CN114552015B - 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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- CN114552015B CN114552015B CN202210184435.0A CN202210184435A CN114552015B CN 114552015 B CN114552015 B CN 114552015B CN 202210184435 A CN202210184435 A CN 202210184435A CN 114552015 B CN114552015 B CN 114552015B
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- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 100
- 239000003792 electrolyte Substances 0.000 title claims abstract description 38
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 125000003368 amide group Chemical group 0.000 claims abstract description 4
- 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
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 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
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000005678 chain carbonates Chemical class 0.000 claims description 2
- 229940125904 compound 1 Drugs 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 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
- 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
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims 1
- 229940125782 compound 2 Drugs 0.000 claims 1
- 229940126214 compound 3 Drugs 0.000 claims 1
- 229940125898 compound 5 Drugs 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 18
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 24
- 238000007599 discharging Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 102000004310 Ion Channels Human genes 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 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
- 230000005540 biological transmission Effects 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 238000005520 cutting process Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000000203 mixture Substances 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
- 238000009966 trimming Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 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
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 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 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000003475 lamination Methods 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
- 239000007774 positive electrode material Substances 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
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 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
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- 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, lithium ion battery electrolyte and a lithium ion battery, wherein the electrolyte additive comprises a compound shown in a structural formula 1:wherein R is 1 ～R 4 Each 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, substituted or unsubstituted nitrogen-containing heterocyclic group. The electrolyte additive is applied to a 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, 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 a plurality of fields of mobile phones, computers, cameras, electric automobiles and the like. However, with the continuous development of science and technology, various application fields put higher demands on the performance of lithium ion batteries. Among them, the most urgent is to increase the energy density of the lithium ion battery on the premise of ensuring safety. At present, the energy density of a lithium ion battery is often improved by increasing the charge cut-off voltage, but at high voltage, some problems exist: when the voltage reaches 4.4V, the common carbonate-based electrolyte starts to generate oxidative decomposition side reaction on the surface of the positive electrode material to influence the performance of the lithium ion battery, and meanwhile, the nickel-cobalt-manganese ternary material can generate irreversible H2-H3 phase change to cause excessive metal dissolution, the side reaction of the electrolyte is aggravated, the gas production of the battery is increased, and the performance of the battery is suddenly attenuated. In particular, at low temperature, the impedance in the lithium ion battery is increased, and the low-temperature discharge performance of the lithium ion battery is obviously insufficient. Therefore, how to ensure the low-temperature discharge performance, the high-temperature storage performance and the cycle performance of the lithium ion battery on the premise of improving the cut-off voltage is the key point of research.
Therefore, an electrolyte additive, a lithium ion battery electrolyte 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.
The invention also aims to provide a lithium ion battery which has better low-temperature discharge performance, high-temperature storage performance and cycle performance under a high-voltage system.
To achieve the above object, the present invention provides an electrolyte additive comprising a compound represented by structural formula 1:
wherein R is 1 ～R 4 Each 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, substituted or unsubstituted nitrogen-containing heterocyclic group.
Compared with the prior art, the compound shown in the structural formula 1 forms a stable interface film (SEI) at the interface of the electrode and the electrolyte, and the interface film is of a multi-layer structure, and one surface close to the electrolyte is porous, so that lithium ions are transmitted; the surface close to the electrode is compact, which is favorable for inhibiting side reaction of electrolyte, and the interface film has good conductive lithium ion channels, so that collapse of the lithium ion channels is not generated in the circulating process, and the circulating 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 enriches the components of the electrode/electrolyte interface film, so that the thermal stability of the interface film is further improved, and the high-temperature storage performance of the lithium ion battery is further improved; meanwhile, N-C=O is not easy to generate gas at high temperature, so that the high-temperature performance of the lithium ion battery is improved; in addition, the structure toughness and stability of SEI film holes can be improved by the sulfimide structure on the side chain of the structural formula 1, the aperture of the SEI film is increased, the lithium ion transmission resistance at low temperature is restrained, and the low-temperature discharge performance of a lithium ion battery is improved, so that 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 at high voltage.
Preferably, R of the present invention 1 ～R 4 Each 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, substituted or unsubstituted nitrogen-containing heterocyclic group.
Preferably, the compound represented by the structural formula 1 of the present invention is at least one selected from the group consisting of compounds 1 to 6:
in order to achieve the above purpose, the invention provides a lithium ion battery electrolyte, which comprises lithium salt, an organic solvent and the electrolyte additive.
Compared with the prior art, the electrolyte additive is included in the lithium ion battery electrolyte, so that the lithium ion battery electrolyte is applied to a lithium ion battery, and the lithium ion battery has good low-temperature discharge performance, high-temperature storage performance and cycle performance under high voltage.
Preferably, the electrolyte additive of the present invention accounts for 0.1 to 5% of the total mass of the lithium salt and the organic solvent.
The inventor of the application found in the experimental process 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 mass of the organic solvent, the high-low temperature performance of the lithium ion battery under high voltage is not optimal, and the inventor finds that the effect of the sulfimide group and the nitrogen-containing heterocyclic group on the compound a is affected by the high-low-temperature content of 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 improvement of the low-temperature performance is obvious, but the high-temperature performance is weakened; when the content of the additive exceeds 1%, the nitrogen-containing heterocycle in the structural formula 1 can inhibit the sulfimide group from improving the structural toughness and stability of the SEI film hole, so that the impedance is increased, and the low-temperature performance is weakened, therefore, the inventor can control the high-temperature and low-temperature performance of the lithium ion battery to be kept optimal 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) 3 SO 3 ) Lithium triflate (LiCF) 3 SO 3 ) Lithium dioxalate borate (LiC) 4 BO 8 ) Lithium difluorooxalato borate (LiC) 2 BF 2 O 4 ) Lithium difluorophosphate (LiPO) 2 F 2 ) At least one of lithium difluorobis (oxalato) phosphate (LiDFBP), lithium difluorosulfonimide (LiFSI), and lithium bistrifluoromethylsulfonimide (LiTFSI).
Preferably, the concentration of the lithium salt of the present invention is 0.5 to 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 ethylene sulfate (DTD).
Preferably, the auxiliary agent accounts for 0.1-6.0% of the sum of the mass of the lithium salt and the mass of 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 purpose, the invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode, and the 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, wherein a stable interface film (SEI) is formed at an electrode/electrolyte interface, the interface film is of a multi-layer structure, one surface close to the electrolyte is porous, and the other surface close to the electrode is compact, and has good lithium ion conduction channels, so that collapse of the lithium ion channels is not generated in the circulating process, and the circulating 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 enriches the components of the electrode/electrolyte interface film, so that the thermal stability of the interface film is further improved, and the high-temperature storage performance of the lithium ion battery is improved; meanwhile, N-C=O is not easy to produce gas at high temperature, so that the high-temperature performance of the lithium ion battery can be improved; in addition, the structure of the sulfonyl imide on the side chain of the structural formula 1 can improve the structural toughness and stability of SEI film holes, increase the aperture of the SEI film 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 invention is made of nickel cobalt manganese oxide material, the nickel cobalt manganese oxide material is high nickelCobalt manganese oxide LiNi x Co y Mn (1-x-y) M z O 2 Wherein 0.6.ltoreq.x<0.9，x+y<1，0≤z<0.08, M is at least one of Al, mg, zr and Ti. Preferably, x=0.6, y=0.2, and z=0 are employed.
Preferably, the negative electrode of the invention is a carbon negative electrode material, a silicon negative electrode material or a silicon carbon negative electrode material. Preferably, the anode of the invention is a silicon-carbon anode material, wherein the mass fraction of the silicon material in the silicon-carbon anode material is 10%.
Detailed Description
For a better description of the objects, technical solutions and advantageous effects 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 limiting the present invention.
Example 1
Preparation of electrolyte
Mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and ethylmethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=29.16:29.16:29.16 to obtain 87.48g of organic solvent, mixing, and adding 1M lithium hexafluorophosphate (LiPF) 6 ) After complete dissolution of the lithium salt, 1g of Vinylene Carbonate (VC) and 5g of additive fluoroethylene carbonate (FEC) and 0.5g of compound 1 are 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 with reference to the preparation method of example 1.
Table 1 electrolyte compositions 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 prepared into lithium ion batteries by referring to the following lithium battery preparation methods.
The preparation method of the lithium ion battery comprises the following steps:
1. ternary material LiNi of nickel cobalt lithium manganate 0.6 Co 0.2 Mn 0.2 O 2 Uniformly mixing a conductive agent SuperP, an adhesive PVDF and a Carbon Nano Tube (CNT) according to a 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 amount is 324g/m 2 Drying at 85 ℃ and then cold pressing; then trimming, cutting pieces and slitting, drying at 85 ℃ for 4 hours under 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 slurry with a conductive agent SuperP, a thickening agent CMC and an adhesive 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 ℃ to obtain a coating weight of 168g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Trimming, cutting pieces, splitting, drying at 110 ℃ for 4 hours under vacuum condition after splitting, and welding tabs to prepare a lithium ion battery negative plate meeting the requirements;
3. the positive plate, the negative plate and the diaphragm prepared according to the process are manufactured into a lithium ion battery with the thickness of 4.7mm, the width of 55mm and the length of 60mm through a lamination process, and the lithium ion battery is baked for 10 hours at the temperature of 75 ℃ in vacuum and injected with electrolyte. After 24 hours of standing, charge to 4.4V with a constant current of 0.lc (180 mA), then charge to a current drop of 0.05C (90 mA) with a constant voltage of 4.4V; then discharging to 3.0V at 0.2C (180 mA), repeating the charging and discharging for 2 times, and finally charging the battery to 3.8V at 0.2C (180 mA) to complete the preparation of the lithium ion battery.
After the electrolytes in the above examples and comparative examples were fabricated 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, according to the following test conditions, and the test results are shown in table 2.
And (3) normal temperature cyclic test:
charging and discharging the lithium ion battery at 1.0C/1.0C at normal temperature (25 ℃) to obtain a battery discharge capacity of C0, wherein the upper limit voltage is 4.4V, and then charging and discharging the lithium ion battery at 1.0C/1.0C at normal temperature for 500 weeks (the battery discharge capacity of C1);
capacity retention = (C1/C0) ×100%
High temperature cycle test:
charging and discharging the lithium ion battery at 1.0C/1.0C once (the discharge capacity of the battery is C0) under the condition of overhigh temperature (45 ℃), wherein the upper limit voltage is 4.4V, and then charging and discharging the lithium ion battery at 1.0C/1.0C for 300 weeks (the discharge capacity of the battery is C1) under the condition of normal temperature;
capacity retention = (C1/C0) ×100%
Low temperature discharge test:
charging and discharging the lithium ion battery at 0.3C/0.3C once (the discharge capacity of the battery is recorded as C0) under the condition of normal temperature (25 ℃), and the upper limit voltage is 4.4V; placing the battery in an oven at the temperature of minus 20 ℃ for 4 hours, discharging at 0.3C, and recording the discharge capacity as C1;
low temperature discharge rate= (C1/C0) 100%
High temperature storage test:
charging and discharging the lithium ion battery at 0.3C/0.3C once (the discharge capacity of the battery is recorded as C0) under the condition of normal temperature (25 ℃), and the upper limit voltage is 4.4V; placing the battery in a 60 ℃ oven for 15d, taking out the battery, placing the battery in a 25 ℃ environment, discharging at 0.3C, and recording the discharge capacity as C1; then charging and discharging the lithium ion battery once at 0.3C/0.3C (the discharge capacity of the battery is recorded as C2);
capacity retention = (C1/C0) ×100%
Capacity recovery = (C2/C0) ×100%
Table 2 results of performance tests of lithium ion batteries of examples and comparative examples
As can be seen from table 2, each performance of the lithium ion battery of the example is superior to that of the comparative example, which shows that the compound of formula 1 of the present invention forms a stable interfacial film at the electrode/electrolyte interface, the interfacial film is a multi-layer structure, the side close to the electrolyte is porous, the side close to the electrode is dense, the interfacial film has good conductive lithium ion channels, so that 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 battery; the N-C=O structure in the structural formula 1 has good thermal stability, and the introduction of sulfur, nitrogen and oxygen enriches the components of the electrode/electrolyte interface film, so that the thermal stability of the interface film is further improved, and the high-temperature storage performance of the lithium ion battery is further improved; meanwhile, N-C=O is not easy to generate gas at high temperature, so that the high-temperature performance of the lithium ion battery is improved; in addition, the structure toughness and stability of SEI film holes can be improved by the sulfimide structure on the side chain of the structural formula 1, the aperture of the SEI film is increased, the lithium ion transmission resistance at low temperature is restrained, and the improvement of the low-temperature performance of a lithium ion battery is facilitated, so that the electrolyte additive is applied to the lithium ion battery, and the lithium ion battery has better high-low temperature performance, storage performance and cycle performance at high voltage.
Comparing examples 5 to 10, it was found that the high and low temperature performance of the lithium ion battery at high voltage was not optimal when the additive content was less than 0.3%, because the compound a formed a thin film and the protective effect on the electrode electrolyte interface was weak at high temperature and high voltage, thereby inhibiting the improvement of the high temperature characteristic of the nitrogen-containing heterocyclic group, resulting in better improvement of the low temperature performance but weakening of the high temperature performance; when the content of the additive exceeds 1%, the high-low temperature performance of the lithium ion battery under high voltage cannot be optimized, because when the content of the additive exceeds 1%, the film formation of the compound A becomes thick, the sulfonamide group can be inhibited from improving the structural toughness and stability of SEI film holes, the impedance is increased, and the low-temperature performance is weakened; meanwhile, as the content of the additive continues to increase to 5%, the actions of the nitrogen-containing heterocycle and the sulfonamide group are inhibited, so that insufficient formation consumption is caused, gas generation is caused, an electrode/electrolyte interface is affected, and the performance of the lithium ion battery is further reduced. The mass of the electrolyte additive of the present application is thus preferably 0.3 to 1% of the sum of the mass of the lithium salt and the mass of the organic solvent.
Comparing example 1 with comparative example 3, it is known that although the side chain of compound 7 also contains a sulfonimide structure, the application of compound 7 to lithium ion batteries 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, resulting in an increase in SEI film resistance, and thus cannot improve the low temperature performance of lithium ion batteries; meanwhile, the thermal stability of the N-C structure on the compound 7 is poorer than that of the N-C=O structure, so that the storage performance of the lithium ion battery is not improved; and the N-C structure is easy to produce gas at high temperature, which 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 for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been 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 to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. A lithium ion battery electrolyte comprising a lithium salt, an organic solvent and an electrolyte additive, wherein the electrolyte additive comprises a compound or compound 2 or compound 3 shown in structural formula I:
wherein R is 1 Is selected from unsubstituted C1-C4 alkyl, R 2 ~R 3 Each independently selected from hydrogen, unsubstituted C1-C4 alkyl, R 4 Selected from hydrogen, unsubstituted amide groups.
2. The lithium-ion battery electrolyte according to claim 1, wherein the compound represented by the structural formula I is at least one selected from the group consisting of compound 1, compound 4, compound 5, and compound 6:
。
3. the lithium ion battery electrolyte according to claim 1, wherein 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.
4. The lithium ion battery electrolyte of claim 1, wherein the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium methylsulfonate, lithium trifluoromethylsulfonate, lithium dioxaborate, lithium difluorooxalato borate, lithium difluorophosphate, lithium difluorobis-oxalato phosphate, lithium bis-fluorosulfonyl imide, and lithium bis-trifluoromethylsulfonyl imide.
5. The lithium ion battery electrolyte of claim 1, wherein the organic solvent is at least one of carboxylic acid esters, ethers, chain carbonates, and heterocyclic compounds.
6. The lithium ion battery electrolyte of claim 1, further comprising an auxiliary agent selected from at least one of vinylene carbonate, fluoroethylene carbonate, ethylene sulfite, 1,3 propane sultone, and ethylene sulfate.
7. A lithium ion battery comprising a positive electrode and a negative electrode, and further comprising the lithium ion battery electrolyte according to any one of claims 1 to 6, wherein the highest charging voltage is 4.4V.
8. The lithium-ion battery of claim 7, wherein the positive electrode is made of a nickel cobalt manganese oxide material that is high nickel cobalt manganese oxide LiNi x Co y Mn (1-x-y) M z O 2 Wherein 0.6.ltoreq.x<0.9，x+y<1，0≤z<0.08, M is at least one of Al, mg, zr and Ti.
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