CN113782836A - Lithium battery electrolyte containing nitrogen atom compound - Google Patents
Lithium battery electrolyte containing nitrogen atom compound Download PDFInfo
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- CN113782836A CN113782836A CN202111000730.8A CN202111000730A CN113782836A CN 113782836 A CN113782836 A CN 113782836A CN 202111000730 A CN202111000730 A CN 202111000730A CN 113782836 A CN113782836 A CN 113782836A
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- lithium
- electrolyte
- containing compound
- nitrogen
- nitrogen atom
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 110
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 105
- -1 nitrogen atom compound Chemical class 0.000 title claims abstract description 88
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 35
- 239000003960 organic solvent Substances 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 239000000654 additive Substances 0.000 claims description 27
- 230000000996 additive effect Effects 0.000 claims description 26
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 16
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-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
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 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 2
- 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 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 8
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 23
- 239000007772 electrode material Substances 0.000 abstract description 22
- 239000002904 solvent Substances 0.000 abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 11
- 159000000002 lithium salts Chemical class 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 238000013459 approach Methods 0.000 abstract description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 18
- 239000002131 composite material Substances 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 6
- 230000002238 attenuated effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 4
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- FINHMKGKINIASC-UHFFFAOYSA-N Tetramethylpyrazine Chemical compound CC1=NC(C)=C(C)N=C1C FINHMKGKINIASC-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 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 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000002000 Electrolyte additive Substances 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 150000003947 ethylamines Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Classifications
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- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of lithium battery electrolyte, and particularly relates to a lithium battery electrolyte containing a nitrogen atom compound. The lithium-containing compound, the organic solvent used as the electrolyte solvent of the lithium battery and the nitrogen-containing compound containing the steric group improve the electrolyte performance of a carbonate system and simultaneously improve the electrochemical stability of the nitrogen-containing compound. The invention has the advantages that the nitrogen-containing compound is added into the lithium battery electrolyte, on one hand, the nitrogen-containing compound with higher thermal stability partially replaces an organic solvent with poorer thermal stability, so that the high-temperature stability of the electrolyte is integrally improved, on the other hand, the nitrogen-containing compound contains lone-pair electrons and can form a complex with lithium ions, so that the solubility of the electrolyte to lithium salts is further improved, and meanwhile, a group with steric hindrance effect is introduced into the position close to a nitrogen atom in a molecular structure, so that ions released by an electrode material are difficult to approach the nitrogen atom, and the electrochemical stability of the nitrogen-containing compound is improved.
Description
Technical Field
The invention belongs to the technical field of lithium battery electrolyte, and particularly relates to a lithium battery electrolyte containing a nitrogen atom compound.
Background
Lithium battery electrolytes, which refer to the ion transport vehicle in lithium batteries, generally consist of a lithium salt and an organic solvent. The electrolyte plays a role in conducting ions between a positive electrode and a negative electrode of a lithium battery, and is a guarantee for the lithium battery to obtain the advantages of high voltage, high specific energy and the like, the electrolyte is generally prepared from raw materials such as a high-purity organic solvent, electrolyte lithium salt, necessary additives and the like according to a certain proportion under a certain condition, since the commercial application of the lithium battery, electrolyte solvents of the lithium battery are systems mainly formed by mixed carbonate, currently applied organic solvents mainly comprise five types of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate and propylene carbonate, non-organic solvents are occasionally used in the electrolyte of a secondary battery, but the comprehensive performance of the organic solvents is not as good as that of the carbonate, so the application is far as good as that of the carbonate, but the electrolyte mainly comprising the carbonate has many problems to be solved urgently, for example: the electrolyte has poor high-temperature stability, far-exerted low-temperature electrical property, gas generation phenomenon, dissolution of electrode materials and the like, so that a chemical substance which partially or completely replaces carbonic ester to be used as an electrolyte solvent of a lithium battery is urgently needed in the market.
