CN117317361A - Gel electrolyte, preparation method, positive plate containing gel electrolyte, secondary battery and device - Google Patents
Gel electrolyte, preparation method, positive plate containing gel electrolyte, secondary battery and device Download PDFInfo
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- CN117317361A CN117317361A CN202311205337.1A CN202311205337A CN117317361A CN 117317361 A CN117317361 A CN 117317361A CN 202311205337 A CN202311205337 A CN 202311205337A CN 117317361 A CN117317361 A CN 117317361A
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- lithium
- gel electrolyte
- imide
- bis
- salt
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- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 8
- -1 fumaric acid nitrile Chemical class 0.000 claims abstract description 32
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 32
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims abstract description 25
- 230000000996 additive effect Effects 0.000 claims abstract description 25
- UNAQSRLBVVDYGP-UHFFFAOYSA-N hex-5-enenitrile Chemical compound C=CCCCC#N UNAQSRLBVVDYGP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 22
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 15
- 239000001530 fumaric acid Substances 0.000 claims abstract description 15
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 15
- BSVZXPLUMFUWHW-OWOJBTEDSA-N (e)-hex-3-enedinitrile Chemical compound N#CC\C=C\CC#N BSVZXPLUMFUWHW-OWOJBTEDSA-N 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 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 16
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 12
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 11
- 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 11
- 239000002904 solvent Substances 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 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 5
- 239000000463 material Substances 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- RXKLBLXXQQRGJH-UHFFFAOYSA-N bis(fluorosulfonyl)azanide 1-methyl-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(C)CCCC1.FS(=O)(=O)[N-]S(F)(=O)=O RXKLBLXXQQRGJH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-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
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 32
- 239000000243 solution Substances 0.000 description 26
- 238000009783 overcharge test Methods 0.000 description 14
- 238000001723 curing Methods 0.000 description 13
- 238000011056 performance test Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
Abstract
The invention relates to a gel electrolyte, a preparation method, a positive plate containing the gel electrolyte, a secondary battery and a device. The present invention relates in particular to a gel electrolyte comprising a gel skeleton, a flexible additive and a first lithium salt, said gel skeleton being formed by polymerization of at least one monomer comprising at least one monomer selected from the group consisting of fumaric acid nitrile, 5-hexenenitrile and 3-hexenedinitrile in the presence of a polymerization initiator. The secondary battery containing the gel electrolyte has improved hot box performance, overcharge performance and needling performance, and further has improved safety.
Description
Technical Field
The invention relates to a gel electrolyte, a preparation method, a positive plate containing the gel electrolyte, a secondary battery and a device.
Background
The safety of current high energy density power cells is of interest. The application of power batteries, especially high energy density power batteries, is limited to a certain extent by the ignition and explosion of automobiles caused by battery safety problems.
Therefore, improving the safety of the battery cell is an urgent need.
Disclosure of Invention
The invention aims to improve the safety of a battery cell in the aspects of hot box, overcharge and needling.
The present invention relates to a gel electrolyte comprising a gel skeleton formed by polymerizing at least one monomer comprising at least one selected from the group consisting of fumaric acid nitrile, 5-hexenenitrile and 3-hexenedinitrile in the presence of a polymerization initiator, a flexible additive and a first lithium salt.
The present invention relates to a method for preparing the gel electrolyte, comprising the steps of:
(i) Mixing the monomer, the flexible additive, the first lithium salt and the polymerization initiator to form a first solution;
(ii) Mixing the nonaqueous solvent with a second lithium salt to form a second solution;
(iii) Mixing the first solution and the second solution to obtain a gel electrolyte forming composition, and polymerizing the gel electrolyte forming composition at 65-85 ℃.
The invention also relates to a positive electrode sheet comprising a positive electrode active material layer and a gel electrolyte positioned on the surface of the positive electrode active material layer, wherein the gel electrolyte is obtained by polymerizing the gel electrolyte forming composition on the positive electrode active material layer.
The invention also relates to a secondary battery comprising the positive plate.
The invention also relates to a device comprising said secondary battery.
