CN116799300A - High-voltage electrolyte suitable for quick-charging lithium battery and lithium battery - Google Patents
High-voltage electrolyte suitable for quick-charging lithium battery and lithium battery Download PDFInfo
- Publication number
- CN116799300A CN116799300A CN202210255700.XA CN202210255700A CN116799300A CN 116799300 A CN116799300 A CN 116799300A CN 202210255700 A CN202210255700 A CN 202210255700A CN 116799300 A CN116799300 A CN 116799300A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- lithium
- lithium battery
- charge
- voltage
- 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 122
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 76
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000000654 additive Substances 0.000 claims abstract description 24
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- -1 inorganic anion lithium salts Chemical class 0.000 claims description 28
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 10
- 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 9
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 8
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 claims description 7
- NEILRVQRJBVMSK-UHFFFAOYSA-N B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C NEILRVQRJBVMSK-UHFFFAOYSA-N 0.000 claims description 7
- XNENYPKLNXFICU-UHFFFAOYSA-N P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C XNENYPKLNXFICU-UHFFFAOYSA-N 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 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 5
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- 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 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 2
- CBTAIOOTRCAMBD-UHFFFAOYSA-N 2-ethoxy-2,4,4,6,6-pentafluoro-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound CCOP1(F)=NP(F)(F)=NP(F)(F)=N1 CBTAIOOTRCAMBD-UHFFFAOYSA-N 0.000 claims description 2
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 2
- DRNJIKRLQJRKMM-UHFFFAOYSA-N 4-(trifluoromethyl)benzonitrile Chemical compound FC(F)(F)C1=CC=C(C#N)C=C1 DRNJIKRLQJRKMM-UHFFFAOYSA-N 0.000 claims description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 2
- UJTPZISIAWDGFF-UHFFFAOYSA-N ethenylsulfonylbenzene Chemical compound C=CS(=O)(=O)C1=CC=CC=C1 UJTPZISIAWDGFF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- 150000002596 lactones Chemical class 0.000 claims 2
- 150000002825 nitriles Chemical class 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 9
- 230000002441 reversible effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000011572 manganese Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- GNFVFPBRMLIKIM-UHFFFAOYSA-N 2-fluoroacetonitrile Chemical compound FCC#N GNFVFPBRMLIKIM-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910010941 LiFSI Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Secondary Cells (AREA)
Abstract
The invention discloses a high-voltage electrolyte suitable for a quick-charging lithium battery and the lithium battery, and belongs to the technical field of lithium battery electrolytes. The electrolyte comprises an organic solvent, wherein the organic solvent is a fluoronitrile compound. The fluoronitrile compound is used as a solvent of the lithium battery electrolyte, so that the electrolyte ensures a wide electrochemical window and ultra-high ionic conductivity of the nitrile electrolyte, ensures excellent film forming property and low interface impedance of the fluoride electrolyte, and simultaneously realizes great progress of the lithium battery in the fields of high voltage and quick charge. According to the invention, the lithium salt, the fluoronitrile compound and the additive in the high-voltage quick-charge electrolyte for the lithium battery are specifically combined, and the concentration and the proportion are further optimized, so that the high-voltage quick-charge electrolyte added with the lithium battery can have excellent compatibility with positive and negative electrodes, and further the long cycle life and high coulombic efficiency of the lithium battery are realized.
Description
Technical Field
The invention belongs to the technical field of lithium battery electrolyte, and particularly relates to high-voltage electrolyte suitable for a quick-charging lithium battery and the lithium battery.
Background
With the continuous rapid development of the fields of electric automobiles, portable electronic products, energy storage power stations, and the like, lithium batteries are being developed toward higher energy density, faster charging speed, and longer cycle life as one of the most preferable energy storage. The high energy density requires that the lithium battery positive electrode material develop towards the high-voltage ternary material, the lithium nickel manganese oxide and the sulfur composite positive electrode, and the negative electrode material develop from graphite towards the high-specific capacity silicon carbon composite negative electrode and the metal lithium negative electrode. Fast charging requires that the polarization of the lithium battery itself be sufficiently small and that the battery material be sufficiently stable. Meanwhile, the conventional commercial electrolyte composed of lithium hexafluorophosphate and carbonate solvent has poor film forming property of anode and cathode and low ionic conductivity, and serious oxidative decomposition can occur at more than 4.3V and high-rate charging cannot be realized. Therefore, it is imperative to design a high-voltage fast-charging electrolyte which can ensure both fast charging and discharging and stable long circulation for lithium batteries.