Chinese patent publication No. CN112271338A, publication No. 2021.01.26, discloses an electrolyte comprising an organic solvent, a lithium salt, and a rapid charge cycle improving additive; the organic solvent comprises ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate and ethyl propionate; the fast fill cycle improving additive comprises vinylene carbonate and methylene methanedisulfonate; based on the total mass of the electrolyte as 100%, the content of the vinylene carbonate is 0.2% -3%, and the content of the methylene methanedisulfonate is 0.1% -2%.
Although the invention can obviously improve the graphite co-intercalation phenomenon of the cathode of the lithium iron phosphate system lithium ion battery by screening specific carbonic ester, carboxylic ester and a quick charge cycle improving additive for combined use, and avoids the powder falling of the cathode, thereby improving the cycle performance and the service life of the battery, the invention has the defects that the adopted improving additive comprises vinylene carbonate and methylene methanedisulfonate which belong to acidic substances, the acid environment of the carbonic ester system is not improved, the gas generation phenomenon easily occurs, and the electrode material is corroded to a certain degree.
Chinese patent publication No. CN111313093B, publication No. 2021.01.29, discloses an electrolyte, which includes a lithium salt, an organic solvent, and an electrolyte additive, wherein the electrolyte additive is an azide compound, and the structural general formula of the azide compound is: wherein the total number of C and O atoms contained in the R group is not less than 6, and the R group is selected from substituted or unsubstituted alkyl, alkenyl, carbonate, carboxylate, phosphate, sulfonyl or heterocyclic group with 3-20 carbon atoms.
Although the alkaline nitrogen-containing compound is added, the acid environment of the carbonate system electrolyte is improved, and the electrode is protected by forming the SEI film with higher toughness, nitrogen atoms are easily oxidized, and the nitrogen atoms are not stable enough in the lithium battery electrolyte environment and easily react with electrode material substances, so that the electrochemical stability is reduced, and the service life of a lithium ion battery is influenced.
Disclosure of Invention
The invention aims to provide a lithium battery electrolyte containing a nitrogen atom compound, which improves the performance of a carbonate system electrolyte and simultaneously improves the electrochemical stability of a nitrogen-containing compound by providing a lithium-containing compound of a lithium element, an organic solvent used as an electrolyte solvent of a lithium battery and the nitrogen-containing compound containing a steric hindrance group. The invention has the advantages that the nitrogen-containing compound is added into the lithium battery electrolyte, on one hand, the nitrogen-containing compound with higher thermal stability partially replaces an organic solvent with poorer thermal stability, so that the high-temperature stability of the electrolyte is integrally improved, on the other hand, the nitrogen-containing compound contains lone-pair electrons and can form a complex with lithium ions, so that the solubility of the electrolyte to lithium salts is further improved, and meanwhile, a group with steric hindrance effect is introduced into the position close to a nitrogen atom in a molecular structure, so that ions released by an electrode material are difficult to approach the nitrogen atom, and the electrochemical stability of the nitrogen-containing compound is improved.
The technical scheme adopted by the invention for solving the problems is as follows: the lithium battery electrolyte containing the nitrogen atom compound comprises a lithium-containing compound for providing lithium elements, an organic solvent serving as an electrolyte solvent of a lithium battery, and a nitrogen-containing compound containing a steric hindrance group, wherein the concentration range of the lithium-containing compound is 0.5-2mol/L, the mass percentage content range of the nitrogen-containing compound is 0.1% -70%, and the mass percentage content range of the organic solvent is 7% -83%.
The further preferred technical scheme is as follows: the nitrogen-containing compound comprises
，
，
，
，
，
Wherein R1, R2 and R33 are hydrocarbon-based groups, and R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R34, R35 and R36 are hydrogen atoms or hydrocarbon-based groups.
The further preferred technical scheme is as follows: and R1 and R2 are alkyl groups containing 1-6 carbon atoms, and at least one of the alkyl groups is isopropyl, cyclopropyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, isopentyl, neopentyl, cyclopentyl or cyclohexyl.
The further preferred technical scheme is as follows: at least one of R5, R6, R7 and R8 is a hydrocarbyl group.
The further preferred technical scheme is as follows: at least two of R5, R7, R6 and R8 are hydrocarbyl groups.
The further preferred technical scheme is as follows: and R5, R6, R7 and R8 are all hydrocarbon-based groups.
The further preferred technical scheme is as follows: at least one of R14, R15, R16 and R17 is a hydrocarbyl group.
The further preferred technical scheme is as follows: at least two of R14, R15, R16 and R17 are hydrocarbyl groups.
The further preferred technical scheme is as follows: and R14, R15, R16 and R17 are all hydrocarbon-based groups.
The further preferred technical scheme is as follows: at least one of R24 and R28 is a hydrocarbyl group.
The further preferred technical scheme is as follows: and R24 and R28 are both hydrocarbyl groups.
The further preferred technical scheme is as follows: at least two of the R29, R30, R31 and R32 are not hydrogen atoms.
The further preferred technical scheme is as follows: at least two of R29, R30, R31 and R32 are hydrocarbyl groups.
The further preferred technical scheme is as follows: and R29, R30, R31 and R32 are all hydrocarbon-based groups.
The further preferred technical scheme is as follows: the organic solvent comprises at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, methyl acetate, ethyl acetate, propyl acetate, butyl ethyl ester and gamma-butyrolactone.
The further preferred technical scheme is as follows: the lithium-containing compound includes at least one of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium tetrafluoroborate, lithium bis oxalato borate, and lithium difluorooxalato borate.
The further preferred technical scheme is as follows: the composite material also comprises an additive, wherein the additive comprises fluoroethylene carbonate (FEC), 1, 3-propane sultone (1, 3-PS), trifluoroethyl methyl carbonate, 1, 2, 2-tetrafluoroethyl-2, 2, 3, 3-tetrafluoropropyl ether, succinonitrile, adiponitrile, lithium difluorophosphate and ethoxy pentafluorophosphazene.
The invention provides a lithium-containing compound of lithium element, an organic solvent used as an electrolyte solvent of a lithium battery, and a nitrogen-containing compound containing a steric group, thereby improving the electrochemical stability of the nitrogen-containing compound while improving the electrolyte performance of a carbonate system. The invention has the advantages that the nitrogen-containing compound is added into the lithium battery electrolyte, on one hand, the nitrogen-containing compound with higher thermal stability partially replaces an organic solvent with poorer thermal stability, so that the high-temperature stability of the electrolyte is integrally improved, on the other hand, the nitrogen-containing compound contains lone-pair electrons and can form a complex with lithium ions, so that the solubility of the electrolyte to lithium salts is further improved, and meanwhile, a group with steric hindrance effect is introduced into the position close to a nitrogen atom in a molecular structure, so that ions released by an electrode material are difficult to approach the nitrogen atom, and the electrochemical stability of the nitrogen-containing compound is improved.
Drawings
Fig. 1 is a schematic diagram of a charging/discharging curve in example 1 of the present invention.
Fig. 2 is a schematic diagram of the charging/discharging curve in example 2 of the present invention.
Fig. 3 is a schematic diagram of the charging/discharging curve in example 3 of the present invention.
Fig. 4 is a schematic diagram of the charging/discharging curve in example 4 of the present invention.
Fig. 5 is a schematic diagram of the charging/discharging curve in example 5 of the present invention.
Fig. 6 is a schematic diagram of the charging/discharging curve in example 6 of the present invention.
FIG. 7 is a schematic diagram showing charging and discharging curves in comparative example 3 of the present invention.
Detailed Description
The following description is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention.
Example 1
A lithium battery electrolyte containing a nitrogen atom-containing compound includes a lithium-containing compound that supplies a lithium element, an organic solvent that is an electrolyte solvent of a lithium battery, and a nitrogen-containing compound that contains a sterically hindered group.
In this embodiment, the lithium-containing compound is a lithium salt to provide lithium ions for the electrolyte, the electrolyte of the lithium battery is a carrier for ion transmission in the battery, and generally consists of a lithium salt and an organic solvent, and the electrolyte plays a role of conducting ions between the positive electrode and the negative electrode of the lithium battery, so that the lithium battery can obtain advantages of high voltage, high specific energy and the like, and the lithium battery has the main advantages of high specific energy, high storage energy density which is about 6 to 7 times that of a lead-acid battery, long service life which can reach more than 6 years, high rated voltage which is about equal to the series voltage of 3 nickel-cadmium or nickel-hydrogen rechargeable batteries, is convenient to form a battery power supply, has high power bearing capacity, low self-discharge rate, and is most important and environment-friendly, and does not contain or generate any lead, mercury, or the like in production, use and scrapping, Cadmium and other toxic and harmful heavy metal elements and substances.
In addition, the electrolyte needs to be added with the organic solvent to play a role, and since the commercial application of lithium batteries, the electrolyte solvent of the lithium batteries is a system mainly composed of mixed carbonate, for example, propylene carbonate has been paid attention and applied in electrochemical research since the propylene carbonate has strong dissolving capacity, wide liquid range and good stability.
In addition, the purpose of adding the nitrogen-containing compound to the electrolyte is to solve the problems of the carbonate electrolyte, such as poor high-temperature stability, far-from-low-temperature electrical properties, occurrence of gassing phenomenon, dissolution of electrode materials, etc., the nitrogen-containing compound has lone-pair electrons, can form a complex with lithium ions, has certain solubility to lithium salts, and can be used as a base of the electrolyte solvent, thereby realizing the function of partially replacing carbonate.
The nitrogen-containing compound comprises 5g (70 percent by mass) of 2, 6-lutidine, wherein R24 and R28 are methyl.
In this embodiment, pyridine is used as a representative substance of the nitrogen-containing aromatic heterocyclic compound, the 2, 6-dimethylpyridine is alkaline, the content of the nitrogen atom-containing compound in the electrolyte is high, and the steric hindrance is increased by adding methyl groups to R24 and R28, so that the stability of the nitrogen atom is improved, and thus the prepared electrolyte has high stability, and the pyridine compound has relatively stronger ability of dissolving lithium salt.
The organic solvent comprises 0.5g (7% by mass) of dimethyl carbonate.
In this embodiment, dimethyl carbonate is a colorless, transparent, pungent and smelly liquid at room temperature, and because dimethyl carbonate is less toxic and has excellent solubility, its melting point range is narrow, surface tension is large, viscosity is low, dielectric interfacial electrical constant is small, and it has high evaporation temperature and high evaporation rate, it can be used as a low-toxicity solvent in an electrolyte.
The lithium-containing compound included 1.5g (concentration: 2 mol/L) of lithium hexafluorophosphate.
In the embodiment, lithium hexafluorophosphate is an inorganic substance, white crystals or powder, is easily soluble in dimethyl carbonate, is the most important component of electrolyte components, and the battery added with lithium hexafluorophosphate has high voltage, large specific energy, long cycle life, generally more than 500 times, even more than 2000 times of cycle use, and high working temperature range.
The electrolyte also includes an additive comprising 0.14g fluoroethylene carbonate.
In this embodiment, fluoroethylene carbonate is mainly used to improve the wetting performance of the Electrolyte, form a more stable SIE (Solid Electrolyte Interface), improve the cycle performance and high/low temperature performance of the battery, and the SIE is a passivation layer, which is an Interface layer formed to cover the surface of the electrode material during the first charge/discharge process of the liquid lithium ion battery, and has the characteristics of a Solid Electrolyte, i.e., an electronic insulator but Li+Of good electrical conductivity, Li+Can be freely inserted and extracted through the passivation layer, and the formation of the SEI film has a crucial influence on the performance of the electrode material. On one hand, the formation of the SEI film consumes part of lithium ions, so that the irreversible capacity of the first charge and discharge is increased, and the charge and discharge efficiency of the electrode material is reduced; on the other hand, the SEI film has organic solvent insolubility and can stably exist in an organic electrolyte solution, and solvent molecules cannot pass through the passivation film, so that the co-intercalation of the solvent molecules can be effectively prevented, the damage to an electrode material caused by the co-intercalation of the solvent molecules is avoided, the cycle performance of the electrode is greatly improved, and the electrode can be used for producing a high-performance organic thin filmService life.
