CN111048840A - Lithium ion battery electrolyte and lithium ion battery - Google Patents
Lithium ion battery electrolyte and lithium ion battery Download PDFInfo
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- CN111048840A CN111048840A CN201911374033.1A CN201911374033A CN111048840A CN 111048840 A CN111048840 A CN 111048840A CN 201911374033 A CN201911374033 A CN 201911374033A CN 111048840 A CN111048840 A CN 111048840A
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- lithium
- ion battery
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- lithium ion
- carbonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 116
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 97
- 239000002904 solvent Substances 0.000 claims abstract description 38
- 239000000654 additive Substances 0.000 claims abstract description 33
- 230000000996 additive effect Effects 0.000 claims abstract description 33
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 25
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 25
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 8
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical group [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 93
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 28
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 22
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 22
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 22
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 20
- 239000007774 positive electrode material Substances 0.000 claims description 18
- 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 17
- 239000003575 carbonaceous material Substances 0.000 claims description 17
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 16
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 11
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 6
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 6
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 6
- 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
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 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 3
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 claims description 3
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 claims description 3
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 claims description 3
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 abstract description 28
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 abstract description 27
- 238000003860 storage Methods 0.000 abstract description 25
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 abstract description 16
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 abstract description 14
- 239000012046 mixed solvent Substances 0.000 abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 87
- 229910052759 nickel Inorganic materials 0.000 description 76
- 230000000052 comparative effect Effects 0.000 description 24
- 239000002002 slurry Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 12
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- 239000004698 Polyethylene Substances 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910013716 LiNi Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
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- 238000007872 degassing Methods 0.000 description 5
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- 229920006255 plastic film Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
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Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The application provides a lithium ion battery electrolyte and a lithium ion battery. The lithium ion battery electrolyte comprises a solvent, electrolyte lithium salt and an additive, wherein the solvent comprises a carbonate solvent and a carboxylate solvent; the additive comprises the following components in percentage by mass based on the total amount of the electrolyte as 100 percent: succinonitrile 0.1% -1%; 0.1 to 1 percent of vinylene carbonate; 2 to 10 percent of fluoroethylene carbonate; 0.1 to 1 percent of 1, 3-propane sultone; 0.1 to 1 percent of additive lithium salt. The lithium ion battery electrolyte composed of the mixed solvent, the mixed additive and the electrolyte lithium salt in a specific ratio can remarkably improve the high-temperature circulation and high-temperature storage performance of the lithium ion battery.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a lithium ion battery electrolyte and a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, high power density, long cycle life, no memory effect, low self-discharge rate, wide working temperature range, safety, reliability, environmental friendliness and the like, is widely applied to the fields of portable consumer electronics, electric tools, medical electronics and the like, and simultaneously has good application prospects in the fields of pure electric vehicles, hybrid electric vehicles, energy storage and the like.
In recent years, the demand for energy density of batteries in various fields is rapidly increased, and the development of lithium ion batteries with higher energy density is urgently needed, so that the application of ternary cathode materials and silicon carbon cathode materials in lithium ion batteries, especially power batteries, is more and more extensive. The gram capacity of the high nickel material is gradually improved along with the improvement of the nickel content, but the high nickel material has an unstable structure and is easy to have the conditions of poor cycle performance, gas expansion and the like in battery application. The silicon-based material is considered to be the most potential high-energy-density lithium ion battery cathode material due to the advantages of high specific capacity (4200mAh/g), low lithium removal potential (< 0.5V), environmental friendliness, abundant reserves, low cost and the like.
However, there are two key problems to be solved in the use of silicon-based negative electrode materials: (1) the silicon material repeatedly expands and contracts in the process of lithium intercalation and deintercalation, so that the negative electrode material is pulverized and falls off, and finally the negative electrode material loses electric contact to completely lose effectiveness of the battery; (2) the continuous growth of the solid electrolyte interface film (SEI) on the surface of the silicon material can irreversibly consume the limited electrolyte and lithium from the positive electrode in the battery, eventually leading to rapid capacity fade of the battery. At present, silicon-based materials applied to a large number of markets are mainly doped with graphite to relieve volume expansion and inhibit rebound, but the problem of volume expansion still exists, and the problems of a high-nickel positive electrode material and a silicon-carbon negative electrode material still need to be further optimized to improve the performance of a battery.
Disclosure of Invention
The technical problem that this application will be solved is through optimizing lithium cell electrolyte to improve battery performance.
In order to solve the technical problem, the application discloses a lithium ion battery electrolyte, which comprises a solvent, electrolyte lithium salt and an additive, wherein the solvent comprises a carbonate solvent and a carboxylate solvent; the additive comprises the following components in percentage by mass based on the total amount of the electrolyte as 100 percent:
preferably, the carbonate solvent includes at least one of ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate, and the carboxylate solvent includes propyl propionate.
Preferably, the carbonate solvent comprises ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, wherein the volume percentage content of the ethylene carbonate is 20-30%, the volume percentage content of the ethyl methyl carbonate is 30-40%, and the volume percentage content of the diethyl carbonate is 20-30% based on 100% of the solvent content; the volume content of the propyl propionate is 5-20%.
Preferably, the additive further comprises at least one of adiponitrile, vinyl ethylene carbonate, and ethylene sulfate.
Preferably, the mass percent of the adiponitrile in the additive is 0.1-1.5% based on 100% of the total electrolyte; the content of the vinyl ethylene carbonate is 0.1-1.5% by mass; the mass percentage content of the vinyl sulfate is 0.5-2%.
Preferably, the electrolyte lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (trifluoromethylsulfonyl) imide, lithium trifluoromethanesulfonate, lithium bis fluoro oxalato borate, lithium bis fluoro sulfonylimide and lithium bis oxalato borate.
Preferably, the concentration of the electrolyte lithium salt is 1mol/L to 1.2 mol/L.
Preferably, the additive lithium salt is one or more of lithium difluorophosphate, lithium tetrafluoroborate, lithium bis (trifluoromethylsulfonyl) imide, lithium trifluoromethylsulfonate, lithium difluorooxalato borate, lithium difluorosulfimide and lithium dioxaoxalato borate.
The application also discloses a lithium ion battery, wherein the battery cell of the lithium ion battery comprises the lithium ion battery electrolyte.
Preferably, the positive electrode material of the lithium ion battery is LiNi1-x-yCoxMnyO2Wherein 1-x-y is more than or equal to 0.8, x is more than 0 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.1; the negative electrode material of the lithium ion battery is a silicon-carbon material, and the silicon content in the silicon-carbon material is 5% -10%.
Compared with the prior art, the technical scheme of the application has at least the following beneficial effects:
the lithium ion battery electrolyte composed of the mixed solvent, the mixed additive and the electrolyte lithium salt in a specific proportion can obviously improve the high-temperature cycle and high-temperature storage performance of the lithium ion battery, and particularly has the most obvious effect on a high-nickel anode silicon-carbon cathode lithium battery.
A solvent system formed by mixing Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) and Propyl Propionate (PP) is used for the lithium battery electrolyte, so that the wettability of the electrolyte on a silicon-carbon negative electrode can be improved, the compatibility of the electrolyte and the silicon-carbon negative electrode is obviously improved, the conductivity of the electrolyte can be improved, and the liquid temperature range of the electrolyte is wider.
Propyl propionate in the solvent system can be oxidized and decomposed on the positive electrode before other carbonate solvents (ethylene carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC)), so that high-temperature gas generation of the high-nickel positive electrode material is inhibited, and the high-temperature storage performance of the high-nickel positive electrode silicon-carbon negative electrode lithium battery is improved.
Succinonitrile (SN) in the mixed additive coordinates with transition metal ions on the surface of the positive electrode to mask active ions on the surface of the positive electrode, so that the positive electrode can be stabilized; the cyano (-CN) functional group in the succinonitrile structure can react with Hydrogen Fluoride (HF) and water (H) in the electrolyte2O), thereby reducing the content of acid and water in the electrolyte, improving the stability of the electrolyte, reducing the occurrence of side reactions, further improving the high-temperature cycle and storage performance of the high-nickel anode silicon carbon cathode lithium ion battery, and simultaneously controlling the mass percent of the butanedinitrile to be between 0.1 and 1 percent, so that the effect of the butanedinitrile can be exerted to the maximum extent.
Vinylene Carbonate (VC) in the mixed additive can perform polymerization reaction on the surface of the silicon-carbon material to form a cross-linked polymer, the cross-linked polymer is attached to the surface of the silicon-carbon material to form an SEI (solid electrolyte interphase) film with better toughness, so that the expansion of the silicon-carbon material is better adapted, the performance of the high-nickel anode silicon-carbon cathode lithium ion battery is improved, and the effect of the mass percent of the Vinylene Carbonate (VC) in the mixed additive is optimal.
The fluoroethylene carbonate (FEC) in the mixed additive can form a cross-linked polymer with low impedance on the surface of the silicon carbon material, and can form an SEI film with good toughness and low impedance on the surface of the silicon carbon cathode when being matched with Vinylene Carbonate (VC) for use, thereby improving the performance of the high-nickel anode silicon carbon cathode lithium ion battery.
The 1, 3-propane sultone (1, 3-PS) in the mixed additive can be decomposed at the positive electrode and the negative electrode to form a protective film, so that the high-temperature storage performance of the high-nickel positive electrode silicon-carbon negative electrode lithium ion battery is improved.
Lithium difluorophosphate (LiPO)2F2) The lithium salt serving as an additive can improve the electron transmission and ion transmission performance of an electrode/electrolyte interface, and an interface protection layer is formed on the surface of the positive electrode material to inhibit the decomposition side reaction of the electrolyte, so that the high-temperature storage performance and the high-temperature cycle performance of the high-nickel positive electrode silicon-carbon negative electrode lithium ion battery are improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a graph showing capacity retention rates under 1C charge/1C discharge cycle conditions of batteries prepared in examples and comparative examples of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application discloses a lithium ion battery electrolyte, which comprises a solvent, electrolyte lithium salt and an additive, wherein the solvent comprises a carbonate solvent and a carboxylate solvent; the additive comprises succinonitrile, vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone and additive lithium salt, wherein the total amount of the electrolyte is 100%.
Wherein, the mass percent content of the succinonitrile is 0.1-1%, and more preferably 0.5-1%, based on 100% of the total amount of the electrolyte.
The content of the vinylene carbonate is 0.1-1% by mass, and more preferably 0.3-0.7% by mass, based on 100% of the total amount of the electrolyte.
The fluoroethylene carbonate accounts for 2-10% by mass, and more preferably 3-8% by mass, based on 100% of the total electrolyte.
The content of the 1, 3-propane sultone is 0.1-1 percent by mass, and more preferably 0.3-0.7 percent by mass, based on 100 percent of the total amount of the electrolyte.
The mass percentage content of the additive lithium salt is 0.1-1%, and more preferably 0.3-1%, based on 100% of the total amount of the electrolyte.
This application forms the mixed additive with succinonitrile, vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone and additive lithium salt and is used for the electrolyte of lithium cell, can stabilize the positive pole, improve the stability of electrolyte, reduce the emergence of side reaction, can take place polymerization on silicon carbon material surface simultaneously and form cross-linked form polymer, and adhere to the surface at silicon carbon material, form the SEI membrane that toughness is good and impedance is low, thereby the inflation of better adaptation silicon carbon material, improve high-nickel positive silicon carbon negative pole lithium ion battery's performance.
The additive may also include at least one of adiponitrile, vinyl ethylene carbonate, and ethylene sulfate. Specifically, the mass percent of adiponitrile in the additive is 0.1-1.5% based on 100% of the total amount of the electrolyte; the content of the vinyl ethylene carbonate is 0.1-1.5% by mass; the mass percentage content of the vinyl sulfate is 0.5-2%. Of course, other functional compounds may be added as desired.
The electrolyte lithium salt can be any one or more existing lithium salts, for example, one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (trifluoromethylsulfonyl) imide, lithium trifluoromethylsulfonate, lithium difluorooxalato borate, lithium difluorosulfonylimide and lithium dioxaoxalato borate can be selected, lithium hexafluorophosphate is preferred, and the concentration of the electrolyte lithium salt is preferably 1 mol/L-1.2 mol/L.
The additive lithium salt can be any one or more existing lithium salts, for example, the additive lithium salt can be one or more of lithium difluorophosphate, lithium tetrafluoroborate, lithium bis (trifluoromethylsulfonyl) imide, lithium trifluoromethylsulfonate, lithium difluorooxalato borate, lithium difluorosulfimide and lithium dioxaoxalato borate, and lithium difluorophosphate is preferred.
Lithium difluorophosphate is used as an additive lithium salt, so that the electron transmission and ion transmission performance of an electrode/electrolyte interface can be improved, an interface protective layer is formed on the surface of the positive electrode material, and the decomposition side reaction of the electrolyte is inhibited, so that the high-temperature storage performance and the high-temperature cycle performance of the high-nickel positive electrode silicon-carbon negative electrode lithium ion battery are improved.
The carbonate solvent may be at least one of ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate, and the carboxylate solvent may be propyl propionate. In addition to these, other carbonate solvents and carboxylate solvents may be used, for example, the carbonate solvents may be propylene carbonate, γ -butyrolactone, butylene carbonate, dimethyl carbonate, and the like. The carboxylic acid ester solvent may also be ethyl butyrate.
Preferably, the carbonate solvent comprises ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, wherein the volume percentage content of the ethylene carbonate is 20-30%, the volume percentage content of the ethyl methyl carbonate is 30-40%, and the volume percentage content of the diethyl carbonate is 20-30% based on 100% of the solvent content; the volume content of the propyl propionate is 5-20%.
A solvent system formed by mixing Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) and Propyl Propionate (PP) is used for the lithium battery electrolyte, so that the wettability of the electrolyte on a silicon-carbon negative electrode can be improved, the compatibility of the electrolyte and the silicon-carbon negative electrode is obviously improved, the conductivity of the electrolyte can be improved, and the liquid temperature range of the electrolyte is wider.
The application also provides a lithium ion battery, the battery cell of the lithium ion battery comprises the lithium ion battery electrolyte, and the lithium ion battery has excellent high-temperature storage performance and high-temperature cycle performance, and is particularly a high-nickel anode silicon-carbon cathode lithium ion battery. The positive electrode material of the high-nickel positive electrode silicon-carbon negative electrode lithium ion battery can be LiNi1-x- yCoxMnyO2Wherein 1-x-y is more than or equal to 0.8, x is more than 0 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.1; the cathode material of the high-nickel cathode silicon-carbon cathode lithium ion battery can be a silicon-carbon material, and the content of silicon in the silicon-carbon material is preferably 5-10%.
To further illustrate the technical solutions of the present application, the following preferred embodiments of the present application are described in connection with examples, but it should be understood that the descriptions are only for further illustrating the features and advantages of the present invention and are not to be construed as limiting the claims of the present application.
The chemical reagents used in the examples of this application are either commercially available or prepared according to methods well known to those skilled in the art and used directly.
Example 1
Preparing the electrolyte of the high-nickel anode silicon-carbon cathode lithium ion battery:
ethylene carbonate, ethyl methyl carbonate, diethyl carbonate and propyl propionate were mixed homogeneously in a glove box (model Universal (1800/750/900)) having a moisture content of <1ppm in a volume ratio of 20: 40: 30: 10.
Then, 1.1mol/L lithium hexafluorophosphate was added to the mixed solvent, and the mixture was stirred to be completely dissolved.
And adding succinonitrile, vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone and lithium difluorophosphate, and uniformly stirring the system to obtain the high-nickel anode silicon-carbon cathode lithium ion battery electrolyte.
Wherein, the mass of the succinonitrile accounts for 0.5 percent of the total mass of the electrolyte, the mass of the vinylene carbonate accounts for 0.5 percent of the total mass of the electrolyte, the mass of the fluoroethylene carbonate accounts for 5 percent of the total mass of the electrolyte, the mass of the 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, and the mass of the lithium difluorophosphate accounts for 1 percent of the total mass of the electrolyte.
Preparing a high-nickel positive electrode material:
ternary high nickel positive electrode material (LiNi) with the mass ratio of 97.2: 0.9: 0.8: 1.10.8Co0.1Mn0.1O2) Dissolving the carbon nano tube, the carbon black and the polyvinylidene fluoride in N-methyl pyrrolidone, stirring and mixing uniformly in vacuum to prepare slurry, uniformly coating the slurry on an aluminum foil with the thickness of 18 mu m, baking, rolling, die-cutting and tabletting.
Preparing a silicon-carbon negative electrode material:
dissolving silicon carbon, carbon black, carboxymethyl cellulose and styrene butadiene rubber in a mass ratio of 96.4: 0.9: 1: 1.5 in distilled water, stirring and mixing uniformly to prepare slurry, uniformly coating the slurry on a copper foil with the thickness of 8 mu m, baking, rolling, die-cutting and tabletting.
Preparing a high-nickel anode silicon-carbon cathode lithium ion battery:
and (3) stacking the high-nickel positive plate, the silicon-carbon negative plate and the Polyethylene (PE) diaphragm with the thickness of 20 mu m prepared in the steps into a naked battery core in a Z-shaped lamination mode, putting the naked battery core into an aluminum-plastic film shell, injecting electrolyte after vacuum baking, packaging, then carrying out formation, aging, secondary sealing, degassing and capacity grading to prepare the soft package battery.
Example 2
Preparing the electrolyte of the high-nickel anode silicon-carbon cathode lithium ion battery:
ethylene carbonate, ethyl methyl carbonate, diethyl carbonate and propyl propionate were mixed homogeneously in a glove box (model Universal (1800/750/900)) with a moisture content of <1ppm in a volume ratio of 20: 40: 30: 10.
Then, 1.1mol/L lithium hexafluorophosphate was added to the mixed solvent, and the mixture was stirred to be completely dissolved.
And adding succinonitrile, vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone and lithium difluorophosphate, and uniformly stirring the system to obtain the high-nickel anode silicon-carbon cathode lithium ion battery electrolyte.
Wherein the mass of the butanedinitrile is increased to 1 percent of the total mass of the electrolyte, the mass of the vinylene carbonate accounts for 0.5 percent of the total mass of the electrolyte, the mass of the fluoroethylene carbonate accounts for 5 percent of the total mass of the electrolyte, the mass of the 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, and the mass of the lithium difluorophosphate accounts for 1 percent of the total mass of the electrolyte.
Preparing a high-nickel positive electrode material:
ternary high nickel positive electrode material (LiNi) with the mass ratio of 97.2: 0.9: 0.8: 1.10.8Co0.1Mn0.1O2) Dissolving the carbon nano tube, the carbon black and the polyvinylidene fluoride in N-methyl pyrrolidone, stirring and mixing uniformly in vacuum to prepare slurry, uniformly coating the slurry on an aluminum foil with the thickness of 18 mu m, baking, rolling, die-cutting and tabletting.
Preparing a silicon-carbon negative electrode material:
dissolving silicon carbon, carbon black, carboxymethyl cellulose and styrene butadiene rubber in a mass ratio of 96.4: 0.9: 1: 1.5 in distilled water, stirring and mixing uniformly to prepare slurry, uniformly coating the slurry on a copper foil with the thickness of 8 mu m, baking, rolling, die-cutting and tabletting.
Preparing a high-nickel anode silicon-carbon cathode lithium ion battery:
and (3) stacking the high-nickel positive plate, the silicon-carbon negative plate and the Polyethylene (PE) diaphragm with the thickness of 20 mu m prepared in the steps into a naked battery core in a Z-shaped lamination mode, putting the naked battery core into an aluminum-plastic film shell, injecting electrolyte after vacuum baking, packaging, then carrying out formation, aging, secondary sealing, degassing and capacity grading to prepare the soft package battery.
Example 3
Preparing the electrolyte of the high-nickel anode silicon-carbon cathode lithium ion battery:
ethylene carbonate, ethyl methyl carbonate, diethyl carbonate and propyl propionate were mixed homogeneously in a glove box (model Universal (1800/750/900)) having a moisture content of <1ppm in a volume ratio of 20: 40: 30: 10.
Then, 1.1mol/L lithium hexafluorophosphate was added to the mixed solvent, and the mixture was stirred to be completely dissolved.
And adding succinonitrile, vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone and lithium difluorophosphate, and uniformly stirring the system to obtain the high-nickel anode silicon-carbon cathode lithium ion battery electrolyte.
Wherein, the mass of the succinonitrile accounts for 0.5 percent of the total mass of the electrolyte, the mass of the vinylene carbonate accounts for 1 percent of the total mass of the electrolyte, the mass of the fluoroethylene carbonate accounts for 5 percent of the total mass of the electrolyte, the mass of the 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, and the mass of the lithium difluorophosphate accounts for 1 percent of the total mass of the electrolyte.
Preparing a high-nickel positive electrode material:
ternary high nickel positive electrode material (LiNi) with the mass ratio of 97.2: 0.9: 0.8: 1.10.8Co0.1Mn0.1O2) Dissolving the carbon nano tube, the carbon black and the polyvinylidene fluoride in N-methyl pyrrolidone, stirring and mixing uniformly in vacuum to prepare slurry, uniformly coating the slurry on an aluminum foil with the thickness of 18 mu m, baking, rolling, die-cutting and tabletting.
Preparing a silicon-carbon negative electrode material:
dissolving silicon carbon, carbon black, carboxymethyl cellulose and styrene butadiene rubber in a mass ratio of 96.4: 0.9: 1: 1.5 in distilled water, stirring and mixing uniformly to prepare slurry, uniformly coating the slurry on a copper foil with the thickness of 8 mu m, baking, rolling, die-cutting and tabletting.
Preparing a high-nickel anode silicon-carbon cathode lithium ion battery:
and (3) stacking the high-nickel positive plate, the silicon-carbon negative plate and the Polyethylene (PE) diaphragm with the thickness of 20 mu m prepared in the steps into a naked battery core in a Z-shaped lamination mode, putting the naked battery core into an aluminum-plastic film shell, injecting electrolyte after vacuum baking, packaging, then carrying out formation, aging, secondary sealing, degassing and capacity grading to prepare the soft package battery.
Comparative example 1
Preparing the electrolyte of the high-nickel anode silicon-carbon cathode lithium ion battery:
ethylene carbonate, ethyl methyl carbonate, diethyl carbonate and propylene carbonate were mixed homogeneously in a glove box (model Universal (1800/750/900)) having a moisture content of <1ppm in a volume ratio of 20: 40: 30: 10.
Then, 1.1mol/L lithium hexafluorophosphate was added to the mixed solvent, and the mixture was stirred to be completely dissolved.
And adding succinonitrile, vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone and lithium difluorophosphate, and uniformly stirring the system to obtain the high-nickel anode silicon-carbon cathode lithium ion battery electrolyte.
Wherein, the mass of the succinonitrile accounts for 0.5 percent of the total mass of the electrolyte, the mass of the vinylene carbonate accounts for 0.5 percent of the total mass of the electrolyte, the mass of the fluoroethylene carbonate accounts for 5 percent of the total mass of the electrolyte, the mass of the 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, and the mass of the lithium difluorophosphate accounts for 1 percent of the total mass of the electrolyte.
Preparing a high-nickel positive electrode material:
ternary high nickel positive electrode material (LiNi) with the mass ratio of 97.2: 0.9: 0.8: 1.10.8Co0.1Mn0.1O2) Carbon nanotube, carbon black and polyvinylidene fluoride in N-methyl pyrrolidoneAnd stirring and mixing uniformly in vacuum to prepare slurry, uniformly coating the slurry on an aluminum foil with the thickness of 18 mu m, baking, and rolling, die-cutting and tabletting.
Preparing a silicon-carbon negative electrode material:
dissolving silicon carbon, carbon black, carboxymethyl cellulose and styrene butadiene rubber in a mass ratio of 96.4: 0.9: 1: 1.5 in distilled water, stirring and mixing uniformly to prepare slurry, uniformly coating the slurry on a copper foil with the thickness of 8 mu m, baking, rolling, die-cutting and tabletting.
Preparing a high-nickel anode silicon-carbon cathode lithium ion battery:
and (3) stacking the high-nickel positive plate, the silicon-carbon negative plate and the Polyethylene (PE) diaphragm with the thickness of 20 mu m prepared in the steps into a naked battery core in a Z-shaped lamination mode, putting the naked battery core into an aluminum-plastic film shell, injecting electrolyte after vacuum baking, packaging, then carrying out formation, aging, secondary sealing, degassing and capacity grading to prepare the soft package battery.
Comparative example 2
Preparing the electrolyte of the high-nickel anode silicon-carbon cathode lithium ion battery:
ethylene carbonate, ethyl methyl carbonate, diethyl carbonate and propyl propionate were mixed homogeneously in a glove box (model Universal (1800/750/900)) having a moisture content of <1ppm in a volume ratio of 20: 40: 30: 10.
Then, 1.1mol/L lithium hexafluorophosphate was added to the mixed solvent, and the mixture was stirred to be completely dissolved.
And adding succinonitrile, vinylene carbonate, fluoroethylene carbonate, vinyl sulfate and lithium difluorophosphate, and uniformly stirring the system to obtain the high-nickel anode silicon-carbon cathode lithium ion battery electrolyte.
Wherein, the mass of the succinonitrile accounts for 0.5 percent of the total mass of the electrolyte, the mass of the vinylene carbonate accounts for 0.5 percent of the total mass of the electrolyte, the mass of the fluoroethylene carbonate accounts for 5 percent of the total mass of the electrolyte, the mass of the vinyl sulfate accounts for 0.5 percent of the total mass of the electrolyte, and the mass of the lithium difluorophosphate accounts for 1 percent of the total mass of the electrolyte.
Preparing a high-nickel positive electrode material:
ternary high nickel positive electrode material (LiNi) with the mass ratio of 97.2: 0.9: 0.8: 1.10.8Co0.1Mn0.1O2) Dissolving the carbon nano tube, the carbon black and the polyvinylidene fluoride in N-methyl pyrrolidone, stirring and mixing uniformly in vacuum to prepare slurry, uniformly coating the slurry on an aluminum foil with the thickness of 18 mu m, baking, rolling, die-cutting and tabletting.
Preparing a silicon-carbon negative electrode material:
dissolving silicon carbon, carbon black, carboxymethyl cellulose and styrene butadiene rubber in a mass ratio of 96.4: 0.9: 1: 1.5 in distilled water, stirring and mixing uniformly to prepare slurry, uniformly coating the slurry on a copper foil with the thickness of 8 mu m, baking, rolling, die-cutting and tabletting.
Preparing a high-nickel anode silicon-carbon cathode lithium ion battery:
and (3) stacking the high-nickel positive plate, the silicon-carbon negative plate and the Polyethylene (PE) diaphragm with the thickness of 20 mu m prepared in the steps into a naked battery core in a Z-shaped lamination mode, putting the naked battery core into an aluminum-plastic film shell, injecting electrolyte after vacuum baking, packaging, then carrying out formation, aging, secondary sealing, degassing and capacity grading to prepare the soft package battery.
Through high-temperature cycle test and high-temperature storage test of the battery, the lithium ion battery electrolyte provided by the application is proved to be capable of remarkably improving the high-temperature storage performance and the high-temperature cycle performance of the high-nickel anode silicon-carbon cathode lithium ion battery. The specific implementation steps are as follows:
high temperature 45 ℃ cycle test:
the lithium ion batteries prepared in example 1, example 2, example 3, comparative example 1 and comparative example 2 were charged at a high temperature of 45 ℃ to 4.2V at a constant current and a constant voltage of 1C and a cutoff current of 0.05C, and then discharged at a constant current of 1C to 2.8V, and were subjected to a charge-discharge cycle test, and cycle data were recorded, with the test results shown in fig. 1.
High temperature 55 ℃ storage test:
the lithium ion batteries prepared in example 1, example 2, example 3, comparative example 1 and comparative example 2 were placed in a high temperature environment of 55 ℃ at full charge, and after standing for 7 days, the thickness, internal resistance, capacity recovery rate and the like of each lithium ion battery were measured, and the test results are shown in table 1.
TABLE 1 high temperature 55 ℃ storage of test data
Referring to fig. 1, under the condition of 1C charge/1C discharge cycle, the capacity retention rate of the high-nickel cathode silicon carbon cathode lithium ion battery manufactured in example 1 is superior to that of other examples and comparative examples, and it can be seen that the capacity retention rate of the high-nickel cathode silicon carbon cathode lithium ion battery can be improved by the electrolyte component and the proportion thereof adopted in example 1, so that the high-nickel cathode silicon carbon cathode lithium ion battery has excellent high-temperature cycle performance.
Comparing example 1 with example 2, it is seen that the mass percent of succinonitrile is increased from 0.5% to 1%, and the high-temperature cycle performance of the high-nickel cathode silicon-carbon anode lithium ion battery is obviously reduced. Therefore, the quality of succinonitrile in the electrolyte has a remarkable influence on the high-temperature cycle performance of the high-nickel anode silicon carbon cathode lithium ion battery, and the quality of succinonitrile is controlled in a reasonable range, so that the succinonitrile is a key factor for enabling the high-nickel anode silicon carbon cathode lithium ion battery to have excellent high-temperature cycle performance.
The results of the high temperature cycle test of comparative example 2, comparative example 1 and comparative example 2 show that, although the high temperature cycle performance of example 2 is lower than that of example 1, the results are much better than those of comparative example 1 and comparative example 2. Therefore, the mass percent of the succinonitrile is between 0.5 and 1 percent, so that the high-nickel anode silicon carbon cathode lithium ion battery has excellent high-temperature cycle performance.
With continued reference to fig. 1, it can be seen from the comparison between example 1 and example 3 that the capacity retention rate of the high nickel cathode silicon carbon anode lithium ion battery is slightly reduced by increasing the mass percentage of the vinylene carbonate from 0.5% to 1%. Therefore, the mass percentage of the vinylene carbonate can also influence the high-temperature cycle performance of the high-nickel cathode silicon carbon cathode lithium ion battery, and the high-temperature cycle performance of the high-nickel cathode silicon carbon cathode lithium ion battery is reduced along with the increase of the mass percentage of the vinylene carbonate.
The results of the high temperature cycle test of comparative example 3, comparative example 1 and comparative example 2 show that, although the high temperature cycle performance of example 3 is slightly lower than that of example 1, it is far better than that of comparative example 1 and comparative example 2. Therefore, the vinylene carbonate accounts for 0.1-1% by mass, so that the high-nickel anode silicon carbon cathode lithium ion battery has excellent high-temperature cycle performance.
The capacity retention rate of the high nickel cathode silicon carbon anode lithium ion batteries prepared in comparative examples 1 and 2 is lower than that of the high nickel cathode silicon carbon anode lithium ion batteries prepared in examples 1 to 3. The propyl propionate adopted in the embodiment of the application is more favorable for improving the high-temperature cycle performance of the high-nickel cathode silicon-carbon cathode lithium ion battery compared with other solvents. The research on the action mechanism of the propyl propionate further discovers that the propyl propionate can generate oxidation reaction on the positive electrode interface, so that the stability of the positive electrode interface is improved, and the high-temperature cycle performance of the battery is further improved.
Therefore, the electrolyte component and the proportion thereof can enable the high-temperature cycle performance of the high-nickel anode silicon-carbon cathode lithium ion battery to reach a better state.
Referring to table 1, the high-nickel cathode silicon carbon cathode lithium ion battery prepared in example 1 of the present application exhibits excellent high-temperature storage performance, and example 2 increases the mass percentage of butanedinitrile based on example 1, and the high-nickel cathode silicon carbon cathode lithium ion battery prepared therefrom tends to have deteriorated high-temperature storage performance. The reason is that although succinonitrile can coordinate with transition metal ions on the surface of the positive electrode to mask active ions on the surface of the positive electrode and play a role in stabilizing the positive electrode, and a cyano group in the structure of succinonitrile can react with hydrogen fluoride and water in the electrolyte, so that the content of acid and water in the electrolyte is reduced, the stability of the electrolyte is improved, side reactions are reduced, and the storage performance of the high-nickel positive electrode silicon carbon negative electrode lithium ion battery is improved, along with the improvement of the mass percentage of succinonitrile, the battery impedance is increased, and finally the high-temperature storage performance is deteriorated.
Example 3 the mass percent of vinylene carbonate is increased on the basis of example 1. Vinylene carbonate can generate a polymerization reaction on the surface of a silicon-carbon material to form a cross-linked polymer, the cross-linked polymer is attached to the surface of the silicon-carbon material to form an SEI (solid electrolyte interphase) film with good toughness, so that the silicon-carbon material can better adapt to the expansion of the silicon-carbon material, and the high-temperature storage performance of the high-nickel anode silicon-carbon cathode lithium ion battery is improved. Therefore, as the mass percentage of the vinylene carbonate increases, the high-temperature storage performance of the high-nickel positive electrode silicon carbon negative electrode lithium ion battery also decreases.
The high-nickel cathode silicon carbon anode lithium ion battery manufactured in comparative example 1 exhibited a lower high-temperature storage performance than that of example 1 of the present application. This is because the propyl propionate in example 1 can be oxidized and decomposed at the positive electrode before other carbonate solvents (ethylene carbonate (EC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC)) to inhibit high-temperature gassing of the high-nickel positive electrode material, thereby improving the high-temperature storage performance of the high-nickel positive electrode silicon carbon negative electrode lithium battery, whereas the propylene carbonate in comparative example 1 cannot achieve the above effects.
The high-nickel cathode silicon carbon anode lithium ion battery manufactured in comparative example 2 also showed inferior high-temperature storage performance to that of example 1 of the present application. Since the vinyl sulfate used in comparative example 2 is unstable itself and is decomposed more at the time of first film formation, the advantages of lowering the resistance and improving the cycle performance thereof are not exhibited at the time of cycle and storage. The 1, 3-propane sultone adopted by the method is stable, and meanwhile, a film is formed on the positive and negative electrode interfaces, so that the high-temperature cycle and high-temperature storage performance of the battery can be improved.
The test results of the high-temperature cycle and the high-temperature storage are comprehensively considered, the lithium ion electrolyte composed of the mixed solvent, the mixed additive and the electrolyte lithium salt in a specific ratio provided in embodiments 1 to 3 of the present application is more suitable for the high-nickel anode silicon carbon cathode lithium battery than the electrolytes of other comparative examples, and the lithium ion electrolyte of the embodiments of the present application can effectively solve the problems of poor battery cycle performance, gas expansion and the like caused by unstable structure of the high-nickel material commonly existing in the high-nickel anode silicon carbon cathode lithium battery, and the problem of rapid battery capacity attenuation caused by continuous growth of the solid electrolyte interface film on the surface of the silicon material, so that the high-nickel anode silicon carbon cathode lithium battery has excellent high-temperature cycle and high-temperature storage performance.
In conclusion, upon reading the present detailed disclosure, those skilled in the art will appreciate that the foregoing detailed disclosure can be presented by way of example only, and not limitation. Those skilled in the art will appreciate that the present application is intended to cover various reasonable variations, adaptations, and modifications of the embodiments described herein, although not explicitly described herein. Such alterations, improvements, and modifications are intended to be suggested by this disclosure, and are within the spirit and scope of the exemplary embodiments of this disclosure.
Furthermore, certain terminology has been used in this application to describe embodiments of the disclosure. For example, "one embodiment," "an embodiment," and/or "some embodiments" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the present disclosure. Therefore, it is emphasized and should be appreciated that two or more references to "an embodiment" or "one embodiment" or "an alternative embodiment" in various portions of this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined as suitable in one or more embodiments of the disclosure.
It should be appreciated that in the foregoing description of embodiments of the disclosure, various features are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure aiding in the understanding of the subject disclosure. Alternatively, various features may be dispersed throughout several embodiments of the application. This is not to be taken as an admission that any of the features of the claims are essential, and it is fully possible for a person skilled in the art to extract some of them as separate embodiments when reading the present application. That is, embodiments in the present application may also be understood as an integration of multiple sub-embodiments. And each sub-embodiment described herein is equally applicable to less than all features of a single foregoing disclosed embodiment.
In some embodiments, numbers expressing quantities or properties used to describe and claim certain embodiments of the application are to be understood as being modified in certain instances by the term "about", "approximately" or "substantially". For example, "about," "approximately," or "substantially" can mean a ± 20% variation of the value it describes, unless otherwise specified. Accordingly, in some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the embodiments of the application are approximations, the numerical values set forth in the specific examples are reported as precisely as possible.
Each patent, patent application, publication of a patent application, and other material, such as articles, books, descriptions, publications, documents, articles, and the like, cited herein is hereby incorporated by reference. All matters hithertofore set forth herein except as related to any prosecution history, may be inconsistent or conflicting with this document or any prosecution history which may have a limiting effect on the broadest scope of the claims. Now or later associated with this document. For example, if there is any inconsistency or conflict in the description, definition, and/or use of terms associated with any of the included materials with respect to the terms, descriptions, definitions, and/or uses associated with this document, the terms in this document are used.
Finally, it should be understood that the embodiments of the application disclosed herein are illustrative of the principles of the embodiments of the present application. Other modified embodiments are also within the scope of the present application. Accordingly, the disclosed embodiments are presented by way of example only, and not limitation. Those skilled in the art may implement the present application in alternative configurations according to the embodiments of the present application. Thus, embodiments of the present application are not limited to those embodiments described with accuracy in the application.
Claims (10)
1. The lithium ion battery electrolyte comprises a solvent, electrolyte lithium salt and an additive, and is characterized in that,
the solvent comprises a carbonate solvent and a carboxylate solvent; the additive comprises the following components in percentage by mass based on the total amount of the electrolyte as 100 percent:
2. the lithium ion battery electrolyte of claim 1, wherein the carbonate solvent comprises at least one of ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate, and the carboxylate solvent comprises propyl propionate.
3. The lithium ion battery electrolyte of claim 2, wherein the carbonate solvent comprises ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, wherein the ethylene carbonate is 20-30% by volume, the ethyl methyl carbonate is 30-40% by volume, and the diethyl carbonate is 20-30% by volume, based on 100% solvent content; the volume content of the propyl propionate is 5-20%.
4. The lithium ion battery electrolyte of claim 1, wherein the additive further comprises at least one of adiponitrile, vinyl ethylene carbonate, and ethylene sulfate.
5. The lithium ion battery electrolyte of claim 4, wherein the mass percent content of adiponitrile in the additive is 0.1-1.5% based on 100% of the total electrolyte; the content of the vinyl ethylene carbonate is 0.1-1.5% by mass; the mass percentage content of the vinyl sulfate is 0.5-2%.
6. The lithium ion battery electrolyte of claim 1, wherein the electrolyte lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (trifluoromethylsulfonyl) imide, lithium trifluoromethanesulfonate, lithium bis-fluorooxalato borate, lithium bis-fluorosulfonimide, and lithium bis-oxalato borate.
7. The lithium ion battery electrolyte of claim 1 or 6, wherein the concentration of the electrolyte lithium salt is 1mol/L to 1.2 mol/L.
8. The lithium ion battery electrolyte of claim 1, wherein the additive lithium salt is one or more of lithium difluorophosphate, lithium tetrafluoroborate, lithium bis (trifluoromethylsulfonyl) imide, lithium trifluoromethylsulfonate, lithium difluorooxalato borate, lithium difluorosulfimide, and lithium dioxaoxalato borate.
9. A lithium ion battery, characterized in that the lithium ion battery electrolyte of any one of claims 1 to 8 is included in a battery cell of the lithium ion battery.
10. The lithium ion battery of claim 9, wherein the positive electrode material of the lithium ion battery is LiNi1-x-yCoxMnyO2Wherein 1-x-y is more than or equal to 0.8, x is more than 0 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.1; the negative electrode material of the lithium ion battery is a silicon-carbon material, and the silicon content in the silicon-carbon material is 5% -10%.
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