CN116742116B - Gel electrolyte, preparation method thereof and lithium ion battery - Google Patents
Gel electrolyte, preparation method thereof and lithium ion battery Download PDFInfo
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- CN116742116B CN116742116B CN202311028829.8A CN202311028829A CN116742116B CN 116742116 B CN116742116 B CN 116742116B CN 202311028829 A CN202311028829 A CN 202311028829A CN 116742116 B CN116742116 B CN 116742116B
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- polyethylene glycol
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- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 75
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 85
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 85
- 239000003792 electrolyte Substances 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 229920002545 silicone oil Polymers 0.000 claims abstract description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 claims description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000001879 gelation Methods 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004971 Cross linker Substances 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003827 glycol group Chemical group 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 abstract description 10
- 239000007773 negative electrode material Substances 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 239000005486 organic electrolyte Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 29
- 239000013543 active substance Substances 0.000 description 19
- 239000006258 conductive agent Substances 0.000 description 18
- 238000001035 drying Methods 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 239000011230 binding agent Substances 0.000 description 14
- 238000011065 in-situ storage Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000011244 liquid electrolyte Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- -1 vinyl compound Chemical class 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
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of secondary batteries, and particularly relates to a gel electrolyte, a preparation method thereof and a lithium ion battery. The gel electrolyte is prepared by reacting a vinyl-terminated polyethylene glycol compound with acrylonitrile, polyvinyl-terminated silicone oil, propylene carbonate, an initiator, a cross-linking agent and electrolyte in a specific ratio, has high ion migration number, high conductivity and excellent electrochemical stability, and overcomes the defects of low conductivity and large direct current impedance of the conventional gel electrolyte; the heat release of the oxidation/combustion reaction of the organic electrolyte can be reduced, and the electrical property and the safety performance of the lithium ion battery are improved. Particularly, the vinyl-terminated polyethylene glycol compound is matched with propylene carbonate for use, so that the wettability of the electrolyte can be effectively improved, the positive and negative electrode active materials can be better coated, and the electrical property and the safety property are improved.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a gel electrolyte, a preparation method thereof and a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, high working voltage and the like, and not only occupies a dominant role in the aspect of automobile power batteries, but also is widely applied to a plurality of high-tech fields such as mobile communication, satellites, high-end electronic equipment and the like. However, with the continuous improvement of the energy density of the lithium ion battery, the production and the use of the lithium ion battery are greatly limited by the potential safety hazard.
Thermal runaway is a major cause of safety accidents of lithium ion batteries, and liquid electrolyte occupies a major role in factors causing thermal runaway. The ionic conductivity and chemical property of the gel polymer electrolyte are closer to those of the liquid electrolyte, and the safety performance is closer to that of the solid electrolyte, so that the gel polymer electrolyte has wide application potential in solving the problem of the safety performance of the lithium battery. However, the gel electrolyte has lower conductivity than the liquid electrolyte and lower lithium ion transmission efficiency, so that the direct current impedance is high, and the electric performance of the lithium battery is adversely affected.
The prior art discloses a three-dimensional crosslinked network gel polymer electrolyte which is obtained by reacting a polyether chain segment compound with two ends blocked by amino groups and diisocyanate in electrolyte under the condition of adding or not adding a catalyst; the obtained product has high ionic conductivity, and the safety performance of the lithium battery prepared by the product is improved. However, the reaction of the amino-terminated polyether chain segment compound and diisocyanate in the electrolyte is gradual polymerization, so that small molecule residues are easy to generate, and the electrical property and the safety performance of the battery are affected. Also disclosed in the prior art is a process based on in situ thermal polymerization and the use of the flame retardant gel electrolyte. The flame-retardant gel electrolyte has high ion migration number, good flame retardant property and excellent electrochemical stability. However, the introduction of a phosphorus-containing vinyl compound (containing a large amount of benzene rings) causes deterioration of the impregnation of the gel electrolyte into the positive and negative electrodes, and the impedance of the battery becomes large.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of low conductivity, high impedance, further improvement of safety and the like of the gel electrolyte in the prior art, thereby providing the gel electrolyte, the preparation method thereof and the lithium ion battery.
Therefore, the invention provides the following technical scheme:
the invention provides a gel electrolyte which comprises the following raw material components in parts by weight:
3-5 parts of vinyl-terminated polyethylene glycol compound;
3-5 parts of acrylonitrile;
3-5 parts of vinyl-terminated silicone oil;
0.5-1 part of initiator;
2-3 parts of a cross-linking agent;
10-15 parts of propylene carbonate;
100-110 parts of electrolyte;
wherein the vinyl-terminated polyethylene glycol compound has the following structural composition:
o-is polyethylene glycol group (i.e. structural unit obtained by reacting polyethylene glycol)），/>Is a diisocyanate group (i.e., a structural unit obtained by reacting a diisocyanate).