Research on high-voltage fast-charging electrolyte has become a hotspot in research on lithium batteries today. This requires that the lithium battery electrolyte has a high ionic conductivity, which ensures rapid transport of lithium ions in the electrolyte, and secondly, the interface protective film formed by the electrolyte at the electrode interface must have a high ionic conductivity. The nitrile electrolyte has the advantages of wide electrochemical window, cheng Kuan, high ionic conductivity, difficult gas production and the like, but has poor compatibility with negative electrode materials such as graphite and the like, and cannot ensure effective circulation. According to the invention, the fluoronitrile electrolyte is used, so that the advantages of the nitrile electrolyte are ensured, an effective solid electrolyte interface film is formed at the positive electrode and the negative electrode, the fundamental problem that the nitrile is not suitable for graphite is thoroughly solved, and the additive is further added to improve the serious lithium precipitation phenomenon of the negative electrode such as graphite under the condition of quick charge, so that the stable long cycle of the high-voltage quick charge lithium battery is realized.
At present, some novel electrolytes have been developed for high-voltage fast-charging lithium batteries, but all have obvious disadvantages. Document "Yamada Y, furukawa K, sodeyama K, et al Unusual Stability of Acetonitrile-Based Superconcentrated Electrolytes for Fast-Charging Lithium-Ion batteries journal of the American Chemical Society,2014,136 (13): 5039-5046. "it is proposed that 4.5M LiFSI/AN electrolyte can achieve a specific capacity of 270mAh/g for NG/Li half-cells at 5C rate, but is not compatible with high voltage positive electrodes. The literature "Zhang XH, zou LF, xu YB, et al advanced Electrolytes for Fast-Charging High-Voltage Lithium-Ion Batteries in Wide-Temperature Range, advanced Energy Materials,2020,10 (22): 2000368." suggests a 1.4M LiFSI/DMC-EC-TTE (2:0.2:3 n: n) electrolyte at 4.3V LiNi 0.8 Co 0.1 Mn 0.1 O 2 The Gr button cell 5C only exhibits a specific capacity of 30mAh/g when charged and discharged at 0.2C.
Therefore, the current research on the high-voltage quick-charging electrolyte can not meet the requirement of the lithium battery.
Disclosure of Invention
Aiming at the defects of narrow electrochemical window, low conductivity, narrow liquid range, easiness in gas production and the like of the current commercial electrolyte, the defects of poor multiplying power performance, low coulomb efficiency, short cycle life and the like caused by the application of the current commercial electrolyte to a high-voltage quick-charging lithium battery, the invention aims to provide the high-voltage electrolyte suitable for the quick-charging lithium battery and the lithium battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides application of a fluoronitrile compound, wherein the fluoronitrile compound is used as an organic solvent of lithium battery electrolyte, and the general formula of the fluoronitrile compound is shown in a structural formula I:
wherein R is: fluoroalkyl, fluorovinyl, or fluorocyano.
Specifically, R is selected from-CH 2 F、-CHF 2 、-CF 3 、-CH(CH 3 )F、-CH 2 CF 3 、-CH 2 CH 2 F、-CHFCH 2 CF 3 、-CHFCF 3 、-CH 2 CH 2 CF 3 、-C(CH 3 )F 2 、-CF(CH 3 ) 2 、-(CF 2 ) 3 CHF 2 、-CF(CF 3 ) 2 、-(CF 2 ) n CF 3 、-CF＝CH 2 、-C(CF 3 )＝CH 2 、-CH＝CHCF 3 、-CF 2 CF＝CF 2 Or- (CF) 2 ) n CN, where n=1-8.
Preferably, R is selected from the group consisting of-CH 2 F、-CH 2 CF 3 、-CHFCF 3 、-CH 2 CH 2 CF 3 、-CF 2 CF＝CF 2 Or- (CF) 2 ) 2 CN。
The invention also provides a high-voltage quick-charge electrolyte for the lithium battery, which is characterized in that the electrolyte comprises an organic solvent, the organic solvent is a fluoronitrile compound, the general formula of the fluoronitrile compound is shown as a structural formula I,
wherein R is: fluoroalkyl, fluorovinyl, or fluorocyano.
Specifically, the R is selected from-CH 2 F、-CHF 2 、-CF 3 、-CH(CH 3 )F、-CH 2 CF 3 、-CH 2 CH 2 F、-CHFCH 2 CF 3 、-CHFCF 3 、-CH 2 CH 2 CF 3 、-C(CH 3 )F 2 、-CF(CH 3 ) 2 、-(CF 2 ) 3 CHF 2 、-CF(CF 3 ) 2 、-(CF 2 ) n CF 3 、-CF＝CH 2 、-C(CF 3 )＝CH 2 、-CH＝CHCF 3 、-CF 2 CF＝CF 2 Or- (CF) 2 ) n CN, where n=1-8.
Preferably, R is selected from the group consisting of-CH 2 F、-CH 2 CF 3 、-CHFCF 3 、-CH 2 CH 2 CF 3 、-CF 2 CF＝CF 2 Or- (CF) 2 ) 2 The CN is set to be a single-layer structure, namely the fluoro-nitrile compound is fluoro-acetonitrile, 3-trifluoropropionitrile, 2, 3-tetrafluoropropionitrile 4, 4-trifluorobutyronitrile, 2,2,3,4,4-pentafluorobutyronitrile or 2, 3-tetrafluorosuccinonitrile.
The high-voltage quick-charge electrolyte also comprises an additive, wherein the additive accounts for 0.1-15% of the total mass of the electrolyte, and the additive is at least one of vinylene carbonate, fluoroethylene carbonate, difluoro ethylene carbonate, ethylene sulfate, dimethyl sulfate, propylene sulfite, 1, 3-propylene sultone, ethyl trifluoroacetate, thiophene, furan, fluorobenzene, cyclohexylbenzene, tris (trimethylsilane) phosphite, tris (trimethylsilane) borate, tetraethoxysilane, 2-cyanoethyl triethoxysilane, 3-sulfolane, phenylvinyl sulfone, triethyl borate, succinonitrile, ethoxy- (pentafluoro) -cyclotriphosphazene and 4- (trifluoromethyl) -benzonitrile.
Preferably, the additive is at least one of vinylene carbonate, fluoroethylene carbonate, 1, 3-propenesulfonlactone, fluorobenzene, tris (trimethylsilane) phosphite, tris (trimethylsilane) borate and 2-cyanoethyltriethoxysilane.
Preferably, the additive is ethylene carbonate and 2-cyanoethyl triethoxysilane in a mass ratio of 1:1.
Preferably, the additive is 1, 3-propenoic acid lactone and tri (trimethylsilane) borate in a mass ratio of 5:1.
Preferably, the additive is fluoroethylene carbonate and tris (trimethylsilane) phosphite in a mass ratio of 2:1.
The high-voltage quick-charge electrolyte also comprises lithium salt, wherein the concentration of the lithium salt is 0.1-3mol/L, and the lithium salt is at least one of inorganic anion lithium salt and organic anion lithium salt such as lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium tetrafluoroborate, lithium difluorophosphate and the like.
Preferably, the lithium salt is lithium bis (trifluoromethylsulfonyl) imide and lithium bis (oxalato) borate in a molar ratio of 2:1.
Preferably, the lithium salt is lithium bis (fluorosulfonyl) imide and lithium difluorooxalato borate in a molar ratio of 1:1.
Preferably, the lithium salt is lithium hexafluorophosphate, lithium tetrafluoroborate and lithium difluorophosphate in a molar ratio of 1:1:1.
The invention can make NG/Li button cell still hold 291.6mAh/g reversible specific capacity under 20C charge-discharge multiplying power in 0.005-1.0V voltage range, with capacity retention rate higher than 80%, average coulomb efficiency as high as 99.9%; liNi 0.8 Co 0.1 Mn 0.1 O 2 The NG button cell still has specific capacity of 171.2mAh/g under 6C charge and discharge in the voltage range of 2.8-4.3V, capacity retention rate of more than 80% after 1000 cycles, average coulomb efficiency as high as 99.9%, and the performance of the current high-voltage fast-charge electrolyte is far better.
The invention also provides a lithium battery, which comprises an anode active material, a cathode active material, a diaphragm and the high-voltage electrolyte for the lithium battery.
The positive electrode active material is LiNi 1-x-y Co x Mn y O 2 、LiNi 1-x-y Co x Al y O 2 、xLi 2 MnO 3 ·LiMO 2 (M＝Ni、Co、Mn)、LiNi 0.5 Mn 1.5 O 4 、LiNiO 2 Or LiCoO 2 Wherein 0.ltoreq.x<1，0≤y<1，0≤x+y<1, a step of; the negative electrode active material is artificial graphite, mesocarbon microbeads, natural graphite, silicon-carbon composite, silicon oxide or metallic lithium sheet.
Preferably, the positive electrode active material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 Or LiCoO 2 The method comprises the steps of carrying out a first treatment on the surface of the The negative electrode active material is artificial graphite or natural graphite.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a high-voltage electrolyte for a lithium battery, which is suitable for quick charge, and thoroughly solves the problem that nitrile electrolyte is incompatible with graphite. The fluoronitrile compound is used as a solvent of the lithium battery electrolyte, so that the electrolyte ensures a wide electrochemical window and ultra-high ionic conductivity of the nitrile electrolyte, ensures excellent film forming property and low interface impedance of the fluoride electrolyte, and simultaneously realizes great progress of the lithium battery in the fields of high voltage and quick charge.
(2) According to the invention, the lithium salt, the fluoronitrile compound and the additive in the high-voltage quick-charge electrolyte for the lithium battery are specifically combined, and the concentration and the proportion are further optimized, so that the high-voltage quick-charge electrolyte added with the lithium battery can have excellent compatibility with the challenging anode and cathode, and further the long cycle life and high coulombic efficiency of the lithium battery are realized.
(3) The high-voltage quick-charging electrolyte for the lithium battery belongs to an electrolyte system which has a wide electrochemical window, ultrahigh ion conductivity, excellent multiplying power performance and good film forming performance, and has wide application prospect in the lithium battery.
Drawings
Fig. 1 is a graph of cycle life of the electrolyte prepared in example 1 in an NG/Li battery.
Fig. 2 is a graph of cycle life in an NG/Li cell of the electrolyte prepared in example 2.
FIG. 3 shows the electrolyte prepared in example 3 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in NG cell.
FIG. 4 shows the electrolyte prepared in example 4 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in NG cell.
Fig. 5 is a charge-discharge curve of the electrolyte prepared in example 5 in an NG/Li battery.
FIG. 6 shows the electrolyte prepared in example 5 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in NG cell.
Fig. 7 is a graph of the cycle life of the commercial ester-based electrolyte prepared in comparative example 1 in an NG/Li cell.
Fig. 8 is a charge-discharge curve of the commercial ester-based electrolyte prepared in comparative example 2 in an NG/Li battery.
FIG. 9 shows a commercial modified ester-based electrolyte prepared in comparative example 3 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in NG cell.
Detailed Description
Example 1
The preparation method of the high-voltage electrolyte for the lithium battery suitable for quick charge comprises the following steps:
and slowly dissolving a certain amount of lithium bis (trifluoromethylsulfonyl) imide in 3, 3-trifluoropropionitrile, slowly adding an additive vinylene carbonate to ensure that the concentration of lithium salt bis (trifluoromethylsulfonyl) imide lithium is 0.1mol/L, and stirring until the electrolyte is completely clarified, thereby obtaining the high-voltage electrolyte suitable for the fast-charging lithium battery.
Fig. 1 is a graph of cycle life of the electrolyte prepared in example 1 in an NG/Li cell. As can be seen from the graph, the specific discharge capacity of the electrolyte can reach 291.6mAh/g at a high multiplying power of 20C, the capacity retention rate is as high as 81%, and the average coulomb efficiency is as high as more than 99.9%. Compared with the traditional commercial ester-based electrolyte, the rate capability and the capacity retention rate are greatly improved.
Example 2
The preparation method of the high-voltage electrolyte for the lithium battery suitable for quick charge comprises the following steps:
and slowly dissolving a certain amount of lithium hexafluorophosphate in 2, 3-tetrafluoropropionitrile, slowly adding an additive fluoroethylene carbonate to ensure that the concentration of lithium hexafluorophosphate is 0.5mol/L, and stirring until the electrolyte is completely clarified, thus obtaining the high-voltage electrolyte suitable for the fast-charging lithium battery.
Fig. 2 is a graph of the cycle life of the electrolyte prepared in example 2 in an NG/Li cell. As can be seen from fig. 2, even when the charge/discharge rate is as high as 20C, the specific discharge capacity of 292.2mAh/g and the capacity retention rate of 80.3% can be obtained, and the average coulomb efficiency is as high as 99.9% or more. The commercial ester-based electrolyte has a specific discharge capacity of only 60.2mAh/g under the condition, a capacity retention rate of less than 17%, and an average coulombic efficiency of less than 99%.
Example 3
The preparation method of the high-voltage electrolyte for the lithium battery suitable for quick charge comprises the following steps:
slowly dissolving a certain amount of lithium bis (fluorosulfonyl) imide in 4, 4-trifluorobutyronitrile, then slowly adding fluorobenzene as an additive to ensure that the concentration of lithium bis (fluorosulfonyl) imide lithium is 1mol/L, and stirring until the electrolyte is completely clear, thereby obtaining the high-voltage electrolyte suitable for the fast-charging lithium battery.
FIG. 3 shows the electrolyte prepared in example 3 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in NG cell. As can be seen from fig. 3, liNi 0.8 Co 0.1 Mn 0.1 O 2 The reversible specific capacity of the/NG full battery is up to 171.2mAh/g at a high multiplying power of 6C, and the capacity retention rate is up to 80%. After 1000 cycles of large multiplying power and long cycle, the capacity retention rate can still reach 80 percent. This demonstrates that the high voltage fast charge electrolyte achieves a high degree of compatibility with challenging high nickel anodes as well as natural graphite cathodes.
Example 4
The preparation method of the high-voltage electrolyte for the lithium battery suitable for quick charge comprises the following steps:
slowly dissolving lithium bis (fluorosulfonyl) imide and lithium difluoro (oxalato) borate in a molar ratio of 1:1 into 2,2,3,4,4-pentafluorobutyronitrile, then slowly adding 1, 3-propenolactone and tris (trimethylsilane) borate which are additives in a mass ratio of 5:1, enabling the total concentration of lithium bis (fluorosulfonyl) imide lithium and lithium difluoro (oxalato) borate to be 2mol/L, enabling the additives 1, 3-propenolactone and tris (trimethylsilane) borate to account for 6% of the total mass of the electrolyte, and stirring until the electrolyte is completely clarified, thus obtaining the high-voltage electrolyte suitable for the lithium battery which is rapidly charged.
FIG. 4 shows the electrolyte prepared in example 4 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in NG cell. As can be seen from fig. 4, the electrolyte realizes high adaptation in a high-voltage fast-charging battery system, the reversible charge/discharge capacity is up to 181.5mAh/g under the condition of high multiplying power 6C, the capacity retention rate is up to 82%, and after 1000 cycles of 6C high multiplying power circulation, the capacity retention rate is still up to 81%, which indicates that the electrolyte can form a stable and low-impedance solid electrolyte interface film at the interface of the anode and the cathode.
Example 5
The preparation method of the high-voltage electrolyte for the lithium battery suitable for quick charge comprises the following steps:
slowly dissolving bis (trifluoromethylsulfonyl) imide lithium and lithium bisoxalato borate with a molar ratio of 2:1 in fluoroacetonitrile, then slowly adding additives of fluoroethylene carbonate and tris (trimethylsilane) phosphite with a mass ratio of 2:1, enabling the total concentration of lithium salt bis (trifluoromethylsulfonyl) imide lithium and lithium bisoxalato borate to be 1.5mol/L, enabling the additives of fluoroethylene carbonate and tris (trimethylsilane) phosphite to account for 15% of the total mass of the electrolyte, and stirring until the electrolyte is completely clarified, thus obtaining the high-voltage electrolyte suitable for the fast-charging lithium battery.
Fig. 5 is a charge-discharge curve of the electrolyte prepared in example 5 in an NG/Li battery. As can be seen from fig. 5, the charge-discharge plateau is evident, and the polarization increase is small with the increasing of the multiplying power. The electrolyte still maintains the reversible specific capacity of 288.6mAh/g at a high multiplying power of 20C, the capacity retention rate is as high as 81%, and the average coulomb efficiency is as high as more than 99.9%. And the capacity retention rate of commercial electrolyte under the condition is far lower than that of the high-voltage fast-charging electrolyte.
Example 6
The preparation method of the high-voltage electrolyte for the lithium battery suitable for quick charge comprises the following steps:
slowly dissolving lithium hexafluorophosphate, lithium tetrafluoroborate and lithium difluorophosphate in a molar ratio of 1:1:1 in 2, 3-tetrafluorosuccinonitrile, slowly adding ethylene carbonate and 2-cyanoethyl triethoxysilane as additives in a mass ratio of 1:1, enabling the total concentration of lithium hexafluorophosphate, lithium tetrafluoroborate and lithium difluorophosphate to be 3mol/L, enabling the ethylene carbonate and 2-cyanoethyl triethoxysilane as additives to account for 4% of the total mass of the electrolyte, and stirring until the electrolyte is completely clarified, thus obtaining the high-voltage electrolyte suitable for the lithium battery which is quickly charged.
FIG. 6 shows the electrolyte prepared in example 6 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in NG cell. As can be seen from fig. 6, the high nickel cathode material has an obvious charge-discharge plateau, and the attenuation trend decreases as the multiplying power increases. The reversible specific capacity of 172.0mAh/g is still maintained under the 6C high multiplying power. Whereas commercial electrolytes have a reversible specific capacity of only 126.3mAh/g at 6C.
Comparative example 1
A certain amount of lithium hexafluorophosphate was slowly dissolved in the ethylene carbonate and the dimethyl carbonate in a volume ratio of 1:1 to make the concentration of lithium hexafluorophosphate as a lithium salt 1mol/L. Stirring until the electrolyte is completely clarified, and obtaining the commercial ester-based electrolyte of the lithium battery.
Fig. 7 is a graph showing the cycle life of the electrolyte prepared in comparative example 1 in an NG/Li battery. As can be seen from the graph, the specific discharge capacity of the electrolyte is only 60.5mAh/g at the rate of 20C, the capacity retention rate is only 16%, and the average coulombic efficiency is 99.5%. Compared with the high-voltage quick-charge electrolyte, the rate capability of the electrolyte is greatly reduced.
Comparative example 2
An amount of lithium hexafluorophosphate was slowly dissolved in the volume ratio of 1:1:1 of ethylene carbonate, diethyl carbonate and methylethyl carbonate to give a lithium salt lithium hexafluorophosphate concentration of 1.2mol/L. Stirring until the electrolyte is completely clarified, and obtaining the commercial ester-based electrolyte of the lithium battery.
Fig. 8 is a charge-discharge curve of the electrolyte prepared in comparative example 2 in an NG/Li battery. As can be seen from fig. 8, the capacity starts to decline rapidly at 5C, the charge-discharge plateau gradually disappears, and the polarization increases sharply. When the charge-discharge rate is increased to 20C, the discharge specific capacity is only 60.0mAh/g, and the capacity retention rate is only 15%. In addition, the coulomb efficiency fluctuation is large, and the commercial standard of the high-pressure quick-charging electrolyte is far from being reached.
Comparative example 3
Slowly dissolving a certain amount of lithium hexafluorophosphate in ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1, slowly adding an additive of ethylene carbonate to ensure that the concentration of lithium hexafluorophosphate is 1mol/L, and stirring until the electrolyte is completely clarified, thereby obtaining the commercial modified ester-based electrolyte for the lithium battery.
FIG. 9 shows the electrolyte prepared in comparative example 3 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in NG cell. As can be seen from fig. 9, in the above commercial modified ester-based electrolyte, after the charge/discharge rate was increased, the reversible capacity was rapidly decayed, and when the charge/discharge rate reached 6C, the reversible specific capacity was 38.3mAh/g, the capacity retention rate was only 29%, and after 1000 cycles for a long period, the reversible specific capacity was only 21.1mAh/g.
NG/Li and LiNi in examples and comparative examples 0.8 Co 0.1 Mn 0.1 O 2 Manufacturing and testing of NG battery:
(1) Positive pole piece: liNi is added to 0.8 Co 0.1 Mn 0.1 O 2 Adding the binder PVDF and the conductive carbon black into N-methyl pyrrolidone (NMP) according to the ratio of 8:1:1, and uniformly mixing to obtain slurry; then coating the aluminum foil current collector, drying at 100 ℃, rolling, and cutting a wafer with the diameter of 12mm by a sheet punching machine;
(2) Negative pole piece: adding NG, binder PAA-Li and conductive carbon black into deionized water according to the ratio of 8:1:1, and uniformly mixing to obtain slurry; then coating the copper foil current collector, drying at 100 ℃, rolling, and cutting a wafer with the diameter of 14mm by a sheet punching machine;
(3) Electrolyte solution: the electrolytes prepared in examples 1 to 6 and comparative examples 1 to 3;
(4) A diaphragm: cutting a polyethylene single-layer diaphragm wafer with the diameter of 19mm by a sheet punching machine;
(5) And (3) battery assembly: in glove box (O) 2 <0.1ppm，H 2 O<0.1 ppm), lithium was assembled in the order of positive electrode case-positive electrode wafer-separator wafer-negative electrode wafer-stainless steel sheet-spring sheet-negative electrode caseBatteries were added with the electrolytes prepared in examples 1 to 6 and comparative examples 1 to 3, and finally packaged to obtain test batteries;
(6) And (3) battery testing:
the electrolytes in examples 1 to 6 and comparative examples 1 to 3 correspond to batteries 1 to 9, and NG/Li (0.005 to 1.0V) batteries were cycled at room temperature (25 ℃) at 5 cycles per rate at 0.1C to 0.5C-1C-2C-3C- … to 20C rate; liNi 0.8 Co 0.1 Mn 0.1 O 2 NG (2.8-4.3V) cells were cycled 5 cycles after 6C long at room temperature (25 ℃) at a rate of 0.1C-0.2C-0.5C-1C-2C-3C- … -6C, and the test results are shown in FIGS. 1-9, and the analysis and conclusion of the results have been described in the examples and comparative examples, respectively.
Claims (10)
1. The application of the fluoronitrile compound is characterized in that the fluoronitrile compound is used as an organic solvent of lithium battery electrolyte, and the general formula of the fluoronitrile compound is shown in the structural formula I:
wherein R is: fluoroalkyl, fluorovinyl, or fluorocyano.
2. The use of a fiuoronitrile compound as defined in claim 1, wherein R is selected from the group consisting of-CH 2 F、-CHF 2 、-CF 3 、-CH(CH 3 )F、-CH 2 CF 3 、-CH 2 CH 2 F、-CHFCH 2 CF 3 、-CHFCF 3 、-CH 2 CH 2 CF 3 、-C(CH 3 )F 2 、-CF(CH 3 ) 2 、-(CF 2 ) 3 CHF 2 、-CF(CF 3 ) 2 、-(CF 2 ) n CF 3 、-CF＝CH 2 、-C(CF 3 )＝CH 2 、-CH＝CHCF 3 、-CF 2 CF＝CF 2 Or- (CF) 2 ) n CN, where n=1-8.
3. The use of a fluoronitrile compound as claimed in claim 2, wherein R is selected from-CH 2 F、-CH 2 CF 3 、-CHFCF 3 、-CH 2 CH 2 CF 3 、-CF 2 CF＝CF 2 Or- (CF) 2 ) 2 CN。
4. A high-voltage quick-charge electrolyte for lithium batteries is characterized in that the electrolyte comprises an organic solvent, wherein the organic solvent is a fluoronitrile compound, the general formula of the fluoronitrile compound is shown as a structural formula I,
wherein R is: fluoroalkyl, fluorovinyl, or fluorocyano.
5. The high voltage fast charge electrolyte according to claim 4, wherein R is selected from the group consisting of-CH 2 F、-CHF 2 、-CF 3 、-CH(CH 3 )F、-CH 2 CF 3 、-CH 2 CH 2 F、-CHFCH 2 CF 3 、-CHFCF 3 、-CH 2 CH 2 CF 3 、-C(CH 3 )F 2 、-CF(CH 3 ) 2 、-(CF 2 ) 3 CHF 2 、-CF(CF 3 ) 2 、-(CF 2 ) n CF 3 、-CF＝CH 2 、-C(CF 3 )＝CH 2 、-CH＝CHCF 3 、-CF 2 CF＝CF 2 Or- (CF) 2 ) n CN, where n=1-8.
6. The high voltage fast charge electrolyte according to claim 4, wherein R is selected from the group consisting of-CH 2 F、-CH 2 CF 3 、-CHFCF 3 、-CH 2 CH 2 CF 3 、-CF 2 CF＝CF 2 Or- (CF) 2 ) 2 CN。
7. The high voltage fast charge electrolyte according to claim 4, further comprising an additive, the additive comprising 0.1% -15% of the total mass of the electrolyte, the additive being at least one of vinylene carbonate, fluoroethylene carbonate, bis-fluoroethylene carbonate, ethylene sulfate, dimethyl sulfate, propylene sulfite, 1, 3-propenesulfonic acid lactone, ethyl trifluoroacetate, thiophene, furan, fluorobenzene, cyclohexylbenzene, tris (trimethylsilane) phosphite, tris (trimethylsilane) borate, tetraethoxysilane, 2-cyanoethyltriethoxysilane, 3-cyclobutanesulfone, phenylvinyl sulfone, triethyl borate, succinonitrile, ethoxy- (pentafluoro) -cyclotriphosphazene, and 4- (trifluoromethyl) -benzonitrile.
8. The high voltage fast charge electrolyte according to claim 4, wherein the additive is at least one of vinylene carbonate, fluoroethylene carbonate, 1, 3-propenesulfonic acid lactone, fluorobenzene, tris (trimethylsilane) phosphite, tris (trimethylsilane) borate and 2-cyanoethyl triethoxysilane.
9. The high-voltage fast-charge electrolyte according to claim 4, further comprising a lithium salt, wherein the concentration of the lithium salt is 0.1-3mol/L, and the lithium salt is at least one of inorganic anion lithium salts and organic anion lithium salts such as lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium tetrafluoroborate and lithium difluorophosphate.
10. A lithium battery comprising a positive electrode active material, a negative electrode active material, and a separator, and further comprising the high-voltage fast-charge electrolyte according to any one of claims 4 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210255700.XA CN116799300A (en) | 2022-03-15 | 2022-03-15 | High-voltage electrolyte suitable for quick-charging lithium battery and lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210255700.XA CN116799300A (en) | 2022-03-15 | 2022-03-15 | High-voltage electrolyte suitable for quick-charging lithium battery and lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116799300A true CN116799300A (en) | 2023-09-22 |
Family
ID=88040765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210255700.XA Pending CN116799300A (en) | 2022-03-15 | 2022-03-15 | High-voltage electrolyte suitable for quick-charging lithium battery and lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116799300A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101548425A (en) * | 2006-12-06 | 2009-09-30 | 三菱化学株式会社 | Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery |
| CN103346347A (en) * | 2013-07-04 | 2013-10-09 | 厦门大学 | High-voltage lithium ion battery |
| CN104617260A (en) * | 2015-01-09 | 2015-05-13 | 潘珊 | Method for improving durability of lithium-ion power battery, and lithium-ion power battery |
| JP2015118852A (en) * | 2013-12-19 | 2015-06-25 | 旭化成株式会社 | Nonaqueous electrolyte and lithium ion secondary battery |
| CN111357144A (en) * | 2018-07-02 | 2020-06-30 | 株式会社Lg化学 | Lithium secondary battery with improved high-temperature characteristics |
| CN112635823A (en) * | 2019-09-24 | 2021-04-09 | 东莞市杉杉电池材料有限公司 | High-voltage lithium cobalt oxide lithium ion battery electrolyte and lithium ion battery |
| CN114039091A (en) * | 2021-10-27 | 2022-02-11 | 武汉理工大学 | Flame-retardant electrolyte suitable for high-voltage lithium ion battery |
-
2022
- 2022-03-15 CN CN202210255700.XA patent/CN116799300A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101548425A (en) * | 2006-12-06 | 2009-09-30 | 三菱化学株式会社 | Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery |
| CN103346347A (en) * | 2013-07-04 | 2013-10-09 | 厦门大学 | High-voltage lithium ion battery |
| JP2015118852A (en) * | 2013-12-19 | 2015-06-25 | 旭化成株式会社 | Nonaqueous electrolyte and lithium ion secondary battery |
| CN104617260A (en) * | 2015-01-09 | 2015-05-13 | 潘珊 | Method for improving durability of lithium-ion power battery, and lithium-ion power battery |
| CN111357144A (en) * | 2018-07-02 | 2020-06-30 | 株式会社Lg化学 | Lithium secondary battery with improved high-temperature characteristics |
| CN112635823A (en) * | 2019-09-24 | 2021-04-09 | 东莞市杉杉电池材料有限公司 | High-voltage lithium cobalt oxide lithium ion battery electrolyte and lithium ion battery |
| CN114039091A (en) * | 2021-10-27 | 2022-02-11 | 武汉理工大学 | Flame-retardant electrolyte suitable for high-voltage lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022042373A1 (en) | Lithium ion battery | |
| KR102164001B1 (en) | Rechargeable lithium battery | |
| CN102637903A (en) | Formation method of lithium ion battery | |
| CN114142088A (en) | High-voltage electrolyte for lithium battery | |
| CN113299996A (en) | Non-aqueous electrolyte for lithium ion battery with ternary positive electrode material and negative electrode silicon-oxygen-carbon composite negative electrode material | |
| CN103594735A (en) | Preparation method for lithium titanate lithium ion battery | |
| CN112736285A (en) | Electrolyte and lithium ion battery | |
| CN114156526A (en) | High-voltage electrolyte for lithium battery | |
| CN115548437A (en) | Anion-regulated lithium metal battery electrolyte | |
| CN112467218B (en) | Lithium metal battery based on copper nitrate electrolyte additive | |
| CN113871712B (en) | Lithium ion battery electrolyte, preparation method thereof and lithium ion battery | |
| CN113611911B (en) | Lithium ion battery | |
| CN113346142B (en) | Low-concentration electrolyte for lithium ion secondary battery and lithium ion secondary battery | |
| CN112310478B (en) | Electrolyte and electrochemical device thereof | |
| CN114927762A (en) | Fluorinated sulfonyl electrolyte, preparation method and application thereof, and lithium metal battery | |
| CN114583281A (en) | High-voltage-resistant ether-based electrolyte for low-temperature lithium metal battery | |
| CN116799300A (en) | High-voltage electrolyte suitable for quick-charging lithium battery and lithium battery | |
| KR100635740B1 (en) | Negative active material for lithium secondary battery and lithium secondary battery comprising same | |
| JP3963611B2 (en) | Non-aqueous electrolyte and secondary battery using the same | |
| CN113851714B (en) | Electrolyte and application thereof | |
| CN114497733B (en) | Electrolyte and battery thereof | |
| JP2004071340A (en) | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery | |
| CN117638231A (en) | Lithium ion battery quick-charge electrolyte, preparation method and lithium ion battery | |
| CN117525589A (en) | Lithium ion battery quick-charge electrolyte, preparation method and lithium ion battery | |
| CN115051030A (en) | Battery electrolyte and lithium ion battery |
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 |