CN116742126A - Lithium ion battery electrolyte and lithium ion battery using same - Google Patents
Lithium ion battery electrolyte and lithium ion battery using same Download PDFInfo
- Publication number
- CN116742126A CN116742126A CN202310758253.4A CN202310758253A CN116742126A CN 116742126 A CN116742126 A CN 116742126A CN 202310758253 A CN202310758253 A CN 202310758253A CN 116742126 A CN116742126 A CN 116742126A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- ion battery
- electrolyte
- lithium
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 101
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 86
- 239000000654 additive Substances 0.000 claims abstract description 45
- 230000000996 additive effect Effects 0.000 claims abstract description 43
- -1 halogenated toluene sulfonyl hydrazone compound Chemical class 0.000 claims abstract description 25
- 125000005597 hydrazone group Chemical group 0.000 claims abstract description 8
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000005678 chain carbonates Chemical class 0.000 claims description 3
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 3
- RBBXSUBZFUWCAV-UHFFFAOYSA-N ethenyl hydrogen sulfite Chemical compound OS(=O)OC=C RBBXSUBZFUWCAV-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- 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 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 150000007857 hydrazones Chemical class 0.000 claims 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 238000007600 charging Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- 239000001307 helium Substances 0.000 description 7
- 229910052734 helium Inorganic materials 0.000 description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- HXBVONWDRVMGCI-UHFFFAOYSA-N 1,3-dioxol-2-one ethene Chemical compound C=C.C1(OC=CO1)=O HXBVONWDRVMGCI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- 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 lithium ion battery electrolyte and a lithium ion battery using the same, and belongs to the field of lithium ion batteries. The lithium ion battery electrolyte comprises an additive A, wherein the additive A is a halogenated toluene sulfonyl hydrazone compound, and the halogenated toluene sulfonyl hydrazone compound contains at least one compound shown in the following structural formula I. In the lithium ion electrolyte, the additive A halogenated toluene sulfonyl hydrazone compound has good electrochemical stability, and can form a stable interface film on the surface of an electrode, so that the interface film component is not easy to decompose; meanwhile, the sulfonyl hydrazone group in the additive A can react with an acidic substance to inhibit HF from damaging the electrode material. The lithium ion battery using the electrolyte has the advantages of long cycle life, less gas production at high temperature cycle and high capacity retention rate, so that the lithium ion battery has excellent high-temperature charging performance and cycle life.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to lithium ion battery electrolyte and a lithium ion battery using the same.
Background
After commercializing lithium ion batteries in sony in 1991, lithium ion batteries bring great convenience to life of people, such as application in mobile phones, energy storage street lamps, electric tools, electric motorcycles, electric automobiles and the like. The lithium ion battery consists of a positive electrode, a negative electrode, a diaphragm, electrolyte and the like, wherein the electrolyte is one of four key constituent materials of the lithium battery, and serves as a carrier for lithium ions to move between the positive electrode and the negative electrode of the lithium battery, so that the electrolyte is one of key factors influencing the performance of the lithium battery.
The lithium ion battery electrolyte mainly comprises lithium salt, a nonaqueous organic solvent and an additive. In the first charge and discharge process of the lithium ion battery, the electrolyte is subjected to oxidation reaction on the positive electrode interface to form a passivation layer covering the surface of the positive electrode, namely a CEI film of the positive electrode interface; on the interface of the negative electrode, the electrolyte undergoes a reduction reaction to form a passivation layer which covers the surface of the negative electrode, namely the SEI film of the interface of the negative electrode. Along with the extension of service life (cycle life and high-temperature storage life), the interface membrane structure of the positive electrode and the negative electrode of the lithium ion battery can be damaged, so that electrolyte is contacted with positive and negative electrode materials to generate oxidation-reduction reaction, gas (carbon monoxide, carbon dioxide, methane, ethane, ethylene and the like) is generated, the lithium ion battery is further degraded, and the service life of the lithium ion battery is shortened.
Therefore, proper film forming additives are selected to form a compact and stable anode-cathode interface film, and the reduction of side reactions of electrolyte and electrode materials is particularly important. In the prior art, a conventional additive fluorocarbonate compound is singly used as a film forming additive, and decomposition reaction can occur under alkaline conditions and high-temperature conditions to generate hydrofluoric acid (HF), and the HF can damage the performance of an electrode material, so that the lithium ion battery is stored at high temperature or swelled after high-temperature circulation, and the performance of the lithium ion battery is deteriorated.
