CN110911749B - 一种高电压锂离子电池电解液、添加剂及该添加剂的制备方法 - Google Patents
一种高电压锂离子电池电解液、添加剂及该添加剂的制备方法 Download PDFInfo
- Publication number
- CN110911749B CN110911749B CN201911217857.8A CN201911217857A CN110911749B CN 110911749 B CN110911749 B CN 110911749B CN 201911217857 A CN201911217857 A CN 201911217857A CN 110911749 B CN110911749 B CN 110911749B
- Authority
- CN
- China
- Prior art keywords
- additive
- lithium ion
- ion battery
- electrolyte
- voltage lithium
- 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.)
- Active
Links
- 239000000654 additive Substances 0.000 title claims abstract description 29
- 230000000996 additive effect Effects 0.000 title claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- 239000003792 electrolyte Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- -1 thiourea derivative salt Chemical class 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000002000 Electrolyte additive Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 150000003585 thioureas Chemical class 0.000 claims abstract description 6
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 5
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000005935 nucleophilic addition reaction Methods 0.000 claims abstract description 3
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 3
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 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
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001942 caesium oxide Inorganic materials 0.000 claims description 2
- 239000012973 diazabicyclooctane Substances 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-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
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 2
- 229940049953 phenylacetate Drugs 0.000 claims description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-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
- 239000008096 xylene Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
