CN115528307A - Electrolyte and battery comprising same - Google Patents
Electrolyte and battery comprising same Download PDFInfo
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- CN115528307A CN115528307A CN202211229294.6A CN202211229294A CN115528307A CN 115528307 A CN115528307 A CN 115528307A CN 202211229294 A CN202211229294 A CN 202211229294A CN 115528307 A CN115528307 A CN 115528307A
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- electrolyte
- additive
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- substituted
- battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 62
- 239000000654 additive Substances 0.000 claims abstract description 34
- 230000000996 additive effect Effects 0.000 claims abstract description 33
- -1 sulfonyl bipyridine compound Chemical class 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 17
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 9
- 229910013872 LiPF Inorganic materials 0.000 claims description 8
- 101150058243 Lipf gene Proteins 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 4
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 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 2
- 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 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- USGDMCWUHFXPCY-UHFFFAOYSA-M C(C(=O)O)(=O)[O-].P(=O)(O)(O)O.[Li+] Chemical compound C(C(=O)O)(=O)[O-].P(=O)(O)(O)O.[Li+] USGDMCWUHFXPCY-UHFFFAOYSA-M 0.000 claims description 2
- 229910013075 LiBF Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- MRDKYAYDMCRFIT-UHFFFAOYSA-N oxalic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O MRDKYAYDMCRFIT-UHFFFAOYSA-N 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 1
- 230000035939 shock Effects 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 238000007086 side reaction Methods 0.000 abstract description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000003111 delayed effect Effects 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 150000003222 pyridines Chemical class 0.000 abstract description 2
- 125000004434 sulfur atom Chemical group 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007773 negative electrode material Substances 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000007600 charging Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 description 2
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 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 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013161 LiNixCo Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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)
- Secondary Cells (AREA)
Abstract
The invention provides an electrolyte and a battery comprising the electrolyte, wherein the electrolyte comprises a sulfonyl bipyridine compound serving as a first additive, the first additive has a lower LUMO (luteo-LUMO) orbit and a higher HOMO (highest occupied molecular orbital), is easy to oxidize and reduce and generates an interface film on the surfaces of a positive electrode and a negative electrode, and the interface film has the characteristics of high inorganic component content, high stability and rich S atoms and N atoms, can improve the transmission efficiency of lithium ions, and can improve the cycle performance of the battery; meanwhile, the first additive and the pyridine derivative which has formed a film are easy to generate polymerization reaction under the limit working condition of thermal shock, so that the short circuit of the anode and the cathode is delayed, the aggravation of side reaction is blocked, and the thermal shock performance is effectively improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an electrolyte and a battery comprising the electrolyte.
Background
The lithium ion battery is one of main systems in a new energy market due to the advantages of high charging speed, high energy density, high voltage interval and the like, but with the continuous improvement of a voltage system, the stability of the battery is reduced, side reactions between an interface and electrolyte are intensified, so that the service life of the battery is reduced, gas is easily generated in a storage process, and thermal shock is easily caused to lose efficacy. In recent years, pursuit of a battery voltage system and energy density, continuous push-out of a positive electrode material matched with high voltage makes research on an electrolyte matched with the high voltage material important, when the voltage system exceeds the bearing capacity of the material system, excessive side reaction can accelerate consumption of the electrolyte, the service life of a lithium ion battery product is seriously influenced, and potential safety hazards of the battery can be caused, so that development of the electrolyte matched with the high voltage system is an important direction for development of the electrolyte at present.
Disclosure of Invention
In order to match a high-voltage system of the lithium ion battery, the side reaction between an electrode material and electrolyte is inhibited, the consumption of the electrolyte is reduced, and the service life and the safety performance of a lithium ion battery product are improved. The invention provides an electrolyte and a battery comprising the electrolyte; the electrolyte has good normal-high temperature cycle performance, and can also give consideration to the thermal shock performance of the battery.
The purpose of the invention is realized by the following technical scheme:
an electrolyte comprises electrolyte salt, an organic solvent and a first additive, wherein the first additive is a sulfonyl bipyridine compound.
According to an embodiment of the invention, the sulfonyl bipyridine compound is a compound containing sulfonyl and two pyridyl groups, and the two pyridyl groups are directly connected with the sulfonyl respectively.
