CN114552015A - Electrolyte additive, lithium ion battery electrolyte and lithium ion battery - Google Patents
Electrolyte additive, lithium ion battery electrolyte and lithium ion battery Download PDFInfo
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- CN114552015A CN114552015A CN202210184435.0A CN202210184435A CN114552015A CN 114552015 A CN114552015 A CN 114552015A CN 202210184435 A CN202210184435 A CN 202210184435A CN 114552015 A CN114552015 A CN 114552015A
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- lithium ion
- ion battery
- lithium
- substituted
- electrolyte
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 98
- 239000003792 electrolyte Substances 0.000 title claims abstract description 37
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003368 amide group Chemical group 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 5
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims abstract description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 2
- 229910014248 MzO2 Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000005678 chain carbonates Chemical class 0.000 claims description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- OWNSEPXOQWKTKG-UHFFFAOYSA-M lithium;methanesulfonate Chemical compound [Li+].CS([O-])(=O)=O OWNSEPXOQWKTKG-UHFFFAOYSA-M 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- AVTOEKKTKXLWDL-UHFFFAOYSA-N acetylene;1,3-dioxolan-2-one Chemical compound C#C.O=C1OCCO1 AVTOEKKTKXLWDL-UHFFFAOYSA-N 0.000 claims 1
- 239000002671 adjuvant Substances 0.000 claims 1
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 18
- 239000010408 film Substances 0.000 description 25
- 238000007599 discharging Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 102000004310 Ion Channels Human genes 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical group C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an electrolyte additive, a lithium ion battery electrolyte and a lithium ion battery, wherein the electrolyte additive comprises a compound shown in a structural formula 1:
wherein R is1～R4Each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 unsaturated group, substituted or unsubstituted amino, substituted or unsubstituted amido, and substituted or unsubstituted nitrogen-containing heterocyclic group. The electrolyte additive is applied to the lithium ion battery, and the lithium ion battery has better low-temperature discharge performance, high-temperature storage performance and cycle performance under high voltage.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an electrolyte additive, a lithium ion battery electrolyte and a lithium ion battery.
Background
The lithium ion battery has the advantages of high specific energy, long cycle life, no memory effect and the like, and is widely applied to the fields of mobile phones, computers, cameras, electric vehicles and the like. However, with the continuous development of scientific technology, various application fields have put higher requirements on the performance of lithium ion batteries. Among them, it is most urgent to improve the energy density of the lithium ion battery on the premise of ensuring safety. At present, the energy density of the lithium ion battery is often improved by increasing the charge cut-off voltage, but some problems also exist under high voltage: when the voltage reaches 4.4V, the frequently used carbonate-based electrolyte begins to generate an oxidative decomposition side reaction on the surface of the anode material, so that the performance of the lithium ion battery is influenced, and meanwhile, the nickel-cobalt-manganese ternary material can generate irreversible H2-H3 phase change, so that excessive metal is dissolved out, the side reaction of the electrolyte is intensified, the gas generation of the battery is increased, and the performance of the battery is suddenly attenuated. Particularly, at low temperatures, the impedance inside the lithium ion battery increases, and the low-temperature discharge performance of the lithium ion battery is significantly insufficient. Therefore, how to ensure the low-temperature discharge performance, the high-temperature storage performance and the cycle performance of the lithium ion battery is the key point of research on the premise of improving the cut-off voltage.
Therefore, an electrolyte additive, an electrolyte for a lithium ion battery and a lithium ion battery are needed to solve the problems of the prior art.
Disclosure of Invention
The invention aims to provide an electrolyte additive which can improve the low-temperature discharge performance, the high-temperature storage performance and the cycle performance of a lithium ion battery.
It is still another object of the present invention to provide a lithium ion battery electrolyte that can improve low-temperature discharge performance, high-temperature storage performance, and cycle performance of a lithium ion battery.
Another object of the present invention is to provide a lithium ion battery having good low-temperature discharge performance, high-temperature storage performance and cycle performance in a high-voltage system.
To achieve the above objects, the present invention provides an electrolyte additive comprising a compound represented by formula 1:
wherein R is1～R4Each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 unsaturated group, substituted or unsubstituted amino, substituted or unsubstituted amido, and substituted or unsubstituted nitrogen-containing heterocyclic group.
Compared with the prior art, the compound shown in the structural formula 1 forms a stable interfacial film (SEI) at the interface of an electrode/electrolyte, the interfacial film is of a multilayer structure, and one surface close to the electrolyte is porous, so that the transmission of lithium ions is facilitated; one surface close to the electrode is compact, which is beneficial to inhibiting the side reaction of the electrolyte, the interface film has a good lithium ion conduction channel, the collapse of the lithium ion channel is not generated in the circulation process, and the cycle performance of the lithium ion battery is improved; the N-C ═ O structure in the structural formula 1 has good thermal stability, and the introduction of sulfur, nitrogen and oxygen elements enriches the components of an electrode/electrolyte interface film, further improves the thermal stability of the interface film, and further improves the high-temperature storage performance of the lithium ion battery; meanwhile, N-C (O) is not easy to generate gas at high temperature, and is favorable for improving the high-temperature performance of the lithium ion battery; in addition, the sulfimide structure on the side chain of the structural formula 1 can improve the structural toughness and stability of an SEI film pore, increase the SEI film pore diameter, inhibit the lithium ion transmission resistance at low temperature and facilitate the improvement of the low-temperature discharge performance of the lithium ion battery, so that the electrolyte additive disclosed by the invention is applied to the lithium ion battery, and the lithium ion battery has better low-temperature discharge performance, high-temperature storage performance and cycle performance at high voltage.
Preferably, R of the present invention1～R4Each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C2-C4 unsaturated group, substituted or unsubstituted amino, substituted or unsubstituted amido, and substituted or unsubstituted nitrogen-containing heterocyclic group.
Preferably, the compound represented by the structural formula 1 of the present invention is selected from at least one of the compounds 1 to 6:
in order to achieve the above purpose, the invention provides a lithium ion battery electrolyte, which comprises a lithium salt, an organic solvent and the above electrolyte additive.
Compared with the prior art, the electrolyte additive is contained in the lithium ion battery electrolyte, so that the lithium ion battery electrolyte is applied to the lithium ion battery, and the lithium ion battery has better low-temperature discharge performance, high-temperature storage performance and cycle performance under high voltage.
Preferably, the mass of the electrolyte additive accounts for 0.1-5% of the sum of the mass of the lithium salt and the mass of the organic solvent.
In the experimental process, the inventor of the application finds that although the compound a can improve the low-temperature discharge performance, the high-temperature storage performance and the cycle performance of the lithium ion battery under high voltage, when the mass of the electrolyte additive accounts for more than 1% or less than 0.3% of the sum of the mass of the lithium salt and the organic solvent, the high-temperature performance and the low-temperature performance of the lithium ion battery under high voltage cannot be all optimal, and the inventor finds that the content of the compound a can influence the exertion of the functions of the sulfimide group and the nitrogen-containing heterocyclic group on the compound a through continuous analysis, more specifically, when the content of the additive is less than 0.3%, the nitrogen-containing heterocyclic group on the structural formula 1 is inhibited, so that the low-temperature performance is obviously improved, but the high-temperature performance is weakened; when the content of the additive exceeds 1%, the nitrogen-containing heterocyclic ring in the structural formula 1 can inhibit the sulfonimide group to improve the structural toughness and stability of an SEI film pore, so that the impedance is increased, and the low-temperature performance is weakened, therefore, the invention can control the high-temperature performance and the low-temperature performance of the lithium ion battery to be optimal under high voltage by controlling the mass of the electrolyte additive to be 0.3-1% of the sum of the mass of the lithium salt and the mass of the organic solvent.
Preferably, the lithium salt of the present invention is selected from lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4) Lithium methylsulfonate (LiCH)3SO3) Lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium bis (oxalato) borate (LiC)4BO8) Lithium difluoroborate (LiC)2BF2O4) Lithium difluorophosphate (LiPO)2F2) Lithium difluorobis (oxalato) phosphate (LiDFBP), lithium bis (fluorosulfonylimide) (LiFSI), and lithium bis (trifluoromethylsulfonyl imide) (LiTFSI).
Preferably, the concentration of the lithium salt of the present invention is 0.5-1.5M.
Preferably, the organic solvent of the present invention is at least one of carboxylic acid esters, ethers, chain carbonates, and heterocyclic compounds.
Preferably, the present invention further comprises an auxiliary agent selected from at least one of Vinylene Carbonate (VC), vinylene carbonate (VEC), fluoroethylene carbonate (FEC), Ethylene Sulfite (ES), 1,3 Propane Sultone (PS), and vinyl sulfate (DTD).
Preferably, the auxiliary agent accounts for 0.1-6.0% of the sum of the mass of the lithium salt and the organic solvent, and can further improve the cycle performance, the high-temperature storage performance and the low-temperature discharge performance of the lithium ion battery.
In order to achieve the above object, the present invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode, and the above lithium ion battery electrolyte, wherein the highest charging voltage is 4.4V.
Compared with the prior art, the lithium ion battery comprises the compound shown in the structural formula 1, a stable interface film (SEI) is formed at an electrode/electrolyte interface, the interface film is of a multilayer structure, one surface close to the electrolyte is porous, one surface close to the electrode is dense, the interface film has good lithium ion conduction channels, collapse of the lithium ion channels is not generated in the circulation process, and the circulation performance of the lithium ion battery can be improved; the N-C ═ O structure in the structural formula 1 has good thermal stability, and the introduction of sulfur, nitrogen and oxygen elements enriches the components of an electrode/electrolyte interface film, further improves the thermal stability of the interface film, and further improves the high-temperature storage performance of the lithium ion battery; meanwhile, N-C ═ O is not easy to generate gas at high temperature, and the high-temperature performance of the lithium ion battery can be improved; in addition, the sulfimide structure on the side chain of the structural formula 1 can improve the structural toughness and stability of an SEI film pore, increase the SEI film pore diameter, and inhibit the lithium ion transmission resistance at low temperature, so that the low-temperature performance of the lithium ion battery is improved, and therefore the lithium ion battery has better low-temperature discharge performance, high-temperature storage performance and cycle performance at high voltage.
Preferably, the positive electrode of the present invention is made of a nickel-cobalt-manganese oxide material, which is a high nickel-cobalt-manganese oxide LiNixCoyMn(1-x-y)MzO2Wherein x is more than or equal to 0.6<0.9，x+y<1，0≤z<0.08, M is at least one of Al, Mg, Zr and Ti. Preferably, x is 0.6, y is 0.2, and z is 0.
Preferably, the cathode of the present invention is a carbon cathode material, a silicon cathode material or a silicon-carbon cathode material. Preferably, the cathode of the invention is a silicon-carbon cathode material, wherein the mass fraction of the silicon material in the silicon-carbon cathode material is 10%.
Detailed Description
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention, and should not be taken as a limitation of the present invention.
Example 1
Preparation of the electrolyte
Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) were mixed at a mass ratio of EC: DEC: EMC: 29.16:29.16:29.16 to prepare 87.48g of an organic solvent, and after mixing, 1M lithium hexafluorophosphate (LiPF) was added to the mixture6) After the lithium salt had completely dissolved, 1g of Vinylene Carbonate (VC) and 5g of additive fluoroethylene carbonate (FEC) and 0.5g of compound 1 were added.
The electrolyte compositions of examples 2 to 13 and comparative examples 1 to 3 are shown in Table 1, and the electrolyte preparation methods of examples 2 to 13 and comparative examples 1 to 3 were performed by referring to the preparation method of example 1.
TABLE 1 electrolyte composition of examples and comparative examples
The structural formula of the above compound 7 is as follows:
the electrolytes of examples 1 to 13 and comparative examples 1 to 3 were fabricated into lithium ion batteries with reference to the following lithium battery fabrication method.
The preparation method of the lithium ion battery comprises the following steps:
1. LiNi prepared from nickel cobalt lithium manganate ternary material0.6Co0.2Mn0.2O2Uniformly mixing the conductive agent SuperP, the adhesive PVDF and the Carbon Nano Tubes (CNT) according to the mass ratio of 97.5:1.5:1:1 to prepare lithium ion battery anode slurry with certain viscosity, and coating the lithium ion battery anode slurry on an aluminum foil for a current collector, wherein the coating weight is 324g/m2Drying at 85 ℃ and then carrying out cold pressing; then trimming, cutting into pieces and slitting, drying for 4 hours at 85 ℃ under a vacuum condition after slitting, and welding tabs to prepare the lithium ion battery positive plate meeting the requirements;
2. mixing artificial graphite and silicon according to a mass ratio of 90:10, preparing the mixture into slurry with a conductive agent SuperP, a thickening agent CMC and a binding agent SBR (styrene butadiene rubber emulsion) according to a mass ratio of 95:1.4:1.4:2.2, uniformly mixing, coating the mixed slurry on two sides of a copper foil, and drying at 85 ℃, wherein the coating weight is 168g/m2(ii) a Cutting edges, cutting pieces and strips, drying for 4h at 110 ℃ under a vacuum condition after the strips are cut, and welding tabs to prepare the lithium ion battery negative plate meeting the requirements;
3. the positive plate, the negative plate and the diaphragm prepared by the process are manufactured into a lithium ion battery with the thickness of 4.7mm, the width of 55mm and the length of 60mm by a lamination process, the lithium ion battery is baked for 10 hours in vacuum at the temperature of 75 ℃, and electrolyte is injected. After standing for 24 hours, the mixture was charged to 4.4V with a constant current of 0.lC (180mA), and then charged at a constant voltage of 4.4V until the current dropped to 0.05C (90 mA); then discharging to 3.0V at 0.2C (180mA), repeating the charging and discharging for 2 times, and finally charging the battery to 3.8V at 0.2C (180mA) to complete the preparation of the lithium ion battery.
After the electrolytes in the above examples and comparative examples were prepared into lithium ion batteries, the lithium ion batteries were subjected to a normal temperature cycle test, a high temperature cycle test, a low temperature test, and a high temperature storage test, respectively, under the following test conditions, and the test results are shown in table 2.
And (3) normal-temperature cycle test:
under the condition of normal temperature (25 ℃), carrying out 1.0C/1.0C charging and discharging (the battery discharge capacity is C0) on the lithium ion battery once, wherein the upper limit voltage is 4.4V, and then carrying out 1.0C/1.0C charging and discharging for 500 weeks (the battery discharge capacity is C1) under the condition of normal temperature;
capacity retention rate (C1/C0) × 100%
High-temperature cycle test:
under the condition of over high temperature (45 ℃), carrying out 1.0C/1.0C charging and discharging (the battery discharge capacity is C0) on the lithium ion battery once, wherein the upper limit voltage is 4.4V, and then carrying out 1.0C/1.0C charging and discharging for 300 weeks (the battery discharge capacity is C1) under the normal temperature condition;
capacity retention rate (C1/C0) × 100%
And (3) low-temperature discharge test:
under the condition of normal temperature (25 ℃), carrying out one-time 0.3C/0.3C charging and discharging on the lithium ion battery (the battery discharge capacity is recorded as C0), wherein the upper limit voltage is 4.4V; placing the battery in an oven at-20 ℃ for standing for 4h, discharging at 0.3C, and recording the discharge capacity as C1;
low-temperature discharge rate (C1/C0) × 100%
And (4) high-temperature storage test:
under the condition of normal temperature (25 ℃), carrying out one-time 0.3C/0.3C charging and discharging on the lithium ion battery (the battery discharge capacity is recorded as C0), wherein the upper limit voltage is 4.4V; placing the battery in a 60 ℃ oven for 15 days, taking out the battery, placing the battery in an environment at 25 ℃, discharging at 0.3 ℃ and recording the discharge capacity as C1; then, the lithium ion battery is charged and discharged at 0.3C/0.3C once (the battery discharge capacity is recorded as C2);
capacity retention rate (C1/C0) × 100%
Capacity recovery rate (C2/C0) × 100%
Table 2 results of performance test of lithium ion batteries of examples and comparative examples
As can be seen from table 2, the performance of the lithium ion batteries of the examples is superior to that of the comparative examples, which indicates that the compound of formula 1 of the present invention forms a stable interfacial film at the electrode/electrolyte interface, the interfacial film has a multi-layer structure, one surface near the electrolyte is porous, and one surface near the electrode is dense, the interfacial film has good conductive lithium ion channels, so that the collapse of the lithium ion channels is not generated during the cycling process, which is beneficial to improving the cycling performance of the lithium ion batteries; the N-C ═ O structure in the structural formula 1 has good thermal stability, and the introduction of sulfur, nitrogen and oxygen elements enriches the components of an electrode/electrolyte interface film, further improves the thermal stability of the interface film, and further improves the high-temperature storage performance of the lithium ion battery; meanwhile, N-C-O is not easy to generate gas at high temperature, which is beneficial to improving the high-temperature performance of the lithium ion battery; in addition, the sulfimide structure on the side chain of the structural formula 1 can improve the structural toughness and stability of an SEI film pore, increase the SEI film pore diameter, inhibit the lithium ion transmission resistance at low temperature and facilitate the improvement of the low-temperature performance of the lithium ion battery, so that the electrolyte additive disclosed by the invention is applied to the lithium ion battery, and the lithium ion battery has better high and low temperature performance, storage performance and cycle performance at high voltage.
Comparing examples 5 to 10, it can be seen that when the additive content is less than 0.3%, the high and low temperature performance of the lithium ion battery under high voltage cannot be all optimal, because when the additive content is less than 0.3%, the compound a forms a thin film, and has weak protective effect on the electrode electrolyte interface under high temperature and high voltage, thereby inhibiting the nitrogenous heterocyclic groups from improving the high temperature property, and further leading to better low temperature performance improvement, but weakening the high temperature performance; when the content of the additive exceeds 1%, the high and low temperature performances of the lithium ion battery under high voltage cannot be all optimal, because when the content of the additive exceeds 1%, the formed film of the compound A becomes thick, the sulfonamide group is inhibited to improve the structural toughness and stability of an SEI film pore, so that the impedance is increased, and further the low temperature performance is weakened; meanwhile, as the content of the additive continues to increase to 5%, the effects of the nitrogen-containing heterocycle and the sulfonamide group are inhibited, so that insufficient formation consumption is caused, gas is generated, the electrode/electrolyte interface is affected, and the performance of the lithium ion battery is reduced. Therefore, the mass of the electrolyte additive accounts for the sum of the mass of the lithium salt and the mass of the organic solvent, and the electrolyte additive preferably accounts for 0.3-1%.
Comparing example 1 with comparative example 3, it is known that although the side chain of compound 7 also contains a sulfonimide structure, when compound 7 is applied to a lithium ion battery, the lithium ion battery does not have good low temperature performance, high temperature storage performance and cycle performance at high voltage, because double bonds in the structure of compound 7 are easily polymerized, the resistance of an SEI film is increased, and the low temperature performance of the lithium ion battery cannot be improved; meanwhile, the thermal stability of the N-C structure on the compound 7 is inferior to that of the N-C ═ O structure, which is not favorable for improving the storage performance of the lithium ion battery; and the N-C structure is easy to generate gas at high temperature, and is not beneficial to improving the high-temperature performance of the lithium ion battery.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. An electrolyte additive, comprising a compound of formula 1:
wherein R is1～R4Each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 unsaturated group, substituted or unsubstituted amino, substituted or unsubstituted amido, and substituted or unsubstituted nitrogen heterocyclic group.
2. The electrolyte additive of claim 1 wherein R is1～R4Each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C2-C4 unsaturated group, substituted or unsubstituted amino, substituted or unsubstituted amido, and substituted or unsubstituted nitrogen-containing heterocyclic group.
3. The electrolyte additive according to claim 1, wherein the compound represented by the structural formula 1 is at least one selected from the group consisting of compounds 1 to 6:
4. a lithium ion battery electrolyte, comprising a lithium salt, an organic solvent, and the additive according to any one of claims 1 to 3.
5. The lithium ion battery electrolyte of claim 4 wherein the electrolyte additive is present in an amount of 0.1 to 5% by weight based on the sum of the amounts by weight of the lithium salt and the organic solvent.
6. The lithium ion battery electrolyte of claim 4 wherein the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium methylsulfonate, lithium trifluoromethylsulfonate, lithium dioxalate borate, lithium difluorooxalate borate, lithium difluorophosphate, lithium difluorobis-oxalate phosphate, lithium difluorosulfonimide and lithium bistrifluoromethylsulfonyl imide.
7. The lithium ion battery electrolyte of claim 4 wherein the organic solvent is at least one of a carboxylic acid ester, an ether, a chain carbonate, and a heterocyclic compound.
8. The lithium ion battery electrolyte of claim 4 further comprising an adjuvant selected from at least one of vinylene carbonate, vinylene ethylene carbonate, fluoroethylene carbonate, ethylene sulfite, 1,3 propane sultone, and ethylene sulfate.
9. A lithium ion battery, which comprises a positive electrode and a negative electrode, and is characterized by further comprising the lithium ion battery electrolyte as claimed in any one of claims 4 to 8, and the maximum charging voltage is 4.4V.
10. The lithium ion battery of claim 9, wherein the positive electrode is made of a nickel cobalt manganese oxide material that is a high nickel cobalt manganese oxide LiNixCoyMn(1-x-y)MzO2Wherein x is more than or equal to 0.6<0.9，x+y<1，0≤z<0.08, M is at least one of Al, Mg, Zr and Ti.
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