In addition, the charge-discharge curve of a button cell (the external diameter is 20mm, the thickness is 3.2 mm) made by taking a lithium titanate material as a positive electrode, a metal lithium sheet as a negative electrode and a PP/PE composite membrane as a diaphragm and matching the electrolyte is shown in figure 1, the first discharge capacity is 150mAh/g, and the discharge capacity is not attenuated after 10 times of charge-discharge cycle experiments, so that the performance of the electrode material can be normally exerted under the condition that the content of the 2, 6-dimethylpyridine in the electrolyte is higher.
Example 2
A lithium battery electrolyte containing a nitrogen atom-containing compound includes a lithium-containing compound that supplies a lithium element, an organic solvent that is an electrolyte solvent of a lithium battery, and a nitrogen-containing compound that contains a sterically hindered group.
The nitrogen-containing compound comprises 0.012g (mass fraction is 0.1%) of N, N-diisopropylethylamine, wherein R1, R2 and R3 are isopropyl.
In this example, an ethylamine derivative was used as a representative of the amine compound.
The organic solvent comprises 9.988g of dimethyl carbonate (mass fraction is 83%).
The lithium-containing compound included 1.5g (concentration: 0.5 mol/L) of lithium hexafluorophosphate.
The electrolyte also comprises an additive, wherein the additive comprises 0.5g of fluoroethylene carbonate.
A button battery (with the external diameter of 20mm and the thickness of 3.2 mm) is manufactured by taking a lithium titanate material as a positive electrode, a metal lithium sheet as a negative electrode and a PP/PE composite membrane as a diaphragm and matching the electrolyte. The charge-discharge curve is shown in figure 2, which shows that the capacity of the first discharge is 170mAh/g, and the discharge capacity is not attenuated after 10 times of charge-discharge cycle experiments, so that the performance of the electrode material is normally exerted under the condition that the content of the N, N-diisopropylethylamine in the electrolyte is very low.
Example 3
A lithium battery electrolyte containing a nitrogen atom-containing compound includes a lithium-containing compound that supplies a lithium element, an organic solvent that is an electrolyte solvent of a lithium battery, and a nitrogen-containing compound that contains a sterically hindered group.
The nitrogen-containing compound comprises 0.5g (mass fraction is 0.4%) of 2, 2, 6, 6-tetramethylpiperidine, wherein R14, R15, R16 and R17 are methyl.
In this example, a piperidine Bay organism was used as a representative of the nitrogenous heterocyclic compound.
The organic solvent comprises 9.5g of dimethyl carbonate (mass fraction is 79%).
The lithium-containing compound included 1.5g (concentration: 0.5 mol/L) of lithium hexafluorophosphate.
The electrolyte also comprises an additive, wherein the additive comprises 0.5g of fluoroethylene carbonate.
A button battery (with the external diameter of 20mm and the thickness of 3.2 mm) is manufactured by taking a lithium titanate material as a positive electrode, a metal lithium sheet as a negative electrode and a PP/PE composite membrane as a diaphragm and matching the electrolyte. The charge-discharge curve is shown in figure 3, which shows that the capacity of the first discharge is 165mAh/g, and the discharge capacity is not attenuated in 10 times of charge-discharge cycle experiments, so that the performance of the electrode material can be normally exerted under the condition that the content of the 2, 2, 6, 6-tetramethyl piperidine in the electrolyte is lower.
Example 4
A lithium battery electrolyte containing a nitrogen atom-containing compound includes a lithium-containing compound that supplies a lithium element, an organic solvent that is an electrolyte solvent of a lithium battery, and a nitrogen-containing compound that contains a sterically hindered group.
The nitrogen-containing compound comprises 0.1g (mass fraction is 0.8%) of 2, 3, 5, 6-tetramethylpyrazine, wherein R24, R25, R27 and R28 are methyl.
The organic solvent comprises 9.9g of dimethyl carbonate (the mass fraction is 82.5%).
The lithium-containing compound included 1.5g (concentration: 0.5 mol/L) of lithium hexafluorophosphate.
The electrolyte also comprises an additive, wherein the additive comprises 0.5g of fluoroethylene carbonate.
A button battery (with the external diameter of 20mm and the thickness of 3.2 mm) is manufactured by taking a lithium titanate material as a positive electrode, a metal lithium sheet as a negative electrode and a PP/PE composite membrane as a diaphragm and matching the electrolyte. The charge-discharge curve is shown in fig. 4, which shows that the capacity of the first discharge is 170mAh/g, and no discharge capacity is found in 10 charge-discharge cycle experiments, and it can be seen that the performance of the electrode material is normally exerted under the condition that the content of 2, 3, 5, 6-tetramethylpyrazine in the electrolyte is low.
Example 5
A lithium battery electrolyte containing a nitrogen atom-containing compound includes a lithium-containing compound that supplies a lithium element, an organic solvent that is an electrolyte solvent of a lithium battery, and a nitrogen-containing compound that contains a sterically hindered group.
The nitrogen-containing compound comprises 6g (mass fraction is 50%) of 2, 4, 6-trimethyl pyridine, wherein R24, R26 and R28 are methyl.
The organic solvent comprises 4g of dimethyl carbonate (mass fraction is 33%).
The lithium-containing compound included 1.5g (concentration: 0.5 mol/L) of lithium hexafluorophosphate.
The electrolyte also comprises an additive, wherein the additive comprises 0.5g of fluoroethylene carbonate.
A button battery (with the external diameter of 20mm and the thickness of 3.2 mm) is manufactured by taking a lithium titanate material as a positive electrode, a metal lithium sheet as a negative electrode and a PP/PE composite membrane as a diaphragm and matching the electrolyte. The charge-discharge curve is shown in figure 5, which shows that the capacity of the first discharge is 170mAh/g, and the discharge capacity is not attenuated in 10 charge-discharge cycle experiments, so that the performance of the electrode material can be normally exerted under the condition that the content of the 2, 4, 6-trimethylpyridine in the electrolyte is higher.
Example 6
A lithium battery electrolyte containing a nitrogen atom-containing compound includes a lithium-containing compound that supplies a lithium element, an organic solvent that is an electrolyte solvent of a lithium battery, and a nitrogen-containing compound that contains a sterically hindered group.
The nitrogen-containing compound comprises 8g (mass fraction is 67%) of 2, 6-lutidine, wherein R24 and R28 are methyl.
The organic solvent comprises 2g (mass fraction is 17%) of propylene carbonate.
The lithium-containing compound included 1.5g (concentration: 0.5 mol/L) of lithium hexafluorophosphate.
The electrolyte also comprises an additive, wherein the additive comprises 0.5g of fluoroethylene carbonate.
A button battery (with the external diameter of 20mm and the thickness of 3.2 mm) is manufactured by taking a lithium titanate material as a positive electrode, a metal lithium sheet as a negative electrode and a PP/PE composite membrane as a diaphragm and matching the electrolyte. The charge-discharge curve is shown in figure 6, which shows that the capacity of the first discharge is 165mAh/g, and the discharge capacity is not attenuated in 10 times of charge-discharge cycle experiments, and the performance of the electrode material is normally exerted under the condition that the content of the 2, 6-lutidine in the electrolyte is higher.
Example 7
A lithium battery electrolyte containing a nitrogen atom-containing compound includes a lithium-containing compound that supplies a lithium element, an organic solvent that is an electrolyte solvent of a lithium battery, and a nitrogen-containing compound that contains a sterically hindered group.
The nitrogen-containing compound comprises 5g (70 percent by mass) of 2-methylpyridine, wherein R14, R15, R16 and R17 are methyl.
In this example, a piperidine derivative was used as a representative of the nitrogen-containing lipid heterocyclic compound.
The organic solvent comprises 0.5g (7% by mass) of dimethyl carbonate.
The lithium-containing compound included 1.5g (concentration: 2 mol/L) of lithium hexafluorophosphate.
The electrolyte also includes an additive comprising 0.14g fluoroethylene carbonate.
A button battery (with the external diameter of 20mm and the thickness of 3.2 mm) is manufactured by taking a lithium titanate material as a positive electrode, a metal lithium sheet as a negative electrode and a PP/PE composite membrane as a diaphragm and matching the electrolyte. The experimental result shows that the capacity of the first discharge is 130mAh/g, and the discharge capacity is not attenuated in 10 times of charge-discharge cycle experiments, so that the performance of the electrode material is normally exerted under the condition that the content of the 2-methylpyridine in the electrolyte is higher, and compared with the example 1, the performance of the electrolyte is still good and is not obviously reduced under the condition that the ortho position of the nitrogen atom is only one methyl group.
Comparative example 1
A lithium battery electrolyte containing a nitrogen atom-containing compound includes a lithium-containing compound that supplies a lithium element, an organic solvent that is an electrolyte solvent of a lithium battery, and a nitrogen-containing compound that contains a sterically hindered group.
The nitrogen-containing compound comprises 5g (42 percent by mass) of n-butylamine, wherein R1, R2 and R3 are all hydrogen atoms.
The organic solvent comprises 5g of dimethyl carbonate (mass fraction is 42%).
The lithium-containing compound included 1.5g (concentration: 0.5 mol/L) of lithium hexafluorophosphate.
The electrolyte also comprises an additive, wherein the additive comprises 0.5g of fluoroethylene carbonate.
A button battery (with the external diameter of 20mm and the thickness of 3.2 mm) is manufactured by taking a lithium titanate material as a positive electrode, a metal lithium sheet as a negative electrode and a PP/PE composite membrane as a diaphragm and matching the electrolyte. The capacity of the first discharge after electricity discharge is 30mAh/g, only 20% (150 mAh/g) under the normal condition, the capacity is close to zero after 10 charge-discharge cycles, and the performance of the electrode material can not be exerted under the condition that the content of n-butylamine in the electrolyte is high.
Compared with the embodiment 2, it is known that under the condition that other conditions are not changed, only N, N-diisopropylethylamine with a mass fraction much smaller than that of N-butylamine is added, so that the performance of the electrolyte can be remarkably improved, and it is indicated that introduction of isopropyl at R1, R2, and R3 has a technical effect of improving the performance of the electrolyte, and when the steric hindrance generated by isopropyl can reach the conclusion of improving the electrochemical stability of the nitrogen-containing compound, cyclopropyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, isopentyl, neopentyl, cyclopentyl, and cyclohexyl with higher steric hindrance can also achieve the same or higher effect under the same conditions.
Comparative example 2
A lithium battery electrolyte containing a nitrogen atom-containing compound includes a lithium-containing compound that supplies a lithium element, an organic solvent that is an electrolyte solvent of a lithium battery, and a nitrogen-containing compound that contains a sterically hindered group.
The nitrogen-containing compound comprises 5g (the mass fraction is 42%) of pyrrolidine, wherein R4, R5, R6, R7, R8, R9, R10, R11 and R12 are all hydrogen atoms.
The organic solvent comprises 5g of dimethyl carbonate (mass fraction is 42%).
The lithium-containing compound included 1.5g (concentration: 0.5 mol/L) of lithium hexafluorophosphate.
The electrolyte also comprises an additive, wherein the additive comprises 0.5g of fluoroethylene carbonate.
A button battery (with the external diameter of 20mm and the thickness of 3.2 mm) is manufactured by taking a lithium titanate material as a positive electrode, a metal lithium sheet as a negative electrode and a PP/PE composite membrane as a diaphragm and matching the electrolyte. The capacity of the first discharge after electricity discharge is 15mAh/g, only 10% (150 mAh/g) under the normal condition, the capacity is close to zero after 7 charge-discharge cycles, and the performance of the electrode material can not be exerted under the condition that the content of the pyrrolidine in the electrolyte is higher.
Compared with the embodiment 3, under the condition that other conditions are not changed, the electrolyte performance can be obviously improved only by adding the 2, 2, 6, 6-tetramethylpiperidine with the mass fraction far smaller than that of the pyrrolidine, which shows that the introduction of methyl groups into R14, R15, R16 and R17 has the technical effect of improving the electrolyte performance.
