CN117747934A - Gel electrolyte and application thereof - Google Patents
Gel electrolyte and application thereof Download PDFInfo
- Publication number
- CN117747934A CN117747934A CN202311769998.7A CN202311769998A CN117747934A CN 117747934 A CN117747934 A CN 117747934A CN 202311769998 A CN202311769998 A CN 202311769998A CN 117747934 A CN117747934 A CN 117747934A
- Authority
- CN
- China
- Prior art keywords
- lithium
- gel electrolyte
- parts
- carbonate
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 28
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000000853 adhesive Substances 0.000 claims abstract description 16
- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 16
- 229920001523 phosphate polymer Polymers 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 150000008282 halocarbons Chemical group 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 16
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 14
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 4
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 claims description 3
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 claims description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 claims description 3
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 claims description 3
- 229940125904 compound 1 Drugs 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims 1
- 125000003709 fluoroalkyl group Chemical group 0.000 claims 1
- 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 1
- 239000002994 raw material Substances 0.000 claims 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002153 silicon-carbon composite material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 2
- 206010003497 Asphyxia Diseases 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- RTTUXDWYMFNHKW-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Na+].[Co+2].[Ni+2] Chemical compound [Mn](=O)(=O)([O-])[O-].[Na+].[Co+2].[Ni+2] RTTUXDWYMFNHKW-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- LNLFLMCWDHZINJ-UHFFFAOYSA-N hexane-1,3,6-tricarbonitrile Chemical compound N#CCCCC(C#N)CCC#N LNLFLMCWDHZINJ-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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 1
- 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 description 1
- 206010000060 Abdominal distension Diseases 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical class [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical class [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 208000024330 bloating Diseases 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FXBLJWDJXBQLEL-UHFFFAOYSA-N ethenyl dimethyl phosphate Chemical compound COP(=O)(OC)OC=C FXBLJWDJXBQLEL-UHFFFAOYSA-N 0.000 description 1
- CRKKKOCFBCJTKQ-UHFFFAOYSA-N ethenyl methyl hydrogen phosphate Chemical compound COP(O)(=O)OC=C CRKKKOCFBCJTKQ-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Landscapes
- Secondary Cells (AREA)
Abstract
The invention provides a gel electrolyte and application thereof. The gel electrolyte is prepared from 40-90 parts of phosphate polymer monomer, 2-20 parts of adhesive, 1-10 parts of filler and 40-90 parts of liquid electrolyte, wherein the filler is a lithium-containing compound, and the structural formula of the phosphate polymer monomer is shown as formula one. Wherein R is hydrocarbon group or halogenated hydrocarbon group, and n is 1-4. The gel electrolyte has electrochemical performance similar to that of liquid electrolyte, and may be compounded with cell to prepare gel lithium ion battery.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to an electrolyte, and more particularly relates to a gel electrolyte and application thereof.
Background
As one of branches of clean energy, a lithium ion battery has a renewable and sustainable energy system, has been widely applied to energy storage systems, even part of material systems have been applied to the automotive field, and along with the pursuit of high-safety and high-endurance products, the battery material system is forced to develop towards two aspects of high nickel, high voltage and the like, but the existing liquid carbonate electrolyte can undergo chemical reactions such as decomposition and gas production under the high nickel and high voltage systems, the performance of the whole battery is rapidly reduced, and safety problems such as fire and the like can also be caused. For this reason, a series of technologies such as gel electrolyte and solid-state battery have been developed, and in many technical routes, gel electrolyte has been attracting attention because of its high toughness and high safety, and gel electrolyte can exert the capacity of high-nickel and high-voltage positive electrode materials while maintaining high safety.
For example, it is reported that a gel type lithium ion battery with high conductivity and high oxidation resistance window is obtained by coating a borate-containing gel polymer monomer in a positive electrode material, but the preparation process of the battery cannot follow the preparation process of the current lithium battery, the preparation process flow of the battery core needs to be adjusted is relatively more, and the manufacturing cost of the battery is relatively high. In addition, a gel lithium ion battery is assembled by a linear phosphate flame-retardant gel electrolyte and positive and negative electrodes, and has good electrochemical performance, but the gel electrolyte uses ionic liquid as a carrier of salt, and the high viscosity of the gel electrolyte brings certain resistance to the application of industrial products.