Optionally, the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate;
and/or, the crosslinker comprises triethylene glycol dimethacrylate;
and/or the lithium salt in the electrolyte comprises at least one of lithium bis (trifluoromethanesulfonyl) imide and lithium bis (fluorosulfonyl) imide;
and/or the solvent in the electrolyte comprises at least one of ethylene carbonate, diethyl carbonate and dimethyl carbonate;
and/or the concentration of lithium salt in the electrolyte is 0.9-1mol/L.
The invention also provides a preparation method of the gel electrolyte, which comprises the following steps:
mixing a vinyl-terminated polyethylene glycol compound, acrylonitrile, vinyl-terminated silicone oil, an initiator, a cross-linking agent, propylene carbonate and electrolyte, and carrying out gelation reaction to obtain the gel electrolyte.
Optionally, the gelation reaction comprises: standing at 42-48deg.C for 40-50 h, and then raising the temperature to 50-60deg.C for further reaction for 10-12 h.
Optionally, the preparation of the vinyl-terminated polyethylene glycol compound comprises the following steps:
s1, dissolving diisocyanate and polyethylene glycol in an organic solvent, reacting for 3-5 hours at 40-60 ℃, and separating a product to obtain isocyanate-terminated polyethylene glycol;
s2, mixing isocyanate-terminated polyethylene glycol with allyl hydroxyethyl ether, reacting for 3-5 hours at 50-70 ℃, and separating the product to obtain the vinyl-terminated polyethylene glycol compound.
Optionally, in step S1, the mass ratio of the diisocyanate to the polyethylene glycol is 2.05-2.25:10;
and/or the dosage ratio of the organic solvent to the polyethylene glycol is 2-3mL/g.
Optionally, in step S1, the diisocyanate includes at least one of isophorone diisocyanate, hexamethylene diisocyanate, methylcyclohexane diisocyanate;
and/or the organic solvent comprises dimethylformamide;
and/or the polyethylene glycol has a number average molecular weight of 1000 to 4000.
Optionally, in step S3, the mass ratio of the allyl hydroxyethyl ether to the isocyanate-terminated polyethylene glycol is 1:12.
the invention also provides a lithium ion battery, which comprises a shell, a positive plate, a negative plate and a diaphragm, and the gel electrolyte or the gel electrolyte prepared by the preparation method.
Optionally, the lithium ion battery is a ternary soft package battery or a ternary square battery.
In the present invention, other components, material selection, preparation methods, etc. of the lithium ion battery are conventional in the art, and are not particularly limited herein.
In the invention, the average molecular weight of the vinyl-terminated silicone oil (vinyl-terminated dimethylpolysiloxane) is between 1000 and 3000.
Specifically, the preparation method of the gel electrolyte provided by the invention comprises the following steps of:
(1) Preparation of vinyl-terminated polyethylene glycol: placing 8.8 g isophorone diisocyanate (IPDI) and 40 g polyethylene glycol (Mn=2000), 100ml dimethylformamide into a 250ml three-neck flask, reacting for 3 hours at 50 ℃, washing the obtained product, filtering and drying to obtain isocyanate-terminated polyethylene glycol; placing 4 g allyl hydroxyethyl ether and 48 g isocyanate-terminated polyethylene glycol into a 250ml three-neck flask, reacting for 3 hours at 60 ℃, washing the prepared product, filtering and drying to obtain a vinyl-terminated polyethylene glycol compound;
(2) In situ thermal polymer process to prepare high conductivity gel electrolyte: 3-5 parts of vinyl-terminated polyethylene glycol compound, 3-5 parts of acrylonitrile, 3-5 parts of vinyl-terminated silicone oil, 0.5-1 part of initiator, 2-3 parts of cross-linking agent and 10-15 parts of Propylene Carbonate (PC) are mixed into 100-110 parts of commercial electrolyte. And then the electrolyte is injected into the assembled lithium ion soft package battery, the lithium ion soft package battery is sealed, and then is kept stand at 45 ℃ for 48 h, and then the temperature is raised to 60 ℃ to continue the reaction for 10 h, so that the high-conductivity gel electrolyte is formed in the lithium ion battery.
In the invention, the provided lithium ion battery is a ternary battery, typically but not limited to, the lithium ion battery is a ternary soft package battery or a ternary square battery, and the ternary soft package battery comprises a positive plate, a negative plate, a diaphragm (a commercially available 12um PP base film) positioned between the positive plate and the negative plate, an external aluminum plastic shell and an internally filled gel electrolyte; the ternary square battery comprises a positive plate, a negative plate, a diaphragm positioned between the positive plate and the negative plate, an external square aluminum shell and an internally filled gel electrolyte.
In the invention, the positive electrode and the negative electrode of the lithium ion battery are conventional in the field, typically but not limited to, the positive electrode sheet comprises a positive electrode material layer and a current collector, the positive electrode material layer comprises a positive electrode active substance, a conductive agent and a binder, the positive electrode active substance is nickel 9 series nickel cobalt lithium manganate (commercial 9 series positive electrode material), the conductive agent is conductive carbon black (SP), the binder is polyvinylidene fluoride (PVDF), and the mass ratio of the positive electrode active substance to the conductive agent is 90:5:5.
The negative electrode plate comprises a negative electrode material layer and a current collector, wherein the negative electrode material layer comprises a negative electrode active substance, a conductive agent and a binder, the negative electrode active substance is lamellar graphite, the conductive agent is conductive carbon black (SP) and multi-wall Carbon Nano Tubes (CNT), the binder is polyacrylic acid (PAA), and the mass ratio of the negative electrode active substance to the conductive agent is 90:2.5:2.5:5.
The technical scheme of the invention has the following advantages:
the gel electrolyte provided by the invention is prepared by reacting a vinyl-terminated polyethylene glycol compound with acrylonitrile, polyvinyl-terminated silicone oil, propylene carbonate, an initiator, a cross-linking agent and electrolyte in a specific proportion, and the obtained gel electrolyte has high ion migration number, high conductivity and excellent electrochemical stability, and overcomes the defects of low conductivity and large direct current impedance of the conventional gel electrolyte; the heat release of the oxidation/combustion reaction of the organic electrolyte can be reduced, and the electrical property and the safety performance of the lithium ion battery are improved. Particularly, the vinyl-terminated polyethylene glycol compound is matched with propylene carbonate for use, so that the wettability of the electrolyte can be effectively improved, the positive and negative electrode active materials can be better coated, and the electrical property and the safety are improved.
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 needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the cycle capacity retention rate of examples 1 to 3 and comparative examples 1 to 3 of the present invention;
FIG. 2 is a schematic diagram of a symmetrical blocking battery in a test example of the present invention;
reference numerals:
1. aluminum foil; 2. a diaphragm.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The present example provides a gel electrolyte, the composition and preparation method of which are as follows:
(1) Preparation of vinyl-terminated polyethylene glycol: 8.8. 8.8 g isophorone diisocyanate (IPDI) and 40 g polyethylene glycol (Mn=2000), 100ml dimethylformamide were placed in a 250ml three-neck flask and reacted at 50℃for 3 hours. Washing the prepared product, filtering and drying to obtain isocyanate-terminated polyethylene glycol; placing 4 g allyl hydroxyethyl ether and 48 g isocyanate group polyethylene glycol into a 250ml three-neck flask, reacting for 3 hours at 60 ℃, washing the prepared product, filtering and drying to obtain the vinyl-terminated polyethylene glycol compound.
(2) In situ thermal polymer process to prepare high conductivity gel electrolyte: 3 parts of a vinyl-terminated polyethylene glycol compound, 3 parts of acrylonitrile, 3 parts of a vinyl-terminated silicone oil (Aba Ding Shiji, molecular weight 2000, the same applies hereinafter), 0.5 part of an initiator azobisisobutyronitrile, 2 parts of a crosslinking agent triethylene glycol dimethacrylate, 10 parts of Propylene Carbonate (PC), and 100 parts of a commercial electrolyte (LB-304, the same applies hereinafter) were mixed. Then injecting the electrolyte into an assembled lithium ion soft package battery, sealing the battery, standing the battery at 45 ℃ for 48 h after sealing, and then raising the temperature to 60 ℃ to continue to react for 10 h to form a high-conductivity gel electrolyte in the lithium ion battery;
the lithium ion soft package battery in the embodiment is a ternary soft package battery (same below), and comprises a positive plate, a negative plate and a diaphragm (a commercially available 12um PP base film) positioned between the positive plate and the negative plate, and an external aluminum-plastic shell;
the positive plate comprises a positive electrode material layer and a current collector, wherein the positive electrode material layer comprises a positive electrode active substance, a conductive agent and a binder, the positive electrode active substance is nickel-9-series nickel-cobalt lithium manganate, the conductive agent is conductive carbon black (SP), the binder is polyvinylidene fluoride (PVDF), and the mass ratio of the positive electrode active substance to the conductive agent to the binder is 90:5:5.
The negative electrode plate comprises a negative electrode material layer and a current collector, wherein the negative electrode material layer comprises a negative electrode active substance, a conductive agent and a binder, the negative electrode active substance is lamellar graphite, the conductive agent is conductive carbon black (SP) and multi-wall Carbon Nano Tubes (CNT), the binder is polyacrylic acid (PAA), and the mass ratio of the negative electrode active substance to the conductive agent is 90:2.5:2.5:5.
Example 2
The present example provides a gel electrolyte, the composition and preparation method of which are as follows:
(1) Preparation of vinyl-terminated polyethylene glycol: 8.8. 8.8 g isophorone diisocyanate (IPDI) and 40 g polyethylene glycol (Mn=2000), 100ml dimethylformamide were placed in a 250ml three-neck flask and reacted at 50℃for 3 hours. Washing the prepared product, filtering and drying to obtain isocyanate-terminated polyethylene glycol; placing 4 g allyl hydroxyethyl ether and 48 g isocyanate group polyethylene glycol into a 250ml three-neck flask, reacting for 3 hours at 60 ℃, washing the prepared product, filtering and drying to obtain the vinyl-terminated polyethylene glycol compound.
(2) In situ thermal polymer process to prepare high conductivity gel electrolyte: 4 parts of a vinyl-terminated polyethylene glycol compound, 4 parts of acrylonitrile, 4 parts of vinyl-terminated silicone oil, 0.75 part of initiator azobisisobutyronitrile, 2.5 parts of cross-linking agent triethylene glycol dimethacrylate, and 12.5 parts of Propylene Carbonate (PC) were mixed into 105 parts of a commercial electrolyte. And then the electrolyte is injected into the assembled lithium ion soft package battery, the lithium ion soft package battery is sealed, and then is kept stand at 45 ℃ for 48 h, and then the temperature is raised to 60 ℃ to continue the reaction for 10 h, so that the high-conductivity gel electrolyte is formed in the lithium ion battery.
Example 3
The present example provides a gel electrolyte, the composition and preparation method of which are as follows:
(1) Preparation of vinyl-terminated polyethylene glycol: 8.8. 8.8 g isophorone diisocyanate (IPDI) and 40 g polyethylene glycol (Mn=2000), 100ml dimethylformamide were placed in a 250ml three-neck flask and reacted at 50℃for 3 hours. Washing the prepared product, filtering and drying to obtain isocyanate-terminated polyethylene glycol; placing 4 g allyl hydroxyethyl ether and 48 g isocyanate group polyethylene glycol into a 250ml three-neck flask, reacting for 3 hours at 60 ℃, washing the prepared product, filtering and drying to obtain the vinyl-terminated polyethylene glycol compound.
(2) In situ thermal polymer process to prepare high conductivity gel electrolyte: 5 parts of a vinyl-terminated polyethylene glycol compound, 5 parts of acrylonitrile, 5 parts of vinyl-terminated silicone oil, 1 part of initiator azobisisobutyronitrile, 3 parts of a crosslinking agent triethylene glycol dimethacrylate, and 15 parts of Propylene Carbonate (PC) were mixed into 110 parts of a commercial electrolyte. And then the electrolyte is injected into the assembled lithium ion soft package battery, the lithium ion soft package battery is sealed, and then is kept stand at 45 ℃ for 48 h, and then the temperature is raised to 60 ℃ to continue the reaction for 10 h, so that the high-conductivity gel electrolyte is formed in the lithium ion battery.
Example 4
The present example provides a gel electrolyte, and compared with the rest of example 3, the difference is that the preparation of vinyl-terminated polyethylene glycol is different, specifically:
8.8. 8.8 g isophorone diisocyanate (IPDI) and 40 g polyethylene glycol (Mn=2000), 100ml dimethylformamide were placed in a 250ml three-neck flask and reacted at 40℃for 4 hours. Washing the prepared product, filtering and drying to obtain isocyanate-terminated polyethylene glycol; placing 4 g allyl hydroxyethyl ether and 48 g isocyanate group polyethylene glycol into a 250ml three-neck flask, reacting for 4 hours at 70 ℃, washing the obtained product, filtering and drying to obtain the vinyl-terminated polyethylene glycol compound.
Example 5
The present example provides a gel electrolyte, and compared with the rest of example 3, the difference is that the preparation of vinyl-terminated polyethylene glycol is different, specifically:
8.8. 8.8 g isophorone diisocyanate (IPDI) and 40 g polyethylene glycol (Mn=2000), 100ml dimethylformamide were placed in a 250ml three-neck flask and reacted at 60℃for 5 hours. Washing the prepared product, filtering and drying to obtain isocyanate-terminated polyethylene glycol; placing 4 g allyl hydroxyethyl ether and 48 g isocyanate group polyethylene glycol into a 250ml three-neck flask, reacting for 5 hours at 50 ℃, washing the obtained product, filtering and drying to obtain the vinyl-terminated polyethylene glycol compound.
Example 6
The present example provides a gel electrolyte, and compared with the rest of example 3, the difference is that the preparation of vinyl-terminated polyethylene glycol is different, specifically:
8.8. 8.8 g isophorone diisocyanate (IPDI) and 40 g polyethylene glycol (Mn=2000), 100ml dimethylformamide were placed in a 250ml three-neck flask and reacted at 50℃for 3 hours. Washing the prepared product, filtering and drying to obtain isocyanate-terminated polyethylene glycol; placing 4 g allyl hydroxyethyl ether and 48 g isocyanate group polyethylene glycol into a 250ml three-neck flask, reacting for 4.5 hours at 65 ℃, washing the prepared product, filtering and drying to obtain the vinyl-terminated polyethylene glycol compound.
Example 7
This example provides a gel electrolyte, and the parameters of step (2) are different from those of example 3, specifically as follows:
in situ thermal polymer process to prepare high conductivity gel electrolyte: 5 parts of a vinyl-terminated polyethylene glycol compound, 5 parts of acrylonitrile, 5 parts of vinyl-terminated silicone oil, 1 part of initiator azobisisobutyronitrile, 3 parts of a crosslinking agent triethylene glycol dimethacrylate, and 15 parts of Propylene Carbonate (PC) were mixed into 110 parts of a commercial electrolyte. And then the electrolyte is injected into the assembled lithium ion soft package battery, the lithium ion soft package battery is sealed, and then is kept stand at 45 ℃ for 48 h, and then the temperature is raised to 50 ℃ for continuous reaction for 12 hours, so that the high-conductivity gel electrolyte is formed in the lithium ion battery.
Example 8
This example provides a gel electrolyte, and the parameters of step (2) are different from those of example 3, specifically as follows:
in situ thermal polymer process to prepare high conductivity gel electrolyte: 5 parts of a vinyl-terminated polyethylene glycol compound, 5 parts of acrylonitrile, 5 parts of vinyl-terminated silicone oil, 1 part of initiator azobisisobutyronitrile, 3 parts of a crosslinking agent triethylene glycol dimethacrylate, and 15 parts of Propylene Carbonate (PC) were mixed into 110 parts of a commercial electrolyte. And then the electrolyte is injected into the assembled lithium ion soft package battery, the lithium ion soft package battery is sealed, and then is kept stand at 45 ℃ for 48 h, and then the temperature is raised to 55 ℃ to continue the reaction for 9 h, so that the high-conductivity gel electrolyte is formed in the lithium ion battery.
Comparative example 1
This comparative example provides an electrolyte prepared by injecting 100 parts of a commercial electrolyte having the same composition as in example 3 into an assembled lithium ion pouch cell, sealing the cell, standing at 45 c for 48 h after sealing, and then raising the temperature to 60 c to continue standing for 10 h.
Comparative example 2
This comparative example provides a gel electrolyte differing from example 3 only in that propylene carbonate was not added in step (2).
Comparative example 3
This comparative example provides a gel electrolyte differing from example 3 only in that no terminal vinyl polyethylene glycol compound was added in step (2).
Comparative example 4
This comparative example provides a gel electrolyte which differs from example 3 only in that the vinyl-terminated polyethylene glycol compound is replaced with polyethylene glycol of equal mass in step (2).
Comparative example 5
This comparative example provides a gel electrolyte differing from example 3 only in that the step (2) uses an equal mass of isocyanate-terminated polyethylene glycol instead of the vinyl-terminated polyethylene glycol compound, and the isocyanate-terminated polyethylene glycol is prepared as follows: preparation of isocyanate-terminated polyethylene glycol: 8.8. 8.8 g isophorone diisocyanate (IPDI) and 40 g polyethylene glycol (Mn=2000), 100ml dimethylformamide were placed in a 250ml three-neck flask and reacted at 50℃for 3 hours. Washing the prepared product, filtering and drying to obtain the isocyanate-terminated polyethylene glycol.
Comparative example 6
This comparative example provides a gel electrolyte which differs from example 3 only in that in step (2), a high conductivity gel electrolyte is prepared by an in situ thermal polymer process: 1 part of a vinyl-terminated polyethylene glycol compound, 1 part of acrylonitrile, 6 parts of vinyl-terminated silicone oil, 1 part of initiator azobisisobutyronitrile, 3 parts of a crosslinking agent triethylene glycol dimethacrylate, and 15 parts of Propylene Carbonate (PC) were mixed into 110 parts of a commercial electrolyte. And then the electrolyte is injected into the assembled lithium ion soft package battery, the lithium ion soft package battery is sealed, and then is kept stand at 45 ℃ for 48 h, and then the temperature is raised to 60 ℃ to continue the reaction for 10 h, so that the high-conductivity gel electrolyte is formed in the lithium ion battery.
Comparative example 7
This comparative example provides a gel electrolyte which differs from example 3 only in that in step (2), a high conductivity gel electrolyte is prepared by an in situ thermal polymer process: 6 parts of a vinyl-terminated polyethylene glycol compound, 6 parts of acrylonitrile, 1 part of vinyl-terminated silicone oil, 1 part of initiator azobisisobutyronitrile, 3 parts of a crosslinking agent triethylene glycol dimethacrylate, and 15 parts of Propylene Carbonate (PC) were mixed into 110 parts of a commercial electrolyte. And then the electrolyte is injected into the assembled lithium ion soft package battery, the lithium ion soft package battery is sealed, and then is kept stand at 45 ℃ for 48 h, and then the temperature is raised to 60 ℃ to continue the reaction for 10 h, so that the high-conductivity gel electrolyte is formed in the lithium ion battery.
Test case
1. Conductivity performance test:
(1) Preparation of lithium ion batteries
The lithium ion battery in the test example is a ternary soft package battery and comprises a positive plate, a negative plate, a diaphragm (a commercially available 12um PP base film) positioned between the positive plate and the negative plate and an external aluminum-plastic shell; the ternary square battery comprises a positive plate, a negative plate, a diaphragm (electrolyte is replaced by the diaphragm in comparative example 1) positioned between the positive plate and the negative plate, and an external square aluminum shell, wherein the square aluminum shell is assembled in sequence, and gel electrolyte (electrolyte is electrolyte in comparative example 1) provided by each example and comparative example is injected to obtain the 5Ah ternary soft-pack battery.
The positive plate comprises a positive electrode material layer and a current collector, wherein the positive electrode material layer comprises a positive electrode active substance, a conductive agent and a binder, the positive electrode active substance is nickel-9-series nickel-cobalt lithium manganate (commercial 9-series positive electrode material), the conductive agent is conductive carbon black (SP), the binder is polyvinylidene fluoride (PVDF), and the mass ratio of the positive electrode active substance to the conductive agent to the binder is 90:5:5.
The negative electrode plate comprises a negative electrode material layer and a current collector, wherein the negative electrode material layer comprises a negative electrode active substance, a conductive agent and a binder, the negative electrode active substance is lamellar graphite, the conductive agent is conductive carbon black (SP) and multi-wall Carbon Nano Tubes (CNT), the binder is polyacrylic acid (PAA), and the mass ratio of the negative electrode active substance to the conductive agent is 90:2.5:2.5:5.
(2) In order to actually test the conductivity of the gel electrolyte, a battery after formation (0.33C, 2.5-4.2V charge-discharge cycles) is selected, disassembled, and a middle diaphragm is taken out to prepare a symmetrical blocking battery (a schematic diagram is shown in fig. 2, wherein aluminum foils 1 are arranged on two sides of the diagram, a diaphragm 2 is arranged in the middle of the diagram, the taken-out diaphragm is arranged in the middle of the diagram during test, the number of layers of the diaphragm is 1, 2, 3 and 4, and the linear slope obtained by fitting four data points is the total impedance of the diaphragm and the gel electrolyte); and its alternating current impedance spectrum (EIS) was tested with an electrochemical workstation to give the total impedance of the separator + gel electrolyte (r=r Ω +R ct ，R Ω Impedance of =ohm, R ct =charge transfer impedance); then using the conductivity calculation formulaDelta is conductivity, d is the thickness cm of the measured sample, R is the total impedance mΩ of the measured sample, S is the effective area cm of the measured sample 2 ) The conductivity of the diaphragm and the electro-gel electrolyte is obtained (the diaphragm is a commercially available 12um PP base film, and the obtained conductivity can be regarded as the conductivity of the electrolyte between the anode and the cathode of the lithium ion battery, because the diaphragm does not conduct ions, only the electrolyte conducts ions; the calculated value is lower than the actual electrolyte conductivity value, but the conductivity of different gel electrolytes can be compared under the same separator). The results are shown in Table 1:
TABLE 1
2. Battery performance test
The lithium ion batteries prepared in each example and comparative example were selected, and the direct current internal resistance and cycle performance of the batteries were tested by using GB/T-31467.1-2015 (lithium ion power storage battery pack and system for electric automobile, part 1: high power application test procedure) and GB/T-31484-2015 (power storage battery cycle life requirement for electric automobile and experimental method), and the results are shown in Table 2 and FIG. 1.
TABLE 2
3. Safety test
Selecting lithium ion batteries prepared in each example and comparative example, and performing needling experiments by using GB/T-31485-2015 (safety requirements and test methods of a power storage battery for an electric automobile), wherein the lithium ion batteries are not exploded and do not fire after the needling experiments in examples 1-8; fires and explosions occurred in each of comparative examples 1-7.
From the above experimental results, it is clear that the high conductivity electrolyte formed by vinyl-terminated polyethylene glycol, acrylonitrile and vinyl-terminated silicone oil has conductivity similar to that of the liquid electrolyte (comparative example 1), and is far higher than that of other gel electrolytes (comparative examples 2 to 7), and the capability of transmitting lithium ions is greatly enhanced (compared with the common gel electrolytes).
From the data of electrical properties, the DC internal resistance (DCR) values in examples 1-8 were not greatly increased compared to comparative example 1 (liquid electrolyte), but the DCR values in examples 1-8 were much lower compared to comparative examples 2-7 (other gel electrolytes), indicating that the introduction of vinyl terminated polyethylene glycol can effectively reduce the DC internal resistance of the gel electrolyte; examples 1 to 8 are excellent in cycle performance, the capacity retention rate after 150 cycles is 95% or more, the cycle test results of examples 1 to 3 and comparative examples 1 to 3 are shown in FIG. 1, the curves of examples 1 to 3 and comparative examples 1 to 3 are shown in the top-down order, and the curves of other examples are not shown. The high-conductivity gel electrolyte prepared by the invention has excellent electrical properties. As can be seen from the data of safety performance, the gel electrolyte can effectively improve the safety performance of the battery. The difference of the results of comparative example 2 shows that the introduction of propylene carbonate has important significance in improving the integrity of the three-dimensional network structure of the gel electrolyte, improving the coating integrity of the gel on positive and negative active substances, improving the safety performance of the battery and the like. The results of comparative examples 2 to 7 demonstrate that only gels constructed from the monomers and monomer ratios specified in this example have the characteristics of high conductivity and high safety.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The gel electrolyte is characterized by comprising the following raw material components in parts by weight:
3-5 parts of vinyl-terminated polyethylene glycol compound;
3-5 parts of acrylonitrile;
3-5 parts of vinyl-terminated silicone oil;
0.5-1 part of initiator;
2-3 parts of a cross-linking agent;
10-15 parts of propylene carbonate;
100-110 parts of electrolyte;
wherein the vinyl-terminated polyethylene glycol compound has the following structural composition:
o-is polyethylene glycol group,is a diisocyanate group.
2. The gel electrolyte of claim 1, wherein the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate;
and/or, the crosslinker comprises triethylene glycol dimethacrylate;
and/or the lithium salt in the electrolyte comprises at least one of lithium bis (trifluoromethanesulfonyl) imide and lithium bis (fluorosulfonyl) imide;
and/or the solvent in the electrolyte comprises at least one of ethylene carbonate, diethyl carbonate and dimethyl carbonate;
and/or the concentration of lithium salt in the electrolyte is 0.9-1mol/L.
3. A method for preparing the gel electrolyte according to any one of claims 1 to 2, comprising the steps of:
mixing a vinyl-terminated polyethylene glycol compound, acrylonitrile, vinyl-terminated silicone oil, an initiator, a cross-linking agent, propylene carbonate and electrolyte, and carrying out gelation reaction to obtain the gel electrolyte.
4. The method for producing a gel electrolyte according to claim 3, wherein the gelation reaction comprises: standing at 42-48deg.C for 40-50 h, and then raising the temperature to 50-60deg.C for further reaction for 10-12 h.
5. The method for preparing a gel electrolyte according to claim 3 or 4, wherein the preparation of the vinyl-terminated polyethylene glycol compound comprises the steps of:
s1, dissolving diisocyanate and polyethylene glycol in an organic solvent, reacting for 3-5 hours at 40-60 ℃, and separating a product to obtain isocyanate-terminated polyethylene glycol;
s2, mixing isocyanate-terminated polyethylene glycol with allyl hydroxyethyl ether, reacting for 3-5 hours at 50-70 ℃, and separating the product to obtain the vinyl-terminated polyethylene glycol compound.
6. The method according to claim 5, wherein in the step S1, the mass ratio of the diisocyanate to the polyethylene glycol is 2.05 to 2.25:10;
and/or the dosage ratio of the organic solvent to the polyethylene glycol is 2-3mL/g.
7. The method for preparing a gel electrolyte according to claim 5, wherein in the step S1, the diisocyanate comprises at least one of isophorone diisocyanate, hexamethylene diisocyanate, methylcyclohexane diisocyanate;
and/or the organic solvent comprises dimethylformamide;
and/or the polyethylene glycol has a number average molecular weight of 1000 to 4000.
8. The method according to claim 5, wherein in the step S3, the mass ratio of the allyl hydroxyethyl ether to the isocyanate-terminated polyethylene glycol is 1:12.
9. a lithium ion battery, comprising a shell, a positive plate, a negative plate, a diaphragm, the gel electrolyte according to any one of claims 1-2 or the gel electrolyte prepared by the preparation method according to any one of claims 3-8.
10. The lithium ion battery of claim 9, wherein the lithium ion battery is a ternary pouch battery or a ternary prismatic battery.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1054465A1 (en) * | 1999-05-20 | 2000-11-22 | Toyo Boseki Kabushiki Kaisha | Polyelectrolytic gel |
| JP2002208436A (en) * | 2001-01-05 | 2002-07-26 | Toyo Tire & Rubber Co Ltd | Celled electrolyte element, and manufacturing method of the same |
| JP2002324735A (en) * | 2001-04-25 | 2002-11-08 | Toyo Tire & Rubber Co Ltd | Method for manufacturing gelled electrolyte |
| JP2003002974A (en) * | 2001-06-21 | 2003-01-08 | Chisso Corp | Polyethylene oxide group-containing polysiloxane cross- linked product and polymer solid electrolyte |
| CN104072533A (en) * | 2014-06-10 | 2014-10-01 | 中国科学院广州能源研究所 | Silicone-nitrile compounds containing low polyoxyethylene units as well as preparation method thereof and application thereof in lithium battery |
| CN106374139A (en) * | 2016-11-04 | 2017-02-01 | 北京大学 | Monomer and polymer for gel electrolyte material, and preparation methods and applications of monomer and polymer |
| CN111253523A (en) * | 2020-01-19 | 2020-06-09 | 四川大学 | Non-combustible gel polymer electrolyte and preparation method and application thereof |
| CN113851707A (en) * | 2021-09-30 | 2021-12-28 | 蜂巢能源科技有限公司 | Gel electrolyte, preparation method thereof and battery |
| CN115020804A (en) * | 2022-06-07 | 2022-09-06 | 华中科技大学 | Flexible energy storage device based on gel polymer electrolyte and preparation method thereof |
| CN116093423A (en) * | 2022-12-13 | 2023-05-09 | 中国电子科技集团公司第十八研究所 | Novel gel electrolyte and lithium ion battery preparation method |
| CN116231060A (en) * | 2023-02-21 | 2023-06-06 | 复旦大学 | Preparation method and application of single lithium ion conductive fluoropolymer solid electrolyte |
| CN116365019A (en) * | 2023-03-31 | 2023-06-30 | 蜂巢能源科技(无锡)有限公司 | Lithium ion battery flame-retardant gel electrolyte and preparation method and application thereof |
| EP4207418A2 (en) * | 2021-12-31 | 2023-07-05 | Beijing WeLion New Energy Technology Co., Ltd | In-situ polymerized solid-state battery with multilayer structural electrolyte and preparation method thereof |
| CN116454371A (en) * | 2023-04-17 | 2023-07-18 | 河南省法恩莱特新能源科技有限公司 | Solid polymer electrolyte of lithium ion battery and preparation method thereof |
-
2023
- 2023-08-16 CN CN202311028829.8A patent/CN116742116B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1054465A1 (en) * | 1999-05-20 | 2000-11-22 | Toyo Boseki Kabushiki Kaisha | Polyelectrolytic gel |
| JP2002208436A (en) * | 2001-01-05 | 2002-07-26 | Toyo Tire & Rubber Co Ltd | Celled electrolyte element, and manufacturing method of the same |
| JP2002324735A (en) * | 2001-04-25 | 2002-11-08 | Toyo Tire & Rubber Co Ltd | Method for manufacturing gelled electrolyte |
| JP2003002974A (en) * | 2001-06-21 | 2003-01-08 | Chisso Corp | Polyethylene oxide group-containing polysiloxane cross- linked product and polymer solid electrolyte |
| CN104072533A (en) * | 2014-06-10 | 2014-10-01 | 中国科学院广州能源研究所 | Silicone-nitrile compounds containing low polyoxyethylene units as well as preparation method thereof and application thereof in lithium battery |
| CN106374139A (en) * | 2016-11-04 | 2017-02-01 | 北京大学 | Monomer and polymer for gel electrolyte material, and preparation methods and applications of monomer and polymer |
| CN111253523A (en) * | 2020-01-19 | 2020-06-09 | 四川大学 | Non-combustible gel polymer electrolyte and preparation method and application thereof |
| CN113851707A (en) * | 2021-09-30 | 2021-12-28 | 蜂巢能源科技有限公司 | Gel electrolyte, preparation method thereof and battery |
| EP4207418A2 (en) * | 2021-12-31 | 2023-07-05 | Beijing WeLion New Energy Technology Co., Ltd | In-situ polymerized solid-state battery with multilayer structural electrolyte and preparation method thereof |
| CN115020804A (en) * | 2022-06-07 | 2022-09-06 | 华中科技大学 | Flexible energy storage device based on gel polymer electrolyte and preparation method thereof |
| CN116093423A (en) * | 2022-12-13 | 2023-05-09 | 中国电子科技集团公司第十八研究所 | Novel gel electrolyte and lithium ion battery preparation method |
| CN116231060A (en) * | 2023-02-21 | 2023-06-06 | 复旦大学 | Preparation method and application of single lithium ion conductive fluoropolymer solid electrolyte |
| CN116365019A (en) * | 2023-03-31 | 2023-06-30 | 蜂巢能源科技(无锡)有限公司 | Lithium ion battery flame-retardant gel electrolyte and preparation method and application thereof |
| CN116454371A (en) * | 2023-04-17 | 2023-07-18 | 河南省法恩莱特新能源科技有限公司 | Solid polymer electrolyte of lithium ion battery and preparation method thereof |
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