The pole piece containing the gel electrolyte can be applied to an automobile power battery, can improve the capacities of a hot box, overcharge and over-needling of the battery, and improves the safety of a high-energy-density lithium ion battery cell.
Drawings
FIG. 1 is a graph of thermal stability of the thermal box performance test of example 1;
FIG. 2 is an overcharge performance graph of the overcharge performance test of example 1;
FIG. 3 is a graph of needling performance from the needling performance test of example 1.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control. Preferred methods and materials are described below, but methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.
For all numerical ranges referred to in this disclosure, it is understood that all specific values within that range are disclosed, as well as subranges defined by any two values within that range. For example, for 1-20, it is to be understood that specific values of 1, 2, 3, 3.5, 4.5, 10, 12, 15, 20, etc., as well as subranges of 1-5,2-6,3.5-7.5, 15-20, etc., are disclosed.
The present invention provides a gel electrolyte comprising a gel skeleton formed by polymerizing at least one monomer comprising at least one selected from the group consisting of fumaric acid nitrile, 5-hexenenitrile and 3-hexenedinitrile in the presence of a polymerization initiator, a flexible additive, and a first lithium salt.
Preferably, the gel skeleton is formed by polymerizing at least one monomer selected from the group consisting of fumaric acid nitrile, 5-hexenenitrile and 3-hexenedinitrile in the presence of a polymerization initiator.
In one embodiment, the monomers include fumaric acid nitrile and/or 3-hexenedinitrile.
In one embodiment, the monomers include a combination of fumaric acid nitrile and 5-hexenenitrile.
In one embodiment, the monomers include a combination of 3-hexenedinitrile and 5-hexenedinitrile.
In one embodiment, the flexible additive comprises at least one of succinonitrile, adiponitrile, glutaronitrile, and an ionic liquid.
In one embodiment, the first lithium salt comprises at least one of lithium perchlorate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate, and lithium tetrafluoroborate.
In one embodiment, the polymerization initiator comprises azobisisobutyronitrile and/or azobisisoheptonitrile.
In one embodiment, the monomer is present in an amount of 20 to 60 wt%, the flexibilizing additive is present in an amount of 20 to 60 wt%, the first lithium salt is present in an amount of 5 to 20 wt%, and the polymerization initiator is present in an amount of 1 to 5 wt%, the percentages being based on the total weight of the monomer, flexibilizing additive, first lithium salt, and polymerization initiator.
In one embodiment, the monomers include a combination of fumaric acid nitrile and 5-hexenenitrile.
In one embodiment, the flexible additive comprises at least one of succinonitrile, adiponitrile, and glutaronitrile.
In one embodiment, the first lithium salt comprises at least one of lithium bis (trifluoromethanesulfonyl) imide and lithium bis (fluorosulfonyl) imide.
In one embodiment, the ionic liquid is selected from at least one of 1-methyl-1-propylpiperidinebis trifluoromethylsulfonyl imide salt, 1-butyl-1-methylpiperidinebis (trifluoromethylsulfonyl) imide salt, 1-butyl-1-methylpyrrolidinone bis (trifluoromethylsulfonyl) imide salt, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-propyl-1-methylpyrrolidinone bis trifluoromethylsulfonyl imide salt, 1-ethyl-3-methylimidazolium bis trifluoromethylsulfonyl imide salt, and 1-ethyl-3-methylimidazolium tetrafluoroborate.
In one embodiment, the gel electrolyte includes a non-aqueous solvent selected from at least one of a cyclic carbonate and a linear carbonate, and a second lithium salt.
In one embodiment, the nonaqueous solvent is selected from at least one of ethylene carbonate, ethylmethyl carbonate, and dimethyl carbonate.
In one embodiment, the ratio of the total weight of the monomer, the flexible additive, the first lithium salt, and the polymerization initiator to the total weight of the nonaqueous solvent and the second lithium salt is 1:9 to 7:3, e.g., 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 7:6, 4:3, 3:2, 5:3, 11:6, 2:1, 13:6, and any range consisting of these ratios as endpoints, preferably 1:2 to 3:2.