According to an embodiment of the present invention, the first additive is at least one selected from the group consisting of compounds represented by formula 1:
wherein X 1 、X 2 The same or different, each independently selected from hydrogen, halogen, cyano, substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstitutedSubstituted alkenyl, substituted or unsubstituted alkoxy; when substituted, the substituent is alkyl, halogen, cyano;
n1 and n2 are the same or different and each independently an integer of 0 to 4.
According to an embodiment of the present invention, X 1 、X 2 Same or different, each independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C 6-12 Aryl, substituted or unsubstituted C 1-12 Alkyl, substituted or unsubstituted C 2-12 Alkenyl, substituted or unsubstituted C 1-12 An alkoxy group; if substituted, the substituent is C 1-12 Alkyl, halogen, cyano.
According to an embodiment of the present invention, X 1 、X 2 Same or different, each independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C 6-10 Aryl, substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 2-6 Alkenyl, substituted or unsubstituted C 1-6 An alkoxy group; if substituted, the substituent is C 1-6 Alkyl, halogen, cyano.
According to an embodiment of the present invention, X 1 、X 2 Same or different, each independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C 6-8 Aryl, substituted or unsubstituted C 1-3 Alkyl, substituted or unsubstituted C 2-3 Alkenyl, substituted or unsubstituted C 1-3 An alkoxy group; if substituted, the substituent is C 1-3 Alkyl, halogen, cyano.
According to an embodiment of the present invention, X 1 、X 2 Identical or different, each independently selected from hydrogen, trifluoromethyl, fluorine, cyano.
According to an embodiment of the invention, n1, n2 are the same or different and are each independently 0, 1, 2, 3 or 4.
According to an embodiment of the invention, the first additive is selected from at least one of the following compounds A1 to A5:
According to an embodiment of the invention, the first additive is present in an amount of 0.5wt% to 3wt%, such as 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.2wt%, 1.3wt%, 1.5wt%, 1.6wt%, 1.8wt%, 2wt%, 2.2wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.8wt%, or 3wt%, based on the total mass of the electrolyte.
According to embodiments of the present invention, the first additive may be obtained after being purchased commercially, or may be prepared by methods known in the art.
According to an embodiment of the present invention, the electrolyte salt is selected from electrolyte lithium salts.
According to an embodiment of the invention, the electrolyte lithium salt is selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium difluorophosphate (LiPF) 2 O 2 ) Lithium difluorobis (oxalato) phosphate (LiPF) 2 (C 2 O 4 ) 2 ) Lithium tetrafluoro oxalate phosphate (LiPF) 4 C 2 O 4 ) Lithium oxalate phosphate (LiPO) 2 C 2 O 4 ) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiODFB), lithium tetrafluoroborate (LiBF) 4 ) Lithium bis (fluorosulfonyl) imide (LiTFSI) and lithium bis (fluorosulfonyl) imide (LiFSI)And (4) seed preparation.
According to an embodiment of the invention, the electrolyte salt is present in an amount of 10wt% to 15wt%, such as 10wt%, 11wt%, 12wt%, 13wt%, 14wt% or 15wt%, based on the total mass of the electrolyte.
According to an embodiment of the present invention, the organic solvent is selected from at least one of Ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC), ethyl Propionate (EP), propyl Propionate (PP), ethyl Acetate (EA), ethyl n-butyrate (EB) and γ -butyrolactone (GBL).
According to an embodiment of the invention, the content of the organic solvent is 60wt% to 90wt%, for example 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt% or 90wt%, based on the total mass of the electrolyte.
According to an embodiment of the present invention, the electrolyte further includes a second additive selected from at least one of fluoroethylene carbonate (FEC), vinylene Carbonate (VC), 1, 3-Propane Sultone (PS), vinyl sulfate (DTD), methylene Methanedisulfonate (MMDS), propylene Sultone (PST), maleic anhydride, diethanol anhydride, succinic anhydride, succinonitrile (SN), adiponitrile (ADN), ethylene glycol bis (propionitrile) ether (EGBE), and Hexanetrinitrile (HTCN).
According to an embodiment of the invention, the second additive is present in an amount of 1wt% to 15wt%, preferably 5wt% to 13wt%, e.g. 1wt%, 1.2wt%, 1.3wt%, 1.5wt%, 1.6wt%, 1.8wt%, 2wt%, 2.2wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.8wt%, 3wt%, 3.3wt%, 3.5wt%, 3.8wt%, 4wt%, 4.2wt%, 4.5wt%, 4.8wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt% or 15wt% based on the total mass of the electrolyte.
The invention also provides a preparation method of the electrolyte, which comprises the following steps:
the electrolyte is obtained after mixing an organic solvent, an electrolyte salt, a first additive and optionally a second additive.
The invention also provides a battery, which comprises the electrolyte.
According to an embodiment of the invention, the battery is a lithium ion battery.
According to an embodiment of the present invention, the battery further includes a positive electrode sheet containing a positive electrode active material, a negative electrode sheet containing a negative electrode active material, and a separator.
According to an embodiment of the present invention, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer coated on one or both surfaces of the positive electrode current collector, the positive electrode active material layer including a positive electrode active material, a conductive agent, and a binder.
According to an embodiment of the present invention, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer coated on one or both surfaces of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a conductive agent, and a binder.
According to the embodiment of the invention, the mass percentage of each component in the positive electrode active material layer is as follows: 80-99.8 wt% of positive active material, 0.1-10 wt% of conductive agent and 0.1-10 wt% of binder.
Preferably, the positive electrode active material layer comprises the following components in percentage by mass: 90-99.6 wt% of positive active material, 0.2-5 wt% of conductive agent and 0.2-5 wt% of binder.
According to the embodiment of the invention, the mass percentage of each component in the negative electrode active material layer is as follows: 80-99.8 wt% of negative electrode active material, 0.1-10 wt% of conductive agent and 0.1-10 wt% of binder.
Preferably, the negative electrode active material layer comprises the following components in percentage by mass: 90 to 99.6 weight percent of negative electrode active material, 0.2 to 5 weight percent of conductive agent and 0.2 to 5 weight percent of binder.
According to an embodiment of the present invention, the conductive agent is selected from at least one of conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, and metal powder.
According to an embodiment of the present invention, the binder is selected from at least one of sodium carboxymethylcellulose, styrene-butadiene latex, polytetrafluoroethylene, polyethylene oxide.
According to an embodiment of the present invention, the negative electrode material is selected from nano silicon (Si), silicon oxygen negative electrode material (SiO) x (0<x<2) Silicon carbon negative electrode material, artificial graphite, natural graphite, mesocarbon microbeads, hard carbon, soft carbon, lithium metal and lithium titanate.
According to an embodiment of the present invention, the positive active material is selected from lithium transition metal composite oxides selected from LiMO 2 (M＝Ni、Co、Mn)、LiMn 2 O 4 、LiMPO 4 (M＝Fe、Mn、Co)、LiNi x Mn 1-x O 2 (M＝Co、Mn)、LiNixCo y M 1 x y O 2 Wherein x is more than or equal to 0, y is less than or equal to 1, and x + y is less than or equal to 1; wherein M is one or more of Mg, zn, ga, ba, al, fe, cr, sn, V, mn, sc, ti, nb, mo, zr, ta, W, B, F and Si.
Advantageous effects
The invention provides an electrolyte and a battery comprising the electrolyte, wherein the electrolyte comprises a sulfonyl bipyridine compound serving as a first additive, the first additive has a lower LUMO (luteo-LUMO) orbit and a higher HOMO (highest occupied molecular orbital), is easy to oxidize and reduce and generates an interface film on the surfaces of a positive electrode and a negative electrode, and the interface film has the characteristics of high inorganic component content, high stability and rich S atoms and N atoms, can improve the transmission efficiency of lithium ions, and can improve the cycle performance of the battery; meanwhile, the first additive and the formed pyridine derivative are easy to generate polymerization reaction under the limit working condition of thermal shock, so that the short circuit of the anode and the cathode is delayed, the aggravation of side reaction is blocked, and the thermal shock performance is effectively improved.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
In the description of the present invention, it should be noted that the terms "first", "second", etc. are used for descriptive purposes only and do not indicate or imply relative importance.
The preparation method of the lithium ion battery comprises the following steps:
[ preparation of Positive electrode sheet ]
Mixing a positive electrode active material Lithium Cobaltate (LCO), a binder polyvinylidene fluoride (PVDF), conductive carbon black and a single-walled carbon nanotube according to a weight ratio of 97.2; uniformly coating the positive electrode slurry on a current collector aluminum foil; baking the coated aluminum foil in 5 sections of baking ovens with different temperature gradients, drying the aluminum foil in a baking oven at 120 ℃ for 8 hours, and rolling and cutting to obtain the required positive plate.
[ preparation of negative electrode sheet ]
Mixing artificial graphite serving as a negative electrode active material, sodium carboxymethyl cellulose (CMC-Na) serving as a thickening agent, styrene butadiene rubber serving as a binder and acetylene black serving as a conductive agent according to a weight ratio of 97; uniformly coating the negative electrode slurry on the high-strength carbon-coated copper foil to obtain a pole piece; and (3) airing the obtained pole piece at room temperature, transferring the pole piece to an oven at 80 ℃ for drying for 10h, and then rolling and slitting to obtain the negative pole piece.
[ preparation of electrolyte ]
In a glove box filled with inert gas (H) 2 O<10ppm，O 2 <5 ppm), ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate were mixed at a mass ratio of EC: PC: DEC =1 = 2 6 ) And obtaining the basic electrolyte after the water and free acid are qualified through detection. Addition of the base electrolyte with the additives of Table 1The electrolytes of the respective examples and comparative examples were obtained with the same contents of the first additive and the second additive.
[ production of Battery ]
And (3) stacking the prepared positive plate, the diaphragm (a PP film with the thickness of 9 microns) and the negative plate in sequence, ensuring that the diaphragm is positioned between the positive plate and the negative plate to play a role of isolation, putting the bare cell into an aluminum-plastic film outer package, injecting the prepared electrolyte into the dried battery, packaging, standing, forming, shaping and grading to finish the preparation of the lithium ion soft package battery.
Examples 1 to 10 and comparative examples 1 to 4 were prepared according to the above-mentioned preparation method.
TABLE 1 composition of electrolyte of batteries of examples and comparative examples
| First additive and content | Second additive and content | |
| Example 1 | 0.5wt% of Compound A1 | FEC:8.0wt％/PS:3.0wt％ |
| Example 2 | Compound A1:1.0wt% | FEC:8.0wt％/PS:3.0wt％ |
| Example 3 | Compound A1:2.0wt% | FEC:8.0wt％/PS:3.0wt％ |
| Example 4 | Compound A1:3.0wt% | FEC:8.0wt％/PS:3.0wt％ |
| Example 5 | Compound A2:1.0wt% | FEC:8.0wt％/PS:3.0wt％ |
| Example 6 | Compound A3:1.0wt% | FEC:8.0wt％/PS:3.0wt％ |
| Example 7 | Compound A4:1.0wt% | FEC:8.0wt％/PS:3.0wt％ |
| Example 8 | Compound A5:1.0wt% | FEC:8.0wt％/PS:3.0wt％ |
| Example 9 | Compound A1:1.0wt% | FEC:8.0wt％ |
| Example 10 | Compound A1:1.0wt% | PS:3.0wt％ |
| Comparative example 1 | / | / |
| Comparative example2 | / | FEC:8.0wt％ |
| Comparative example 3 | / | PS:3.0wt％ |
| Comparative example 4 | / | FEC:8.0wt％/PS:3.0wt％ |
Performance testing
The lithium ion batteries and the electrolytes thereof obtained in the above examples and comparative examples were subjected to a relevant performance test.
(1) High-temperature cycle performance test: at 45 ℃, the battery after capacity grading is charged to 4.48V at constant current and constant voltage of 0.7C, the current is cut off at 0.05C, then the battery is discharged to 3.0V at constant current of 0.5C, and the capacity retention rate in 500 weeks is calculated after the battery is charged and discharged for 500 cycles according to the circulation, wherein the calculation formula is as follows: cycle capacity retention rate (%) at 500 weeks (= (cycle discharge capacity at 500 weeks/first cycle discharge capacity) × 100%.
(2) And (3) testing the normal-temperature cycle performance: at 25 ℃, the battery after capacity grading is charged to 4.48V at constant current and constant voltage of 0.7C, the current is cut off at 0.05C, then the battery is discharged to 3.0V at constant current of 0.5C, and the capacity retention rate at 500 weeks is calculated after the battery is charged and discharged for 500 cycles according to the cycle, wherein the calculation formula is as follows: cycle capacity retention (%) at 500 weeks (= cycle discharge capacity at 500 weeks/first cycle discharge capacity) × 100%.
(3) Thermal shock performance: discharging to 3.0V at 25 ℃ at a given current of 0.2C; standing for 5min; charging to 4.48V at a charging current of 0.2C, and changing to 4.48V constant-voltage charging when the cell voltage reaches 4.48V until the charging current is less than or equal to a given cutoff current of 0.05C; and (3) placing the battery cell into an oven after standing for 1h, raising the temperature of the oven to 135 +/-2 ℃ at the speed of 5 +/-2 ℃/min, keeping for 30min, and stopping, wherein the judgment standard is that the battery cell does not catch fire and does not explode.
Table 2 results of performance test of batteries of examples and comparative examples
As can be seen from a comparison of the test results of comparative example 4 and examples 1 to 10 in Table 2: in the embodiment, the first additive is added, so that the normal-temperature and high-temperature cycle performance and the thermal shock performance of the lithium ion battery can be effectively improved.
Comparison of comparative examples 1 to 4 with examples 1 to 10 shows that: the thermal shock performance of the battery can be obviously improved by adding the first additive, and the thermal shock performance of the battery is improved more obviously along with the increase of the addition amount of the first additive, and the possible reason is that under the thermal shock working condition, the anode and the cathode can be isolated by the accelerated polymerization of the first additive, and meanwhile, the blocking effect is more obvious as the addition amount of the first additive is higher, so that the thermal shock performance of the battery is effectively improved.
Comparison of comparative example 4 with examples 1 to 3 shows that: the first additive is in a proper amount range (0.5-3 wt%) to improve the cycle performance, the cycle performance is not obviously improved when the addition amount is excessive, and the cycle performance is possibly caused by overlarge polarization due to the increase of the addition amount;
in conclusion, the electrolyte provided by the invention can effectively improve the cycle and thermal shock performance and has extremely high application potential.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The electrolyte is characterized by comprising electrolyte salt, an organic solvent and a first additive, wherein the first additive is a sulfonyl bipyridine compound.
2. The electrolyte of claim 1, wherein the sulfonyl bipyridine compound is a compound containing a sulfonyl group and two pyridyl groups, and the two pyridyl groups are directly connected to the sulfonyl group respectively.
3. The electrolyte of claim 1, wherein the first additive is at least one selected from compounds represented by formula 1:
wherein X 1 、X 2 The same or different, each is independently selected from hydrogen, halogen, cyano, substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy; when substituted, the substituent is alkyl, halogen, cyano;
n1 and n2 are the same or different and each independently an integer of 0 to 4.
4. The electrolyte of claim 1, wherein the first additive is selected from at least one of the following compounds A1 to A5:
5. the electrolyte of claim 1, wherein the first additive is present in an amount of 0.5 to 3wt% based on the total mass of the electrolyte.
6. The electrolyte of claim 1, wherein the electrolyte is characterized byThe electrolyte salt is selected from electrolyte lithium salts selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium difluorophosphate (LiPF) 2 O 2 ) Lithium difluorobis (oxalato) phosphate (LiPF) 2 (C 2 O 4 ) 2 ) Lithium tetrafluoro oxalate phosphate (LiPF) 4 C 2 O 4 ) Lithium oxalate phosphate (LiPO) 2 C 2 O 4 ) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiODFB), lithium tetrafluoroborate (LiBF) 4 ) At least one of lithium bis (fluorosulfonyl) imide (LiTFSI) and lithium bis (fluorosulfonyl) imide (LiFSI); and/or the content of the electrolyte salt accounts for 10-15 wt% of the total mass of the electrolyte.
7. The electrolyte of claim 1, wherein the organic solvent is selected from at least one of Ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC), ethyl Propionate (EP), propyl Propionate (PP), ethyl Acetate (EA), ethyl n-butyrate (EB), and gamma-butyrolactone (GBL); and/or the content of the organic solvent accounts for 60-90 wt% of the total mass of the electrolyte.
8. The electrolyte of claim 1, further comprising a second additive selected from at least one of fluoroethylene carbonate (FEC), vinylene Carbonate (VC), 1, 3-Propane Sultone (PS), vinyl sulfate (DTD), methylene Methanedisulfonate (MMDS), propylene Sultone (PST), maleic anhydride, diethanol anhydride, succinic anhydride, succinonitrile (SN), adiponitrile (ADN), ethylene glycol bis (propionitrile) ether (EGBE), and Hexanetrinitrile (HTCN).
9. The electrolyte of claim 8, wherein the second additive is present in an amount of 1wt% to 15wt% based on the total mass of the electrolyte.
10. A battery comprising the electrolyte of any one of claims 1-9.
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