CN109103031B - Solid polymer capacitor and preparation method thereof - Google Patents

Solid polymer capacitor and preparation method thereof Download PDF

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CN109103031B
CN109103031B CN201710473618.3A CN201710473618A CN109103031B CN 109103031 B CN109103031 B CN 109103031B CN 201710473618 A CN201710473618 A CN 201710473618A CN 109103031 B CN109103031 B CN 109103031B
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lithium
tetrafluoroborate
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CN109103031A (en
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郭玉国
段惠
殷雅侠
李林
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Institute of Chemistry CAS
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    • 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
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • 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
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    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention discloses a solid polymer capacitor and a preparation method thereof. The solid polymer capacitor comprises a positive electrode, an electrolyte, a diaphragm and a negative electrode, wherein the electrolyte is a polymer electrolyte and comprises a solvent, a polymeric monomer and a lithium salt. The method has the advantages of strong controllability, simple and convenient operation, low price and good application prospect. The solid polymer capacitor obtained by the method has higher energy density and cycling stability.

Description

Solid polymer capacitor and preparation method thereof
The technical field is as follows:
the invention belongs to the field of energy storage device manufacturing, and relates to a novel solid polymer capacitor and a preparation process thereof.
Background art:
at present, the environmental pollution is increasingly severe, fossil fuels are increasingly deficient, and the development of clean, cheap and safe energy storage technology is particularly important. With the rise of hybrid electric vehicles, the super capacitor receives more and more attention with higher power density, good cycle life, larger capacity, faster discharge process and wider working temperature range, but the liquid capacitor has the safety problems of electrolyte leakage, combustion or explosion in case of open fire and the like, thereby limiting the development of flexible capacitors. The solid capacitor replaces flammable electrolyte with relatively safe solid electrolyte, and solves the safety problem of liquid capacitor. And the polymer electrolyte has certain flexibility, and even the transparent polymer electrolyte can realize the shape diversity of the transparent capacitor and the preparation of a flexible device. However, many of the existing solid polymer capacitors have difficulty in maintaining the original excellent electrochemical properties under various bending deformations due to the contradiction between the mechanical strength and high conductivity of the polymer electrolyte. It is therefore important to design polymer electrolytes suitable for solid state capacitors and having both high ionic conductance and flexibility.
The invention skillfully designs a novel solid polymer capacitor by an in-situ polymer method, and the polymer electrolyte has high ionic conductivity and outstanding mechanical flexibility. The electrolyte leakage of the traditional liquid capacitor is solved, and meanwhile, the solid capacitor is endowed with excellent flexibility, so that the realization of a safe flexible energy storage device becomes possible.
The invention content is as follows:
the invention provides a novel solid polymer capacitor which is characterized by comprising a positive electrode, a polymer electrolyte, a diaphragm and a negative electrode, wherein the positive electrode is composed of an active substance, a conductive additive and a binder, the polymer electrolyte is composed of a solvent, a polymer monomer and a lithium salt, and the diaphragm and the negative electrode are arranged in a sealed mode.
The solvent comprises Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), Acetonitrile (ACN), Dichloromethane (DCM), ethylene glycol dimethyl ether (DME), Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), spiro quaternary ammonium tetrafluoroborate (SBP-BF)4) 1-alkyl-3-methylimidazolium tetrafluoroborate (Rnim-BF)4R ═ C1, C2, C4), tetraethylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, trimethyl-ethylamine tetrafluoroborate and tetrabutylammonium tetrafluoroborate, preferably tetraethylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, trimethyl-ethylamine tetrafluoroborate and tetrabutylammonium tetrafluoroborate; the volume fraction of the solvent is 10-90%. Preferably, it is 20% to 50%.
The monomer is selected from cyclic ether organic matters at least containing one oxygen atom. Preferably, the cyclic ether-based organic compound is selected from C2-C20 cycloalkane containing at least 1 oxygen atom, or C3-C20 cycloalkene containing at least 1 oxygen atom. Preferably, the cycloalkane ether organic compound is selected from (CH) containing at least 1 oxygen atom2)nOmMonocycloalkanes, CnH2n-2OmSpiro or bridged cycloalkane, wherein n is more than or equal to 2 and less than or equal to 20, and m is more than or equal to 1 and less than or equal to 6. Preferably, 2. ltoreq. n.ltoreq.12, 1. ltoreq. m.ltoreq.3. The volume fraction of the monomers is 10% to 90%, preferably 50% to 80%.
Preferably, the (CH) containing 1 oxygen atom2)nOmThe mono-naphthenic organic substance is
Figure BDA0001327295530000021
Said (CH) containing 2 oxygen atoms2)nOmThe mono-naphthenic organic substance is
Figure BDA00013272955300000213
Said (CH) containing 3 oxygen atoms2)nOmThe mono-naphthenic organic substance is
Figure BDA00013272955300000212
Preferably, said CnH2n-2OmThe bridged cycloalkane ether organic substance is selected from those containing 1 oxygen atom
Figure BDA00013272955300000210
Containing 2 oxygen atoms
Figure BDA00013272955300000211
Containing 3 oxygen atoms
Figure BDA0001327295530000029
Preferably, said CnH2n-2OmThe spirocycloalkane ether organic substance is selected from those containing 1 oxygen atom
Figure BDA0001327295530000022
Containing 2 oxygen atoms
Figure BDA0001327295530000023
Containing 3 oxygen atoms
Figure BDA0001327295530000024
Preferably, at least one H on at least one carbon atom of the cycloalkane or cycloalkene ring may be substituted with an R1 group; the R1 group is selected from one of the following groups: alkyl, cycloalkyl, aryl, hydroxyl, carboxyl, amino, ester, halogen, acyl, aldehyde, sulfhydryl and alkoxy.
Preferably, the cyclic ether organic containing one oxygen is selected from substituted oxirane, substituted or unsubstituted oxetane, substituted or unsubstituted tetrahydrofuran, substituted or unsubstituted tetrahydropyran; the number of the substituents may be one or more; the substituent is the R1 group described above.
The cyclic ether organic matter containing two oxygens is selected from substituted or unsubstituted 1, 3-dioxolane and substituted or unsubstituted 1, 4-dioxane; the number of the substituents may be one or more; the substituent is the R1 group described above.
The cyclic ether organic matter containing three oxygens is selected from substituted or unsubstituted trioxymethylene; the number of the substituents may be one or more; the substituent is the R1 group described above.
Preferably, the monomer is selected from a mixture of at least two cyclic ether organic compounds, including a mixture of ethylene oxide and 1, 3-dioxolane, a mixture of ethylene oxide and 1, 4-dioxane, a mixture of tetrahydrofuran and 1, 3-dioxolane, a mixture of tetrahydrofuran and 1, 4-dioxane, a mixture of tetrahydrofuran and trioxymethylene, and a mixture of 1, 3-dioxolane and trioxymethylene. More preferably, the monomers are selected from at least one of mixtures of ethylene oxide and 1, 3-dioxolane, mixtures of ethylene oxide and 1, 4-dioxane, mixtures of tetrahydrofuran and 1, 3-dioxolane, mixtures of tetrahydrofuran and 1, 4-dioxane, mixtures of 1, 3-dioxolane and trioxymethylene, wherein the volume ratio between the two monomers in these mixtures is from 1:9 to 9:1, preferably from 1:3 to 3: 1.
The lithium salt is one or more of lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate) imide, lithium hexafluorophosphate, lithium hexafluoroborate, lithium tetrafluoroborate, lithium perchlorate, lithium chloride, lithium iodide, lithium tris (pentafluoroethyl) trifluorophosphate and lithium dioxalate borate; preferably, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium hexafluoroborate, lithium tetrafluoroborate, lithium perchlorate and lithium chloride; the molar concentration of the lithium salt in the electrolyte solution is 0.05 to 7M, preferably 1.0 to 4.0M.
Preferably, the lithium salt is selected from at least one of the mixtures of at least two of the above lithium salts, including at least one of a mixture of lithium trifluoromethanesulfonate and lithium hexafluorophosphate, a mixture of lithium bis (trifluoromethanesulfonate) imide and lithium hexafluorophosphate, a mixture of lithium hexafluoroborate and lithium trifluoromethanesulfonate, a mixture of lithium trifluoromethanesulfonate and lithium tetrafluoroborate, a mixture of lithium bis (trifluoromethanesulfonate) imide and lithium tetrafluoroborate, a mixture of lithium trifluoromethanesulfonate and lithium perchlorate, and a mixture of lithium bis (trifluoromethanesulfonate) imide and lithium perchlorate; more preferably, the lithium salt may be selected from a group consisting of a mixture of lithium trifluoromethanesulfonate and lithium hexafluorophosphate, a mixture of lithium hexafluoroborate and lithium trifluoromethanesulfonate, a mixture of lithium bis (trifluoromethanesulfonate) imide and lithium hexafluorophosphate, a mixture of lithium trifluoromethanesulfonate and lithium tetrafluoroborate, and a mixture of lithium bis (trifluoromethanesulfonate) imide and lithium tetrafluoroborate, wherein the molar concentration of lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate) imide in the electrolyte solution is 0.5-2.0M, and the molar concentration of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroborate is 0.03-0.08M. .
In the anode of the solid polymer capacitor, the active substance is Active Carbon (AC), graphene, carbon nano tube, carbon nano fiber, biochar, a compound of a carbon material and a metal oxide (active carbon and TiO)2,ZnO,Al2O3,Cr2O3,CoO,SiO2,NiO,MnO2Complex of (2), etc.), metal oxide (RuO)2,RuO2.H2O,MnO2,NiO,CoO,TiO2Etc.), lithium-containing metal oxides (LiFePO)4Lithium manganate, lithium cobaltate, LiNiO2、LiVO2Etc.), conductive polymers (polypyrrole, polythiophene, polyaniline, polyparaphenylene, polyacene, polyvinylferrocene, etc.); the conductive additive is one or more of Super P, ketjen black, graphene and conductive carbon nano tubes, and the binder is one or more of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR).
In the solid polymer capacitor anode, the mass of the active substance accounts for 70-99% of the total mass of the anode, the mass of the conductive additive accounts for 0.5-20% of the total mass of the anode, and the mass of the binder accounts for 0.5-20% of the total mass of the anode.
The diaphragm in the solid polymer capacitor comprises a PP film, a PE film, a PP/PE/PP film and the like.
The active substance of the cathode of the solid polymer capacitor is active carbon, biochar and metal oxide (RuO)2,RuO2.H2O,MnO2,NiO,CoO,TiO2Etc.), lithium-containing metal oxide (Li)4Ti5O12Etc.), one or more of lithium-carbon composite, lithium-embedded silicon-based composite, lithium-embedded tin-carbon composite and graphene.
The invention provides a preparation method of a solid polymer capacitor, which is characterized by comprising the following steps:
step 1) assembling a naked battery cell: assembling a positive electrode, a diaphragm and a negative electrode into a bare cell in a battery case or an aluminum-plastic film in a certain sequence under an inert atmosphere, and waiting for liquid injection;
step 2) preparing a polymer electrolyte precursor solution: adding a polymeric monomer and lithium salt into a solvent, and stirring and dissolving completely to obtain a polymer electrolyte precursor solution;
step 3) liquid injection and in-situ polymerization: infiltrating the bare cell with the polymer precursor solution obtained in the step 2), completely sealing the cell shell or the aluminum-plastic film after the cell is fully infiltrated, standing for a period of time, finishing and exhausting after the in-situ polymerization is completed, and obtaining the solid polymer capacitor. The polymerization temperature is from 10 to 40 ℃ and preferably from 15 to 30 ℃. The polymerization time is from 2 to 200 hours, preferably from 3 to 24 hours.
In addition, the application of the solid polymer capacitor provided by the invention in the preparation of a high energy density energy storage device also belongs to the protection scope of the invention.
Compared with the prior art, the solid polymer capacitor provided by the invention has the advantages of good safety, high power performance and stable chemical property.
The present invention will be described in detail with reference to specific examples. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.
Drawings
FIG. 1 optical photographs of a solid polymer electrolyte prepared in example 1 of the present invention before and after polymerization.
Detailed description of the invention
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
(I) assembling solid polymer capacitors
Step 1) preparing a naked battery cell: according to the following steps of 80: 10: weighing lithium iron phosphate according to the mass ratio of 10: adding N-methyl pyrrolidone (NMP) into the Super P and PVDF, grinding and mixing, and coating on an aluminum foil to obtain a positive electrode film; according to the following steps of 80: 10: weighing Activated Carbon (AC) according to the mass ratio of 10: adding N-methyl pyrrolidone (NMP) into the Super P and PVDF, grinding and mixing, and coating the mixture on a copper foil to obtain a negative electrode film; and after drying, stacking the positive electrode membrane, the diaphragm Celgard2523 and the negative electrode membrane in turn in the electrode shell under high-purity argon to form a bare cell.
Step 2) preparing a polymer precursor solution: preparing a polymer precursor solution under high-purity argon, wherein the solvent is an EC/DEC/DMC mixed solution (the volume ratio is 1: 1: 1), the volume fraction of the EC/DEC/DMC mixed solution accounts for 50% of the total volume of the solution, the polymeric monomer is trioxymethylene, the volume fraction of the trioxymethylene accounts for 50% of the total volume of the solution, and the lithium salt concentration in the finally obtained solution is 1 mol.L-1Lithium hexafluorophosphate. Stirring and mixing uniformly to obtain the polymer precursor solution. Step 3) liquid injection and in-situ polymerization: injecting the polymer precursor solution obtained in the step 2) into the bare cell, completely sealing the cell shell after the cell is fully soaked, standing at room temperature (25 ℃) for 24 hours, completing in-situ polymerization, and packaging to obtain the solid polymer capacitor.
(II) electrochemical Performance testing of solid Polymer capacitors
And respectively carrying out constant-current charge and discharge tests on the solid polymer capacitor by using an electrochemical workstation and a charge and discharge instrument, wherein the test voltage interval is 1-2.6V. The test temperature was 25 ℃. The test results of the obtained capacitor are shown in Table 1. And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending.
Example 2
The other conditions were the same as in example 1 except that the volume fraction of the solvent in step 2) was reduced to 20% and the volume fraction of the polymerized monomer was increased to 80%. The results of the tests on the obtained capacitors are shown in Table 1.
Example 3
The other conditions were the same as in example 1 except that the standing temperature in step 3) was raised to 35 ℃ and the test results for the obtained capacitor were as shown in Table 1.
Example 4
The other conditions were the same as in example 1 except that tetrahydrofuran was used as the monomer for polymerization and the volume fraction thereof was 50%, and tetraethylammonium tetrafluoroborate was used as the solvent. The results of the tests on the obtained capacitors are shown in Table 1. And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending.
Example 5
The other conditions were the same as in example 4 except that the monomer was 1, 3-dioxolane. The results of the tests on the obtained capacitors are shown in Table 1. And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending.
Example 6
The other conditions were the same as in example 5 except that the lithium salt was in a concentration of 3 mol. L-1Lithium hexafluorophosphate. And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending. The results of the tests on the obtained capacitors are shown in Table 1.
Example 7
The other conditions were the same as in example 1 except that the solvent was triethylene glycol dimethyl ether (TEGDME). And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending. The results of the tests on the obtained capacitors are shown in Table 1.
Example 8
The other conditions were the same as in example 1 except that polythiophene was polymerized onto a thin carbon electrode by electrochemical polymerization while preparing a positive electrode material; preparing a negative electrode material according to the following steps of 80: 10: 10, adding N-methyl pyrrolidone (NMP), grinding and mixing, and coating the copper foil to form a negative electrode. And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending. The results of the tests on the obtained capacitors are shown in Table 1.
Example 9
The other conditions were the same as in example 1 except that, in the preparation of the positive electrode material, the ratio of 80: 10: 10, adding N-methylpyrrolidone (NMP), grinding and mixing, and coating an aluminum foil to form a positive electrode; when preparing the anode material, the ratio of 80: 10: 10, adding N-methyl pyrrolidone (NMP), grinding and mixing the silicon-carbon compound, the Super P and the PVDF according to the mass ratio, and coating the mixture on a copper foil to form a negative electrode; the solvent is tetraethylammonium tetrafluoroborate. And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending. The results of the tests on the obtained capacitors are shown in Table 1.
Example 10
Otherwise, the monomer was 1, 3-dioxolane and the lithium salt was 0.05 mol. multidot.L in the same manner as in example 9-1Lithium hexafluorophosphate and 1.0 mol. L-1Mixtures of lithium bis (trifluoromethanesulphonate) imides. And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending. The results of the tests on the obtained capacitors are shown in Table 1.
Example 11
The other conditions were the same as in example 9 except that the monomers were mixed in a volume ratio of 2: 1 mixture of tetrahydrofuran and 1, 3-dioxolane, lithium salt 0.05 mol.L-1Lithium hexafluorophosphate and 1.0 mol. L-1Mixtures of lithium bis (trifluoromethanesulphonate) imides. And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending.The results of the tests on the obtained capacitors are shown in Table 1.
Example 12
The other conditions were the same as in example 5 except that the lithium salt was used in a concentration of 0.05 mol. L-1And 1.0 mol.L of lithium hexafluorophosphate-1Lithium bis (trifluoromethanesulfonate) imide. And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending. The test results for the obtained batteries are shown in table 1.
Example 13
The other conditions were the same as in example 5 except that the lithium salt was used in a concentration of 0.05 mol. L-1And 1.0 mol.L of lithium hexafluoroborate-1Lithium trifluoromethanesulfonate (5). And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending. The test results for the obtained batteries are shown in table 1. This result should be comparable to example 13.
Example 14
The other conditions were the same as in example 13 except that the monomers were mixed in a volume ratio of 1: 1 of trioxymethylene and 1, 3-dioxolane. And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending. The test results for the obtained batteries are shown in table 1.
Example 15
The other conditions were the same as in example 13 except that the monomers were mixed in a volume ratio of 2: 1 tetrahydrofuran and 1, 3-dioxolane. And bending the capacitor by 45 degrees, and carrying out electrochemical performance test without leakage, wherein the result is the same as that before bending. The test results for the obtained batteries are shown in table 1.
Comparative example 1
The other conditions were the same as in example 1 except that the polymer monomer in step 2 was replaced with polyethylene glycol diacrylate and the initiator was dibenzoyl peroxide. The test results for the obtained batteries are shown in table 1. The capacitor is bent by 45 degrees, no leakage occurs, but the polymer electrolyte is broken, and the capacitor cannot be subjected to a normal electrochemical performance test.
The electrochemical performance tests of the above examples are shown in Table 1
Figure BDA0001327295530000071
Figure BDA0001327295530000081
As can be seen from the above examples and comparative examples, the prepared solid polymer capacitor has higher energy density and longer cycle life, and has higher safety and flexibility compared to the conventional liquid capacitor, while the solid electrolyte is colorless and transparent and is suitable for preparing flexible transparent devices.
In conclusion, the solid polymer capacitor prepared by the invention has better energy density and cycling stability. Meanwhile, the electrolyte also shows better safety and flexibility, and is suitable for preparing flexible devices. The invention provides a method for preparing a solid polymer capacitor with high energy density and cycle life at the same time, which is simple to operate and low in cost, and has excellent application prospect. The above description is only a preferred embodiment of the present invention, and it should be understood that the present invention is not limited to the embodiment, and those skilled in the art can easily make various changes and modifications according to the main concept and spirit of the present invention, and therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
From the above examples, it can be seen that it is preferable that the electrolyte monomer contains trioxymethylene and 1, 3-dioxolane, and that the lithium salt contains lithium hexafluorophosphate or a mixture of lithium hexafluoroborate. The most preferable scheme is that the electrolyte monomer contains 1, 3-dioxolane, the solvent is an ionic liquid selected from tetraethyl amine borate, tetramethyl amine tetrafluoroborate, trimethyl-ethylamine tetrafluoroborate and tetrabutyl amine tetrafluoroborate, and the lithium salt is selected from lithium hexafluorophosphate or a mixture of lithium hexafluoroborate and bis (trifluoromethanesulfonic acid) imide lithium, and a mixture of lithium hexafluoroborate and lithium trifluoromethanesulfonate.

Claims (12)

1. A solid polymer capacitor comprising a positive electrode and a negative electrode each composed of an active material, a conductive additive and a binder, a polymer electrolyte composed of a solvent, a polymer monomer and a lithium salt, and a separator; the polymer monomer is selected from one or more of cyclic ether organic matters at least containing one oxygen atom, and the volume fraction of the monomer is 50-80%; the cyclic ether organic matter is at least one of a mixture of tetrahydrofuran and 1, 3-dioxolane and a mixture of 1, 3-dioxolane and trioxymethylene, wherein in the mixtures, the volume ratio of two monomers is 1:3-3: 1; the polymer electrolyte is obtained by in-situ polymerization of polymer monomers;
the lithium salt is selected from a mixture of lithium bis (trifluoromethanesulfonate) imide and lithium hexafluorophosphate or a mixture of lithium hexafluoroborate and lithium trifluoromethanesulfonate, wherein the molar concentration of the lithium trifluoromethanesulfonate or the lithium bis (trifluoromethanesulfonate) imide in the electrolyte solution is 0.5-2.0M, and the molar concentration of the lithium hexafluorophosphate or the lithium hexafluoroborate is 0.03-0.08M.
2. The solid polymer capacitor of claim 1, wherein the solvent comprises Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), Acetonitrile (ACN), Dichloromethane (DCM), ethylene glycol dimethyl ether (DME), Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), spiro quaternary ammonium tetrafluoroborate (SBP-BF)4) One or more of 1-alkyl-3-methylimidazole tetrafluoroborate, tetraethylamine tetrafluoroborate, tetramethylamine tetrafluoroborate, trimethyl-ethylamine tetrafluoroborate and tetrabutylamine tetrafluoroborate; the volume fraction of the solvent is 10-90%.
3. The solid polymer capacitor of claim 1, wherein the solvent is selected from one or more of tetraethylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, trimethyl-ethylamine tetrafluoroborate, tetrabutylammonium tetrafluoroborate; the volume fraction of the solvent is 20-50%.
4. The solid polymer capacitor according to claim 1, wherein in the positive electrode, the active material is one or more of Activated Carbon (AC), graphene, carbon nanotubes, carbon nanofibers, biochar, a composite of a carbon material and a metal oxide, a lithium-containing metal oxide, and a conductive polymer; the conductive additive is one or more of Super P, ketjen black, graphene and conductive carbon nano tubes, and the binder is one or more of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR).
5. The solid state polymer capacitor according to claim 4, wherein the composite of the carbon material and the metal oxide is selected from activated carbon and TiO2, ZnO, Al2O3, Cr2O3, CoO, SiO2, NiO, MnO2A complex of at least one of the above; the metal oxide is selected from RuO2, RuO2.H2O, MnO2, NiO, CoO, TiO2At least one of; the lithium-containing metal oxide is selected from LiFePO4Lithium manganate, lithium cobaltate, LiNiO2、LiVO2At least one of; the conductive polymer is at least one selected from polypyrrole, polythiophene, polyaniline, poly-p-benzene, polyacene and polyvinyl ferrocene.
6. A solid state polymer capacitor according to any one of claims 1 to 5, wherein the positive electrode comprises 70 to 99% by mass of the active material, 0.5 to 20% by mass of the conductive additive, and 0.5 to 20% by mass of the binder, based on the total mass of the positive electrode.
7. The solid state polymer capacitor of claim 1, wherein the separator is selected from one of a PP film, a PE film, a PP/PE/PP film.
8. The solid state polymer capacitor of claim 1, wherein the negative electrode is one or more of activated carbon, biochar, metal oxide, lithium-containing metal oxide, lithium-carbon composite, lithium-intercalated silicon-based composite, lithium-intercalated tin-carbon composite, and graphene.
9. The solid polymer capacitor of claim 8, wherein the metal oxide is selected from RuO2,RuO2.H2O, MnO2, NiO, CoO, TiO2At least one of; the lithium-containing metal oxide is selected from Li4Ti5O12。
10. A method for producing a solid polymer capacitor as claimed in any one of claims 1 to 9, characterized by comprising the steps of:
step 1) assembling a naked battery cell: assembling a positive electrode, a diaphragm and a negative electrode into a bare cell in a battery case or an aluminum-plastic film in a certain sequence under an inert atmosphere, and waiting for liquid injection;
step 2) preparing a polymer electrolyte precursor solution: adding a polymer monomer and lithium salt into a solvent, and stirring and dissolving completely to obtain a polymer electrolyte precursor solution;
step 3) liquid injection and in-situ polymerization: infiltrating the bare cell with the polymer precursor solution obtained in the step 2), completely sealing a battery shell or an aluminum-plastic film after the cell is infiltrated fully, standing for a period of time, finishing and exhausting after in-situ polymerization is completed, and obtaining the solid polymer capacitor, wherein the polymerization temperature is 10-40 ℃, and the polymerization time is 2-200 hours.
11. The process according to claim 10, wherein the polymerization temperature is 15 to 30 ℃ and the polymerization time is 3 to 24 hours.
12. An energy storage device characterized by: a solid polymer capacitor comprising the solid polymer capacitor of any one of claims 1-9.
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