CN110112463A - A kind of electrolysis additive, high-voltage electrolyte and battery containing the additive - Google Patents
A kind of electrolysis additive, high-voltage electrolyte and battery containing the additive Download PDFInfo
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- CN110112463A CN110112463A CN201910269683.3A CN201910269683A CN110112463A CN 110112463 A CN110112463 A CN 110112463A CN 201910269683 A CN201910269683 A CN 201910269683A CN 110112463 A CN110112463 A CN 110112463A
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- Prior art keywords
- lithium
- organic
- additive
- electrolyte
- phosphoric acid
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 90
- 239000000654 additive Substances 0.000 title claims abstract description 68
- 230000000996 additive effect Effects 0.000 title claims abstract description 68
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 57
- OQPHEVHDBFEJRQ-UHFFFAOYSA-N [Li].P(O)(O)(O)=O Chemical class [Li].P(O)(O)(O)=O OQPHEVHDBFEJRQ-UHFFFAOYSA-N 0.000 claims abstract description 39
- -1 organic acid lithium analog Chemical class 0.000 claims abstract description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 47
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 45
- 229910052744 lithium Inorganic materials 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- 150000007524 organic acids Chemical class 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 6
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 5
- QRMHDYCPNIVCBO-UHFFFAOYSA-N [SH2]=N.[F] Chemical compound [SH2]=N.[F] QRMHDYCPNIVCBO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- MWQJGSUQGMJVCS-UHFFFAOYSA-N N=[S+]C(F)(F)F.[Li] Chemical compound N=[S+]C(F)(F)F.[Li] MWQJGSUQGMJVCS-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims 4
- 150000001336 alkenes Chemical group 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims 2
- 229960001826 dimethylphthalate Drugs 0.000 claims 2
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims 2
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical group O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 19
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 90
- 239000002904 solvent Substances 0.000 description 37
- 230000015572 biosynthetic process Effects 0.000 description 32
- 238000003786 synthesis reaction Methods 0.000 description 32
- 238000005160 1H NMR spectroscopy Methods 0.000 description 30
- 238000005481 NMR spectroscopy Methods 0.000 description 30
- 238000000034 method Methods 0.000 description 18
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- IRHGPRUKFSWULZ-UHFFFAOYSA-N S(O)(O)(=O)=O.FC(CO)(F)F Chemical compound S(O)(O)(=O)=O.FC(CO)(F)F IRHGPRUKFSWULZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000009966 trimming Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010277 constant-current charging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011356 non-aqueous organic solvent Substances 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910010941 LiFSI Inorganic materials 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- QVZJIDDGYMVUJG-UHFFFAOYSA-N acetonitrile;carbonic acid Chemical compound CC#N.OC(O)=O QVZJIDDGYMVUJG-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 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 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010067484 Adverse reaction Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010058490 Hyperoxia Diseases 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 230000000222 hyperoxic effect Effects 0.000 description 1
- ALTVCFKRYOLNPF-UHFFFAOYSA-N imino(trifluoromethyl)sulfanium Chemical compound FC(F)(F)[S+]=N ALTVCFKRYOLNPF-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- MGNVWUDMMXZUDI-UHFFFAOYSA-N propane-1,3-disulfonic acid Chemical compound OS(=O)(=O)CCCS(O)(=O)=O MGNVWUDMMXZUDI-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/094—Esters of phosphoric acids with arylalkanols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Secondary Cells (AREA)
Abstract
High-voltage electrolyte and battery the purpose of the present invention is to provide a kind of electrolysis additive and containing the additive；Belong to technical field of lithium ion.The electrolysis additive is organic phosphoric acid lithium, organic acid lithium analog derivative.High-voltage electrolyte is made in the additive that 1% or so are added into conventional electrolysis liquid by the present invention, so that electrolyte has high oxidation potential (4.5V or more), and then high-voltage anode material can be matched, this provides necessary condition to obtain the lithium ion battery of high-energy density, and the addition of the additive, stable SEI film is contributed to form, so as to extend the cycle performance of battery.Electrolysis additive of the present invention is reasonable in design, and preparation method is simple, products obtained therefrom function admirable, is convenient for large-scale industrialization application.
Description
Technical field
The present invention relates to field of batteries, especially provide a kind of electrolyte and the battery including the electrolyte.
Background technique
Lithium ion battery is electric car optimal power supply selection scheme at present, and electrolyte is the important composition of lithium ion battery
Part decides capacity, service life and the discharge-rate of battery.Electrolyte is made of lithium salts, solvent and additive, traditional electrolyte
Using lithium hexafluoro phosphate as main body lithium salts, lithium hexafluoro phosphate decomposition temperature is low, Conductivity at low temperature is poor, limits lithium ion battery
Application in electric car field.
The voltage of lithium ion battery is higher, and the energy density of battery is also higher, but simultaneously, positive/negative plate and electrolyte it is anti-
Answer activity can also greatly enhance, cause battery accelerate decaying, cycle life significantly reduce the problems such as.Especially when battery is in high temperature
Under the conditions of in use, electrolyte is further exacerbated by under high temperature action with cathode, anode surface reactivity, the oxidation of electrolyte
Reduction reaction aggravation generates gas, leads to cell expansion along with the generation of a large amount of side reactions.This does not only result in cell damage,
The security risk of battery is also increased simultaneously, it is therefore desirable to which effective technology solves electrolyte and divides under high temperature, high voltage condition
The problem of solution, battery inflatable.
In actual use, although the problem of additive can solve electrolyte decomposition and battery inflatable, additive reaction
The positive and negative anodes surface protection film (SEI film) of generation may cause battery performance to be affected since impedance is excessive；It is especially high
Battery impedance increases too fast in temperature circulation, often brings very detrimental effect to circulating battery；And improves cycle performance and bring
(side reaction often occurs under the high temperature conditions for I film causes lithium ion secondary battery to have security risk at high temperature to thick and solid SE.Cause
It is always the direction that industry is made joint efforts that this, which takes into account high-temperature storage performance, cycle performance and security performance,.
In consideration of it, special propose the application.
Summary of the invention
It is reacted to solve electrolyte under high temperature and high voltage condition with anode, cathode aggravation, causes battery inflatable, puts certainly
The problems such as electricity and capacity are decayed rapidly, the applicant has found under study for action: when in electrolyte while including organic phosphoric acid lithium class
When closing object and organic acid lithium class compound, high-temperature storage performance, circulation of the electrolyte under high voltage condition can be improved simultaneously
Performance and high temperature safety, to complete the application.
The application's is designed to provide a kind of electrolyte, including organic solvent, electrolyte salt and additive, the addition
Agent includes organic phosphoric acid lithium class compound and/or organic acid lithium class compound.
The another object of the application is to provide a kind of lithium ion secondary battery, including the anode containing positive electrode active materials
Piece, the negative electrode tab containing negative electrode active material, isolation film and electrolyte provided herein.
The technical solution of the application at least has following beneficial effect:
When including simultaneously organic phosphoric acid lithium and organic acid lithium compound in herein described electrolyte, can improve simultaneously
High-temperature storage performance, high temperature cyclic performance and high temperature safety of the lithium secondary battery under high voltage condition.Organic phosphoric acid lithiumation
Object is closed to be added in electrolyte and can be obviously improved high temperature cyclic performance of the battery under high voltage system in cathode filming.
Organic acid lithium compound decomposes during charging and discharging, and being formed in anode surface has low resistance and improvement durability
Secured SEI film is so as to improving high temperature storing stabilization of the secondary cell under high voltage system.Therefore, two classes in the present invention
Compound is used cooperatively, and is capable of forming low resistance protective film in anode, negative terminal surface, can not only be significantly improved secondary cell and exist
Cycle performance under high voltage, while high-temperature storage performance can be significantly improved；And secondary cell also can be improved under high voltages
High temperature safe performance.
Electrolysis additive of the present invention, which is characterized in that the organic phosphoric acid lithium class compound has such as Formulas I institute
The general structure shown:
Wherein, R1Selected from substituted or unsubstituted C1~C12Alkane, substituted or unsubstituted C2~C12Alkene, substitution or not
Substituted C6~C16Aryl.
Specifically, R1It can be straight chained alkyl, branched alkyl, contain fluoroalkyl, naphthenic base, alkenyl, aryl, aryloxy group, three
Methyl methoxy base aryl, alkoxy, alkenyloxy group etc..
Further, the organic phosphoric acid lithium class compound is one of following structural formula compound represented:
The organic acid lithium class compound has the general structure as shown in Formula Il:
Wherein, R2Selected from substituted or unsubstituted C1~C12Alkane, substituted or unsubstituted C2~C12Alkene, substitution or not
Substituted C6~C16Aryl.
Specifically, R2It can be straight chained alkyl, branched alkyl, contain fluoroalkyl, naphthenic base, alkenyl, aryl, aryloxy group, three
Methyl methoxy base aryl, alkoxy, alkenyloxy group etc..
Further, the organic acid lithium class compound is one of following structural formula compound represented:
The present invention also provides the synthetic methods of the electrolysis additive, it is characterised in that:
The organic phosphoric acid lithium class compound is synthesized using following steps: raw material organic phosphoric acid, lithium carbonate, reaction is molten
Agent-dimethyl carbonate is added to reaction kettle, and reaction terminates for 2~10 hours under the conditions of 20~40 DEG C and 0.1Mpa, reaction solution warp
Concentration, crystallization, separation, the dry organic phosphoric acid lithium finished product for obtaining high-purity, wherein organic phosphoric acid is with lithium carbonate molar ratio
2:1；
The organic phosphoric acid has the general structure as shown in formula III:
The organic acid lithium class compound is synthesized using following steps: the organic sulfuric acid of raw material, lithium carbonate, reaction is molten
Agent-dimethyl carbonate is added to reaction kettle, and reaction terminates for 2~10 hours under the conditions of 20~40 DEG C and 0.1Mpa, reaction solution warp
Concentration, crystallization, separation, the dry organic acid lithium finished product for obtaining high-purity, wherein organic sulfuric acid is with lithium carbonate molar ratio
2:1；
Organic sulfuric acid has the general structure as shown in formula IV:
The organic phosphoric acid is one of following structural formula compound represented III-1~III-15:
Organic sulfuric acid is one of following structural formula compound represented IV-1~IV-15:
The present invention also provides a kind of electrolyte containing the additive, it is characterised in that: the electrolyte contains non-
Aqueous organic solvent, electrolyte lithium salt and additive, the additive are organic phosphoric acid lithium class compound and/or organic acid lithium class
Compound, in which:
The content of organic phosphoric acid lithium salt compounds is the 0.5%~1.5% of electrolyte total weight；The organic acid lithium
The content of salt compounds is the 0.5%~1.5% of electrolyte total weight.
Organic solvent is ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, vinylene carbonate, 1,3- propane sulfonic acid
The mixture of lactone；The electrolyte lithium salt is selected from lithium hexafluoro phosphate, double fluorine sulfimide lithiums, bis trifluoromethyl sulfimide
One of lithium, LiBF4.
The present invention additive is added into conventional electrolysis liquid, high-voltage electrolyte is made, so that electrolyte has hyperoxia
Change current potential (4.5V or more), and then high-voltage anode material can be matched, this is provided to obtain the lithium ion battery of high-energy density
Necessary condition, and the addition of the additive, contribute to form stable SEI film, so as to extend the cycle performance of battery.This
Invention electrolysis additive is reasonable in design, and preparation method is simple, products obtained therefrom function admirable, is convenient for large-scale industrialization
Using.
The present invention also provides a kind of lithium ion secondary batteries containing above-mentioned electrolyte, it is characterised in that: the lithium from
Sub- secondary cell includes positive plate, negative electrode tab, the diaphragm and electrolyte being interval between adjacent positive/negative plate.
The preparation method of the positive plate is: LiNi0.8Co0.1Mn0.1O2, conductive agent SuperP, binder PVDF press quality
It is uniformly mixed the cathode plate for lithium secondary battery slurry that certain viscosity is made than 96.5:3.0:2.0, is coated in current collector aluminum foil,
Coating weight is 0.0194g/cm2, it is cold-pressed after being dried at 85 DEG C；Then after trimming, cut-parts, slitting, under vacuum conditions
The anode of secondary battery for meeting and needing is made in drying 4 hours, soldering polar ear.
The preparation method of the negative electrode tab is: by graphite and conductive agent SuperP, thickener CMC, binder SBR by quality
It is mixed and made into slurry than 96.5:1.0:1.0:1.5, be coated on copper foil of affluxion body and is dried at 85 DEG C, coating weight 0.011g/
cm2；After carrying out trimming, cut-parts, slitting, 110 DEG C drying 4 hours, soldering polar ear, are made the lithium ion for meeting and needing under vacuum
Secondary battery negative pole.
The diaphragm uses Celgard2400.
The specific preparation and application of electrolyte of lithium-ion secondary battery of the present invention is:
The electrolyte of lithium-ion secondary battery uses non-aqueous organic solvent, by ethylene carbonate (EC), methyl ethyl carbonate
It is molten that ester (EMC), diethyl carbonate (DEC), vinylene carbonate (VC) and 1,3- propane sultone (PS) dissolution form mixing
Agent, electrolyte lithium salt are selected from lithium hexafluoro phosphate (LiPF6), double fluorine sulfimide lithiums (LiFSI), bis trifluoromethyl sulfimide lithium
(LiTFSI), LiBF4 (LiBF4One of), aforementioned in the mixed solvent is dissolved in, and the organic phosphoric acid lithium is added
With organic acid lithium class additive, electrolyte of lithium-ion secondary battery is formed.
Ethylene carbonate EC, methyl ethyl carbonate EMC, diethyl carbonate DEC, 1,3- propane sultone PS, carbonic acid is sub-
Vinyl acetate VC, electrolyte lithium salt and organic phosphoric acid lithium, organic acid lithium class compound additive are molten according to the ratio mixing of table 1
Solution, can be configured to electrolyte.
1 electrolyte composition of table matches (mass percent):
Detailed description of the invention
Fig. 1 structural formula I-1 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Fig. 2 structural formula I-2 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Fig. 3 structural formula I-3 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Fig. 4 structural formula I-4 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Fig. 5 structural formula I-5 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Fig. 6 structural formula I-6 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Fig. 7 structural formula I-7 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Fig. 8 structural formula I-8 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Fig. 9 structural formula I-9 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Figure 10 structural formula I-10 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Figure 11 structural formula I-11 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Figure 12 structural formula I-12 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Figure 13 structural formula I-13 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Figure 14 structural formula I-14 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
Figure 15 structural formula I-15 nuclear magnetic resonance1H NMR (solvent=DMSO 300MHz).
- 1 nuclear magnetic resonance of Figure 16 formula II1H NMR (solvent=DMSO 300MHz).
- 2 nuclear magnetic resonance of Figure 17 formula II1H NMR (solvent=DMSO 300MHz).
- 3 nuclear magnetic resonance of Figure 18 formula II1H NMR (solvent=DMSO 300MHz).
- 4 nuclear magnetic resonance of Figure 19 formula II1H NMR (solvent=DMSO 300MHz).
- 5 nuclear magnetic resonance of Figure 20 formula II1H NMR (solvent=DMSO 300MHz).
- 6 nuclear magnetic resonance of Figure 21 formula II1H NMR (solvent=DMSO 300MHz).
- 7 nuclear magnetic resonance of Figure 22 formula II1H NMR (solvent=DMSO 300MHz).
- 8 nuclear magnetic resonance of Figure 23 formula II1H NMR (solvent=DMSO 300MHz).
- 9 nuclear magnetic resonance of Figure 24 formula II1H NMR (solvent=DMSO 300MHz).
- 10 nuclear magnetic resonance of Figure 25 formula II1H NMR (solvent=DMSO 300MHz).
- 11 nuclear magnetic resonance of Figure 26 formula II1H NMR (solvent=DMSO 300MHz).
- 12 nuclear magnetic resonance of Figure 27 formula II1H NMR (solvent=DMSO 300MHz).
- 13 nuclear magnetic resonance of Figure 28 formula II1H NMR (solvent=DMSO 300MHz).
- 14 nuclear magnetic resonance of Figure 29 formula II1H NMR (solvent=DMSO 300MHz).
- 15 nuclear magnetic resonance of Figure 30 formula II1H NMR (solvent=DMSO 300MHz).
Specific embodiment
Combined with specific embodiments below, the application is further described.It should be understood that these embodiments are merely to illustrate the application
Rather than limitation scope of the present application.
Embodiment 1
Lithium secondary battery used in the present invention, including positive plate, negative electrode tab, the diaphragm that is interval between positive/negative plate with
And electrolyte.
The preparation method of the positive plate is: LiNi0.8Co0.1Mn0.1O2, conductive agent SuperP, binder PVDF press matter
The cathode plate for lithium secondary battery slurry for being uniformly mixed than 96.5:3.0:2.0 and certain viscosity being made is measured, is coated in current collector aluminum foil,
Its coating weight is 0.0194g/cm2, it is cold-pressed after being dried at 85 DEG C；After subsequent trimming, cut-parts, slitting, in vacuum condition
The secondary battery positive plate for meeting and needing is made in lower drying 4 hours, welding machine tab.
The preparation method of the negative electrode tab is: by graphite and conductive agent SuperP, thickener CMC, binder SBR by quality
It is mixed and made into slurry than 96.5:1.0:1.0:1.5, is coated on copper foil of affluxion body, and is dried at 85 DEG C, coating weight
0.011g/cm2；After carrying out trimming, cut-parts, slitting, dry 4 hours for 110 DEG C under vacuum, soldering polar ear is made and meets needs
Lithium ion secondary battery negative pole.
The diaphragm uses Celgard2400.
The specific preparation and application of the electrolyte of lithium-ion secondary battery is:
The electrolyte of lithium-ion secondary battery uses non-aqueous organic solvent, by ethylene carbonate (EC), methyl ethyl carbonate
It is molten that ester (EMC), diethyl carbonate (DEC), vinylene carbonate (VC) and 1,3- propane sultone (PS) dissolution form mixing
Agent, electrolyte lithium salt are selected from lithium hexafluoro phosphate (LiPF6), double fluorine sulfimide lithiums (LiFSI), bis trifluoromethyl sulfimide lithium
(LiTFSI), one of LiBF4 (LiBF4) dissolves in aforementioned in the mixed solvent, and the organic phosphoric acid lithium is added
With organic acid lithium class additive, electrolyte of lithium-ion secondary battery is formed.
Ethylene carbonate EC, methyl ethyl carbonate EMC, diethyl carbonate DEC, 1,3- propane sultone PS, carbonic acid is sub-
Vinyl acetate VC, electrolyte lithium salt and organic phosphoric acid lithium, organic acid lithium class compound additive are according in the ratio and table 2 of table 1
The combined hybrid of " electrolyte 1 " dissolves, and is configured to electrolyte 1.
The production of lithium ion secondary battery:
The lithium-ion secondary battery positive plate, negative electrode tab and the diaphragm that are prepared according to previous process are made by winding process
At with a thickness of 4.2mm, wide 34mm, length is the lithium ion secondary battery of 82mm.Table is injected in vacuum bakeout 10 hours at 75 DEG C
Group becomes " electrolyte 1 " corresponding electrolyte in 2；After standing 24 hours, with the constant current charging of 0.1C to 4.5V, then with
4.5V constant-voltage charge to electric current drops to 0.05C, is then discharged to 3.0V with 0.1C, is repeated twice, finally with 0.1C by battery
3.8V is charged to, battery production is completed.
Embodiment 2
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 2 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 2.
Embodiment 3
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 2 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 3.
Embodiment 4
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 4 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 4.
Embodiment 5
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 5 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 5.
Embodiment 6
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 6 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 6.
Embodiment 7
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 7 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 7.
Embodiment 8
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 8 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 8.
Embodiment 9
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 9 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 9.
Embodiment 10
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 10 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 10.
Embodiment 11
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 11 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 11.
Embodiment 12
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 12 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 12.
Embodiment 13
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 13 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 13.
Embodiment 14
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 14 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 14.
Embodiment 15
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " electrolyte 15 " in table 2, is added corresponding organic phosphoric acid lithium additive and organic acid lithium additive, is configured to be electrolysed
Liquid 15.
Comparative example 1
Lithium ion secondary battery is prepared referring to the method for embodiment 1, only when preparing lithium-ion battery electrolytes, according to
The combination of " blank electrolysis liquid ", is added without organic phosphoric acid lithium additive and organic acid lithium additive in table 2, is configured to blank ratio
Compared with electrolyte.
Circulation experiment:
For the lithium ion secondary battery in embodiment 1~15 and comparative example 1, at room temperature first with the constant of 0.7C
Current versus cell charges to 4.5V, is further less than 0.05C in 4.5V constant current charging to electric current, then with the constant of 0.5C
Current versus cell is discharged to 3.0V, and this time discharge capacity is the discharge capacity of circulation for the first time.According to above-mentioned test method, is taken
400 cyclic discharge capacities.
The cycle performance of battery is evaluated by the capacity retention ratio of lithium ion secondary battery, capacity retention ratio is counted as the following formula
It calculates, resulting result charges to table 2.
Capacity retention ratio (%)=400th time cyclic discharge capacity/first time cyclic discharge capacity * 100%.
Full electricity high temperature storage experiment:
For the lithium ion secondary battery in embodiment 1~15 and comparative example 1, at room temperature first with the constant of 0.7C
Current versus cell charges to 4.5V, is further less than 0.05C in 4.5V constant current charging to electric current, state recording is full at this time
Electricity condition, thickness before being stored with vernier caliper measurement heat, is subsequently placed in 60 DEG C of baking ovens, keeps high temperature, stores 72 hours；It takes out
Battery, after being cooled to room temperature, thickness after being stored with vernier caliper measurement, cubical expansivity is calculated with following formula, gained knot
Fruit is recorded into table 2；
Thickness * 100% before cubical expansivity=(thickness before thickness-heat stores after heat storage)/heat stores.
The different electrolytic salts of table 2 combine the high-temperature behavior of corresponding electrolyte and battery with additive:
Embodiment 16
The synthesis of double-trifluoroethanol lithium phosphate (I-1): in 2000mL reaction flask, double-trifluoroethyl phosphoric acid is added
(III-1) solvent dimethyl carbonate 1000g is added in 263g (1mol), under stirring, is added lithium carbonate 37.08g (0.502mol),
It reacts, terminates within 10 hours, reaction solution is concentrated, crystallizes, separates, being dried to obtain under the conditions of 20 DEG C of temperature and pressure 0.1Mpa
Double-trifluoroethanol lithium phosphate 265g, yield 98.53%.
Embodiment 17
The synthesis of trifluoroethanol lithium sulfate (II-1): it in 2000mL reaction flask, is added trifluoroethanol sulfuric acid (IV-1)
Solvent dimethyl carbonate 1000g is added in 180.5g (1mol), under stirring, is added lithium carbonate 37.03g (0.501mol), in temperature
It is reacted under the conditions of 20 DEG C and pressure 0.1Mpa.Terminate within 10 hours, reaction solution is concentrated, crystallizes, separates, being dried to obtain trifluoroethanol
Lithium sulfate 92.0g, yield 98.69%.
Embodiment 18
Organic phosphoric acid lithium I-2 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-2.
Embodiment 19
Organic phosphoric acid lithium I-3 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-3.
Embodiment 20
Organic phosphoric acid lithium I-4 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-4.
Embodiment 21
Organic phosphoric acid lithium I-5 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-5.
Embodiment 22
Organic phosphoric acid lithium I-6 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-6.
Embodiment 23
Organic phosphoric acid lithium I-7 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-7.
Embodiment 24
Organic phosphoric acid lithium I-8 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-8.
Embodiment 25
Organic phosphoric acid lithium I-9 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-9.
Embodiment 26
Organic phosphoric acid lithium I-10 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-10.
Embodiment 27
Organic phosphoric acid lithium I-11 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-11.
Embodiment 28
Organic phosphoric acid lithium I-12 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-12.
Embodiment 29
Organic phosphoric acid lithium I-13 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-13.
Embodiment 30
Organic phosphoric acid lithium I-14 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-14.
Embodiment 31
Organic phosphoric acid lithium I-15 synthesis: operated with embodiment 16 identical, only organic phosphoric acid replaces with III-15.
Embodiment 32
Organic acid lithium II-2 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-2.
Embodiment 33
Organic acid lithium II-3 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-3.
Embodiment 34
Organic acid lithium II-4 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-4.
Embodiment 35
Organic acid lithium II-5 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-5.
Embodiment 36
Organic acid lithium II-6 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-6.
Embodiment 37
Organic acid lithium II-7 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-7.
Embodiment 38
Organic acid lithium II-8 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-8.
Embodiment 39
Organic acid lithium II-9 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-9.
Embodiment 40
Organic acid lithium II-10 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-10.
Embodiment 41
Organic acid lithium II-11 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-11.
Embodiment 42
Organic acid lithium II-12 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-12.
Embodiment 43
Organic acid lithium II-13 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-13.
Embodiment 44
Organic acid lithium II-14 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-14.
Embodiment 45
Organic acid lithium II-15 synthesis: operated with embodiment 17 identical, only organic sulfuric acid replaces with IV-15.
Embodiment 46
The synthesis of double-trifluoroethanol phosphoric acid (III-1): in 1000mL reaction flask, phosphorus oxychloride 50g is added
(326.11mmol) is added solvent carbonic acid acetonitrile 500g, under stirring, deionized water 5.87g (326.11mmol) is slowly added dropwise, with
Trifluoroethanol 65.25g (652.22mmol) is added afterwards, back flow reaction 4 hours under normal pressure, solvent is then evaporated under reduced pressure, obtains nothing
Color transparency liquid 85.0g, yield 99.4%.
Embodiment 47
The synthesis of trifluoroethanol sulfuric acid (IV-1): in 1000mL reaction flask, being added dichloro sulfone 50g (370.49mmol),
Solvent carbonic acid acetonitrile 500g is added, under stirring, deionized water 6.67g (370.49mmol) is slowly added dropwise, trifluoro second is then added
Alcohol 37.06g (370.49mmol) is then evaporated under reduced pressure solvent, obtains colourless transparent liquid back flow reaction 4 hours under normal pressure
72.0g, yield 97.87%.
Result above discloses organic acid lithium and organic phosphoric acid lithium additive in lithium ion secondary battery high temperature high voltage
Under the conditions of use advantage, it should be pointed out that although this specification has used some specific terms, not to the present invention constitute
Any restrictions, the change and modification that the announcement and guidance of book are done according to the above description similarly should be attributed to right of the present invention and want
It asks in the range of protecting.
Claims (9)
1. a kind of electrolysis additive, which is characterized in that the additive is organic phosphoric acid lithium class compound and/or organic sulfuric acid
Lithium class compound.
2. according to electrolysis additive described in claim 1, which is characterized in that the organic phosphoric acid lithium class compound has such as formula
General structure shown in I:
Wherein, R1Selected from substituted or unsubstituted C1~C12Alkane, substituted or unsubstituted C2~C12It is alkene, substituted or unsubstituted
C6~C16Aryl.
3. according to electrolysis additive as claimed in claim 1 or 2, which is characterized in that the organic phosphoric acid lithium class compound be with
One of flowering structure formula compound represented:
4. according to electrolysis additive described in claim 1, which is characterized in that the organic acid lithium class compound has such as formula
General structure shown in II:
Wherein, R2Selected from substituted or unsubstituted C1~C12Alkane, substituted or unsubstituted C2~C12It is alkene, substituted or unsubstituted
C6~C16Aryl.
5. according to the electrolysis additive of claim 1 or 4, which is characterized in that the organic acid lithium class compound be with
One of flowering structure formula compound represented:
6. a kind of synthetic method of electrolysis additive described in claim 1, it is characterised in that:
The organic phosphoric acid lithium class compound is synthesized using following steps: by raw material organic phosphoric acid, lithium carbonate, reaction dissolvent-carbon
Dimethyl phthalate is added to reaction kettle, and reaction terminates for 2~10 hours at 20~40 DEG C and under the conditions of 0.1Mpa, reaction solution is concentrated,
It crystallizes, separation, the dry organic phosphoric acid lithium finished product for obtaining high-purity, wherein organic phosphoric acid is 2:1 with lithium carbonate molar ratio；
The organic phosphoric acid has the general structure as shown in formula III:
The organic acid lithium class compound is synthesized using following steps: by the organic sulfuric acid of raw material, lithium carbonate, reaction dissolvent-carbon
Dimethyl phthalate is added to reaction kettle, and reaction terminates for 2~10 hours at 20~40 DEG C and under the conditions of 0.1Mpa, reaction solution is concentrated,
It crystallizes, separation, the dry organic acid lithium finished product for obtaining high-purity, wherein organic sulfuric acid is 2:1 with lithium carbonate molar ratio；
Organic sulfuric acid has the general structure as shown in formula IV:
7. a kind of electrolyte containing additive described in claim 1, it is characterised in that: the electrolyte contains non-aqueous organic molten
Agent, electrolyte lithium salt and additive, the additive be organic phosphoric acid lithium class compound and/or organic acid lithium class compound,
Wherein:
The content of organic phosphoric acid lithium salt compounds is the 0.5%~1.5% of electrolyte total weight；The organic acid lithium salt
The content of compound is the 0.5%~1.5% of electrolyte total weight.
8. according to electrolyte described in claim 7, it is characterised in that: the organic solvent be ethylene carbonate, methyl ethyl carbonate,
Diethyl carbonate, vinylene carbonate, 1,3- propane sultone mixture；The electrolyte lithium salt is selected from hexafluorophosphoric acid
One of lithium, double fluorine sulfimide lithiums, bis trifluoromethyl sulfimide lithium, LiBF4.
9. a kind of lithium ion secondary battery containing electrolyte described in claim 7, it is characterised in that: the lithium ion secondary electricity
Pond includes positive plate, negative electrode tab, diaphragm and electrolyte.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111740163A (en) * | 2020-03-23 | 2020-10-02 | 杉杉新材料（衢州）有限公司 | High-voltage lithium ion battery electrolyte and lithium ion battery using same |
| CN112490497A (en) * | 2019-09-11 | 2021-03-12 | 杉杉新材料（衢州）有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same |
| CN114957317A (en) * | 2022-06-30 | 2022-08-30 | 山东海科创新研究院有限公司 | Lithium cyanophosphate, preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925837A (en) * | 2015-03-18 | 2015-09-23 | 江西赣锋锂业股份有限公司 | Method of preparing lithium salt by recovering lithium deposition mother liquor of battery grade lithium carbonate |
| CN105074996A (en) * | 2013-04-01 | 2015-11-18 | 宇部兴产株式会社 | Nonaqueous electrolyte solution and electricity storage device using same |
| CN106252724A (en) * | 2016-08-29 | 2016-12-21 | 宁德时代新能源科技股份有限公司 | Additive, preparation method thereof and lithium ion battery containing additive |
| CN106471664A (en) * | 2014-07-15 | 2017-03-01 | 宇部兴产株式会社 | Nonaqueous electrolytic solution and the electric energy storage device employing this nonaqueous electrolytic solution |
| CN108306048A (en) * | 2017-12-28 | 2018-07-20 | 骆驼集团武汉光谷研发中心有限公司 | A kind of lithium-ion battery electrolytes and its lithium ion battery of preparation |
| CN108630989A (en) * | 2017-03-16 | 2018-10-09 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery |
| JP2018172266A (en) * | 2017-03-31 | 2018-11-08 | 三井化学株式会社 | Lithium salt complex compound, additive for lithium secondary battery and method for producing lithium salt complex compound |
-
2019
- 2019-04-04 CN CN201910269683.3A patent/CN110112463A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105074996A (en) * | 2013-04-01 | 2015-11-18 | 宇部兴产株式会社 | Nonaqueous electrolyte solution and electricity storage device using same |
| CN106471664A (en) * | 2014-07-15 | 2017-03-01 | 宇部兴产株式会社 | Nonaqueous electrolytic solution and the electric energy storage device employing this nonaqueous electrolytic solution |
| CN104925837A (en) * | 2015-03-18 | 2015-09-23 | 江西赣锋锂业股份有限公司 | Method of preparing lithium salt by recovering lithium deposition mother liquor of battery grade lithium carbonate |
| CN106252724A (en) * | 2016-08-29 | 2016-12-21 | 宁德时代新能源科技股份有限公司 | Additive, preparation method thereof and lithium ion battery containing additive |
| CN108630989A (en) * | 2017-03-16 | 2018-10-09 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery |
| JP2018172266A (en) * | 2017-03-31 | 2018-11-08 | 三井化学株式会社 | Lithium salt complex compound, additive for lithium secondary battery and method for producing lithium salt complex compound |
| CN108306048A (en) * | 2017-12-28 | 2018-07-20 | 骆驼集团武汉光谷研发中心有限公司 | A kind of lithium-ion battery electrolytes and its lithium ion battery of preparation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112490497A (en) * | 2019-09-11 | 2021-03-12 | 杉杉新材料（衢州）有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same |
| CN111740163A (en) * | 2020-03-23 | 2020-10-02 | 杉杉新材料（衢州）有限公司 | High-voltage lithium ion battery electrolyte and lithium ion battery using same |
| CN111740163B (en) * | 2020-03-23 | 2021-11-05 | 杉杉新材料（衢州）有限公司 | High-voltage lithium ion battery electrolyte and lithium ion battery using same |
| CN114957317A (en) * | 2022-06-30 | 2022-08-30 | 山东海科创新研究院有限公司 | Lithium cyanophosphate, preparation method and application thereof |
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