Therefore, there is a need for the development of gel electrolytes and gel lithium ion batteries that can be industrialized, that can maintain high safety, and that can exhibit high nickel and high voltage positive electrode material capacities.
Disclosure of Invention
Based on the above problems, an object of the present invention is to provide a gel electrolyte and its application. The gel electrolyte has electrochemical performance similar to that of liquid electrolyte, and may be compounded with cell to prepare gel lithium ion battery.
To achieve the above object, the present invention provides, in one aspect, a gel electrolyte. The gel electrolyte is prepared from 40-90 parts by weight of phosphate polymer monomer, 2-20 parts by weight of adhesive, 1-10 parts by weight of filler and 40-90 parts by weight of liquid electrolyte, wherein the filler is a lithium-containing compound, and the structural formula of the phosphate polymer monomer is shown as formula one. Wherein R is hydrocarbon group or halogenated hydrocarbon group, and n is 1-4.
According to the technical scheme adopted by the invention, the polymer monomer containing the cyclic phosphate can absorb active oxygen released from the positive electrode material, so that the side reaction of the interface of the positive electrode material is reduced, and meanwhile, the polymer monomer can undergo self-polymerization reaction at the high temperature of subsequent formation, and the probability of the initiator to generate flatulence in the battery in the cycle process can be greatly reduced without using an initiator. In addition, the lithium-containing compound as a filler can enhance the conductivity of the gel electrolyte, so that the electrochemical performance of the gel electrolyte can be close to that of the liquid electrolyte. The gel electrolyte is prepared by compounding a polymer and a liquid electrolyte, and the gel lithium ion battery can be prepared by compounding a phosphate polymer monomer and an adhesive with a battery core, so that the gel lithium ion battery can maintain high safety and high electrochemical performance, can also be used along with the preparation process of the lithium ion battery of the current liquid electrolyte, and has the feasibility of industrial production.
As one embodiment of the present invention, R in formula I is C 1 ～C 5 Alkyl or C of (2) 1 ～C 5 N is 1 to 2.
As an embodiment of the present invention, the phosphate polymer monomer is selected from at least one of compounds 1 to 6.
As an aspect of the present invention, the adhesive is at least one selected from polyethylene glycol diacrylate (PEGDA), N methylene bisacrylamide, triethylene glycol dimethacrylate (TEGDMA), and pentaerythritol tetraacrylate (PETEA).
As an aspect of the present invention, the lithium-containing compound is at least one selected from the group consisting of Lithium Lanthanum Zirconium Oxide (LLZO), lithium nitride, lithium phosphide, and lithium nitrate.
As an aspect of the present invention, the liquid electrolyte includes a lithium salt, a solvent, and an additive.
As an embodiment of the present invention, the lithium salt is at least one selected from the group consisting of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorobis-oxalato-phosphate, lithium difluorooxalato-borate, lithium tetrafluoroborate, lithium perchlorate, lithium tetrafluorobis-oxalato-phosphate, lithium fluorosulfonate, lithium trifluoromethanesulfonate, and lithium bistrifluoromethane-sulfonyl imide.
As an aspect of the present invention, the solvent is at least one selected from the group consisting of methylethyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate and dipropyl carbonate.
As one technical scheme of the invention, the additive is at least one selected from vinylene carbonate, tri (trimethylsilyl) phosphate, tri (trimethylsilyl) borate, fluoroethylene carbonate, 1, 3-propane sulfonate lactone, ethylene sulfate, methylene methane disulfonate, adiponitrile, succinonitrile and 1,3, 6-hexane tricarbonitrile.
In another aspect, the invention provides the use of the gel electrolyte described above in a lithium ion battery.
Detailed Description
The gel electrolyte provided by the invention can be used for lithium ion batteries. The lithium ion battery includes a positive electrode material, a negative electrode material, and a gel electrolyte. Wherein the positive electrode material can be, but is not limited to, liNi x Co y Mn z M (1 -x-y-z)O 2 M is at least one of Fe, mg, cu, zn, al, sn, B, ga, cr, sr and Ti, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x+y+z is more than or equal to 1. The negative electrode material may be, but is not limited to, at least one of artificial graphite, hard carbon, natural graphite, mesophase microspheres, silicon oxygen compounds, silicon carbon composites, silicon and silicon alloys.
The gel electrolyte is prepared from 40-90 parts of phosphate polymer monomer, 2-20 parts of adhesive, 1-10 parts of filler and 40-90 parts of liquid electrolyte.
The content of the phosphate polymer monomer may be, but is not limited to, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts. Preferably, the content of the phosphate polymer monomer is 45 to 60 parts. The structural formula of the phosphate polymer monomer is shown as formula one.
R is a hydrocarbon group or a halogenated hydrocarbon group. Further, R is C 1 ～C 5 Alkyl or C of (2) 1 ～C 5 Is a fluorinated alkyl group of (2). Further, R is propyl, isopropyl, tert-butyl, trifluoropropylmethyl, di (trifluoromethyl) isopropyl, tri (trifluoromethyl) tert-butyl. n is 1 to 4, and further n is 1 to 2. Further, n is 1.
The phosphate polymer monomer is selected from at least one of compounds 1 to 6.
CAS：53969-09-8
Compound 2-Compound 6 the corresponding product was obtained according to the above reaction.
The phosphate polymer monomer can undergo self-polymerization reaction at high temperature of formation, and the reaction formula for self-polymerization is as follows.
The content of the adhesive may be, but is not limited to, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, preferably 1 to 10 parts, more preferably 1 to 4 parts. The adhesive is at least one selected from polyethylene glycol diacrylate, N-methylene bisacrylamide, triethylene glycol dimethacrylate and pentaerythritol tetraacrylate.
The content of the filler may be, but is not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, and preferably 1 to 4 parts. The filler is a lithium-containing compound and is at least one selected from lithium lanthanum zirconium oxide, lithium nitride, lithium phosphide and lithium nitrate.
The content of the liquid electrolyte may be, but is not limited to, 40 parts, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts. The liquid electrolyte includes a lithium salt, a solvent, and an additive. The lithium salt is 0.5-2M, and is at least one selected from lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorobis (oxalato) phosphate, lithium difluorooxalato borate, lithium tetrafluoroborate, lithium perchlorate, lithium tetrafluorobis (oxalato) phosphate, lithium fluorosulfonate, lithium trifluoromethanesulfonate and lithium bistrifluoromethane sulfonyl imide. The solvent is at least one selected from methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate and dipropyl carbonate. The additive accounts for 0.1-10.0% of the weight of the liquid electrolyte, and the additive is at least one selected from Vinylene Carbonate (VC), tri (trimethylsilyl) phosphate, tri (trimethylsilyl) borate, fluoroethylene carbonate (FEC), 1, 3-propane sulfonate lactone (PS), ethylene sulfate (DTD), methylene methane disulfonate, adiponitrile, succinonitrile and 1,3, 6-hexane tricarbonitrile.
The preparation method of the lithium ion battery comprises the following steps:
(1) Mixing a phosphate polymer monomer, an adhesive, a filler and a liquid electrolyte in a glove box according to a formula ratio to obtain a gel electrolyte;
(2) Preparing a battery cell, packaging the battery cell in a packaging piece, injecting gel electrolyte into a battery, sealing the battery cell after liquid injection, and standing for 24 hours at normal temperature.
(3) The battery is charged in a formation cabinet with high temperature (45-80 ℃) and high pressure (1-80 Mpa) after standing, and the charging cut-off voltage is 4.4V.
For a better description of the objects, technical solutions and advantageous effects of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention and should not be taken as limiting the present invention.
Example 1
(1) Preparation of liquid electrolyte
In a glove box filled with argon (O) 2 ＜1ppm，H 2 O < 1 ppm), mixing Ethylene Carbonate (EC), propylene Carbonate (PC) and diethyl carbonate (DEC) according to the weight ratio of EC: PC: DEC=1:1:1 to obtain 86.5g of solvent, adding 1g of vinylene carbonate for dissolution, fully stirring, adding 12.5g of lithium hexafluorophosphate, and uniformly mixing to obtain a liquid electrolyte.
(2) Preparation of gel electrolyte
In a glove box filled with argon (O 2 ＜1ppm，H 2 O < 1 ppm), 100g of mixed solution is prepared by the compound 1, the adhesive TEGDMA and the filler LLZO according to the weight ratio of 8:1.5:0.5, and the mixed solution and the liquid electrolyte are mixed according to the weight ratio of 5:5 to obtain the gel electrolyte.
(3) Preparation of the positive electrode
Ternary material LiNi of nickel cobalt sodium manganate 0.9 Co 0.05 Mn 0.05 O 2 Uniformly mixing the adhesive PVDF and the conductive agent SuperP according to the weight ratio of 95:1:4 to prepare lithium ion battery anode slurry with certain viscosity, coating the mixed slurry on two sides of an aluminum foil, and drying and rolling to obtain the anode plate.
(4) Preparation of negative electrode
And (3) preparing the silicon-carbon composite material, the conductive agent SuperP and the adhesive PVDF into slurry according to a weight ratio of 97:1:2, uniformly mixing, coating the mixed slurry on two sides of a copper foil, and drying and rolling to obtain the negative plate.
(5) Preparation of gel-type lithium ion battery
And (3) manufacturing the positive plate, the diaphragm and the negative plate into square battery cells in a lamination mode, packaging by adopting a polymer film, filling gel electrolyte for sealing, standing for 24 hours at normal temperature, charging the battery after standing in a formation cabinet with high temperature of 60 ℃ and high pressure of 20Mpa, and manufacturing the lithium ion battery with 1000mAh capacity after formation, capacity division and other working procedures, wherein the charging cut-off voltage is 4.4V.
The formulations of examples 2 to 11 and comparative examples 1 to 3 are shown in Table 1, and the gel type lithium ion battery was prepared in the same manner as in example 1, and the battery prepared in comparative example 1 was a liquid type lithium ion battery.
TABLE 1 formulation of gel electrolytes of examples 1 to 11 and comparative examples 1 to 3
Comparative example 4
(1) Preparation of liquid electrolyte
In a glove box filled with argon (O) 2 ＜1ppm，H 2 O < 1 ppm), mixing Ethylene Carbonate (EC), propylene Carbonate (PC) and diethyl carbonate (DEC) according to the weight ratio of EC: PC: DEC=1:1:1 to obtain 86.5g of solvent, adding 1g of vinylene carbonate for dissolution, fully stirring, adding 12.5g of lithium hexafluorophosphate, and uniformly mixing to obtain a liquid electrolyte.
(2) Preparation of gel electrolyte
In a glove box filled with argon (O 2 ＜1ppm，H 2 O < 1 ppm), preparing 100g of mixed solution by using methyl vinyl phosphate, adhesive TEGDMA, filler LLZO and azodiisobutyronitrile according to the weight ratio of 8:1.5:0.5:0.1, and mixing the mixed solution and the liquid electrolyte according to the weight ratio of 5:5 to obtain the gel electrolyte.
(3) Preparation of the positive electrode
Ternary material LiNi of nickel cobalt sodium manganate 0.9 Co 0.05 Mn 0.05 O 2 Uniformly mixing the adhesive PVDF and the conductive agent SuperP according to the weight ratio of 95:1:4 to prepare lithium ion battery anode slurry with certain viscosity, coating the mixed slurry on two sides of an aluminum foil, and drying and rolling to obtain the anode plate.
(4) Preparation of negative electrode
And (3) preparing the silicon-carbon composite material, the conductive agent SuperP and the adhesive PVDF into slurry according to a weight ratio of 97:1:2, uniformly mixing, coating the mixed slurry on two sides of a copper foil, and drying and rolling to obtain the negative plate.