In one embodiment, the second lithium salt comprises at least one of lithium hexafluorophosphate, lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethanesulfonyl imide, lithium bis-oxalato-borate, lithium difluorooxalato-borate, lithium difluorophosphate, and lithium bis-oxalato-difluorophosphate, preferably comprising lithium hexafluorophosphate.
The invention also provides a method for preparing the gel electrolyte, which comprises the following steps:
(i) Mixing the monomer, the flexible additive, the first lithium salt and the polymerization initiator to form a first solution;
(ii) Mixing the nonaqueous solvent with a second lithium salt to form a second solution;
(iii) Mixing the first solution and the second solution to obtain a gel electrolyte forming composition, and polymerizing the gel electrolyte forming composition at 65-85 ℃.
The invention also provides a positive electrode sheet comprising a positive electrode active material layer and a gel electrolyte positioned on the surface of the positive electrode active material layer, wherein the gel electrolyte is obtained by polymerizing the gel electrolyte forming composition on the positive electrode active material layer.
In one embodiment, the positive electrode active material includes a material selected from the group consisting of the formula LiNi m Co n A (1-m-n) O 2 At least one of the lithium nickel transition metal oxides is selected from the group consisting of manganese, aluminum, magnesium, zirconium, strontium, yttrium, lanthanum, molybdenum, silver, niobium, iron, titanium, copper, zinc, chromium, calcium, barium and tungsten, wherein m is more than or equal to 0.5 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 0.5, and m+n is more than or equal to 1. In some embodiments, m is 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or a range consisting of any two of these values, specifically 0.86.ltoreq.m.ltoreq.1. In some embodiments, n is 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, or a range consisting of any two of these values.
The invention also provides a secondary battery comprising the positive plate.
In one embodiment, the secondary battery includes a negative electrode sheet including a negative electrode active material including a silicon-based material including a silicon oxide and/or a silicon carbon compound, the mass content g of the silicon-based material satisfying: g is more than or equal to 10 and less than or equal to 100. In some embodiments, g is 11, 13, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or a range of any two of these values. In some embodiments, 10.ltoreq.g.ltoreq.50. In other embodiments, 12.ltoreq.g.ltoreq.35.
The invention also provides a device comprising the secondary battery.
The flexible additive has a certain heat absorption capacity, so that the thermal stability of the battery and the high-temperature safety of the battery core can be improved; the decomposition of the flexible additive under high potential can consume the charging electric energy of the battery, and plays a role in overcharge protection of the battery; because the ionic conductivity of the gel electrolyte obtained by monomer polymerization is lower, the short circuit of the anode and the cathode can be inhibited to a certain extent, and the gel electrolyte is helpful for the cell over-needling. Particularly, as the fumaric acid nitrile can be decomposed under high potential, electric energy can be consumed, and in addition, the internal resistance of the battery cell can be greatly improved by the decomposition products, so that the polarization of the battery cell is increased during overcharging, the cut-off potential can be reached, and the overcharge protection effect is realized.
If acrylonitrile is used as a monomer for forming a gel skeleton, the acrylonitrile has very good crystallinity after polymerization, and the internal resistance of the battery cell is greatly influenced. The monomer for forming the gel skeleton of the invention disturbs the distribution of cyano structures, so that the crystallinity is greatly reduced, and the difference of space structures obviously affects the performance.
When the cell is overcharged, it is found that the nitrile substance has improved cell overcharged performance on the positive electrode side, which is unexpected.
Example 1
Mixing the following components to form a first solution
The monomer used to form the gel skeleton is fumaric acid nitrile: 42%;
the flexible additive is succinonitrile: 42%;
the polymerization initiator is azobisisobutyronitrile: 1%;
the first lithium salt is lithium bis (trifluoromethanesulfonyl) imide: 15%.
And mixing the first solution and the second solution together at room temperature, and uniformly stirring to obtain the gel electrolyte forming composition. The weight ratio of the first solution to the second solution is 1:1. The second solution comprises nonaqueous solvent with volume ratio of ethylene carbonate to dimethyl carbonate to ethylmethyl carbonate of 2:4:4 and second lithium salt lithium hexafluorophosphate (LiPF) with molar concentration of 1.00mol/L 6 ). And (3) coating the gel electrolyte forming composition on the positive electrode active material layer of the positive electrode plate, heating at 80 ℃ for 24 hours, and polymerizing and gelling to obtain the positive electrode plate containing the gel electrolyte.
The preparation method of the positive plate comprises the following steps: the positive electrode active material LiNi 0.9 Co 0.05 Mn 0.05 O 2 Carbon Nanotube (CNT)/acetylene black (Super-P) as conductive agent, polyvinylidene fluoride PVDF as binder, and LiNi as binder in weight ratio 0.9 Co 0.05 Mn 0.05 O 2 And (2) fully homogenizing CNT/Super-P (polyvinylidene fluoride) =95:2.0/1.0:2 in an N-methylpyrrolidone (NMP) solvent system, then coating the mixture on an aluminum-coated current collector with the thickness of 12 mu m, and drying and rolling the mixture to obtain the positive plate. And (3) coating the gel electrolyte forming composition on the positive electrode active material layer of the positive electrode plate, heating at 80 ℃ for 24 hours, and polymerizing and gelling to obtain the positive electrode plate containing the gel electrolyte.
The preparation steps of the negative plate are as follows: silicon oxide (SiO) as a negative electrode active material x X is more than or equal to 0.5 and less than or equal to 1.5), graphite compound (the mass ratio of silicon oxide to graphite in the compound is 30:70), conductive agent acetylene black, adhesive styrene-butadiene rubber SBR, thickener sodium carboxymethyl cellulose CMCNa and polyacrylic acid PAA are fully homogenized in deionized water according to the weight ratio of 96:2:1.5:1:0.5, and then the mixture is coated on the surface of an 8 mu m thick copper current collector, and the negative plate is obtained after drying, rolling and stripping.
Preparation of lithium ion secondary battery: sequentially stacking the prepared positive plate, the diaphragm and the negative plate, enabling the diaphragm to be positioned between the positive plate and the negative plate, and winding to obtain a bare cell; and placing the bare cell in an aluminum plastic film outer package, and performing liquid injection, formation, secondary sealing and capacity division to obtain the lithium ion secondary battery (cell) with the rated capacity of 75 Ah.
1. Hot box performance test
The hot box test is carried out on the fully charged 75Ah battery cell, and the specific test steps are as follows:
1-1) placing the battery in a temperature box, and raising the temperature of the temperature box from the ambient temperature to 130+/-2 ℃ at a speed of 5 ℃/min, and keeping the temperature for 60min;
1-2) continuously heating the temperature box at a speed of 5 ℃/min for 60min at each temperature rise of 5 ℃;
1-3) cycle steps 1-2) until runaway.
The results of the thermal stability test are shown in FIG. 1.
By adopting the curing technology of the embodiment 1, the 75Ah battery cell is subjected to the hot box test according to the scheme, when the temperature of the hot box is 155 ℃, the battery cell is out of control in the heat preservation process, and the battery cell cannot pass the test of the high temperature of 155 ℃, and the final hot box result is 150 ℃.
2. Overcharge Performance test
The overcharging test is carried out on the fully charged 75Ah battery cell, and the specific test steps are as follows:
2-1) standing for 5min;
2-2) charging at 1C rated CC, starting from 100% overcharge;
2-3) overcharge up to 200% SOC;
2-4) cell upper clamping plate, torque 1.5Nm.
The overcharge performance test results are shown in fig. 2.
By adopting the curing technology of the embodiment 1, the 75Ah battery cell is subjected to overcharging test according to the scheme, the charging current is 1C rated current, the charging is started from 100% SOC, the voltage of the battery cell rises to 26V after 2200s of charging, the battery cell is subjected to thermal runaway, the voltage is rapidly reduced to 0V, and the battery cell overcharging test is 160% SOC according to the charging capacity.
3. Needling performance test
The full-charged 75Ah cell was subjected to a needling test, which comprises the following steps:
3-1) needling position, namely the center of the large surface of the battery cell;
3-2) needle diameter: 1mm;
3-3) needle tip angle: 30 °;
3-4) needling speed: 2mm/s.
3-5) needling depth: penetrating into the center of the large surface by 1.25mm in the direction perpendicular to the battery, standing for 15s, and if the battery is not out of control, continuing to step by 1.25mm until the battery core penetrates.
The results of the needling performance test are shown in FIG. 3.
The step needling test was performed on a 75Ah cell using the curing technique of example 1 according to the protocol described above, with the voltage drop of the cell being found in fig. 3, showing that the needle has penetrated 1.25mm and that the cell has short circuited, while the temperature of the cell slowly increases. After standing for 15s, further penetration is carried out until the depth of the needling of the battery cell is 3.75mm after 37s, the battery cell rapidly releases heat, the temperature of the battery cell rapidly rises, and then thermal runaway occurs. It is demonstrated that this test result can keep the cell safe by a stepped needling depth of 2.5 mm.
Example 2
Mixing the following components to form a first solution
The monomer used to form the gel skeleton is 3-hexenedinitrile: 42%;
the flexible additive is succinonitrile: 42%;
the polymerization initiator is azobisisobutyronitrile: 0.5%;
the first lithium salt is lithium bis (trifluoromethanesulfonyl) imide: 15.5%.
Curing temperature is 75 ℃ and curing time is 20h.
Other procedures and test criteria were the same as in example 1.
The hot box test was performed according to the protocol described above, with a final hot box result of 155 ℃.
The overcharge test was performed according to the above protocol, and the cell overcharge test showed thermal runaway at 148% soc.
The step needling test was performed according to the above scheme, and as a result, the safety of the cell was maintained by a step needling depth of 2.5 mm.
Example 3
Mixing the following components to form a first solution
Monomers used to form the gel skeleton were fumaric acid nitrile and 3-hexenedinitrile (mass ratio 1:1): 42%;
the flexible additive is succinonitrile: 42%;
the polymerization initiator is azobisisobutyronitrile: 0.5%;
the first lithium salt is lithium bis (trifluoromethanesulfonyl) imide: 15.5%.
Curing temperature is 70 ℃ and curing time is 30 hours.
Other procedures and test criteria were the same as in example 1.
The hot box test was performed according to the protocol described above, with a final hot box result of 155 ℃.
The overcharge test was performed according to the above protocol, and the cell overcharge test showed thermal runaway at 155% soc.
The step needling test was performed according to the above scheme, and as a result, the safety of the cell was maintained by a step needling depth of 2.5 mm.
Example 4
Mixing the following components to form a first solution
The monomer used to form the gel skeleton is 5-hexenenitrile: 42%;
the flexible additive is succinonitrile: 42%;
the polymerization initiator is azobisisobutyronitrile: 1%;
the first lithium salt is lithium bis (trifluoromethanesulfonyl) imide: 15%.
Curing temperature is 70 ℃ and curing time is 24 hours.
Other procedures and test criteria were the same as in example 1.
The hot box test was performed according to the above protocol with a final hot box result of 150 ℃.
The overcharge test was performed according to the above protocol, and the cell overcharge test showed thermal runaway at 138% soc.
The step needling test was performed according to the above scheme, and as a result, the safety of the cell was maintained by a step needling depth of 2.5 mm.
Example 5
Mixing the following components to form a first solution
Monomers used to form the gel skeleton were fumaric acid nitrile and 5-hexenenitrile (mass ratio 2:1): 42%;
the flexible additive is succinonitrile: 42%;
the polymerization initiator is azobisisobutyronitrile: 0.5%;
the first lithium salt is lithium bis (trifluoromethanesulfonyl) imide: 15.5%.
Curing temperature is 68 ℃ and curing time is 24 hours.
Other procedures and test criteria were the same as in example 1.
The hot box test was performed according to the protocol described above, with a final hot box result of 155 ℃.
The overcharge test was performed according to the above protocol, and the cell overcharge test showed thermal runaway at 160% soc.
The step needling test was performed according to the above protocol, and as a result, the cell safety was maintained by a step needling depth of 3.75 mm.
Example 6
The composition of the first solution was the same as in example 1.
The preparation method of the positive plate containing the gel electrolyte comprises the following steps: and mixing the first solution and the second solution together at room temperature, and uniformly stirring to obtain the gel electrolyte forming composition. The weight ratio of the first solution to the second solution is 1:2. The second solution comprises nonaqueous solvent with volume ratio of ethylene carbonate to dimethyl carbonate to ethylmethyl carbonate of 2:4:4 and second lithium salt lithium hexafluorophosphate (LiPF) with molar concentration of 1.00mol/L 6 ). And (3) coating the gel electrolyte forming composition on the positive electrode active material layer of the positive electrode sheet, heating at 70 ℃ for 24 hours, and polymerizing and gelling to obtain the positive electrode sheet containing the gel electrolyte.
And preparing the battery cell containing the positive plate according to a conventional method.
The other operating steps and test criteria were the same as in example 1, except that the gel electrolyte was used in an amount of 1/2 of the original amount and the heating temperature was changed to 70 ℃.
The hot box test was performed according to the above protocol with a final hot box result of 150 ℃.
The overcharge test was performed according to the above protocol, and the cell overcharge test showed thermal runaway at 143% soc.
The step needling test was performed according to the above scheme, and as a result, the safety of the cell was maintained by a step needling depth of 2.5 mm.
Comparative example 1
The positive electrode sheet and electrolyte (second solution) were identical to example 1, and were conventional liquid cells, without using a solidified electrolyte.
The hot box test was performed according to the above protocol with a final hot box result of 150 ℃.
The overcharge test was performed according to the above protocol, and the cell overcharge test showed thermal runaway at 125% soc.
The step needling test was performed according to the above protocol, with the result that the cell could be kept safe only by a step needling depth of 1.25 mm.
Comparative example 2
Mixing the following components to form a first solution
The monomer used to form the gel skeleton is acrylonitrile: 42%;
the flexible additive is succinonitrile: 42%;
the polymerization initiator is azobisisobutyronitrile: 0.5%;
the first lithium salt is lithium bis (trifluoromethanesulfonyl) imide: 15.5%.
Curing temperature is 68 ℃ and curing time is 24 hours.
Other procedures and test criteria were the same as in example 1.
The hot box test was performed according to the above protocol with a final hot box result of 150 ℃.
The overcharge test was performed according to the above protocol, and the cell overcharge test showed thermal runaway at 133% soc.
The step needling test was performed according to the above scheme, and as a result, the safety of the cell was maintained by a step needling depth of 2.5 mm.
Summary of examples and comparative examples data:
| experiment number | The temperature of the hot box is DEG C | Overcharge SOC | Needling depth mm |
| Example 1 | 150 | 160％ | 2.5 |
| Example 2 | 155 | 148％ | 2.5 |
| Example 3 | 155 | 155％ | 2.5 |
| Example 4 | 150 | 138％ | 2.5 |
| Example 5 | 155 | 160％ | 3.75 |
| Example 6 | 150 | 143％ | 2.5 |
| Comparative example 1 | 150 | 125％ | 1.25 |
| Comparative example 2 | 150 | 133％ | 2.5 |
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (11)
1. A gel electrolyte comprising a gel skeleton, a flexible additive, and a first lithium salt, the gel skeleton being formed by polymerization of at least one monomer comprising at least one selected from the group consisting of fumaric acid nitrile, 5-hexenenitrile, and 3-hexenedinitrile in the presence of a polymerization initiator.
2. The gel electrolyte of claim 1, wherein the gel electrolyte satisfies at least one of the following conditions:
(a1) The monomer comprises fumaric acid nitrile and/or 3-hexenedinitrile;
(a2) The monomers include a combination of fumaric acid nitrile and 5-hexenenitrile;
(a3) The monomers comprise a combination of 3-hexenedinitrile and 5-hexenedinitrile;
(b) The flexible additive comprises at least one of succinonitrile, adiponitrile, glutaronitrile and an ionic liquid;
(c) The first lithium salt comprises at least one of lithium perchlorate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate and lithium tetrafluoroborate;
(d) The polymerization initiator includes azobisisobutyronitrile and/or azobisisoheptonitrile;
(e) The monomer is present in an amount of 20 to 60 wt%, the flexible additive is present in an amount of 20 to 60 wt%, the first lithium salt is present in an amount of 5 to 20 wt%, and the polymerization initiator is present in an amount of 1 to 5 wt%, the percentages being based on the total weight of the monomer, flexible additive, first lithium salt and polymerization initiator.
3. The gel electrolyte according to claim 2, wherein,
the monomers include a combination of fumaric acid nitrile and 5-hexenenitrile; and/or the number of the groups of groups,
the flexible additive comprises at least one of succinonitrile, adiponitrile and glutaronitrile; and/or the number of the groups of groups,
the first lithium salt comprises at least one of lithium bis (trifluoromethanesulfonyl) imide and lithium bis (fluorosulfonyl) imide; and/or the number of the groups of groups,
the ionic liquid is at least one selected from 1-methyl-1-propylpiperidine bis (trifluoromethylsulfonyl) imide salt, 1-butyl-1-methylpiperidine bis (trifluoromethylsulfonyl) imide salt, 1-butyl-1-methylpyrrolidine bis (trifluoromethylsulfonyl) imide salt, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-propyl-1-methylpyrrolidine bis (trifluoromethylsulfonyl) imide salt, 1-ethyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide salt and 1-ethyl-3-methylimidazole tetrafluoroborate.
4. The gel electrolyte according to claim 1 or 2, wherein the gel electrolyte comprises a nonaqueous solvent selected from at least one of a cyclic carbonate and a linear carbonate, and a second lithium salt.
5. The gel electrolyte according to claim 4, wherein the gel electrolyte satisfies at least one of the following conditions,
(f) The nonaqueous solvent is at least one selected from ethylene carbonate, ethylmethyl carbonate and dimethyl carbonate;
(g) The ratio of the total weight of the monomer, the flexibilizing additive, the first lithium salt, and the polymerization initiator to the total weight of the nonaqueous solvent and the second lithium salt is from 1:9 to 7:3, preferably from 1:2 to 3:2;
(h) The second lithium salt includes at least one of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium difluorophosphate and lithium bis (oxalato) difluorophosphate, and preferably includes lithium hexafluorophosphate.
6. A method of preparing the gel electrolyte of any one of claims 1-5, comprising the steps of:
(i) Mixing the monomer of any one of claims 1-5, a flexibilizing additive, a first lithium salt, and a polymerization initiator to form a first solution;
(ii) Mixing the nonaqueous solvent of claim 4 or 5 with a second lithium salt to form a second solution;
(iii) Mixing the first solution and the second solution to obtain a gel electrolyte forming composition, and polymerizing the gel electrolyte forming composition at 65-85 ℃.
7. A positive electrode sheet comprising a positive electrode active material layer and a gel electrolyte provided on a surface of the positive electrode active material layer, characterized in that the gel electrolyte is obtained by polymerizing the gel electrolyte forming composition according to claim 6 on the positive electrode active material layer.
8. The positive electrode sheet according to claim 7, the positive electrode active material comprising a material selected from the group consisting of LiNi m Co n A (1-m-n) O 2 At least one of the lithium nickel transition metal oxides, A is selected from at least one of manganese, aluminum, magnesium, zirconium, strontium, yttrium, lanthanum, molybdenum, silver, niobium, iron, titanium, copper, zinc, chromium, calcium, barium and tungsten, m is more than or equal to 0.5 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 0.5,m+n≤1。
9. a secondary battery comprising the positive electrode sheet according to claim 7 or 8.
10. The secondary battery according to claim 9, comprising a negative electrode sheet including a negative electrode active material including a silicon-based material including a silicon oxide and/or a silicon carbon compound, the mass content g of the silicon-based material satisfying, based on the mass of the negative electrode active material: g is more than or equal to 10 and less than or equal to 100.
11. An apparatus comprising the secondary battery according to claim 9 or 10.
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