Disclosure of Invention
Aiming at the defects of the prior art, one of the purposes of the invention is to provide a lithium ion battery electrolyte which can form a stable interface film on the surface of an electrode and inhibit HF from damaging electrode materials, so that the lithium ion battery using the electrolyte has the characteristics of long cycle life, less high-temperature cycle gas production and high capacity retention rate.
The above object of the present invention is achieved by the following technical solutions:
the lithium ion battery electrolyte comprises an additive A, wherein the additive A is a halogenated toluene sulfonyl hydrazone compound, and the halogenated toluene sulfonyl hydrazone compound contains at least one of compounds shown in the following structural formula I:
wherein R1 is independently halogenated toluene, the number of halogen atoms is 1-3, and the positions of methyl and sulfonyl hydrazone groups on the benzene ring can be ortho, meta and para; r2 and R3 are each independently selected from one of a linear or branched unsaturated hydrocarbon group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms and a hydrogen atom.
In the lithium ion electrolyte, the additive A halogenated toluene sulfonyl hydrazone compound has good electrochemical stability, and can form a stable interface film on the surface of an electrode, so that the interface film component is not easy to decompose; meanwhile, the sulfonyl hydrazone group in the additive A can react with an acidic substance to inhibit HF from damaging the electrode material. The lithium ion battery using the electrolyte has the advantages of long cycle life, less gas production at high temperature cycle and high capacity retention rate, so that the lithium ion battery has excellent high-temperature charging performance and cycle life.
Optionally, the additive A comprises at least one of N-o-trifluoromethyl benzenesulfonyl hydrazone, N-m-trifluoromethyl benzenesulfonyl hydrazone and N-p-trifluoromethyl benzenesulfonyl hydrazone.
Optionally, the dosage of the additive A is 0.01-3.50% of the total mass of the lithium ion battery electrolyte.
Optionally, the electrolyte further comprises a nonaqueous organic solvent and an electrolyte lithium salt.
Optionally, the electrolyte lithium salt includes at least one of lithium hexafluorophosphate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorobis oxalato phosphate.
Optionally, the usage amount of the electrolyte lithium salt is 10-15% of the total mass of the lithium ion battery electrolyte.
Optionally, the nonaqueous organic solvent includes a cyclic carbonate and/or a chain carbonate.
Further preferably, the cyclic carbonate comprises at least one of ethylene carbonate, propylene carbonate, vinylene carbonate, ethylene vinylene carbonate.
The chain carbonate comprises at least one of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate.
Optionally, the electrolyte further comprises an additive B comprising at least one of 1, 3-propane sultone, 1, 3-propenesulfonlactone, ethylene sulfate, vinyl sulfite, succinonitrile, adiponitrile, 1, 2-bis (2-cyanoethoxy) ethane, 1,3, 6-hexanetrinitrile.
Optionally, the dosage of the additive B is 0.5-10.0% of the total mass of the lithium ion battery electrolyte.
Another object of the present invention is to provide a lithium ion battery, which includes a positive electrode material, a negative electrode material, a separator, and the lithium ion battery electrolyte.
Compared with the prior art, the invention has the following advantages:
in the lithium ion electrolyte, the additive A halogenated toluene sulfonyl hydrazone compound has good electrochemical stability, and can form a stable interface film on the surface of an electrode, so that the interface film component is not easy to decompose; meanwhile, the sulfonyl hydrazone group in the additive A can react with an acidic substance to inhibit HF from damaging the electrode material. The lithium ion battery using the electrolyte has the advantages of long cycle life, less gas production at high temperature cycle and high capacity retention rate, so that the lithium ion battery has excellent high-temperature charging performance and cycle life.
Drawings
Fig. 1 is a graph of the cycling performance of the lithium ion batteries of example 4, comparative examples 1 and 2 at a current density of 1C.
Detailed Description
The applicant will now make further details of the process of the present invention with reference to specific embodiments in order to make it clear to a person skilled in the art.
The lithium ion battery electrolyte comprises a nonaqueous organic solvent, electrolyte lithium salt, an additive A and an additive B, wherein the additive A is a halogenated toluene sulfonyl hydrazone compound, and the halogenated toluene sulfonyl hydrazone compound contains at least one of compounds shown in the following structural formula I:
wherein R1 is independently halogenated toluene, the number of halogen atoms is 1-3, and the positions of methyl and sulfonyl hydrazone groups on the benzene ring can be ortho, meta and para; r2 and R3 are each independently selected from one of a linear or branched unsaturated hydrocarbon group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms and a hydrogen atom.
Wherein, the dosage of the nonaqueous organic solvent is 72-89% of the total mass of the electrolyte, and the dosage of the electrolyte lithium salt is 10-15% of the total mass of the electrolyte; the dosage of the additive A is 0.01 to 3.50 percent of the total mass of the electrolyte; the dosage of the additive B is 0.5 to 10.0 percent of the total mass of the electrolyte.
As an alternative embodiment, the electrolyte lithium salt may be selected from at least one of lithium hexafluorophosphate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluorophosphate, lithium difluorooxalato borate, and lithium difluorobis oxalato phosphate.
As an alternative embodiment, additive B may be selected from at least one of 1, 3-propane sultone, 1, 3-propenesulfonic acid lactone, ethylene sulfate, vinyl sulfite, succinonitrile, adiponitrile, 1, 2-bis (2-cyanoethoxy) ethane, 1,3, 6-hexanetrinitrile.
The following examples are merely illustrative of specific embodiments of the invention, and are described as examples only of some of the embodiments of the invention, but are not to be construed as limiting the scope of the invention as claimed in any way.
Example 1
The embodiment provides a lithium ion battery electrolyte, which is prepared by the following steps:
in a glove box filled with helium, firstly uniformly mixing non-aqueous organic solvents of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) according to a mass ratio of 35:40:25 to obtain a mixed non-aqueous organic solvent, then adding an additive A N-o-trifluoromethyl benzenesulfonyl hydrazone (the dosage is 0.5% of the total mass of the electrolyte) and an additive B of ethylene sulfate (the dosage is 1.5% of the total mass of the electrolyte), then slowly adding an electrolyte lithium salt lithium hexafluorophosphate (the dosage is 12.5% of the total mass of the electrolyte) into the mixed solution, and uniformly stirring to obtain the lithium ion battery electrolyte.
Example 2
The embodiment provides a lithium ion battery electrolyte, which is prepared by the following steps:
in a glove box filled with helium, firstly uniformly mixing non-aqueous organic solvents of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) according to a mass ratio of 35:40:25 to obtain a mixed non-aqueous organic solvent, then adding an additive of A N-m-trifluoromethyl benzenesulfonyl hydrazone (the dosage is 1% of the total mass of the electrolyte) and an additive of ethylene sulfate (the dosage is 1.5% of the total mass of the electrolyte), then slowly adding an electrolyte lithium salt of lithium hexafluorophosphate (the dosage is 12.5% of the total mass of the electrolyte) into the mixed solution, and uniformly stirring to obtain the lithium ion battery electrolyte.
Example 3
The embodiment provides a lithium ion battery electrolyte, which is prepared by the following steps:
in a glove box filled with helium, firstly uniformly mixing non-aqueous organic solvents of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) according to a mass ratio of 35:40:25 to obtain a mixed non-aqueous organic solvent, then adding an additive A N-p-trifluoromethylsulfonyl hydrazone (the dosage is 2% of the total mass of the electrolyte) and an additive B of ethylene sulfate (the dosage is 1.5% of the total mass of the electrolyte), then slowly adding an electrolyte lithium salt lithium hexafluorophosphate (the dosage is 12.5% of the total mass of the electrolyte) into the mixed solution, and uniformly stirring to obtain the lithium ion battery electrolyte.