本发明公开了一种高电压锂离子电池电解液、添加剂及该添加剂的制备方法，该添加剂为硫脲衍生物盐，该添加剂制备方法包括以下步骤：(1)首先将溶剂、催化剂和硫脲置于反应容器中，逐渐滴加二硫化碳，进行亲核加成反应得到二硫代氨基甲酸中间体；(2)之后加入无机碱反应得到硫脲衍生物盐粗品；(3)旋蒸去除溶剂后得到固体，将所得固体粗品进行重结晶，干燥后得到硫脲衍生物精品。该硫脲衍生物盐可做为高压锂离子电池电解液的添加剂，可捕获正极材料在高电压下产生的氧自由基。本发明原料易得，成本低廉，工艺简单，生产效率高，纯度高，产品有望作为电解液添加剂使用。
Description
[技术领域]
本发明涉及锂离子电池电解液添加剂技术领域，具体涉及一种高电压锂离子电池电解液、添加剂及该添加剂的制备方法，该添加剂为硫脲衍生物盐。
[背景技术]
近年来锂离子电池在电动汽车、混合动力汽车、储能系统和便携式电子设备中已经广泛应用，消费者对锂离子电池的能量密度的要求也越来越高。为了提高锂离子电池的能量密度，最有效的方式是提高正极材料的工作电压。研究人员开发出多种高电压正极材料，例如LiCoPO4、LiCoMnO4、LiNi0.5Mn1.5O4、富锂材料等。但高电压正极材料在实际使用过程中还存在几个问题：1.其工作电压都高于4.5V，而常规碳酸酯电解液的氧化电位都低于4.5V，因此限制了高电压正极材料在商业锂离子电池中的应用；2.高电压正极材料在充电过程中会缓慢释放晶格氧，晶格氧会氧化分解碳酸酯溶剂并影响电池性能。相对于正极材料改性工艺的复杂性，电解液的改性研究更加经济和方便。因此开发适用于高压锂离子电池的电解质意义重大。
在正极表面形成稳定的CEI膜可以有效抑制电解液的分解，提高其化学稳定性。在电解液中添加不同添加剂是解决此问题的最有效和最经济的方法。在充电过程中，正极成膜添加剂(例如：VC，PS，VES，PST等)可以优于碳酸酯溶剂提前在正极材料界面发生氧化反应，形成SEI膜，隔绝正极材料与电解液之间的副反应，从而保护正极材料。这些添加剂在高电压下成膜时，会产生气体，造成电池气胀，影响电池性能，而且这些添加剂不能吸收正极材料产生的晶格氧，不能有效提高电池性能。因此寻找既能够在正极材料界面参与成膜并能有效吸收氧自由基的添加剂具有非常大的理论和现实意义。
[发明内容]
为了解决以上问题，本发明提供了一种锂离子电池电解液添加剂，具体的该添加剂为硫脲衍生物盐，同时提供该添加剂的合成方法。本发明通过以下技术方案实现：
本发明的高电压锂离子电池电解液添加剂-硫脲衍生物盐分子式为：
另一方面，本发明提供上述硫脲衍生物盐的制备方法，该方法包括以下步骤：(1)首先将溶剂、催化剂和硫脲置于反应容器中，逐渐滴加二硫化碳，进行亲核加成反应得到二硫代氨基甲酸中间体；(2)之后加入无机碱反应得到硫脲衍生物盐粗品；(3)旋蒸去除溶剂后得到固体，将所得固体粗品进行重结晶，干燥后得到硫脲衍生物精品。
作为优选的，上述制备方法中，所述的溶剂为丙酮、丁酮、戊酮、苯甲酮、苯乙酮、甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸丁酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸苯酯、乙腈、丙腈、丁腈、二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷中的任意一种或几种。
作为优选的，上述制备方法中，所述的催化剂为三乙胺、吡啶、哌啶、1,8-二氮杂二环十一碳-7-烯(DBU)、三正丙胺、吗啉、三乙烯二胺(DABCO)中的任意一种或几种。
作为优选的，上述制备方法中，所述的催化剂用量为底物的1％-10％。
作为优选的，上述制备方法中，所述的反应温度为0-30℃。
作为优选的，上述制备方法中，所述的无机碱为氢化锂、氧化锂、氢氧化锂、碳酸锂、二异丙基氨基锂(LDA)、六甲基二硅基氨基锂(LiHMDS)、氢化钠、氧化钠、氢氧化钠、碳酸钠、氧化铯、氢氧化铯、碳酸铯、氢化钾、氢氧化钾、碳酸钾、氢氧化銣的任意一种或几种。
作为优选的，上述制备方法中，所述重结晶的溶剂为甲醇、乙醇、乙腈、四氢呋喃、正丁烷、正戊烷、正己烷、正庚烷、正辛烷、乙醚、二甲醚、甲乙醚、二丙醚、石油醚、苯甲醚、苯乙醚、苯、甲苯、二甲苯的任意一种或几种。
作为优选的，上述制备方法中，所述的干燥方式为真空干燥，干燥温度为40-70℃。
同时，本发明还提供一种高电压锂离子电池电解液，该锂离子电池的电解液包含上述的硫脲衍生物盐添加剂或者电解液含有通过上述方法制备的硫脲衍生物盐添加剂。
在上述制备方法中，萃取、重结晶所得溶剂可回收并进行精馏分离，重复利用。
上述制备的硫脲衍生物盐可做为高压锂离子电池电解液的添加剂，可捕获正极材料在高电压下产生的氧自由基，有效的提高了高电压锂离子电池性能。同时本发明制备方法原料易得，成本低廉，工艺简单，生产效率高、产品纯度高，为其在锂离子电池电解液中的应用打下良好的基础。
[具体实施方式]
本发明列举实施例如下，所举实施例仅仅用于帮助理解本发明，并非用于限定本发明的范围。
实施例1：
往1000mL三口烧瓶中投入300g二氯甲烷，然后向其投入100g硫脲和3g三乙胺，放入搅拌子，通入氮气，将三口烧瓶浸没在0℃的水浴锅中并开启磁力搅拌器，充分搅拌反应，反应2h，然后滴加300g二硫化碳，反应4h，反应完毕。加入126.3g氢氧化锂，反应2h。
将上述反应物50℃减压蒸馏，得到固体，加入300g正己烷进行重结晶，然后用正己烷洗涤三次得到橙黄色固体，40℃真空干燥12h，得到硫脲衍生物锂盐305.1g，产率92.0％，产品纯度99.4％。
实施例2：
往1000mL三口烧瓶中投入300g乙酸乙酯，然后向其投入100g硫脲和9g吡啶，放入搅拌子，通入氮气，将三口烧瓶浸没在10℃的水浴锅中并开启磁力搅拌器，充分搅拌反应，反应2h，然后滴加300g二硫化碳，反应4h，反应完毕。加入789.6g氢氧化铯，反应2h。
将上述反应物50℃减压蒸馏，得到固体，加入300g乙醚进行重结晶，然后用乙醚洗涤三次得到橙黄色，40℃真空干燥12h，得到硫脲衍生物铯盐898.4g，产率90.4％，产品纯度99.8％。
实施例3：
往1000mL三口烧瓶中投入300g丙酮，然后向其投入100g硫脲和21gDBU，放入搅拌子，通入氮气，将三口烧瓶浸没在30℃的水浴锅中并开启磁力搅拌器，充分搅拌反应，反应2h，然后滴加300g二硫化碳，反应4h，反应完毕。加入79.0g氧化锂，反应2h。
将上述反应物50℃减压蒸馏，得到橙黄色固体，加入300g石油醚进行重结晶，然后用石油醚洗涤三次得到白色固体，40℃真空干燥12h，得到硫脲衍生物锂盐318.4g，产率96.0％，产品纯度99.9％。
实施例4：
往1000mL三口烧瓶中投入300g丁酮，然后向其投入100g硫脲和30gDABCD，放入搅拌子，通入氮气，将三口烧瓶浸没在20℃的水浴锅中并开启磁力搅拌器，充分搅拌反应，反应2h，然后滴加300g二硫化碳，反应4h，反应完毕。加入210.6g氢化钾，反应2h。
将上述反应物50℃减压蒸馏，得到固体，加入300g苯进行重结晶，然后用苯洗涤三次得到橙黄色固体，40℃真空干燥12h，得到硫脲衍生物钾盐295.4g，产率93.5％，产品纯度99.3％。
上述实施例对本发明作了详细的说明，但并不意味着本发明仅仅局限于这些实例。在不脱离本发明技术原理的情况下，对其进行改进和变形在本发明权利要求和技术之内，也应属于本发明的保护范围。
Claims (9)
1.一种高电压锂离子电池电解液添加剂，其特征在于，该添加剂为硫脲衍生物盐，其化学结构式为：
2.一种如权利要求1所述的高电压锂离子电池电解液添加剂的制备方法，其特征在于，包括以下步骤：
步骤1：将溶剂、催化剂和硫脲置于反应容器中，滴加二硫化碳，进行亲核加成反应得到二硫代氨基甲酸中间体；
步骤2：反应完成后加入无机碱制备得到硫脲衍生物盐粗品；
步骤3：旋蒸去除溶剂后得到固体，将所得固体粗品进行重结晶，干燥后得到硫脲衍生物精品。
3.根据权利要求2所述的高电压锂离子电池电解液添加剂的制备方法，其特征在于，步骤1的溶剂为丙酮、丁酮、戊酮、苯甲酮、苯乙酮、甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸丁酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸苯酯、乙腈、丙腈、丁腈、二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷中的任意一种或几种。
4.根据权利要求2所述的高电压锂离子电池电解液添加剂的制备方法，其特征在于，步骤1的催化剂为三乙胺、吡啶、哌啶、1,8-二氮杂二环十一碳-7-烯（DBU)、三正丙胺、吗啉、三乙烯二胺（DABCO）中的任意一种或几种。
5.根据权利要求2所述的高电压锂离子电池电解液添加剂的制备方法，其特征在于，步骤1-3的反应温度为0-30℃。
6.根据权利要求2所述的高电压锂离子电池电解液添加剂的制备方法，其特征在于，步骤2的无机碱为氢化锂、氧化锂、氢氧化锂、碳酸锂、氢化钠、氧化钠、氢氧化钠、碳酸钠、氧化铯、氢氧化铯、碳酸铯、氢化钾、氢氧化钾、碳酸钾、氢氧化铷的任意一种或几种。
7.根据权利要求2所述的高电压锂离子电池电解液添加剂的制备方法，其特征在于，步骤3重结晶的溶剂为甲醇、乙醇、乙腈、四氢呋喃、正丁烷、正戊烷、正己烷、正庚烷、正辛烷、乙醚、二甲醚、甲乙醚、二丙醚、石油醚、苯甲醚、苯乙醚、苯、甲苯、二甲苯的任意一种或几种。
8.根据权利要求2所述的高电压锂离子电池电解液添加剂的制备方法，其特征在于，步骤3的干燥方式为真空干燥，干燥温度为40-70℃。
9.一种高电压锂离子电池电解液，其特征在于，所述锂离子电池的电解液包含如权利要求1所述的硫脲衍生物盐添加剂或者电解液含有通过权利要求2-8中任一项所述方法制备的硫脲衍生物盐添加剂。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911217857.8A CN110911749B (zh) | 2019-12-03 | 2019-12-03 | 一种高电压锂离子电池电解液、添加剂及该添加剂的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911217857.8A CN110911749B (zh) | 2019-12-03 | 2019-12-03 | 一种高电压锂离子电池电解液、添加剂及该添加剂的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110911749A CN110911749A (zh) | 2020-03-24 |
| CN110911749B true CN110911749B (zh) | 2023-02-03 |
Family
ID=69821421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911217857.8A Active CN110911749B (zh) | 2019-12-03 | 2019-12-03 | 一种高电压锂离子电池电解液、添加剂及该添加剂的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110911749B (zh) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3784632A (en) * | 1971-07-01 | 1974-01-08 | Banyu Pharma Co Ltd | 2,6-bis(thiourea) derivatives of pyridine |
| US5610311A (en) * | 1993-05-18 | 1997-03-11 | Buckman Laboratories International, Inc. | Reaction of metal salt of an S-substituted N-cyanodithiominocarbonate with hydrazine or hydrazine hydrate |
| CN101735129A (zh) * | 2009-12-03 | 2010-06-16 | 西北师范大学 | N-苯基-n′-(2-乙酰氧基苯甲酰基)硫脲衍生物及其制备和应用 |
| CN108642926A (zh) * | 2018-04-26 | 2018-10-12 | 浙江汉邦化工有限公司 | 一种涤纶染色清洗用的硫脲衍生物及其制备方法 |
| CN109256587A (zh) * | 2018-07-18 | 2019-01-22 | 青海泰丰先行锂能科技有限公司 | 金属锂二次电池用电解液以及使用该电解液的金属锂二次电池 |
| CN109400511A (zh) * | 2018-11-21 | 2019-03-01 | 中南大学 | 一种制备硫脲衍生物并联产巯基丙酸的方法 |
| CN109962289A (zh) * | 2017-12-22 | 2019-07-02 | 财团法人工业技术研究院 | 电解质组合物及包含其的金属离子电池 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5935913A (en) * | 1998-10-16 | 1999-08-10 | Uniroyal Chemical Company, Inc. | Cyclic thiourea additives for lubricants |
-
2019
- 2019-12-03 CN CN201911217857.8A patent/CN110911749B/zh active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3784632A (en) * | 1971-07-01 | 1974-01-08 | Banyu Pharma Co Ltd | 2,6-bis(thiourea) derivatives of pyridine |
| US5610311A (en) * | 1993-05-18 | 1997-03-11 | Buckman Laboratories International, Inc. | Reaction of metal salt of an S-substituted N-cyanodithiominocarbonate with hydrazine or hydrazine hydrate |
| CN101735129A (zh) * | 2009-12-03 | 2010-06-16 | 西北师范大学 | N-苯基-n′-(2-乙酰氧基苯甲酰基)硫脲衍生物及其制备和应用 |
| CN109962289A (zh) * | 2017-12-22 | 2019-07-02 | 财团法人工业技术研究院 | 电解质组合物及包含其的金属离子电池 |
| CN108642926A (zh) * | 2018-04-26 | 2018-10-12 | 浙江汉邦化工有限公司 | 一种涤纶染色清洗用的硫脲衍生物及其制备方法 |
| CN109256587A (zh) * | 2018-07-18 | 2019-01-22 | 青海泰丰先行锂能科技有限公司 | 金属锂二次电池用电解液以及使用该电解液的金属锂二次电池 |
| CN109400511A (zh) * | 2018-11-21 | 2019-03-01 | 中南大学 | 一种制备硫脲衍生物并联产巯基丙酸的方法 |
Non-Patent Citations (1)
| Title |
|---|
| N-苯基硫脲衍生物新的合成方法;刘海灵等;《化学试剂》;20171215(第12期);102-106 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110911749A (zh) | 2020-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111755753B (zh) | 一种锂离子电池电解液添加剂环碳酸硫酸乙烯酯及其制备方法 | |
| EP3086397B1 (en) | Nonaqueous electrolyte solution, electricity storage device using same, and phosphonoformic acid compound used in same | |
| JP6689926B2 (ja) | 硫酸エステルの生成方法 | |
| KR102617501B1 (ko) | 전해질 조성물, 이차 전지, 및 이차 전지의 사용 방법 | |
| CN111763200A (zh) | 一种锂离子电池电解液添加剂环碳酸硫酸乙烯酯及其制备方法 | |
| CN106558731A (zh) | 一种锂离子电池电解液和锂离子电池 | |
| KR102179846B1 (ko) | 리튬 이차전지용 전해질 첨가제 조성물 및 그 제조방법 | |
| CN104649932A (zh) | 用于锂二次电池的非水电解质溶液以及包含该非水电解质溶液的锂二次电池 | |
| CN110003265A (zh) | 一种1,4-丁炔二（三烷基硅基）酯的制备方法 | |
| CN110911750B (zh) | 一种高电压锂离子电池电解液、添加剂及该添加剂的制备方法 | |
| EP4480954A1 (en) | Silicon-based phosphate and preparation method therefor | |
| CN110911749B (zh) | 一种高电压锂离子电池电解液、添加剂及该添加剂的制备方法 | |
| CN110590735B (zh) | 一种环状硫酸酯的制备方法 | |
| CN113444066A (zh) | 一种硫酸乙烯酯的制备方法 | |
| JP6010252B2 (ja) | 双性イオン化合物およびイオン伝導体 | |
| CN112744843B (zh) | 一种电池级硫化锂的合成方法及电池级硫化锂 | |
| CN112928329B (zh) | 一种锂离子电池电解液添加剂及其制备方法和应用 | |
| EP4424691A1 (en) | Cyclic phosphine compound preparation method | |
| CN112201852B (zh) | 一种锂离子电池电解液添加剂及其制备方法以及锂离子电池电解液 | |
| CN103030621A (zh) | 一种不饱和环状碳酸酯的制备方法 | |
| US20240300915A1 (en) | Method for Preparing Cyclic Sulfonic Acid Ester Derivative Compound | |
| KR102504826B1 (ko) | 하이드록시-치환된 디메틸디옥솔론의 제조방법 | |
| KR102638391B1 (ko) | 다이알칸설포닐 아이소소바이드 화합물의 제조 방법, 리튬이차전지용 전해액 첨가제, 리튬이차전지용 전해액 및 리튬이차전지 | |
| KR102771022B1 (ko) | 이차전지용 전해질 첨가제, 이의 제조방법, 이를 포함하는 전해질 및 이차전지 | |
| JP5703009B2 (ja) | スルホン化合物、スルホン化合物の製造方法、および電気化学デバイス用電解液 |
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 |