Comparative example 3
A lithium battery electrolyte containing a nitrogen atom-containing compound includes a lithium-containing compound that supplies a lithium element, an organic solvent that is an electrolyte solvent of a lithium battery, and a nitrogen-containing compound that contains a sterically hindered group.
The nitrogen-containing compound comprises 5g (42 percent by mass) of pyridine, wherein R24, R25, R26, R27 and R28 are all hydrogen atoms.
The organic solvent comprises 5g of dimethyl carbonate (mass fraction is 42%).
The lithium-containing compound included 1.5g (concentration: 0.5 mol/L) of lithium hexafluorophosphate.
The electrolyte also comprises an additive, wherein the additive comprises 0.5g of fluoroethylene carbonate.
A button battery (with the external diameter of 20mm and the thickness of 3.2 mm) is manufactured by taking a lithium titanate material as a positive electrode, a metal lithium sheet as a negative electrode and a PP/PE composite membrane as a diaphragm and matching the electrolyte. As shown in fig. 7, it was found that the electrode material performance was not exhibited when the content of pyridine in the electrolyte was high.
Compared with the example 1, the 2, 6-lutidine with similar mass fraction enables the electrolyte performance to be improved obviously higher than that of pyridine under the condition of no change of other conditions, and the introduction of methyl groups at R24 and R28 has the technical effect of improving the electrolyte performance.
In conclusion, it can be extended from the above conclusion that the introduction of the organic group at the ortho-position of the nitrogen atom can make the ions released from the electrode material difficult to approach the nitrogen atom, thereby greatly improving the electrochemical stability of the nitrogen-containing compound.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the above embodiments, and various modifications can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. These are non-inventive modifications, which are intended to be protected by patent laws within the scope of the present invention.
Claims (10)
1. The lithium battery electrolyte containing the nitrogen atom compound is characterized by comprising a lithium-containing compound, an organic solvent and a nitrogen-containing compound containing a steric hindrance group, wherein the concentration range of the lithium-containing compound is 0.5-2mol/L, the mass percentage content range of the nitrogen-containing compound is 0.1% -70%, and the mass percentage content range of the organic solvent is 7% -83%.
2. The electrolytic solution of claim 1, wherein the nitrogen-containing compound comprises
，
，
，
，
，
Wherein R1, R2 and R33 are hydrocarbon-based groups, and R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R34, R35 and R36 are hydrogen atoms or hydrocarbon-based groups.
3. The nitrogen atom compound-containing electrolyte solution of claim 2, wherein R1 and R2 are each a hydrocarbon group having 1 to 6 carbon atoms, and at least one of the groups is isopropyl, cyclopropyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, isopentyl, neopentyl, cyclopentyl, or cyclohexyl.
4. The nitrogen atom compound-containing electrolyte solution of claim 2, wherein at least one of R5, R6, R7 and R8 is a hydrocarbon group.
5. The electrolytic solution of claim 2, wherein at least one of R14, R15, R16 and R17 is a hydrocarbon group.
6. The nitrogen atom compound-containing electrolyte solution of claim 2, wherein at least one of R24 and R28 is a hydrocarbon group.
7. The nitrogen atom compound-containing electrolyte solution of claim 2, wherein at least two of R29, R30, R31 and R32 are hydrocarbon groups.
8. The nitrogen atom compound-containing electrolyte according to claim 1, wherein the organic solvent comprises at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, methyl acetate, ethyl acetate, propyl acetate, ethyl butyl ester, and γ -butyrolactone.
9. The electrolytic solution containing a nitrogen atom compound according to claim 1, wherein the lithium-containing compound comprises at least one of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium tetrafluoroborate, lithium bis (oxalato) borate, and lithium difluorooxalato borate.
10. The nitrogen atom compound-containing electrolyte solution according to claim 1, further comprising an additive, wherein the additive comprises fluoroethylene carbonate (FEC), 1, 3-propane sultone (1, 3-PS), trifluoroethyl methyl carbonate, 1, 2, 2-tetrafluoroethyl-2, 2, 3, 3-tetrafluoropropyl ether, succinonitrile, adiponitrile, lithium difluorophosphate, and ethoxypentafluorophosphazene.
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