Example 4
The embodiment provides a lithium ion battery electrolyte, which is prepared by the following steps:
in a glove box filled with helium, firstly uniformly mixing non-aqueous organic solvents of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) according to a mass ratio of 35:40:25 to obtain a mixed non-aqueous organic solvent, then adding an additive A N-o-trifluoromethyl benzenesulfonyl hydrazone (the dosage is 3.5% of the total mass of the electrolyte) and an additive B of ethylene sulfate (the dosage is 1.5% of the total mass of the electrolyte), then slowly adding an electrolyte lithium salt lithium hexafluorophosphate (the dosage is 12.5% of the total mass of the electrolyte) into the mixed solution, and uniformly stirring to obtain the lithium ion battery electrolyte.
Comparative example 1
The comparative example provides a lithium ion battery electrolyte, which is prepared by the following steps:
in a glove box filled with helium, firstly uniformly mixing non-aqueous organic solvents of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) according to a mass ratio of 35:40:25 to obtain a mixed non-aqueous organic solvent, then adding an additive B of ethylene sulfate (the dosage is 1.5% of the total mass of the electrolyte), then slowly adding electrolyte lithium salt lithium hexafluorophosphate (the dosage is 12.5% of the total mass of the electrolyte) into the mixed solution, and uniformly stirring to obtain the lithium ion battery electrolyte.
That is, the electrolyte of this comparative example was substantially the same as in example 4, except that additive a was not contained in the electrolyte of this comparative example.
Comparative example 2
The comparative example provides a lithium ion battery electrolyte, which is prepared by the following steps:
in a glove box filled with helium, firstly uniformly mixing non-aqueous organic solvents of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) according to a mass ratio of 35:40:25 to obtain a mixed non-aqueous organic solvent, then sequentially adding fluoroethylene carbonate (the dosage is 3.5% of the total mass of the electrolyte) and ethylene sulfate (the dosage is 1.5% of the total mass of the electrolyte), then slowly adding lithium hexafluorophosphate (the dosage is 12.5% of the total mass of the electrolyte) into the mixed solution, and uniformly stirring to obtain the lithium ion battery electrolyte.
That is, the electrolyte of this comparative example was substantially the same as in example 4, except that N-o-trifluoromethylbenzenesulfonyl hydrazone was replaced with fluoroethylene carbonate.
Comparative example 3
In a glove box filled with helium, firstly uniformly mixing non-aqueous organic solvents of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) according to a mass ratio of 35:40:25 to obtain a mixed non-aqueous organic solvent, then sequentially adding an additive A N-o-trifluoromethyl benzenesulfonamide (the dosage is 3.5% of the total mass of the electrolyte) and an additive B of ethylene sulfate (the dosage is 1.5% of the total mass of the electrolyte), then slowly adding an electrolyte lithium salt lithium hexafluorophosphate (the dosage is 12.5% of the total mass of the electrolyte) into the mixed solution, and uniformly stirring to obtain the lithium ion battery electrolyte.
That is, the electrolyte of this comparative example was substantially the same as in example 4 except that N-o-trifluoromethylbenzenesulfonyl hydrazone was replaced with N-o-trifluoromethylbenzenesulfonamide.
Preparation of a lithium battery:
the preparation method comprises the steps of taking a nickel-cobalt-manganese ternary positive electrode active material as a positive electrode material, dissolving the nickel-cobalt-manganese ternary positive electrode active material, a conductive agent carbon black and a binder carbon nano tube in an N-methyl pyrrolidone solvent according to a mass ratio of 94:3:3, fully stirring and uniformly mixing, controlling the solid content to be 68%, preparing positive electrode slurry, coating the positive electrode slurry on an aluminum foil positive electrode current collector with a thickness of 13 mu m, and sequentially carrying out rolling, drying and punching to obtain a positive electrode plate.
The method comprises the steps of taking an artificial graphite anode active substance as an anode material, dissolving the anode material, a conductive agent carbon black, a binder styrene-butadiene rubber and a thickener sodium carboxymethyl cellulose in a deionized water solvent according to a mass ratio of 96:1:2:1, fully stirring and uniformly mixing, controlling the solid content to be 50%, preparing anode slurry, coating the anode slurry on a copper foil anode current collector with the thickness of 6 mu m, and sequentially carrying out rolling, drying and punching to obtain an anode sheet.
Polyethylene (PE) is taken as a base film, and a nano alumina coating is coated on the base film to be taken as a diaphragm.
And (3) laminating the negative plate, the positive plate and the diaphragm, packaging in an aluminum plastic film, and then respectively injecting the lithium ion battery electrolyte prepared in the examples 1-4 and the comparative examples 1-3, and sequentially packaging, activating, forming, aging, secondarily packaging and separating to obtain the lithium ion battery.
Lithium ion battery performance test 1
After the lithium ion battery is prepared, the capacity test and the internal resistance test are respectively carried out on the lithium ion battery, the test steps are shown in table 1, and the test results of the capacity, the internal resistance and the first charge and discharge efficiency of the battery are shown in table 2.
TABLE 1 Capacity test and internal resistance test procedure
Table 2 results of testing the capacity, internal resistance and first charge/discharge efficiency of the battery
Note that: the data in the table are averages of 20 lithium ion battery data.
From the test results in table 2, it can be seen that: compared with comparative example 1, the lithium ion battery electrolytes of examples 1 to 4 were applied to lithium ion batteries, which increased the capacity of the lithium ion batteries by about 2.0%, increased the initial efficiency of the lithium ion batteries by about 1.5%, and decreased the direct current internal resistance of the lithium ion batteries by about 4.0%. The halogenated toluene sulfonyl hydrazone compound has an improvement effect on capacity and initial effect of a lithium ion battery and reduces direct current internal resistance.
Lithium ion battery performance test 2
After the capacity and the first charge and discharge efficiency are tested, the lithium ion batteries prepared in the examples and the comparative examples are respectively subjected to 2.75V-4.2V and 1C/1C cyclic charge and discharge tests, the test steps are shown in Table 3, and the capacity retention rate data are shown in Table 4.
TABLE 3 cycle test procedure
| Step number | 45 ℃ and 2.75-4.2V and 1C/1C charge-discharge cycle |
| 1 | Rest for 4h |
| 2 | Constant current discharge at 1C rate to 2.75V |
| 3 | Rest for 30min |
| 4 | Constant-current and constant-voltage charging with 1C multiplying power to 4.2V, and cut-off current of 0.05C multiplying power |
| 5 | Rest for 30min |
| 6 | Constant current discharge at 1C rate to 2.75V |
| 7 | Rest for 30min |
| 8 | And (3) circulation: the method comprises the following steps: 4, cycle number: 500 |
Table 4 capacity retention after 500 cycles
Note that: the data in the table are averages of 2 lithium ion battery data.
From the test results in table 4, it can be seen that: compared with comparative example 1, the lithium ion battery electrolytes of examples 1 to 4 are applied to lithium ion batteries, and the halogenated toluene sulfonyl hydrazone compound additive obviously improves the cycle performance of the lithium ion batteries; the additive halotoluene sulfonyl hydrazone compound of example 4 improved cycle performance over the fluoroethylene carbonate and N-o-trifluoromethylbenzenesulfonamide additives, as compared to comparative examples 2 and 3.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The lithium ion battery electrolyte is characterized by comprising an additive A, wherein the additive A is a halogenated toluene sulfonyl hydrazone compound, and the halogenated toluene sulfonyl hydrazone compound contains at least one of compounds shown in the following structural formula I:
wherein R1 is independently halogenated toluene, the number of halogen atoms is 1-3, and the positions of methyl and sulfonyl hydrazone groups on the benzene ring are ortho, meta or para; r2 and R3 are each independently selected from one of a linear or branched unsaturated hydrocarbon group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms and a hydrogen atom.
2. The lithium ion battery electrolyte according to claim 1, wherein the additive A comprises at least one of N-o-trifluoromethylbenzenesulfonyl hydrazone, N-m-trifluoromethylbenzenesulfonyl hydrazone and N-p-trifluoromethylbenzenesulfonyl hydrazone.
3. The lithium ion battery electrolyte according to claim 1, wherein the amount of the additive A is 0.01-3.50% of the total mass of the lithium ion battery electrolyte.
4. The lithium ion battery electrolyte of claim 1, wherein the electrolyte further comprises a nonaqueous organic solvent and an electrolyte lithium salt.
5. The lithium ion battery electrolyte of claim 4, wherein the electrolyte lithium salt comprises at least one of lithium hexafluorophosphate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluorophosphate, lithium difluorooxalato borate, and lithium difluorobisoxalato phosphate.
6. The lithium ion battery electrolyte according to claim 4, wherein the amount of the electrolyte lithium salt is 10-15% of the total mass of the lithium ion battery electrolyte.
7. The lithium ion battery electrolyte of claim 4, wherein the non-aqueous organic solvent comprises a cyclic carbonate and/or a chain carbonate.
8. The lithium ion battery electrolyte of claim 1, further comprising an additive B comprising at least one of 1, 3-propane sultone, 1, 3-propenolactone, ethylene sulfate, vinyl sulfite, succinonitrile, adiponitrile, 1, 2-bis (2-cyanoethoxy) ethane, 1,3, 6-hexanetrinitrile.
9. The lithium ion battery electrolyte according to claim 8, wherein the amount of the additive B is 0.5-10.0% of the total mass of the lithium ion battery electrolyte.
10. A lithium ion battery, characterized by comprising a positive electrode material, a negative electrode material, a separator and the lithium ion battery electrolyte as claimed in any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310758253.4A CN116742126A (en) | 2023-06-26 | 2023-06-26 | Lithium ion battery electrolyte and lithium ion battery using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310758253.4A CN116742126A (en) | 2023-06-26 | 2023-06-26 | Lithium ion battery electrolyte and lithium ion battery using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116742126A true CN116742126A (en) | 2023-09-12 |
Family
ID=87911330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310758253.4A Pending CN116742126A (en) | 2023-06-26 | 2023-06-26 | Lithium ion battery electrolyte and lithium ion battery using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116742126A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117199526A (en) * | 2023-09-21 | 2023-12-08 | 中能瑞新(深圳)能源科技有限公司 | Nonaqueous electrolyte and secondary battery |
-
2023
- 2023-06-26 CN CN202310758253.4A patent/CN116742126A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117199526A (en) * | 2023-09-21 | 2023-12-08 | 中能瑞新(深圳)能源科技有限公司 | Nonaqueous electrolyte and secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105684208B (en) | The manufacturing method of lithium secondary battery | |
| CN111628218A (en) | Lithium ion battery and preparation method thereof | |
| CN105845980B (en) | Electrolyte and lithium ion battery containing same | |
| CN110970621B (en) | Lithium ion battery | |
| CN114447333B (en) | Sodium ion battery | |
| Lin et al. | Using phenyl methanesulfonate as an electrolyte additive to improve performance of LiNi0. 5Co0. 2Mn0. 3O2/graphite cells at low temperature | |
| CN113078354A (en) | Ternary lithium ion battery non-aqueous electrolyte and lithium ion battery thereof | |
| CN112701349B (en) | Electrolyte solution, electrochemical device and electronic apparatus including the same | |
| CN111525190A (en) | Electrolyte and lithium ion battery | |
| CN112448034A (en) | Non-aqueous electrolyte for high-voltage lithium ion battery and lithium ion battery | |
| CN108987802B (en) | Non-aqueous electrolyte for high-voltage lithium ion battery | |
| CN111129590A (en) | High-voltage lithium ion battery non-aqueous electrolyte and high-voltage lithium ion battery | |
| CN110676511A (en) | Lithium ion battery electrolyte and lithium ion secondary battery | |
| CN110911754B (en) | Lithium ion battery electrolyte and preparation method thereof | |
| KR102651812B1 (en) | Secondary batteries and devices containing secondary batteries | |
| CN114552007B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery | |
| CN112928328B (en) | Lithium ion battery electrolyte containing silane group sulfonamide compound and lithium ion secondary battery | |
| CN116742126A (en) | Lithium ion battery electrolyte and lithium ion battery using same | |
| CN112615056B (en) | Additive composition for preparing electrolyte, electrolyte containing additive composition and lithium ion secondary battery | |
| CN112038696B (en) | High-voltage electrolyte and lithium ion battery comprising same | |
| CN112701353A (en) | Electrolyte and application thereof | |
| CN117219859A (en) | Lithium ion battery electrolyte, preparation method and application | |
| CN116666754A (en) | Novel additive of sodium ion battery and sodium ion battery | |
| CN112838269B (en) | Electrolyte solution, electrochemical device and electronic apparatus including the same | |
| CN114267877A (en) | Lithium ion battery electrolyte and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |