CN113140795A - High-voltage lithium ion battery electrolyte - Google Patents
High-voltage lithium ion battery electrolyte Download PDFInfo
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- CN113140795A CN113140795A CN202110340759.4A CN202110340759A CN113140795A CN 113140795 A CN113140795 A CN 113140795A CN 202110340759 A CN202110340759 A CN 202110340759A CN 113140795 A CN113140795 A CN 113140795A
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- carbonate
- lithium ion
- ion battery
- battery electrolyte
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 38
- 230000000996 additive effect Effects 0.000 claims abstract description 30
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- SNZXFRFQGXSSGN-UHFFFAOYSA-N phenylsulfanyloxysulfanylbenzene Chemical compound C=1C=CC=CC=1SOSC1=CC=CC=C1 SNZXFRFQGXSSGN-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 alkyl halogen Chemical class 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 20
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 20
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 16
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 16
- QGNRLAFFKKBSIM-UHFFFAOYSA-N prop-2-enylsulfanylbenzene Chemical group C=CCSC1=CC=CC=C1 QGNRLAFFKKBSIM-UHFFFAOYSA-N 0.000 claims description 15
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 14
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910012265 LiPO2F2 Inorganic materials 0.000 claims description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 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
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 2
- 229910013872 LiPF Inorganic materials 0.000 claims 1
- 101150058243 Lipf gene Proteins 0.000 claims 1
- 150000005685 straight-chain carbonates Chemical class 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical group 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- YQQKTCBMKQQOSM-UHFFFAOYSA-N trifluoromethylsulfanylbenzene Chemical compound FC(F)(F)SC1=CC=CC=C1 YQQKTCBMKQQOSM-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
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
- H01M10/052—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
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a high-voltage lithium ion battery electrolyte, which comprises: lithium salt, organic solvent, phenyl thioether additive and other additives, wherein the structural general formula of the phenyl thioether additive is as follows: [ chemical formula 1]
Said [ chemical formula 1]In, R1Is (C1-C5) alkyl, cyano, (C6-C12) aryl, and (C1-C5) alkyl halogen; r2Is (C1-C5) alkyl or hydrogen radical;
is a double or triple bond. By adopting the technical scheme of the invention, a good electrode-interface film can be formed, the high-voltage lithium ion battery can be applied, and the battery performance can be improvedThe capacity retention rate obviously improves the cycling stability of the battery under the condition of high voltage.
Description
Technical Field
The invention relates to the technical field of battery electrolyte, in particular to a high-voltage lithium ion battery electrolyte.
Background
In order to meet the development and demand of electric vehicles and renewable energy, research and development of high-voltage lithium ion batteries are imperative. However, the development of lithium ion batteries has a series of problems such as poor safety, severe cycle life decay, high cost, and narrow electrochemical window. Breakthroughs in lithium battery technology require improvements in positive and negative electrode materials and electrolytes, where electrolytes have significant impact on the capacity, cycle life, and safety issues of lithium ion batteries.
In the related art, 1, 3-Propane Sultone (PS) and trifluoromethylphenyl sulfide (PTS) are generally used as common film forming additives, although the cycling stability of the battery under high voltage is improved to a certain extent, the high-temperature and high-pressure cycling performance and safety performance of the electrolyte still need to be improved. The electrolyte is easy to be oxidized and decomposed under the condition of high voltage, the generated gas can cause the battery to bulge, and meanwhile, the active material is consumed in the process, so that the battery performance is poor; the oxidation products of the electrolyte can cause the transition metal elements in the anode material to be dissolved in the circulation process, thereby causing the capacity attenuation of the battery.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art or the related art.
Therefore, an object of the present invention is to provide a high voltage lithium ion battery electrolyte, wherein a phenylsulfide additive is added to the electrolyte, so as to stabilize the interface between the positive electrode material and the electrolyte, thereby avoiding decomposition of the electrolyte, and also to consider a high-capacity silicon-carbon negative electrode, thereby avoiding a large amount of electrolyte consumption caused by repeated "cracking-regeneration" of a solid electrolyte membrane (SEI) due to volume expansion of the negative electrode material, and thus, improving high temperature and high voltage cycle performance and safety performance of the electrolyte.
In order to achieve the above object, the present invention provides an electrolyte for a high voltage lithium ion battery, comprising: lithium salt, organic solvent, phenyl thioether additive and other additives, wherein the structural general formula of the phenyl thioether additive is as follows:
[ chemical formula 1]
Said [ chemical formula 1]In, R1Is (C1-C5) alkyl, cyano, (C6-C12) aryl, and (C1-C5) alkyl halogen; r2Is (C1-C5) alkyl or hydrogen radical;
is a double or triple bond.
In the above technical solution, preferably, the phenylsulfide additive is selected from the following structures, but not limited thereto:
the substituents described in the present invention, which include "alkyl", "alkoxy" and the remaining "alkyl" moiety, include all forms of straight-chain or branched-chain forms, preferably having 1 to 4 carbon atoms.
The "aryl group" described in the present invention is preferably a monocyclic or fused ring type form containing 5 or 6 ring atoms as an organic radical derived from an aromatic hydrocarbon by removing one hydrogen, and also includes a form in which a plurality of aryl groups are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, and anthracenyl.
In the technical scheme, the phenyl sulfide additive is preferentially decomposed by a solvent, the phenyl sulfide additive comprises a phenyl sulfide structure, an unsaturated double bond or an aromatic compound structure, a compact and uniform CEI film can be formed on the surface of a positive electrode material by utilizing the phenyl sulfide structure, the uniformity and stability of an electrode and an electrolyte liquid phase interface film are improved, the further oxidation of an electrolyte is inhibited, the dissolution of metal ions is effectively prevented, the occurrence of side reactions on the surface of the electrode is inhibited, the circulation stability of the battery under high voltage is improved, meanwhile, a high-capacity silicon-carbon negative electrode can be considered, and the problems of large-amount electrolyte consumption and the like caused by repeated 'cracking-regeneration' of a solid electrolyte film (SEI film) due to the volume expansion of a negative electrode material are solved. The electrochemical polymerization can be performed in a high voltage state by using an unsaturated double bond or an aromatic compound structure to improve the safety of the battery. The phenyl thioether additive has good compatibility in the electrolyte, can be fully dissolved in the lithium ion battery electrolyte while obviously improving the high-temperature and high-pressure cycle performance and the safety performance of the electrolyte, and ensures the performance of the electrolyte.
In any one of the above technical solutions, preferably, the mass percentage concentration of the phenylsulfide additive is controlled to be 0.1% -10.0%. Namely, 0.1g to 10.0g of the additive is added to 100g of the electrolyte.
In any of the above embodiments, preferably, the phenylsulfide additive is allyl phenylsulfide.
In any of the above embodiments, preferably, the linear carbonate organic solvent is one or a combination of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), and Methyl Propyl Carbonate (MPC);
the cyclic carbonate solvent is selected from one or a combination of several of Ethylene Carbonate (EC), Propylene Carbonate (PC), Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC).
In any of the above technical solutions, preferably, the lithium salt is LiPF6、LiBF4LiBOB, LiTFSi, LiFSI and LiPO2F2Any one of them or a mixture of several of them.
In any of the above solutions, preferably, the main lithium salt LiPF6The concentration of the lithium salt is controlled to be 0.5-1.5mol/L, and the concentration of other lithium salts is controlled to be 0.1-1.5 mol/L.
In any of the above technical solutions, preferably, the other additive is selected from one or more of Biphenyl (BP), 1, 3-Propane Sultone (PS), triphenyl phosphite (TPP), 1, 4-Butane Sultone (BS), Succinic Anhydride (SA), succinonitrile (NA), AND Adiponitrile (AND).
In any of the above technical solutions, preferably, a mixed solution of dimethyl carbonate (DMC), Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 1:1:1 is used as the organic solvent; the lithium salt is lithium hexafluorophosphate, and the concentration is 1.2 mol/L; the phenyl sulfide additive is allyl phenyl sulfide, the mass percent concentration is 5 wt%, and the other additives are 0.2 wt% of Vinylene Carbonate (VC), 5 wt% of fluoroethylene carbonate (FEC) and 4 wt% of 1, 3-Propane Sultone (PS).
In the technical scheme, 0.2 wt% of Vinylene Carbonate (VC), 5 wt% of fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS) and allyl phenyl sulfide are jointly used for promoting film formation, a more compact and uniform CEI film can be formed on the surface of a positive electrode, the dissolution of metal ions is effectively prevented, the occurrence of side reactions on the surface of the electrode is further inhibited, the circulation stability of the battery under high voltage is improved, meanwhile, the high-capacity silicon-carbon cathode can be considered, the problems of consumption of a large amount of electrolyte and the like caused by repeated 'cracking-regeneration' of a Solid Electrolyte Interface (SEI) film due to volume expansion of a cathode material are solved, electrochemical polymerization can be carried out under a high-voltage state, the safety of the battery is improved, the capacity and the cycle life of the battery can be prolonged, overcharge protection is carried out, and good high-low temperature performance and an anti-gas expansion function are realized. The high-voltage lithium ion battery electrolyte is qualified in moisture and acidity control, high in safety, high in capacity, long in cycle life and high in safety, and the moisture is 4.8ppm, the acidity is 25.6 ppm. The addition of the allyl phenyl sulfide additive can obviously improve the first discharge efficiency and the discharge capacity of the lithium ion battery, the first discharge efficiency can reach 81.23%, and the 1C discharge capacity can reach 1947.15 mAh. The addition of the allyl phenyl sulfide additive obviously improves the high-temperature cycle performance of the lithium ion battery, the cycle lasts for 600 weeks, and the capacity retention rate is about 87%.
In any of the above technical solutions, the lithium ion battery, the quasi-solid lithium battery, the solid lithium battery, and the lithium air battery may be preferably used.
The high-voltage lithium ion battery electrolyte provided by the invention has the following beneficial technical effects:
(1) the phenyl thioether additive is added into the high-voltage lithium ion battery electrolyte, so that a good electrode-interface film can be formed, the capacity retention rate of the battery can be improved when the phenyl thioether additive is applied to the high-voltage lithium ion battery, and the cycling stability of the battery is obviously improved under the high-voltage condition.
(2) The compact and uniform CEI film can be formed on the surface of the anode by utilizing the phenyl sulfide structure, the dissolution of metal ions is effectively prevented, the occurrence of side reactions on the surface of an electrode is further inhibited, the cycling stability of the battery under high voltage is improved, meanwhile, a high-capacity silicon-carbon cathode can be considered, and the problems of large amount of electrolyte consumption and the like caused by repeated 'cracking-regeneration' of a Solid Electrolyte Interface (SEI) film due to the volume expansion of a cathode material are avoided. The electrochemical polymerization can be performed in a high voltage state by using an unsaturated double bond or an aromatic compound structure to improve the safety of the battery. The phenyl thioether additive has good compatibility in the electrolyte, can be fully dissolved in the lithium ion battery electrolyte while obviously improving the high-temperature and high-pressure cycle performance and the safety performance of the electrolyte, and ensures the performance of the electrolyte.
(3) The phenyl thioether additive and other film forming additives, namely Vinylene Carbonate (VC), fluoroethylene carbonate (FEC) and 1, 3-Propane Sultone (PS) act together to promote film formation, the capacity, the cycle life and the safety of the battery are high, the first discharge efficiency can reach 81.23%, and the 1C discharge capacity can reach 1947.15 mAh. The addition of the allyl phenyl sulfide additive obviously improves the high-temperature cycle performance of the lithium ion battery, the cycle lasts for 600 weeks, and the capacity retention rate is about 87%.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 shows a graph of capacity retention rate versus cycle number of a battery according to one embodiment of the present invention.
Detailed Description
The invention discloses a high-voltage lithium ion battery electrolyte, which can be realized by appropriately improving process parameters by referring to the contents in the field. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention is further illustrated by the following examples:
the preparation method of the allyl phenyl sulfide comprises the following steps:
putting 1.5mmol of palladium catalyst into a three-neck flask, introducing inert gas for protection, then adding 1.5mmol of disulfide and 1.5mmol of allyl bromide, adding 15mL of tetrahydrofuran, heating to 65 ℃, reacting for 48 hours, extracting the reaction product with diethyl ether, and purifying by passing through a column.
