CN118315664A - Lithium ion battery electrolyte, lithium ion battery and preparation method of lithium ion battery - Google Patents
Lithium ion battery electrolyte, lithium ion battery and preparation method of lithium ion battery Download PDFInfo
- Publication number
- CN118315664A CN118315664A CN202410419790.0A CN202410419790A CN118315664A CN 118315664 A CN118315664 A CN 118315664A CN 202410419790 A CN202410419790 A CN 202410419790A CN 118315664 A CN118315664 A CN 118315664A
- Authority
- CN
- China
- Prior art keywords
- lithium
- electrolyte
- ion battery
- lithium ion
- group
- 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
- 239000003792 electrolyte Substances 0.000 title claims abstract description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 239000013538 functional additive Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 3
- 239000007774 positive electrode material Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000007773 negative electrode material Substances 0.000 claims description 15
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 150000001555 benzenes Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 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
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 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 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 238000009461 vacuum packaging Methods 0.000 claims description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910012258 LiPO Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-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
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000011056 performance test Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002000 Electrolyte additive Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium ion battery electrolyte, a lithium ion battery and a preparation method thereof, wherein the electrolyte consists of an organic solvent, electrolyte salt and a functional additive, and the organic solvent comprises polyfluorinated benzene; the functional additive comprises a functional additive I and a functional additive II; wherein, R 1～R4 is independently selected from one of hydrogen atom, substituted or unsubstituted C 1～C6 alkyl, substituted or unsubstituted C 1～C6 unsaturated hydrocarbon group, substituted or unsubstituted C 2～C20 alkenyl, cyano group, aryl group with 6-18 carbon atoms substituted by carbonyl group, cyano group, halogen atom, nitro group, carboxyl group and sulfonic group, wherein halogen atom is F, cl and Br; x is any one selected from C, N or B; the mass of the additive I accounts for 0.2-3% of the total mass of the electrolyte; the mass of the additive II accounts for 0.3-2.4% of the total mass of the electrolyte.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte, a lithium ion battery and a preparation method of the lithium ion battery electrolyte.
Background
Lithium ion batteries are rechargeable batteries that operate primarily by virtue of lithium ions moving between a positive electrode and a negative electrode. Li + is inserted and extracted back and forth between the two electrodes during charge and discharge: during charging, li + is deintercalated from the positive electrode, and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true when discharging. The lithium ion battery has the advantages of high specific energy, no memory effect, long cycle life, small self-discharge and the like, and is widely applied to the fields of digital codes, energy storage, electric automobiles and the like.
Along with the improvement of the living standard of people and the trend of better life, higher requirements are also put on the energy density of the battery. The limiting voltage of the positive electrode material needs to be further increased when the energy density of the battery is increased, and the gram capacity of the positive electrode material gradually increases with the continuous increase of the limiting voltage of the positive electrode material, but the high temperature performance of the battery is seriously deteriorated, and the long cycle life cannot be ensured. Especially under high voltage (4.5V), in the long-term cyclic charge and discharge process, electrolyte enters the positive electrode material to damage the structure of the positive electrode material due to the fragmentation and falling of positive electrode material particles, and meanwhile, the release of active oxygen further accelerates the oxidative decomposition of the electrolyte, and a protective film on the surface of a negative electrode can be continuously damaged, so that the problem of serious attenuation of the battery capacity is finally caused.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims to provide lithium ion battery electrolyte, which consists of an organic solvent, electrolyte salt and a functional additive, wherein the organic solvent contains polyfluorinated benzene; the functional additive comprises a functional additive I and a functional additive II;
The functional additive I is of the formula (1), and the additive II is of the formula (2):
Wherein, R 1～R4 is independently selected from one of hydrogen atom, substituted or unsubstituted C 1～C6 alkyl, substituted or unsubstituted C 1～C6 unsaturated hydrocarbon group, substituted or unsubstituted C 2～C20 alkenyl, cyano group, aryl group with 6-18 carbon atoms substituted by carbonyl group, cyano group, halogen atom, nitro group, carboxyl group and sulfonic group, wherein halogen atom is F, cl and Br;
The respective value ranges of n 1 and n 2 are 1-10;
x is any one selected from C, N or B;
the mass of the additive I accounts for 0.2-3% of the total mass of the electrolyte;
The mass of the additive II accounts for 0.3-2.4% of the total mass of the electrolyte.