(5) Preparation of gel-type lithium ion battery
And (3) manufacturing the positive plate, the diaphragm and the negative plate into square battery cells in a lamination mode, packaging by adopting a polymer film, filling gel electrolyte for sealing, standing for 24 hours at normal temperature, charging the battery after standing in a formation cabinet with high temperature of 60 ℃ and high pressure of 20Mpa, and manufacturing the lithium ion battery with 1000mAh capacity after formation, capacity division and other working procedures, wherein the charging cut-off voltage is 4.4V.
The lithium ion batteries manufactured in examples 1 to 11 and comparative examples 1 to 4 were respectively subjected to performance tests under the following specific test conditions, and the performance test results are shown in table 2.
(1) High temperature cycle test
The lithium ion battery is placed in a constant temperature box at 45 ℃ and kept stand for 30min to keep constant temperature. Charging with 1C constant current to 4.4V, charging with 4.4V constant voltage to 0.05C current, discharging with 1C constant current to 4.4V voltage, and recording the first-turn discharge capacity of the battery as C 0 . This is a charge-discharge cycle. Then charging and discharging at 45 ℃ for 30 weeks at 1C/1C, and the discharge capacity is marked as C 1 。
Capacity retention = C 1 /C 0 *100％
(2) Asphyxia time test
In a glove box filled with argon (O 2 ＜1ppm，H 2 O < 1 ppm), discharging the separated lithium ion battery to 3.0V, disassembling and taking out the membranes with the same positions and the same areas, igniting the membranes by adopting a lighter, and counting the time from the starting of the ignition of the membranes to the extinguishing of the flame, wherein the asphyxiation time T of the membranes is calculated 0 。
Table 2 test results of examples 1 to 11 and comparative examples 1 to 4
As is evident from the results of Table 2 and the combined choking test, in the gel type lithium ion batteries of examples 1 to 11, the separator containing the gel electrolyte monomer had a gel reaction, the separator was very viscous, and the ignition time by the lighter was longer, and the choking time was significantly shorter than that of the liquid electrolyte, indicating that the safety performance of the gel type lithium ion battery was improved, and the capacity was relatively close to that of the liquid electrolyte. The gel type lithium ion battery prepared by adopting the polymer monomer containing the cyclic phosphate for self-polymerization, combining the filler containing the lithium compound and the gel electrolyte obtained by compounding the filler with the liquid electrolyte has better high-temperature circulation and safety.
While comparative example 1 was a pure liquid electrolyte, the safety performance of the battery was not good. Comparative example 2 is a pure gel state electrolyte and the electrochemical performance of the battery is poor. The lack of lithium-containing filler material in comparative example 3 resulted in large formation polarization and low volumetric capacity. Comparative example 4 using dimethyl vinylphosphate as a monomer, an initiator was added to polymerize into a gel state, and the addition of the initiator resulted in bloating, thereby deteriorating the cycle performance.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The gel electrolyte is characterized in that the preparation raw materials comprise 40-90 parts by weight of phosphate polymer monomer, 2-20 parts by weight of adhesive, 1-10 parts by weight of filler and 40-90 parts by weight of liquid electrolyte, wherein the filler is a lithium-containing compound, the structural formula of the phosphate polymer monomer is shown as formula one,
wherein R is hydrocarbon group or halogenated hydrocarbon group, and n is 1-4.
2. The gel electrolyte of claim 1, wherein R is C 1 ～C 5 Alkyl or C of (2) 1 ～C 5 Is a fluoroalkyl group and n is 1 to the whole range2。
3. The gel electrolyte according to claim 1, wherein the phosphate polymer monomer is selected from at least one of the group consisting of compound 1 to compound 6,
4. the gel electrolyte of claim 1, wherein the adhesive is selected from at least one of polyethylene glycol diacrylate, N methylene bisacrylamide, triethylene glycol dimethacrylate, and pentaerythritol tetraacrylate.
5. The gel electrolyte of claim 1, wherein the lithium-containing compound is selected from at least one of lithium lanthanum zirconium oxide, lithium nitride, lithium phosphide, and lithium nitrate.
6. The gel electrolyte of claim 1, wherein the liquid electrolyte comprises a lithium salt, a solvent, and an additive.
7. The gel electrolyte according to claim 6, wherein the lithium salt is at least one selected from the group consisting of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorobis-oxalato-phosphate, lithium difluorooxalato-borate, lithium tetrafluoroborate, lithium perchlorate, lithium tetrafluorobis-oxalato-phosphate, lithium fluorosulfonate, lithium trifluoromethanesulfonate, and lithium bistrifluoromethanesulfonimide.
8. The gel electrolyte according to claim 7, wherein the solvent is at least one selected from the group consisting of methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and dipropyl carbonate.
9. The gel electrolyte of claim 7, wherein the additive is selected from at least one of vinylene carbonate, tris (trimethylsilyl) phosphate, tris (trimethylsilyl) borate, fluoroethylene carbonate, 1, 3-propane sulfonate lactone, vinyl sulfate, methylene methane disulfonate, adiponitrile, succinonitrile, and 1,3, 6-hexanetrinitrile.
10. Use of a gel electrolyte according to any one of claims 1 to 9 in a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311769998.7A CN117747934A (en) | 2023-12-21 | 2023-12-21 | Gel electrolyte and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311769998.7A CN117747934A (en) | 2023-12-21 | 2023-12-21 | Gel electrolyte and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117747934A true CN117747934A (en) | 2024-03-22 |
Family
ID=90279043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311769998.7A Pending CN117747934A (en) | 2023-12-21 | 2023-12-21 | Gel electrolyte and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117747934A (en) |
-
2023
- 2023-12-21 CN CN202311769998.7A patent/CN117747934A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021110165A1 (en) | Lithium secondary battery electrolyte with low internal resistance and lithium secondary battery | |
| CN109904521B (en) | Electrolyte and battery comprising same | |
| CN110112465B (en) | Electrolyte for battery with lithium-rich manganese-based positive electrode material system and lithium ion battery | |
| CN109755635A (en) | A kind of battery electrolyte additive that taking into account high temperature performance, electrolyte and nickelic ternary lithium ion battery | |
| CN109768326B (en) | Electrolyte and electrochemical energy storage device | |
| JP6799085B2 (en) | Lithium ion battery | |
| CN111430793B (en) | Electrolyte solution, and electrochemical device and electronic device using same | |
| CN113078354A (en) | Ternary lithium ion battery non-aqueous electrolyte and lithium ion battery thereof | |
| CN111883830A (en) | Lithium ion battery electrolyte, battery cathode and electrochemical energy storage device | |
| CN113851713B (en) | Electrolyte additive, electrolyte containing additive and lithium ion battery | |
| CN111834665B (en) | High-nickel ternary lithium ion battery electrolyte and lithium ion battery | |
| CN113437363A (en) | Non-aqueous electrolyte and secondary battery thereof | |
| CN113429504A (en) | Preparation method of semi-solid polyion liquid electrolyte for lithium battery | |
| CN111934015A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery containing non-aqueous electrolyte | |
| CN117039153A (en) | Functional non-aqueous electrolyte and lithium secondary battery | |
| Palluzzi et al. | Ionic liquids and their derivatives for lithium batteries: role, design strategy, and perspectives | |
| CN117691190A (en) | Electrolyte for lithium-rich manganese-based positive electrode high-voltage lithium ion battery and lithium ion battery | |
| CN108878976A (en) | A kind of silicon-carbon system lithium-ion battery electrolytes and silicon-carbon system lithium ion battery | |
| CN113889667B (en) | High-voltage electrolyte adaptive to lithium cobaltate battery capable of being charged quickly and application of high-voltage electrolyte | |
| CN114566712B (en) | High-voltage lithium ion battery electrolyte containing lithium difluorophosphate, preparation method thereof and lithium ion battery | |
| CN115108558A (en) | Lithium salt for preparing lithium ion electrolyte and lithium ion electrolyte | |
| CN112467221B (en) | Additive for inhibiting silicon negative electrode expansion and electrolyte containing additive | |
| CN114843609A (en) | Non-aqueous electrolyte and secondary battery thereof | |
| CN114927758A (en) | Electrolyte for improving high-temperature performance of lithium ion battery and lithium ion battery | |
| CN117747934A (en) | Gel electrolyte and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |