CN111129596A - High-voltage additive and high-voltage electrolyte for lithium battery - Google Patents
High-voltage additive and high-voltage electrolyte for lithium battery Download PDFInfo
- Publication number
- CN111129596A CN111129596A CN201911369254.XA CN201911369254A CN111129596A CN 111129596 A CN111129596 A CN 111129596A CN 201911369254 A CN201911369254 A CN 201911369254A CN 111129596 A CN111129596 A CN 111129596A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- lithium
- voltage
- additive
- halogenated
- 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.)
- Granted
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 63
- 239000000654 additive Substances 0.000 title claims abstract description 54
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 230000000996 additive effect Effects 0.000 title claims abstract description 41
- -1 cyclic enamine Chemical class 0.000 claims abstract description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- XNENYPKLNXFICU-UHFFFAOYSA-N P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C XNENYPKLNXFICU-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 230000026030 halogenation Effects 0.000 claims description 2
- 238000005658 halogenation reaction Methods 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- OWNSEPXOQWKTKG-UHFFFAOYSA-M lithium;methanesulfonate Chemical compound [Li+].CS([O-])(=O)=O OWNSEPXOQWKTKG-UHFFFAOYSA-M 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 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
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims 1
- BZQRBEVTLZHKEA-UHFFFAOYSA-L magnesium;trifluoromethanesulfonate Chemical compound [Mg+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F BZQRBEVTLZHKEA-UHFFFAOYSA-L 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 description 14
- 229910012258 LiPO Inorganic materials 0.000 description 13
- 238000004090 dissolution Methods 0.000 description 13
- 239000012300 argon atmosphere Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AHIWWUJXDLMOKI-UHFFFAOYSA-N methoxysulfonylmethanesulfonic acid Chemical compound COS(=O)(=O)CS(O)(=O)=O AHIWWUJXDLMOKI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-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
-
- 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)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-voltage additive and a high-voltage electrolyte for a lithium battery, wherein the high-voltage additive is a compound containing a cyclic enamine and thiophosphonate structure, and the structural formula I is as follows:
wherein R is1，R2Respectively one of alkyl with 1-8 carbon atoms, halogenated alkyl, alkenyl with 2-8 carbon atoms, halogenated alkenyl, alkynyl with 2-8 carbon atoms, halogenated alkynyl, aryl with 6-8 carbon atoms or halogenated aryl. The high-voltage additive disclosed by the invention can form a stable and compact CEI film on the positive electrode, stabilize transition metal ions on the surface of a positive electrode material, inhibit oxygen precipitation of the positive electrode material and reduce oxidative decomposition of electrolyte; can also form a film on the negative electrode, improve the stability of the SEI film of the negative electrode and improve the lithium battery under the condition of high voltageAnd (4) performance.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a high-voltage additive and a high-voltage electrolyte for a lithium battery.
Background
Since the commercialization in the 90 s of the 20 th century, lithium batteries have been widely used because of their advantages of high energy density, high charge and discharge efficiency, low self-discharge, long service life, and environmental friendliness. The method is applied to the fields of consumer electronics, aerospace, military, electric tools, electric automobiles and the like. With the development of technology, no matter in the consumer field or the power battery field, people have higher and higher requirements on the cruising ability of lithium ion batteries, and the development of high energy density (mass energy density and volume energy density) lithium batteries becomes a key point. The development of a high-energy density lithium battery can be started from two aspects, namely, the development of a new high-gram-capacity anode and cathode material; and secondly, the charging and discharging voltage of the lithium battery is improved. The charging and discharging voltage of the lithium battery is improved, the mass energy density and the volume energy density of the lithium battery can be improved, the cost of the lithium battery can be reduced, and the lithium battery becomes a hotspot of research of people.
However, in the study of high voltage lithium batteries, it was found that the deterioration of the battery performance was significant as the voltage of the lithium battery was increased. The main reason is that when the voltage of the lithium battery rises, the anode material can react with the electrolyte in the battery, and the performance of the lithium battery is affected. Therefore, the development of electrolyte matching with high voltage lithium battery becomes key.
Disclosure of Invention
In view of the above, the present invention is directed to a high voltage additive and a high voltage electrolyte for a lithium battery, which can improve the stability of a CEI film on the surface of a positive electrode material of the battery and improve the cycle performance and storage performance of the lithium battery.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a high voltage additive, said high voltage additive being a compound containing cyclic enamine and thiophosphonate structures, having the following structural formula I:
wherein R is1，R2Respectively one of alkyl with 1-8 carbon atoms, halogenated alkyl, alkenyl with 2-8 carbon atoms, halogenated alkenyl, alkynyl with 2-8 carbon atoms, halogenated alkynyl, aryl with 6-8 carbon atoms or halogenated aryl.
Furthermore, the halogenation in the halogenated alkyl, halogenated alkenyl and halogenated aryl is partial substitution or full substitution.
Further, the halogen is one or more of fluorine, chlorine and bromine.
The invention also provides a high-voltage electrolyte for the lithium battery, which comprises the following components: the electrolyte comprises a lithium salt electrolyte, an organic solvent, a high-voltage additive and an auxiliary additive, wherein the addition amount of the high-voltage additive is 0.01-5 wt% of the total mass of the electrolyte.
Further, the lithium salt electrolyte is one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium methylsulfonate, lithium trifluoromethylsulfonate, lithium bis (pentafluoroethylsulfonimide), lithium bis (trifluoromethylsulfonimide) and lithium bis (fluorosulfonimide).
Further, the addition amount of the lithium salt electrolyte is 1 wt% -20 wt% of the total mass of the electrolyte.
Further, the organic solvent is any one or a mixture of more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, 1, 4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate and halogenated derivatives thereof.
Furthermore, the adding amount of the organic solvent is 70 wt% -90 wt% of the total mass of the electrolyte.
Further, the auxiliary additive is one or more of vinylene carbonate, vinyl ethylene carbonate, vinyl acetate, ethylene sulfite, propylene sulfite, vinyl sulfate, 1, 3-propane sultone, propenyl-1, 3-propane sultone, 1, 4-butane sultone, methyl methane disulfonate, hexamethyl disilazane, magnesium imine trifluoromethanesulfonate, tris (pentafluorophenyl) boron, tris (trimethylsilane) phosphate, tris (trimethylsilane) phosphite, nitriles, sulfones and acid anhydride.
Furthermore, the addition amount of the auxiliary additive is 1 wt% -10 wt% of the total mass of the electrolyte.
Compared with the prior art, the high-voltage additive and the high-voltage electrolyte for the lithium battery have the following advantages:
the high-voltage additive is a compound containing a cyclic enamine and thiophosphonate structure, and the additive can form a stable and compact CEI film on the positive electrode, stabilize transition metal ions on the surface of the positive electrode material, inhibit oxygen precipitation of the positive electrode material and reduce oxidative decomposition of the electrolyte; and a film can be formed on the negative electrode, so that the stability of the SEI film of the negative electrode is improved, and the performance of the lithium battery under a high-voltage condition is improved.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
A high voltage additive having the formula:
example 1: preparation of lithium batteries
(1) Selecting lithium cobaltate suitable for high voltage as a positive electrode material, and preparing the positive electrode material LiCoO2Mixing CNTs and PVDF uniformly according to the ratio of 98:1:1, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector through an oven, rolling the aluminum foil current collector on a roller press, and compacting the aluminum foil current collector to obtain the aluminum foil current collector with the compaction density of 4.1g/cm3And obtaining the required positive plate.
(2) Selecting artificial graphite as a negative electrode material, and mixing graphite, CMC, a conductive agent and a binder according to a ratio of 95: 1.2: 1.8: 2 to obtain a negative pole piece, wherein the compacted density of the pole piece is 1.7g/cm3。
(3) Selecting a PE film coated with ceramic as an isolating film (9+3) um, and manufacturing the pole piece into a small soft package battery of 1Ah by a lamination method for testing high-voltage electrolyte.
Example 2: lithium battery performance test
The charging and discharging voltage window of the lithium battery is 2.8-4.5V; the cycle test of the battery is that the room temperature is 25 ℃ and the high temperature is 45 ℃, and the cyclic charge-discharge current is 0.5C; the high-temperature storage performance test is that the temperature is 60 ℃, the 100 percent SOC is stored for 7 days, and the charge and discharge current is 0.5C.
Example 3:
in argon atmosphere, the environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2PS, and then adding 1% of high-voltage additive A to prepare electrolyte I.
Example 4:
in argon atmosphere, the environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2PS, and then adding 1% of high-voltage additive B to prepare electrolyte II.
Example 5:
in argon atmosphere, the environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2PS, and then adding 1% of high-voltage additive C to prepare electrolyte III.
Example 6:
in an argon atmosphereThe environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2PS, and then adding 1% of high-voltage additive D to prepare electrolyte IV.
Example 7:
in argon atmosphere, the environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2PS, and then adding 1% of high-voltage additive E to prepare electrolyte V.
Example 8:
in argon atmosphere, the environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2PS, and then adding 1% of high-voltage additive F to prepare electrolyte VI.
Example 9:
in argon atmosphere, the environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2PS, and then adding 0.5% of high-voltage additive F to prepare the electrolyte VII.
Example 10:
in argon atmosphere, the environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2PS, and then adding 1% of high-voltage additive G to prepare electrolyte VIII.
Example 11:
in argon atmosphere, the environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2PS, and then 0.5% of high voltage additive G is added to prepare electrolyte IX.
Example 12:
in argon atmosphere, the environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2PS, and then 0.5% of high-voltage additive H is added to prepare electrolyte X.
Example 13:
in argon atmosphere, the environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2And PS, then0.1% of high voltage additive B was added to obtain electrolyte XI.
Comparative example 1:
in argon atmosphere, the environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2And PS, comparative electrolyte 1 was prepared.
Comparative example 2:
in argon atmosphere, the environmental index is H2O≤0.5ppm，O2In a glove box with the mass ratio of EC/FEC/DEC being equal to or less than 2.0ppm, organic solvents EC, FEC and DEC are mixed according to the mass ratio of EC/FEC/DEC being 25/5/70, then lithium hexafluorophosphate is added for dissolution, electrolyte with the concentration of lithium hexafluorophosphate being 1M is prepared, and then auxiliary additives VC and LiPO are added according to the mass fractions of 1 percent, 0.7 percent and 1 percent respectively2F2PS, and then 7% of high-voltage additive D is added to prepare electrolyte XII.
Table 1 shows the results of the electrical property tests of examples 3 to 13 and comparative examples 1 and 2.
Table 1 summary of electrical property data for different electrolytes
It can be seen from the data in table 1 that, compared to comparative electrolyte 1, the cycle life and high temperature storage life of the lithium battery are improved to some extent within a suitable addition range after the high voltage additive of the present invention is used. The high-voltage additive disclosed by the invention is excellent in performance and the prepared high-voltage electrolyte is good in performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A high voltage additive, characterized by: the high-voltage additive is a compound containing a cyclic enamine and thiophosphonate structure, and the structural formula I is as follows:
wherein R is1，R2Respectively one of alkyl with 1-8 carbon atoms, halogenated alkyl, alkenyl with 2-8 carbon atoms, halogenated alkenyl, alkynyl with 2-8 carbon atoms, halogenated alkynyl, aryl with 6-8 carbon atoms or halogenated aryl.
2. The high voltage additive of claim 1, wherein: the halogenation in the halogenated alkyl, the halogenated alkenyl and the halogenated aryl is partial substitution or complete substitution.
3. A high voltage additive according to any one of claims 1 or 2, wherein: halogen is one or more of fluorine, chlorine and bromine.
4. A high-voltage electrolyte for a lithium battery is characterized in that: comprises the following components: a lithium salt electrolyte, an organic solvent, the high voltage additive according to any one of claims 1 to 3, and an auxiliary additive, wherein the high voltage additive is added in an amount of 0.01 to 5 wt% based on the total mass of the electrolyte.
5. The high-voltage electrolyte for a lithium battery as claimed in claim 4, wherein: the lithium salt electrolyte is one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium tetrafluoroborate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium methylsulfonate, lithium trifluoromethylsulfonate, lithium bis (pentafluoroethylsulfonimide), lithium bis (trifluoromethylsulfonimide) and lithium bis (fluorosulfonimide).
6. The high-voltage electrolyte for a lithium battery as claimed in claim 4, wherein: the addition amount of the lithium salt electrolyte is 1-20 wt% of the total mass of the electrolyte.
7. The high-voltage electrolyte for a lithium battery as claimed in claim 4, wherein: the organic solvent is any one or a mixture of more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, 1, 4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate and halogenated derivatives thereof.
8. The high-voltage electrolyte for a lithium battery as claimed in claim 4, wherein: the adding amount of the organic solvent is 70-90 wt% of the total mass of the electrolyte.
9. The high-voltage electrolyte for a lithium battery as claimed in claim 4, wherein: the auxiliary additive is one or more of vinylene carbonate, vinyl ethylene carbonate, vinyl acetate, ethylene sulfite, propylene sulfite, vinyl sulfate, 1, 3-propane sultone, propenyl-1, 3-propane sultone, 1, 4-butane sultone, methyl disulfonate, hexamethyldisilazane, magnesium trifluoromethanesulfonate, tris (penta-fluorinated phenyl) boron, tris (trimethylsilane) phosphate, tris (trimethylsilane) phosphite, nitriles, sulfones and anhydride.
10. The high-voltage electrolyte for a lithium battery as claimed in claim 4, wherein: the addition amount of the auxiliary additive is 1-10 wt% of the total mass of the electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911369254.XA CN111129596B (en) | 2019-12-26 | 2019-12-26 | High-voltage additive and high-voltage electrolyte for lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911369254.XA CN111129596B (en) | 2019-12-26 | 2019-12-26 | High-voltage additive and high-voltage electrolyte for lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111129596A true CN111129596A (en) | 2020-05-08 |
| CN111129596B CN111129596B (en) | 2022-06-17 |
Family
ID=70503347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911369254.XA Active CN111129596B (en) | 2019-12-26 | 2019-12-26 | High-voltage additive and high-voltage electrolyte for lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111129596B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710909A (en) * | 2020-06-28 | 2020-09-25 | 天目湖先进储能技术研究院有限公司 | Multifunctional additive for lithium battery electrolyte, preparation method and application thereof |
| CN112310478A (en) * | 2020-10-23 | 2021-02-02 | 惠州锂威新能源科技有限公司 | Electrolyte and electrochemical device thereof |
| CN112838270A (en) * | 2021-03-18 | 2021-05-25 | 合肥国轩高科动力能源有限公司 | Electrolyte additive for improving battery high temperature flatulence, electrolyte and lithium ion battery containing the same |
| CN115000518A (en) * | 2022-06-27 | 2022-09-02 | 天目湖先进储能技术研究院有限公司 | Application of compound with sulfur ring phosphoryl ester structure as electrolyte high-voltage additive |
| TWI777912B (en) * | 2022-06-02 | 2022-09-11 | 台灣中油股份有限公司 | Lithium-ion battery electrolyte and lithium-ion battery |
| CN119994195A (en) * | 2025-04-14 | 2025-05-13 | 上海如鲲新材料股份有限公司 | Non-aqueous electrolyte, lithium-ion battery, battery module, battery pack and power-consuming device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1494723A (en) * | 2001-12-28 | 2004-05-05 | 如碧空株式会社 | Electrolytic Capacitors and Electrolytic Solutions for Driving Electrolytic Capacitors |
| CN1518544A (en) * | 2001-06-15 | 2004-08-04 | 三井化学株式会社 | Piperazine derivative, method for producing same, polymer solid electrolyte, and secondary battery |
| US20170301952A1 (en) * | 2016-04-15 | 2017-10-19 | Contemporary Amperex Technology Co., Limited | Electrolyte and lithium-ion battery containing the same |
| CN108808091A (en) * | 2018-07-19 | 2018-11-13 | 合肥国轩高科动力能源有限公司 | A kind of high wettability electrolytic solution and lithium ion battery for lithium ion battery |
-
2019
- 2019-12-26 CN CN201911369254.XA patent/CN111129596B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1518544A (en) * | 2001-06-15 | 2004-08-04 | 三井化学株式会社 | Piperazine derivative, method for producing same, polymer solid electrolyte, and secondary battery |
| CN1494723A (en) * | 2001-12-28 | 2004-05-05 | 如碧空株式会社 | Electrolytic Capacitors and Electrolytic Solutions for Driving Electrolytic Capacitors |
| US20170301952A1 (en) * | 2016-04-15 | 2017-10-19 | Contemporary Amperex Technology Co., Limited | Electrolyte and lithium-ion battery containing the same |
| CN108808091A (en) * | 2018-07-19 | 2018-11-13 | 合肥国轩高科动力能源有限公司 | A kind of high wettability electrolytic solution and lithium ion battery for lithium ion battery |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710909A (en) * | 2020-06-28 | 2020-09-25 | 天目湖先进储能技术研究院有限公司 | Multifunctional additive for lithium battery electrolyte, preparation method and application thereof |
| CN111710909B (en) * | 2020-06-28 | 2022-06-17 | 天目湖先进储能技术研究院有限公司 | Multifunctional additive for lithium battery electrolyte, preparation method and application thereof |
| CN112310478A (en) * | 2020-10-23 | 2021-02-02 | 惠州锂威新能源科技有限公司 | Electrolyte and electrochemical device thereof |
| CN112310478B (en) * | 2020-10-23 | 2022-04-01 | 惠州锂威新能源科技有限公司 | Electrolyte and electrochemical device thereof |
| CN112838270A (en) * | 2021-03-18 | 2021-05-25 | 合肥国轩高科动力能源有限公司 | Electrolyte additive for improving battery high temperature flatulence, electrolyte and lithium ion battery containing the same |
| TWI777912B (en) * | 2022-06-02 | 2022-09-11 | 台灣中油股份有限公司 | Lithium-ion battery electrolyte and lithium-ion battery |
| CN115000518A (en) * | 2022-06-27 | 2022-09-02 | 天目湖先进储能技术研究院有限公司 | Application of compound with sulfur ring phosphoryl ester structure as electrolyte high-voltage additive |
| CN119994195A (en) * | 2025-04-14 | 2025-05-13 | 上海如鲲新材料股份有限公司 | Non-aqueous electrolyte, lithium-ion battery, battery module, battery pack and power-consuming device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111129596B (en) | 2022-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111129596B (en) | High-voltage additive and high-voltage electrolyte for lithium battery | |
| CN109921092B (en) | Non-aqueous electrolyte of silicon-based negative electrode lithium ion battery and silicon-based negative electrode lithium ion battery containing electrolyte | |
| CN109193029B (en) | High-nickel ternary lithium ion battery non-aqueous electrolyte and high-nickel ternary lithium ion battery containing electrolyte | |
| CN109873206B (en) | Lithium ion battery electrolyte and lithium ion battery | |
| CN108987808B (en) | High-voltage lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN116247301B (en) | Electrolyte and lithium ion battery | |
| CN113078358A (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery thereof | |
| CN110911754A (en) | Lithium ion battery electrolyte and preparation method thereof | |
| CN108987802B (en) | Non-aqueous electrolyte for high-voltage lithium ion battery | |
| CN112510261A (en) | Electrolyte for high-voltage cobalt acid lithium battery and lithium cobalt acid battery | |
| CN112002944B (en) | High-temperature electrolyte for silicon-carbon composite cathode and secondary battery | |
| CN114188608B (en) | Boron-containing sulfonate non-aqueous electrolyte additive and lithium ion battery prepared from same | |
| CN110265718A (en) | Electrolysis additive, electrolyte and battery | |
| CN115189025A (en) | Electrolyte and battery comprising same | |
| CN111755752A (en) | High-voltage additive, electrolyte and lithium battery | |
| CN113394461B (en) | High-voltage additive for lithium battery electrolyte, electrolyte and lithium battery | |
| CN112331916A (en) | Electrolyte and application thereof | |
| CN108987803B (en) | Lithium metal negative electrode film-forming electrolyte for lithium-sulfur battery and additive thereof | |
| CN117013076A (en) | A kind of lithium ion electrolyte and lithium ion battery | |
| CN114583263B (en) | Electrolyte, positive electrode, lithium ion battery and vehicle | |
| CN115000518B (en) | Application of compound with phosphorothioate structure as electrolyte high-voltage additive | |
| CN114927758A (en) | Electrolyte for improving high-temperature performance of lithium ion battery and lithium ion battery | |
| CN118919848B (en) | Sodium ion battery electrolyte additive, electrolyte and sodium ion battery | |
| CN119069790B (en) | Applications of polyazine compounds in electrolytes, as well as electrolytes, their preparation methods and applications, lithium-ion batteries and electrical equipment. | |
| CN117790895B (en) | High-entropy suspension ether electrolyte and lithium ion battery thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |