel electrolyte is characterized in that the sulfonic acid functionalized polyethyleneimine polymer gel electrolyte is prepared by soaking the sulfonic acid functionalized polyethyleneimine polymer solid electrolyte in a plasticizer solution for a certain time according to any one of claims 2 to 5, and absorbing a certain amount of the plasticizer solution.
7. Use of the sulfonic acid functionalized polyethyleneimine based polymer solid electrolyte of claim 2 or the sulfonic acid functionalized polyethyleneimine based polymer gel electrolyte of claim 6, wherein the use is for an electrochemical energy storage device.
8. Use of the sulfonic acid functionalized polyethyleneimine based polymer solid or gel electrolyte according to claim 7, wherein the electrochemical energy storage device comprises a lithium ion battery, a supercapacitor, a lithium sulfur battery, and a solar cell.
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