Further, the polyfluorinated benzene is selected from any one of formulas 1-1 to 1-7:
1-7。
Further, the functional additive I is selected from any one of the formulas (1) -1 to (1) -8:
further, the functional additive II is selected from any one of the formulas (2) -1 to (2) -5:
Further, the electrolyte lithium salt is selected from one or more of lithium hexafluorophosphate (LiPF 6), lithium difluorophosphate (LiPO 2F2), lithium difluorooxalato borate (lipfob), lithium bis (trifluoromethylsulfonyl) imide, lithium difluorobis (oxalato) phosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methyllithium or lithium bis (trifluoromethylsulfonyl) imide.
Further, the mass of the lithium salt accounts for 5-25% of the total mass of the electrolyte.
Further, the organic solvent further comprises carbonate and/or carboxylic ester, wherein the carbonate is selected from one or more of the following solvents: ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate, diethyl carbonate (DEC), ethylmethyl carbonate;
The carboxylic acid ester is selected from one or more of the following solvents: propyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, propyl Propionate (PP), ethyl Propionate (EP), methyl butyrate, ethyl n-butyrate.
The invention also has another object to provide a lithium ion battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte;
the electrolyte is the electrolyte;
The positive plate comprises a current collector and positive electrode active material layers coated on one side or two side surfaces of the positive electrode current collector, wherein the positive electrode active material layers comprise positive electrode active materials, a conductive agent and a binder;
The negative electrode sheet comprises a current collector and a negative electrode active material layer coated on one side or two side surfaces of the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material, a conductive agent and a binder;
the positive electrode active material layer comprises the following components in percentage by mass: 80-99.8wt% of positive electrode active material, 0.1-10wt% of conductive agent, and 0.1-10wt% of binder;
the positive electrode active material layer comprises the following components in percentage by mass: 90-99.6wt% of positive electrode active material, 0.2-5wt% of conductive agent, and 0.2-5wt% of binder;
the negative electrode active material layer comprises the following components in percentage by mass: 80-99.8wt% of negative electrode active material, 0.1-10wt% of conductive agent, 0.1-10wt% of binder;
The negative electrode active material layer comprises the following components in percentage by mass: 90-99.6wt% of negative electrode active material, 0.2-5wt% of conductive agent, and 0.2-5wt% of binder;
The conductive agent is at least one selected from conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, metal powder and carbon fiber.
The binder is at least one selected from sodium carboxymethyl cellulose, styrene-butadiene latex, polytetrafluoroethylene and polyethylene oxide.
The negative electrode active material is artificial graphite.
The carbon-based negative electrode material comprises at least one of artificial graphite, natural graphite, mesophase carbon microspheres, hard carbon and soft carbon.
The positive electrode active material is selected from one or more of lithium iron phosphate and lithium manganate.
A third object of the present invention is to provide a method for manufacturing a lithium ion battery, the method comprising the steps of: the positive plate, the negative plate and the isolating film are laminated according to the sequence of the positive plate, the isolating film and the negative plate, and then are wound to obtain an electric core; and placing the battery core in an outer packaging aluminum foil, injecting electrolyte into the outer packaging, and performing the procedures of vacuum packaging, standing, formation, shaping, sorting and the like to obtain the lithium ion battery.
The invention also has the following beneficial effects:
1. According to the invention, the additive I and the additive II are used as lithium ion battery electrolyte additives, under the cooperation of the additive I and the additive II, the Si alkane in the additive I is easy to form an SEI protective film on the negative electrode, and the five-membered ring forms an interfacial film on the outer layer of the positive electrode, so that the lithium ion battery electrolyte additive has good high temperature resistance and low impedance, is favorable for migration of lithium ions, and further improves the cycle performance of the battery.
2. According to the invention, after the additive I is easy to form a protective film, the-C (identical to) N and-O-functional groups contained in the additive II have higher oxidation potential, so that the oxidation resistance of the electrolyte under high voltage is greatly improved, and the polyfluorobenzene contained in the organic solvent in the electrolyte has more-F functional groups, so that the reduction potential of the additive can be effectively improved, a stable LiF-rich interface layer is formed on the surface of the anode, the anode interface is optimized, the-C (identical to) N functional groups contained in the additive II can be combined with transition metal ions on the surface of the anode to participate in the formation of an SEI film, thereby inhibiting the deposition of transition metal ions dissolved out from the anode on the anode, reducing the adverse effect of the second additive on the SEI interface, improving the incompatibility of the second additive on graphite or lithium metal anode, so that the mutual cooperation of the additives I and II and the polyfluorobenzene solvent improves the comprehensive performance of the battery.
Detailed Description
The following detailed description of the embodiments of the present invention is provided on the premise of the technical solution of the present invention, and the detailed implementation manner and specific operation process are provided, and it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.
The lithium ion battery comprises a negative plate, electrolyte, a positive plate, a separation film and an outer package. The positive plate, the isolating film and the negative plate are laminated to obtain a battery cell or the battery cell is obtained by winding the positive plate, the isolating film and the negative plate after being laminated, the battery cell is placed in an outer package, and electrolyte is injected into the outer package, so that the lithium ion battery can be obtained:
the lithium ion batteries of examples 1 to 10 and comparative examples 1 to 2 were prepared by the following steps:
Preparation of positive plate
Mixing positive active materials lithium cobaltate (LiCoO 2), polyvinylidene fluoride (PVDF), SP (super P) and Carbon Nano Tube (CNT) according to the mass ratio of 96:2:1.5:0.5, adding N-methyl pyrrolidone (NMP), and stirring under the action of a vacuum stirrer until the mixed system becomes positive active slurry with uniform fluidity; uniformly coating anode active slurry on two surfaces of an aluminum foil; and drying the coated aluminum foil, and then rolling and slitting to obtain the required positive plate.
Preparation of negative plate
Mixing negative electrode active materials of artificial graphite, silicon oxide, sodium carboxymethylcellulose (CMC-Na), styrene-butadiene rubber, conductive carbon black (SP) and single-walled carbon nanotubes (SWCNTs) according to the mass ratio of 79.5:15:2.5:1.5:1:0.5, adding deionized water, and obtaining negative electrode active slurry under the action of a vacuum stirrer; uniformly coating the anode active slurry on two surfaces of a copper foil; and (3) airing the coated copper foil at room temperature, transferring to an 80 ℃ oven for drying for 10 hours, and then carrying out cold pressing and slitting to obtain the negative plate.
Preparation of electrolyte
In a glove box filled with argon (H 2O＜0.1ppm,O2 < 0.1 ppm), EC/PC/DEC/PP is uniformly mixed according to the mass ratio of 10/20/40/30, then 1mol/L of fully dried lithium hexafluorophosphate (LiPF 6) is rapidly added into the mixture, 9wt% of fluoroethylene carbonate based on the total mass of the electrolyte is added after the mixture is dissolved, 4wt% of 1, 3-Propane Sultone (PS) based on the total mass of the electrolyte, 3wt% of 1,3, 6-Hexanetrinitrile (HTCN) based on the total mass of the electrolyte, and additives I, II and polyfluorophenyl are mixed uniformly, the specific electrolyte formula is shown in a table 1, and the required electrolyte is obtained after the water and free acid are detected to be qualified.
The preparation of the lithium ion battery comprises the following steps of
The positive plate, the negative plate and the isolating film are laminated according to the sequence of the positive plate, the isolating film and the negative plate, and then are wound to obtain an electric core; and (3) placing the battery cell in an outer packaging aluminum foil, injecting the electrolyte in the step (3) into the outer packaging, and performing the procedures of vacuum packaging, standing, formation, shaping, sorting and the like to obtain the lithium ion battery. The charge and discharge range of the battery is 3.0-4.45V.
Table 1. Composition of electrolyte additives in lithium ion batteries of comparative examples and examples:
the lithium ion batteries obtained in examples 1 to 10 and comparative examples 1 to 2 were respectively subjected to the following performance tests,
Performance test:
(1) 25 ℃ cycle performance test
The batteries in table 1 were subjected to charge-discharge cycles at 25 ℃ within a charge-discharge cut-off voltage range at a rate of 1C, the discharge capacity at the 1 st week was measured as x 1 mAh, and the discharge capacity at the N week was measured as y 1 mAh; the capacity at week N divided by the capacity at week 1 gives the cycle capacity retention rate at week N R 1＝y1/x1.
(2) 45 ℃ Cycle performance test
The batteries in table 1 were subjected to charge-discharge cycles at 45 ℃ within a charge-discharge cut-off voltage range at a rate of 1C, and the discharge capacity at the 1 st week was measured as x 2 mAh and the discharge capacity at the N week was measured as y 2 mAh; the capacity at week N divided by the capacity at week 1 gives the cycle capacity retention rate at week N R 2＝y2/x2.
Table 2. Results of performance test:
as can be seen from table 2, the additive I and the additive II can significantly improve the normal temperature cycle performance at 25 ℃ and the high temperature cycle performance at 45 ℃ of the battery when used in combination under the cycle performance test of different weeks for the examples and the comparative examples.
Claims (10)
1. The lithium ion battery electrolyte is characterized by comprising an organic solvent, electrolyte salt and a functional additive, wherein the organic solvent comprises polyfluorinated benzene; the functional additive comprises a functional additive I and a functional additive II;
The functional additive I is of the formula (1), and the additive II is of the formula (2):
Wherein, R 1～R4 is independently selected from one of hydrogen atom, substituted or unsubstituted C 1～C6 alkyl, substituted or unsubstituted C 1～C6 unsaturated hydrocarbon group, substituted or unsubstituted C 2～C20 alkenyl, cyano group, aryl group with 6-18 carbon atoms substituted by carbonyl group, cyano group, halogen atom, nitro group, carboxyl group and sulfonic group, wherein halogen atom is F, cl and Br;
The respective value ranges of n 1 and n 2 are 1-10;
x is any one selected from C, N or B;
the mass of the additive I accounts for 0.2-3% of the total mass of the electrolyte;
The mass of the additive II accounts for 0.3-2.4% of the total mass of the electrolyte.
2. The lithium ion battery electrolyte according to claim 1, wherein the polyfluorinated benzene is selected from any one of formulas 1-1 to 1-7:
3. the lithium ion battery electrolyte according to claim 1, wherein the functional additive I is selected from any one of formulas (1) -1 to (1) -8:
4. The lithium ion battery electrolyte according to claim 1, wherein the functional additive II is selected from any one of formulas (2) -1 to (2) -5:
5. The lithium ion battery electrolyte of claim 1, wherein the electrolyte lithium salt is selected from one or more of lithium hexafluorophosphate (LiPF 6), lithium difluorophosphate (LiPO 2F2), lithium difluorooxalato borate (lidaob), lithium bis (trifluoromethylsulfonyl) imide, lithium difluorobis (oxalato) phosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methyl lithium, or lithium bis (trifluoromethylsulfonyl) imide.
6. The lithium ion battery electrolyte according to claim 1, wherein the mass of the lithium salt is 5-25% of the total mass of the electrolyte.
7. The lithium ion battery electrolyte according to claim 1, wherein the organic solvent further comprises a carbonate and/or a carboxylate, the carbonate being selected from one or more of the following solvents: ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate, diethyl carbonate (DEC), ethylmethyl carbonate;
The carboxylic acid ester is selected from one or more of the following solvents: propyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, propyl Propionate (PP), ethyl Propionate (EP), methyl butyrate, ethyl n-butyrate.
8. The lithium ion battery of any one of claims 1-7, wherein the battery comprises a positive plate, a negative plate, a separator, and an electrolyte;
the electrolyte is the electrolyte;
The positive plate comprises a current collector and positive electrode active material layers coated on one side or two side surfaces of the positive electrode current collector, wherein the positive electrode active material layers comprise positive electrode active materials, a conductive agent and a binder;
The negative electrode sheet includes a current collector and a negative electrode active material layer coated on and on one or both side surfaces of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a conductive agent, and a binder.
9. The lithium ion battery of claim 8, wherein the conductive agent is at least one selected from the group consisting of conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotubes, metal powder, and carbon fiber;
the binder is at least one selected from sodium carboxymethyl cellulose, styrene-butadiene latex, polytetrafluoroethylene and polyethylene oxide;
the negative electrode active material is artificial graphite;
The carbon-based negative electrode material comprises at least one of artificial graphite, natural graphite, mesophase carbon microspheres, hard carbon and soft carbon.
The positive electrode active material is selected from one or more of lithium iron phosphate and lithium manganate.
10. The method for preparing a lithium ion battery according to any one of claims 8 to 9, characterized in that the method comprises the steps of: the positive plate, the negative plate and the isolating film are laminated according to the sequence of the positive plate, the isolating film and the negative plate, and then are wound to obtain an electric core; and placing the battery core in an outer packaging aluminum foil, injecting electrolyte into the outer packaging, and performing the procedures of vacuum packaging, standing, formation, shaping, sorting and the like to obtain the lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410419790.0A CN118315664A (en) | 2024-04-09 | 2024-04-09 | Lithium ion battery electrolyte, lithium ion battery and preparation method of lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410419790.0A CN118315664A (en) | 2024-04-09 | 2024-04-09 | Lithium ion battery electrolyte, lithium ion battery and preparation method of lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118315664A true CN118315664A (en) | 2024-07-09 |
Family
ID=91721887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410419790.0A Pending CN118315664A (en) | 2024-04-09 | 2024-04-09 | Lithium ion battery electrolyte, lithium ion battery and preparation method of lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118315664A (en) |
-
2024
- 2024-04-09 CN CN202410419790.0A patent/CN118315664A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110265627B (en) | Positive electrode plate and lithium ion secondary battery | |
| CN109728340B (en) | Lithium ion battery | |
| CN110739484A (en) | wide-temperature-resistant lithium battery and manufacturing method thereof | |
| CN112151865B (en) | Electrolyte for lithium ion battery and lithium ion battery comprising same | |
| WO2024066447A1 (en) | Electrolyte solution and battery | |
| CN109119631B (en) | Secondary battery | |
| CN111640987B (en) | High-power electrolyte and lithium ion battery containing same | |
| CN110808413A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same | |
| CN115939317A (en) | Lithium-rich positive electrode, preparation method thereof and secondary battery | |
| CN114899476A (en) | Electrolyte and battery comprising same | |
| CN116231105A (en) | Battery cell | |
| CN115441057A (en) | Electrolyte and battery comprising same | |
| CN115312861A (en) | Electrolyte comprises battery of the electrolyte | |
| CN114976247A (en) | Electrolyte and battery containing same | |
| CN109904520B (en) | Nonaqueous electrolyte solution and secondary battery | |
| CN118315664A (en) | Lithium ion battery electrolyte, lithium ion battery and preparation method of lithium ion battery | |
| CN114243109B (en) | Electrolyte and battery comprising same | |
| CN112117493B (en) | Electrolyte for lithium ion battery and lithium ion battery comprising same | |
| CN114300745B (en) | Non-aqueous electrolyte, secondary battery and application of thiophosphamide as electrolyte additive | |
| CN114497733B (en) | Electrolyte and battery thereof | |
| CN114335718B (en) | Nonaqueous electrolyte, preparation method thereof and secondary battery | |
| CN117096419A (en) | Electrolyte and battery comprising same | |
| CN114976248A (en) | Electrolyte and battery comprising same | |
| CN117673467A (en) | Electrolyte and battery comprising same | |
| CN116666758A (en) | Electrolyte and battery comprising same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |