CN117638221A - High-voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte and lithium ion battery - Google Patents
High-voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte and lithium ion battery Download PDFInfo
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- CN117638221A CN117638221A CN202210974200.1A CN202210974200A CN117638221A CN 117638221 A CN117638221 A CN 117638221A CN 202210974200 A CN202210974200 A CN 202210974200A CN 117638221 A CN117638221 A CN 117638221A
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 26
- FLAFBICRVKZSCF-UHFFFAOYSA-N [Li].[Co]=O.[Li] Chemical compound [Li].[Co]=O.[Li] FLAFBICRVKZSCF-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 51
- 239000003792 electrolyte Substances 0.000 claims abstract description 43
- 230000000996 additive effect Effects 0.000 claims abstract description 34
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims abstract description 27
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims abstract description 16
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- -1 hexanetrinitrile Chemical compound 0.000 claims abstract description 9
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 5
- 125000001424 substituent group Chemical group 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 21
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 16
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 10
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 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 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 5
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 229910012820 LiCoO Inorganic materials 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000009517 secondary packaging Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of lithium ion batteries, and discloses a high-voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte and a lithium ion battery. The nonaqueous electrolyte of the high-voltage lithium cobalt oxide lithium ion battery comprises a nonaqueous organic solvent, electrolyte lithium salt and a film forming additive, wherein the film forming additive comprises a silicon-containing isocyanate group additive and other additives; wherein the other additives comprise fluoroethylene carbonate, 1, 3-propane sultone, hexanetrinitrile, succinonitrile and ethylene sulfate; the structural formula of the silicon-containing isocyanate group additive is shown as the formula (I):
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte and a lithium ion battery.
Background
With technological progress, people continuously increase the requirements on the quality of living environment, and the environmental pollution problem caused by the increasingly depleted and consumed fossil energy is more serious, so that the research and development of clean renewable new energy becomes urgent. A large amount of new energy sources such as solar energy, wind energy, tidal energy, geothermal energy and the like are developed and used at present, but the energy sources are limited in time and space and need to be properly converted and stored for use.
The lithium ion battery is used as a green environment-friendly high-energy battery and is the most ideal and potential rechargeable battery in the world at present. Compared with other batteries, the battery has a series of advantages of no memory effect, rapid charge and discharge, high energy density, long cycle life, no environmental pollution and the like, and is widely applied to small electronic equipment such as notebook computers, video cameras, mobile phones, electronic watches and the like. With the continuous improvement of the capacity requirements of pure electric vehicles, hybrid electric vehicles, portable energy storage devices and the like on lithium ion batteries, the development of lithium ion batteries with higher energy density and power density is expected to realize long-term endurance and energy storage.
The energy density of the lithium ion battery can be improved by improving the working voltage, but the development of the high-voltage lithium ion battery is limited by the oxidative decomposition of the common electrolyte under high voltage. Therefore, development of an electrolyte resistant to high pressure is required. The electrochemical window of the traditional carbonate electrolyte is narrower, and after the voltage is increased, the electrolyte can be decomposed; on the other hand, the oxidation capability of the positive electrode under high pressure is enhanced, a large amount of metal is dissolved, gas is separated out, and the phase change of the material causes the battery to fail and even be dangerous.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide a high-voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte and a lithium ion battery. According to the nonaqueous electrolyte for the high-voltage lithium ion battery, through optimizing the formula, under the combined action of multiple components of a unique combination, the electrolyte system has high energy density and high safety performance, and the requirement of the battery on the cycle performance under high voltage is met.
In order to achieve the aim of the invention, the nonaqueous electrolyte of the high-voltage lithium cobalt oxide lithium ion battery comprises a nonaqueous organic solvent, electrolyte lithium salt and a film-forming additive, wherein the film-forming additive comprises a silicon-containing isocyanate-based additive and other additives; wherein the other additives comprise fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), hexanetrinitrile (HTCN), succinonitrile (SN) and ethylene sulfate (DTD); the structural formula of the silicon-containing isocyanate group additive is shown as the formula (I):
wherein the substituent R is selected from alkyl, alkoxy, isocyanate groups containing 1-6 carbons or silicon, or combinations thereof.
Preferably, in some embodiments of the present invention, the silicon-containing isocyanate-based additive is selected from at least one of the compounds represented by the following structural formulas:
further, in some embodiments of the invention, the silicon-containing isocyanate-based additive is present in the high voltage lithium ion battery nonaqueous electrolyte at a mass percent of 0.2 to 5%.
Preferably, in some embodiments of the present invention, the fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), hexanetrinitrile (HTCN), succinonitrile (SN), and ethylene sulfate (DTD) are 6-13%, 2-5%, 1.5-2.5%, 1-2%, and 0.3-0.7% by mass, respectively, in the electrolyte.
Further, in some embodiments of the invention, the lithium salt is lithium hexafluorophosphate.
Preferably, in some embodiments of the present invention, the lithium salt is 10 to 20% by mass in the electrolyte.
Further, in some embodiments of the invention, the other additive further comprises lithium difluorooxalato borate; preferably, the mass percentages of the lithium difluoro oxalato borate in the electrolyte are respectively 0.5-0.9%.
Preferably, in some embodiments of the present invention, the lithium salt is lithium hexafluorophosphate, and the other additive comprises fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), hexanetrinitrile (HTCN), succinonitrile (SN), vinyl sulfate (DTD) and lithium difluorooxalato borate; more preferably, the fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), hexanetrinitrile (HTCN), succinonitrile (SN), ethylene sulfate (DTD) and lithium difluorooxalate borate are respectively 9-11%, 3-5%, 1.5-2.5%, 1-2%, 0.4-0.6% and 0.6-0.8% by mass in the electrolyte.
Further, in some embodiments of the invention, the other additives further comprise lithium difluorooxalato borate, lithium dioxaato borate, and Vinylene Carbonate (VC); preferably, the mass percentages of the lithium difluorooxalato borate, the lithium difluorooxalato borate and the Vinylene Carbonate (VC) in the electrolyte are respectively 0.6-0.8%, 0.1-0.3% and 0.1-0.3%.
Preferably, in some embodiments of the present invention, the lithium salt is lithium hexafluorophosphate, and the other additive comprises fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), hexanetrinitrile (HTCN), succinonitrile (SN), vinyl sulfate (DTD), lithium difluorooxalato borate, lithium dioxaato borate, and Vinylene Carbonate (VC); more preferably, the fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), hexanetrinitrile (HTCN), succinonitrile (SN), ethylene sulfate (DTD), lithium difluorooxalato borate, lithium dioxaato borate and Vinylene Carbonate (VC) are 6-8%, 2-4%, 1.5-2.5%, 0.4-0.6%, 0.6-0.8%, 0.1-0.3% and 0.1-0.3% by mass, respectively, in the electrolyte.
Further, in some embodiments of the present invention, the nonaqueous organic solvent comprises Ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC), propyl Propionate (PP); preferably, the Ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC) and Propyl Propionate (PP) are present in an amount of 5-15:10-20:20-40: and mixing uniformly in a mass ratio of 40-50.
On the other hand, the invention also provides a high-voltage lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and the non-aqueous electrolyte of the high-voltage lithium cobalt oxide lithium ion battery.
Further, in some embodiments of the invention, the active material of the positive electrode is lithium cobaltate; the negative electrode material is one or more of natural graphite, artificial graphite, silicon-oxygen negative electrode and silicon negative electrode.
Further, in some embodiments of the invention, the upper cutoff voltage of the lithium ion battery is 4.5V.
Compared with the prior art, the invention has the following advantages:
(1) In the nonaqueous electrolyte of the high-voltage lithium ion battery, functional groups contained in the silicon-containing isocyanate group additive with a specific structural formula can form an organic-inorganic composite interface film containing N at the positive electrode and the negative electrode, so that the impedance is optimized to increase, the water-acid environment is optimized, the cycling stability and the thermal stability of the battery are further ensured, the storage performance of the battery is improved, and the internal resistance increase and the gas production in the use process are reduced; the introduced silicon element can also promote the wettability of the electrolyte; meanwhile, the effects of removing water and inhibiting acid of isocyanate groups, stabilizing the anode and reducing side reactions are exerted, and the use of the battery is ensured.
(2) The nonaqueous electrolyte of the high-voltage lithium ion battery can ensure that the high-voltage lithium ion battery obtains excellent cycle performance by optimizing the formula, improving the solvent and combining the combined action of other additives such as the silicon-containing isocyanate group additive, the oxalate additive and the like with a specific structural formula, so that the electrolyte system has high energy density and high stability.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is intended to be illustrative of the invention and not restrictive.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
The singular forms include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or event may or may not occur, and that the description includes both cases where the event occurs and cases where the event does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Furthermore, the descriptions of the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., described below mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily for the same embodiment or example. The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
The silicon-containing isocyanate group additives in the examples and comparative examples of the present invention are characterized as follows:
the structural formula of M1 is:
the structural formula of M2 is:
the structural formula of M3 is:
the structural formula of M4 is:
m5 has the structural formula:
example 1
Preparation of electrolyte: in a glove box filled with argon gas (oxygen content. Ltoreq.1 ppm, water content. Ltoreq.1 ppm), ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC), propyl Propionate (PP) were mixed at 10:15:45:30 to obtain a mixed solution, and adding lithium hexafluorophosphate (LiPF) 15% based on the total mass of the electrolyte to the mixed solution 6 ) Subsequently, 0.2% of a silicon-containing isocyanate-based additive M1 based on the total mass of the electrolyte, 3% of 1, 3-Propane Sultone (PS) based on the total mass of the electrolyte, 10% of fluoroethylene carbonate (FEC) based on the total mass of the electrolyte, 2% of Hexanedinitrile (HTCN) based on the total mass of the electrolyte, 1.5% of Succinonitrile (SN) based on the total mass of the electrolyte, and 0.5% of ethylene sulfate (DTD) based on the total mass of the electrolyte were added to the mixed solution and stirred to be completely dissolved, to obtain an electrolyte of example 1.
Examples 2 to 11
Examples 2 to 11 are also specific examples of the preparation of the electrolyte, and the parameters and preparation method are the same as in example 1 except that the composition ratios of the components of the electrolyte are added as shown in Table 1.
Comparative examples 1 to 7
Comparative examples 1 to 7 the procedure of example 1 was followed except that the electrolyte was added in the composition ratio shown in Table 1.
Table 1 electrolyte compositions of examples and comparative examples
Note that: the content of each component in the lithium salt is the mass percentage content in the electrolyte;
the content of the silicon-containing isocyanate group additive is the mass percentage content in the electrolyte;
the content of each component in other additives is the mass percentage content in the electrolyte;
the proportion of each component in the solvent is mass ratio.
Preparation of lithium cobaltate battery:
LiCoO as positive electrode active material 2 And (3) fully stirring and uniformly mixing the conductive agent acetylene black and the binder polyvinylidene fluoride in an N-methyl pyrrolidone system according to a mass ratio of 95:3:2, coating the mixture on an aluminum foil, drying and cold pressing the aluminum foil, and thus obtaining the positive plate.
And (3) fully stirring and uniformly mixing a negative electrode active substance AG, a conductive agent super carbon black, a thickener sodium carboxymethyl cellulose and a binder styrene-butadiene rubber in a deionized water solvent system according to a mass ratio of 95:1:2:2, coating the mixture on a copper foil, drying, and cold pressing to obtain the negative electrode plate.
Polyethylene is used as a base film, and a nano alumina coating is coated on the base film to be used as a diaphragm.
And sequentially stacking the positive plate, the diaphragm and the negative plate, enabling the diaphragm to be positioned between the positive plate and the negative plate to play a role in isolation, and winding to obtain the bare cell. And placing the bare cell in an outer package, injecting the prepared electrolyte, and performing the procedures of packaging, placing, formation, aging, secondary packaging, capacity division and the like to obtain the lithium cobalt oxide graphite lithium ion battery.
Lithium ion battery performance test
(1) And (3) testing normal temperature cycle performance: at 25 ℃, the LiCoO is added with 2 And the graphite lithium ion battery is charged to 4.5V according to a constant current and a constant voltage of 1C, the cut-off current is 0.05C, and then the graphite lithium ion battery is discharged to 3.0V according to the constant current of 1C. The 500 th cycle capacity retention rate was calculated after 500 cycles of charge/discharge. The calculation formula is as follows:
500 th week capacity retention = 500 th week cycle discharge capacity/first week cycle discharge capacity x 100%.
(2) High temperature storage performance at 60 ℃): the LiCoO is treated at room temperature 2 The graphite lithium ion battery is charged and discharged once according to 1C, the cut-off current is 0.05C, and the initial capacity is recorded. Then, the battery is fully charged according to the constant current and constant voltage of 1C, and the initial thickness and the initial internal resistance of the battery are tested; placing the full-charge battery in a constant temperature environment at 60 ℃ for 14 days, and calculating the thermal expansion rate; after the battery is cooled to normal temperatureDischarging to 3.0V according to 1C after 6 hours, recording the residual capacity of the battery, and calculating the residual capacity rate of the battery according to the following calculation formula:
battery thermal state expansion ratio (%) = (thermal thickness-initial thickness)/initial thickness×100%;
battery capacity remaining rate (%) =remaining capacity/initial capacity×100%;
battery capacity recovery (%) =recovery capacity/initial capacity×100%.
Table 2 battery performance of each of examples and comparative examples
As can be seen from examples 1 to 11 and comparative examples 1 to 7, the lithium ion batteries using the electrolytes of examples 1 to 11 were superior to those of comparative examples 1 to 7 in normal temperature cycle performance, high temperature cycle performance, and high temperature storage performance. The nonaqueous electrolyte of the high-voltage lithium ion battery plays a film forming role of an oxalate additive through optimizing a formula under the combined action of a plurality of components which are combined uniquely, particularly through the combined use of the silicon-containing isocyanate group additive with other additives, and improves the gas production side effect brought by oxalate through isocyanate groups, improves the water-acid environment in the battery, inhibits the impedance increase in the high-temperature circulation and storage process, and ensures the long cycle life and excellent high-temperature storage performance of the high-capacity lithium cobalt oxide-graphite battery. Meanwhile, the optimum addition amount of the silicon-containing isocyanate group additive is 2%.
The data of comparative examples 1-5 show that the combination of additives in the electrolyte can provide excellent electrochemical performance to the battery, and that the lack of some additives can greatly affect the normal use of the battery. The data of comparative examples 6-7 and examples 10-11 show that the introduction of the silicon-containing isocyanate-based additive can significantly reduce the increase in cell resistance, indicating that the silicon-containing isocyanate-based additive in combination with the oxalate-based additive forms a relatively excellent CEI film with reduced resistance increase, which can improve the overall performance of the cell. Meanwhile, the silicon-containing isocyanate group additives with different substituents are compared, and the data show that the M3 additive has better comprehensive performance.
In summary, the nonaqueous electrolyte for high-voltage lithium ion battery of the present invention can ensure high-voltage LiCoO by improving the carbonate solvent at the electrode/electrolyte interface, and combining the silicon-containing isocyanate group additive with a specific structural formula with other conventional additives 2 The graphite lithium ion battery has excellent cycle performance and high-temperature storage performance.
It will be readily appreciated by those skilled in the art that the foregoing is merely illustrative of the present invention and is not intended to limit the invention, but any modifications, equivalents, improvements or the like which fall within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The high-voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte is characterized by comprising a nonaqueous organic solvent, electrolyte lithium salt and a film-forming additive, wherein the film-forming additive comprises a silicon-containing isocyanate-based additive and other additives; wherein the other additives comprise fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), hexanetrinitrile (HTCN), succinonitrile (SN) and ethylene sulfate (DTD); the structural formula of the silicon-containing isocyanate group additive is shown as the formula (I):
wherein the substituent R is selected from alkyl, alkoxy, isocyanate groups containing 1-6 carbons or silicon, or combinations thereof.
2. The high voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte according to claim 1, wherein the silicon-containing isocyanate group additive is selected from at least one of the compounds represented by the following structural formulas:
preferably, the mass percentage of the silicon-containing isocyanate-based additive in the nonaqueous electrolyte of the high-voltage lithium ion battery is 0.2-5%.
3. The nonaqueous electrolyte for a high-voltage lithium cobalt oxide lithium ion battery according to claim 1, wherein the mass percentages of fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), hexanetrinitrile (HTCN), succinonitrile (SN) and vinyl sulfate (DTD) in the electrolyte are 6-13%, 2-5%, 1.5-2.5%, 1-2% and 0.3-0.7%, respectively.
4. The high-voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte according to claim 3, wherein the lithium salt is lithium hexafluorophosphate; preferably, the mass percentage of the lithium salt in the electrolyte is 10-20%.
5. The high voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte according to claim 4, wherein the other additive further comprises lithium difluorooxalato borate; preferably, the mass percentages of the lithium difluoro oxalato borate in the electrolyte are respectively 0.5-0.9%.
6. The high voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte according to claim 1, wherein the lithium salt is lithium hexafluorophosphate, and the other additives include fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), hexanetrinitrile (HTCN), succinonitrile (SN), vinyl sulfate (DTD), and lithium difluoroborate; more preferably, the fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), hexanetrinitrile (HTCN), succinonitrile (SN), ethylene sulfate (DTD) and lithium difluorooxalate borate are respectively 9-11%, 3-5%, 1.5-2.5%, 1-2%, 0.4-0.6% and 0.6-0.8% by mass in the electrolyte.
7. The high voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte according to claim 4, wherein the other additives further comprise lithium difluorooxalato borate, lithium dioxaoxalato borate and Vinylene Carbonate (VC); preferably, the mass percentages of the lithium difluorooxalato borate, the lithium difluorooxalato borate and the Vinylene Carbonate (VC) in the electrolyte are respectively 0.6-0.8%, 0.1-0.3% and 0.1-0.3%.
8. The high voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte according to claim 1, wherein the lithium salt is lithium hexafluorophosphate, and the other additive comprises fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), hexanetrinitrile (HTCN), succinonitrile (SN), vinyl sulfate (DTD), lithium difluorooxalato borate, lithium dioxaato borate and Vinylene Carbonate (VC); more preferably, the fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), hexanetrinitrile (HTCN), succinonitrile (SN), ethylene sulfate (DTD), lithium difluorooxalato borate, lithium dioxaato borate and Vinylene Carbonate (VC) are 6-8%, 2-4%, 1.5-2.5%, 0.4-0.6%, 0.6-0.8%, 0.1-0.3% and 0.1-0.3% by mass, respectively, in the electrolyte.
9. The nonaqueous electrolyte for a high-voltage lithium cobalt oxide lithium ion battery according to claim 1, wherein the nonaqueous organic solvent comprises Ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC), propyl Propionate (PP); preferably, the Ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC) and Propyl Propionate (PP) are present in an amount of 5-15:10-20:20-40: and mixing uniformly in a mass ratio of 40-50.
10. A high-voltage lithium ion battery, characterized in that the high-voltage lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and the high-voltage lithium cobalt oxide lithium ion battery nonaqueous electrolyte according to any one of claims 1 to 9; preferably, the active material of the positive electrode is lithium cobaltate; the negative electrode material is one or more of natural graphite, artificial graphite, silicon-oxygen negative electrode and silicon negative electrode; preferably, the upper limit cutoff voltage of the lithium ion battery is 4.5V.
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