The main chemical reaction equation is as follows:
the obtained allylphenylsulfide is used in the preparation of the following electrolyte.
Example 1
Keeping the water content of the glove box at about 0.1ppm and the oxygen content at about 0.1ppm, sequentially adding dimethyl carbonate (DMC), Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) into a beaker according to the volume ratio of 1:1:1, cooling, slowly adding lithium hexafluorophosphate at the temperature of not higher than 10 ℃, adjusting the concentration to be 1.2mol/L, then adding 0.2 wt% of Vinylene Carbonate (VC), 5 wt% of fluoroethylene carbonate (FEC) and 4 wt% of 1, 3-Propane Sultone (PS), finally adding 1 wt% of allyl phenyl sulfide, and continuing stirring until the solution becomes clear, wherein the process is carried out under the protection of nitrogen.
Example 2
Keeping the water content of the glove box at about 0.1ppm and the oxygen content at about 0.1ppm, sequentially adding dimethyl carbonate (DMC), Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) into a beaker according to the volume ratio of 1:1:1, cooling, slowly adding lithium hexafluorophosphate at the temperature of not higher than 10 ℃, adjusting the concentration to be 1.2mol/L, then adding 0.2 wt% of Vinylene Carbonate (VC), 5 wt% of fluoroethylene carbonate (FEC), 4 wt% of 1, 3-Propane Sultone (PS), finally adding 3 wt% of allyl phenyl sulfide, and continuing stirring until the solution becomes clear, wherein the process is carried out under the protection of nitrogen.
Example 3
Keeping the water content of the glove box at about 0.1ppm and the oxygen content at about 0.1ppm, sequentially adding dimethyl carbonate (DMC), Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) into a beaker according to the volume ratio of 1:1:1, cooling, slowly adding lithium hexafluorophosphate at the temperature of not higher than 10 ℃, adjusting the concentration to be 1.2mol/L, then adding 0.2 wt% of Vinylene Carbonate (VC), 5 wt% of fluoroethylene carbonate (FEC), 4 wt% of 1, 3-Propane Sultone (PS), finally adding 5 wt% of allyl phenyl sulfide, and continuing stirring until the solution becomes clear, wherein the process is carried out under the protection of nitrogen.
Comparative example 1
Keeping the water content of the glove box at 0.1ppm and the oxygen content at 0.1ppm, sequentially adding dimethyl carbonate (DMC), Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) into a beaker according to the volume ratio of 1:1:1, cooling, slowly adding lithium hexafluorophosphate at the temperature of not higher than 10 ℃, adjusting the concentration to be 1.2mol/L, then adding 0.2 wt% of Vinylene Carbonate (VC), 5 wt% of fluoroethylene carbonate (FEC) and 4 wt% of 1, 3-Propane Sultone (PS) and continuing stirring until the solution becomes clear, wherein the process is carried out under the protection of nitrogen.
According to GB/T19282-. The test results are shown in table 1 below:
TABLE 1
| Comparative example | Example 1 | Example 2 | Example 3 | |
| Moisture (ppm) | 5.6 | 6.2 | 5.3 | 4.8 |
| Acidity (ppm) | 27.5 | 27.0 | 26.3 | 25.6 |
As can be seen from Table 1, the water content and acidity control was acceptable, and the water content in example 3 was 4.8ppm, and the acidity was lower than 25.6 ppm.
The experimental anode adopts a composite conductive agent Super-P, a binder PVDF-900, a 811 nickel cobalt manganese ternary anode material and a solvent NMP (N-methyl pyrrolidone), the cathode adopts graphite, a solvent CMC, ultrapure water, a conductive agent Super-P and a binder SBR as raw materials, a slurry is prepared by a wet pulping process, the viscosity of the anode is controlled to be 10000-12000 mPa & s, the viscosity of the cathode is controlled to be 1500-3000 mPa & s, the lithium ion soft package battery is prepared by coating, cutting into large sheets, rolling, slitting, drying at 85 ℃ for 48h, sticking an adhesive tape, winding and drying at 80 ℃ for 48h, injecting the different electrolyte formulas into a battery core, sealing, standing at 45 ℃ for 24h, forming and vacuum secondary sealing, and then the battery is subjected to cycle performance test.
And (2) circulating according to the charging and discharging current of 1.0/1.0C, recording the first discharging efficiency and the 1C discharging capacity under the condition of 45 ℃ and within the testing voltage range of 3.0-4.45V, wherein the following table 2 shows the circulating performance testing result as shown in figure 1, and figure 1 shows the relation curve graph of the capacity retention rate and the circulating times of the circulating battery.
TABLE 2
It can be seen from table 2 that the addition of the allyl phenyl sulfide additive can significantly improve the first discharge efficiency and discharge capacity of the lithium ion battery, wherein the performance of example 3 is better, the first discharge efficiency can reach 81.23%, and the 1C discharge capacity can reach 1947.15 mAh.
As can be seen from fig. 1, the addition of the allyl phenyl sulfide additive significantly improves the high-temperature cycle performance of the lithium ion battery, and in example 3, after 600 cycles, the capacity retention rate is about 87%, and the performance is better.
The phenyl sulfide additive is added into the high-voltage lithium ion battery electrolyte provided by the invention, so that the dissolution of metal ions can be effectively prevented, the occurrence of side reactions on the surface of an electrode can be inhibited, and the cycling stability of the battery under high voltage is improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A high voltage lithium ion battery electrolyte, comprising: lithium salt, organic solvent, phenyl thioether additive and other additives, wherein the structural general formula of the phenyl thioether additive is as follows:
[ chemical formula 1]
Said [ chemical formula 1]In, R1Is (C1-C5) alkyl, cyano, (C6-C12) aryl, and (C1-C5) alkyl halogen; r2Is (C1-C5) alkyl or hydrogen radical;
is a double or triple bond.
2. The high voltage lithium ion battery electrolyte of claim 1 wherein the phenyl thioether additive is selected from the following structures, but not limited thereto:
3. the high-voltage lithium ion battery electrolyte of claim 1, wherein the concentration of the phenylsulfide additive is controlled to be 0.1-10.0% by mass.
4. The high voltage lithium ion battery electrolyte of claim 3,
the phenyl sulfide additive is allyl phenyl sulfide.
5. The high voltage lithium ion battery electrolyte of claim 4,
the straight-chain carbonate organic solvent is one or a combination of more of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC) and Methyl Propyl Carbonate (MPC);
the cyclic carbonate solvent is selected from one or a combination of several of Ethylene Carbonate (EC), Propylene Carbonate (PC), Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC).
6. The high voltage lithium ion battery electrolyte of claim 5, wherein the lithium salt is LiPF6、LiBF4LiBOB, LiTFSi, LiFSI and LiPO2F2Any one of them or a mixture of several of them.
7. The high voltage lithium ion battery electrolyte of claim 6,
LiPF as the main lithium salt6The concentration of the lithium salt is controlled to be 0.5-1.5mol/L, and the concentration of other lithium salts is controlled to be 0.1-1.5 mol/L.
8. The high voltage lithium ion battery electrolyte of claim 7 wherein the other additives are selected from one or more combinations of Biphenyl (BP), 1, 3-Propane Sultone (PS), triphenyl phosphite (TPP), 1, 4-Butane Sultone (BS), Succinic Anhydride (SA), succinonitrile (NA) AND Adiponitrile (AND).
9. The high-voltage lithium ion battery electrolyte of claim 8, wherein a mixed solution of dimethyl carbonate (DMC), Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 1:1:1 is used as the organic solvent; the lithium salt is lithium hexafluorophosphate, and the concentration is 1.2 mol/L; the phenyl sulfide additive is allyl phenyl sulfide, the mass percent concentration is 5 wt%, and the other additives are 0.2 wt% of Vinylene Carbonate (VC), 5 wt% of fluoroethylene carbonate (FEC) and 4 wt% of 1, 3-Propane Sultone (PS).
10. The high voltage lithium ion battery electrolyte of claim 1, wherein the electrolyte is used in a lithium ion battery, a quasi-solid lithium battery, a solid lithium battery, and a lithium air battery.
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