CN116581373A - Quasi-solid electrolyte and preparation method thereof - Google Patents
Quasi-solid electrolyte and preparation method thereof Download PDFInfo
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- CN116581373A CN116581373A CN202310253311.8A CN202310253311A CN116581373A CN 116581373 A CN116581373 A CN 116581373A CN 202310253311 A CN202310253311 A CN 202310253311A CN 116581373 A CN116581373 A CN 116581373A
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- solid electrolyte
- lithium
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- dianhydride
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 34
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000004985 diamines Chemical class 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000002608 ionic liquid Substances 0.000 claims abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 28
- -1 4' -diaminoaniline Chemical compound 0.000 claims description 23
- 239000005457 ice water Substances 0.000 claims description 9
- 229920005575 poly(amic acid) Polymers 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 claims description 2
- MNUHUVIZSPCLFF-UHFFFAOYSA-N 1-methylhept-6-ene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)CC(C(O)=O)C(C=C)C(O)=O MNUHUVIZSPCLFF-UHFFFAOYSA-N 0.000 claims description 2
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-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
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- RFJSVARKFQELLL-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole;1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound CCN1CN(C)C=C1.FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F RFJSVARKFQELLL-UHFFFAOYSA-N 0.000 claims 1
- IHEZPUSMTSLNCD-UHFFFAOYSA-N C1=CNC=N1.CCCC[P+](CCCC)(CCCC)CCCC Chemical compound C1=CNC=N1.CCCC[P+](CCCC)(CCCC)CCCC IHEZPUSMTSLNCD-UHFFFAOYSA-N 0.000 claims 1
- 230000005012 migration Effects 0.000 abstract description 7
- 238000013508 migration Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 230000010287 polarization Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JVEZJOVOWAFEKU-UHFFFAOYSA-N N1C=NC=C1.C(CCC)[P](CCCC)(CCCC)CCCC Chemical compound N1C=NC=C1.C(CCC)[P](CCCC)(CCCC)CCCC JVEZJOVOWAFEKU-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a quasi-solid electrolyte and a preparation method thereof. Relates to the technical field of lithium battery materials. The preparation method comprises the following raw materials: dianhydride monomer, diamine monomer, ionic liquid, lithium salt and organic solvent, and a preparation method thereof are provided. The ion conductivity of the quasi-solid electrolyte is 10 ‑4 ～10 ‑1 Scm ‑1 The ion migration number is 0.10-0.95.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a quasi-solid electrolyte and a preparation method thereof.
Background
Lithium batteries have been widely used in portable mobile devices, new energy automobiles, large-scale power storage systems, and the like due to their various advantages of high specific energy density, high operating voltage, low self-discharge rate, long cycle life, no memory effect, wide operating temperature range, and the like. However, the traditional lithium ion battery uses organic liquid electrolyte which is easy to volatilize, inflammable and explosive; most of the separators used in lithium batteries are made of polyolefin materials, and have the defects of easy combustion, poor heat shrinkage performance, no high temperature resistance and the like; lithium dendrites can be formed on the surface of the negative electrode in the charge-discharge cycle process, and when the lithium dendrites develop to a certain extent, the lithium dendrites possibly penetrate through the diaphragm, so that the positive electrode and the negative electrode are short-circuited, a large amount of heat is released, the thermal runaway of the lithium battery is caused, and serious safety accidents are caused. Solid state electrolytes are effective methods to solve the above problems.
The solid electrolyte has good mechanical properties, can effectively inhibit the formation of lithium dendrites, and greatly improves the stability of the solid lithium battery. The solid electrolyte is divided into: inorganic solid state electrolytes and polymer solid state electrolytes. The inorganic electrolyte has high ionic conductivity, but also has the problems of rigid interface contact, serious side reaction and the like, so that the application range is limited; the polymer electrolyte has good interfacial compatibility and processability, but low ionic conductivity at room temperature.
Therefore, it is an urgent need to solve the above-mentioned technical drawbacks.
Disclosure of Invention
In view of this, the present invention provides a quasi-solid electrolyte and a method for preparing the same. The quasi-solid electrolyte has the advantages of good toughness, high temperature resistance, good chemical stability, high ion conductivity, ion migration number, wide electrochemical window and the like, and the preparation process is simple, so that the requirement of mass production can be met.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a quasi-solid electrolyte comprising the following raw materials: dianhydride monomer, diamine monomer, ionic liquid, lithium salt and organic solvent; the mass ratio of diamine monomer to dianhydride monomer is 1:1.01 to 1.03; the total mass of the diamine monomer and the dianhydride monomer is 5-25% of the total mass of the dianhydride monomer, the diamine monomer and the organic solvent; the mass of the ionic liquid is 0.1-300% of the total mass of diamine monomer and dianhydride monomer; the mass of the lithium salt is 0.1-50% of the mass of the ionic liquid.
Preferably: the dianhydride monomer is selected from pyromellitic dianhydride, 4' -oxydiphthalic anhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 3', one or more of 4,4' -benzophenone tetracarboxylic dianhydride, bicyclo [2, 2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride and 3,3', 4' -diphenyl sulfone tetracarboxylic dianhydride.
Preferably: the diamine monomer is selected from one or more than two of 4,4' -diaminodiphenyl ether, 3, 5-diaminobenzoic acid, 2' -bis (trifluoromethyl) -4,4' -diaminodiphenyl, 4' -diaminodiphenyl methane, 2-bis [4 (4-aminophenoxy) phenyl ] propane, 4' -diaminoaniline, 1, 6-hexamethylenediamine, 1, 10-decanediamine and 1, 12-diaminododecane.
Preferably: the ionic liquid is selected from one or more than two of 1-methyl-3-butyl imidazole tetrafluoroborate, 1-methyl-3-butyl imidazole hexafluorophosphate, 1-ethyl-3-methyl imidazole acetate, 1-methyl-butyl imidazole bisulfate, tetrabutyl phosphorus imidazole salt, 1-ethyl-3-methyl imidazole tetrafluoroborate, 1-amyl-3-methyl imidazole tetrafluoroborate, 1-n-butyl-1-methyl pyrrolidine bis (trifluoromethyl sulfonyl) imide, 1-dodecyl-3-methyl imidazole tetrafluoroborate, 1-ethyl-3-methyl imidazole bis (trifluoromethyl sulfonyl) imide salt and 1-ethyl-3-methyl imidazole dicyan amine salt.
Preferably: the lithium salt is selected from one or more of lithium perchlorate, lithium nitrate, lithium bis (difluoro) sulfonyl imide, lithium bis (oxalato) borate, lithium tetrafluoroborate, lithium difluoro (oxalato) borate, lithium hexafluorophosphate and lithium bis (trifluoromethyl) sulfonyl imide.
Preferably: the organic solvent is one or more selected from dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dioxane and tetrahydrofuran.
The invention also provides a preparation method of the quasi-solid electrolyte, which comprises the steps of dissolving dianhydride monomer, diamine monomer, ionic liquid and lithium salt in an organic solvent, and reacting to obtain polyamic acid solution; after the polyamide acid solution is scraped into a film, heating and imidizing are carried out to obtain the quasi-solid electrolyte.
The beneficial effects are that: the method is simple, convenient to operate and suitable for popularization and application.
Preferably: the reaction: dissolving diamine monomer after vacuum dehydration treatment into an organic solvent, and placing the organic solvent into an ice water bath for stirring to obtain a solution; adding the ionic liquid and lithium salt into the solution, and stirring to obtain a first mixed solution; adding dianhydride monomer into the first mixed solution for a small amount for multiple times, and continuously stirring in an ice water bath at the temperature of-10-20 ℃ for 0.5-12 hours; before blade coating, standing the polyamic acid solution for 0.5 to 36 hours under vacuum condition; the polyamide acid solution is coated by a doctor blade and then comprises the step of waiting for volatilizing the organic solvent for 1 hour; heating imidization: under the vacuum condition, the temperature is programmed to be raised three times, the temperature range is 80-250 ℃, and the heating time is 1-12 hours.
The beneficial effects are that: the polyamic acid solution was allowed to stand under vacuum to remove bubbles before blade coating.
Further, the temperature programming is carried out three times: vacuum drying at 80deg.C for 2 hours, followed by vacuum drying at 160deg.C for 1 hour, and finally vacuum drying at 250deg.C for 12 hours.
The invention also provides the quasi-solid electrolyte prepared by any preparation method.
The invention also provides application of the quasi-solid electrolyte in preparing batteries.
Compared with the prior art, the invention discloses a quasi-solid electrolyte and a preparation method thereof, which have the technical effects that the ion conductivity of the quasi-solid electrolyte is 10 -4 ～10 -1 Scm -1 The ion migration number is 0.10-0.95.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
Fig. 1 is a diagram of a quasi-solid electrolyte film according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention discloses a quasi-solid electrolyte and a preparation method thereof.
Example 1
Under the protection of nitrogen, 1.60g of 4,4' -diaminodiphenyl ether and 0.28g of 3, 5-diaminobenzoic acid after vacuum dehydration treatment are dissolved into 55ml of N, N-dimethylacetamide solution, and the solution is placed in an ice-water bath and stirred for 30 minutes to obtain a clear and transparent solution; 3.10g of 1-methyl-3-butylimidazole tetrafluoroborate and 0.34g of lithium bistrifluoromethylsulfonylimide are added into the above clarified solution and stirred for 30 minutes to obtain a first mixed solution; and adding 2.20g of pyromellitic dianhydride into the first mixed solution for a small amount for multiple times, and continuously stirring in an ice-water bath for 12 hours to obtain a viscous polyamic acid solution. After the reaction was completed, the solution was left to stand in a vacuum oven for 12 hours, after which a proper amount of the polyamic acid solution was scraped on a clean glass substrate using a 50 μm doctor blade, the organic solvent was volatilized at room temperature for 1 hour, then dried in vacuo at 80℃for 2 hours, then dried in vacuo at 160℃for 1 hour, and finally dried in vacuo at 250℃for 12 hours.
A quasi-solid electrolyte membrane as shown in fig. 1 was obtained.
Example 2
Under the protection of nitrogen, 1.58g of 4,4' -diaminodiphenylmethane and 0.30g of 3, 5-diaminobenzoic acid after vacuum dehydration treatment are dissolved into 50ml of N, N-dimethylacetamide solution, and the solution is placed in an ice-water bath and stirred for 30 minutes to obtain clear and transparent solution; 5.12g of 1-amyl-3-methylimidazole tetrafluoroborate and 0.53g of lithium bis (difluorosulfonimide) are added into the clear solution and stirred for 30 minutes to obtain a first mixed solution; 2.98g of 3,3', 4' -biphenyl tetracarboxylic dianhydride was added to the first mixed solution a small amount of a plurality of times, and stirring was continued in an ice-water bath for 12 hours to obtain a viscous polyamic acid solution. After the reaction, the solution was left to stand in a vacuum oven for 12 hours, then a proper amount of the polyamic acid solution was scraped on a clean glass substrate using a 50 μm doctor blade, the organic solvent was volatilized at room temperature for 1 hour, then dried in vacuum at 80℃for 2 hours, then dried in vacuum at 160℃for 1 hour, and finally dried in vacuum at 250℃for 12 hours, to obtain a quasi-solid electrolyte membrane.
Technical effects
Ion conductivity test:
the quasi-solid obtained in example 1The electrolyte membrane is arranged in a stainless steel symmetrical button cell, an electrochemical workstation is used for measuring an alternating current impedance spectrum (frequency range: 1000 KHz-1 Hz), and ion conductivity is calculated according to the formula sigma=L/(R×S). Wherein sigma is ion conductivity of the electrolyte, L is thickness of the electrolyte, R is resistance value of the electrolyte, and S is contact area of the electrolyte and the test electrode. The ion conductivity at room temperature of the quasi-solid electrolyte prepared in example 1 was calculated to be 3.2X10 -3 Scm -1 。
Ion migration number test:
in the quasi-solid electrolyte membrane-shaped Li symmetric battery prepared in the example 1, an alternating current impedance spectrum of the battery is measured by an electrochemical workstation to obtain a resistance value before direct current polarization. Measuring a current-time curve, measuring time of 5000 seconds, setting bias voltage of 10mV, measuring alternating current impedance spectrum after direct current polarization, obtaining resistance value after direct current polarization, and obtaining the resistance value after direct current polarization according to the formula t=I s (ΔV-I 0 R 0 )/I 0 (ΔV-I s R s ) And calculating to obtain the migration number of the electrolyte. Wherein t is the migration number of the electrolyte, deltaV is the bias voltage, I 0 For the initial current value, R 0 For initial resistance value, I s Is a steady-state current value after direct current polarization, R s The resistance value after DC polarization. The ion migration number of the quasi-solid electrolyte prepared in example 1 was calculated to be 0.48.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A quasi-solid electrolyte comprising the following materials: dianhydride monomer, diamine monomer, ionic liquid, lithium salt and organic solvent; the mass ratio of the diamine monomer to the dianhydride monomer is 1:1.01 to 1.03; the total mass of the diamine monomer and the dianhydride monomer is 5-25% of the total mass of the dianhydride monomer, the diamine monomer and the organic solvent; the mass of the ionic liquid is 0.1-300% of the total mass of diamine monomer and dianhydride monomer; the mass of the lithium salt is 0.1-50% of the mass of the ionic liquid.
2. The quasi-solid electrolyte of claim 1 wherein said dianhydride monomer is selected from the group consisting of pyromellitic dianhydride, 4' -oxydiphthalic anhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 3', one or more of 4,4' -benzophenone tetracarboxylic dianhydride, bicyclo [2, 2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride and 3,3', 4' -diphenyl sulfone tetracarboxylic dianhydride.
3. The quasi-solid electrolyte of claim 2 wherein said diamine monomer is selected from one or more of 4,4' -diaminodiphenyl ether, 3, 5-diaminobenzoic acid, 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 4' -diaminodiphenylmethane, 2-bis [4 (4-aminophenoxy) phenyl ] propane, 4' -diaminoaniline, 1, 6-hexamethylenediamine, 1, 10-decamethylenediamine, 1, 12-diaminododecane.
4. A quasi-solid electrolyte as claimed in claim 3 wherein said ionic liquid is selected from one or more of 1-methyl-3-butylimidazole tetrafluoroborate, 1-methyl-3-butylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole acetate, 1-methyl-butylimidazole bisulfate, tetrabutyl phosphonium imidazole salt, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-pentyl-3-methylimidazole tetrafluoroborate, 1-n-butyl-1-methylpyrrolidine bis (trifluoromethylsulfonyl) imide, 1-dodecyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt, 1-ethyl-3-methylimidazole dicyano amine salt.
5. The quasi-solid electrolyte of claim 4 wherein said lithium salt is selected from one or more of lithium perchlorate, lithium nitrate, lithium bis-difluorosulfonimide, lithium bis-oxalato-borate, lithium tetrafluoroborate, lithium difluoro-oxalato-borate, lithium hexafluorophosphate, lithium bis-trifluoromethylsulfonimide.
6. The quasi-solid electrolyte of claim 5 wherein said organic solvent is selected from one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dioxane, tetrahydrofuran.
7. The method for preparing a quasi-solid electrolyte according to any one of claims 1 to 6, characterized in that dianhydride monomer, diamine monomer, ionic liquid and lithium salt are dissolved in an organic solvent and reacted to obtain a polyamic acid solution; and (3) after the polyamide acid solution is scraped into a film, heating and imidizing to obtain the quasi-solid electrolyte.
8. The method of claim 7, wherein the reacting: dissolving diamine monomer after vacuum dehydration treatment into an organic solvent, and placing the organic solvent into an ice water bath for stirring to obtain a solution; adding the ionic liquid and lithium salt into the solution, and stirring to obtain a first mixed solution; adding a small amount of dianhydride monomer into the first mixed solution for multiple times, and continuously stirring in an ice water bath, wherein the temperature of the ice water bath is between-10 and 20 ℃, and the stirring time is between 0.5 and 12 hours; before blade coating, standing the polyamic acid solution for 0.5 to 36 hours under vacuum condition; the polyamide acid solution is coated by a doctor blade and then comprises the step of waiting for volatilizing the organic solvent for 1 hour; the thermal imidization: under the vacuum condition, the temperature is programmed to be raised three times, the temperature range is 80-250 ℃, and the heating time is 1-12 hours.
9. A quasi-solid electrolyte prepared by the preparation method of any one of claims 7 or 8.
10. Use of the quasi-solid electrolyte of claim 9 in the preparation of a battery.
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