CN115010759A - Oxalic acid phosphate derivative, preparation method thereof, electrolyte and secondary battery - Google Patents
Oxalic acid phosphate derivative, preparation method thereof, electrolyte and secondary battery Download PDFInfo
- Publication number
- CN115010759A CN115010759A CN202110233620.XA CN202110233620A CN115010759A CN 115010759 A CN115010759 A CN 115010759A CN 202110233620 A CN202110233620 A CN 202110233620A CN 115010759 A CN115010759 A CN 115010759A
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- CN
- China
- Prior art keywords
- oxalate
- phosphate
- oxalic acid
- electrolyte
- tetrafluoro
- Prior art date
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- MRDKYAYDMCRFIT-UHFFFAOYSA-N oxalic acid;phosphoric acid Chemical class OP(O)(O)=O.OC(=O)C(O)=O MRDKYAYDMCRFIT-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000003792 electrolyte Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 64
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 41
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 claims abstract description 20
- NONOKGVFTBWRLD-UHFFFAOYSA-N thioisocyanate group Chemical group S(N=C=O)N=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 oxalate thioisocyanate trifluorophosphate Chemical compound 0.000 claims description 87
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000011734 sodium Substances 0.000 claims description 41
- 239000002210 silicon-based material Substances 0.000 claims description 37
- OKRNAGIARSXQFC-UHFFFAOYSA-N sulfosilicon Chemical compound OS([Si])(=O)=O OKRNAGIARSXQFC-UHFFFAOYSA-N 0.000 claims description 33
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 30
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 28
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 claims description 25
- 239000003125 aqueous solvent Substances 0.000 claims description 23
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- 239000010452 phosphate Substances 0.000 claims description 16
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 claims description 14
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 0.000 claims description 13
- 238000006467 substitution reaction Methods 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 150000003891 oxalate salts Chemical class 0.000 claims description 9
- OJOUOVMLFBIHRQ-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Na+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Na+] OJOUOVMLFBIHRQ-UHFFFAOYSA-M 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
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- XFXIRAGUWFFKDE-UHFFFAOYSA-N trimethylsilyl thiocyanate Chemical compound C[Si](C)(C)SC#N XFXIRAGUWFFKDE-UHFFFAOYSA-N 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- USGDMCWUHFXPCY-UHFFFAOYSA-M C(C(=O)O)(=O)[O-].P(=O)(O)(O)O.[Li+] Chemical class C(C(=O)O)(=O)[O-].P(=O)(O)(O)O.[Li+] USGDMCWUHFXPCY-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910018279 LaSrMnO Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910013417 LiN(SO3C2F5)2 Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011884 anode binding agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- ZYMJSAWYDBRZIC-UHFFFAOYSA-N oxalic acid phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O.OC(=O)C(O)=O.OC(=O)C(O)=O ZYMJSAWYDBRZIC-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UQKPVYOQWVOLIW-UHFFFAOYSA-M potassium dihydrogen phosphate oxalic acid Chemical class C(C(=O)O)(=O)O.P(=O)(O)(O)[O-].[K+] UQKPVYOQWVOLIW-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LTPKTTHIQCHIPA-UHFFFAOYSA-M sodium 2-hydroxy-2-oxoacetate phosphoric acid Chemical class C(C(=O)O)(=O)[O-].[Na+].P(=O)(O)(O)O LTPKTTHIQCHIPA-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QUBMWJKTLKIJNN-UHFFFAOYSA-B tin(4+);tetraphosphate Chemical compound [Sn+4].[Sn+4].[Sn+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QUBMWJKTLKIJNN-UHFFFAOYSA-B 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of battery materials, and particularly relates to an oxalic acid phosphate derivative, a preparation method thereof, an electrolyte and a secondary battery. The structural general formula of the oxalic acid phosphate derivative is shown as the formula (I):
wherein M is Li, Na or K, R 1 、R 2 、R 3 、R 4 Are each selected from F, thiocyano or thioisocyanate groups, and R 1 、R 2 、R 3 And R 4 Not being F at the same time. The oxalic acid phosphate derivative has good thermal stability and high ionic conductivity, can effectively inhibit the rising of water and acidity of the electrolyte in the storage process, has important significance for improving the stability and safety of the electrolyte, can ensure that the secondary battery has good cycle performance and storage performance at normal temperature and high temperature, and has longer service life.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to an oxalic acid phosphate derivative and a preparation method thereof, an electrolyte and a secondary battery.
Background
The lithium ion battery is a novel high-energy secondary battery which is developed in the 90 s, has the excellent performances of high energy density, small volume, light weight, high discharge rate, low self-discharge rate, long cycle life, no memory effect and the like, and is widely applied to the fields of digital products, power and energy storage.
With the continuous development of social requirements, the service life, high and low temperature performance, safety performance, rate performance and the like of the lithium ion battery can not meet the requirements of power battery development. There are various ways to improve the performance of the power battery, and one way is to improve the performance of the electrolyte. The composition and the property of the electrolyte play a crucial role in the electrochemical performance of the lithium ion battery, and the additives in the electrolyte are small additives for improving the electrochemical performance of the electrolyte. So far, a plurality of salts used as electrolyte additives have been developed, and although the salts have better thermal stability and high and low temperature performance, the salts also have some obvious disadvantages, such as large toxicity of raw materials, complex preparation process, low purity, high energy consumption in the preparation process, high difficulty in product purification, high content of chloride ions in products, high content of free acid and the like.
Therefore, it is one of the current research directions to find a new nonaqueous electrolyte additive.
Disclosure of Invention
The invention aims to provide an oxalic acid phosphate derivative and a preparation method thereof, an electrolyte and a secondary battery, and aims to solve the technical problems of complex preparation process, low product purity and the like of the existing electrolyte additive.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
on one hand, the invention provides an oxalate phosphate derivative, which has a structural general formula shown in formula (I):
wherein M is Li, Na or K, R 1 、R 2 、R 3 、R 4 Are each selected from F, thiocyano or thioisocyanate groups, and R 1 、R 2 、R 3 And R 4 Not simultaneously F.
The oxalic acid phosphate derivative provided by the invention is a series of new compounds derived from oxalic acid phosphate, and the series of compounds have good thermal stability and high ionic conductivity and have wide application prospects.
In another aspect of the present invention, there is provided a method for preparing an oxalate derivative, comprising the steps of:
providing tetrafluoro oxalate phosphate, a sulfo-silicon-based compound and a non-aqueous solvent, wherein the tetrafluoro oxalate phosphate is at least one of lithium tetrafluorooxalate phosphate, sodium tetrafluorooxalate phosphate and potassium tetrafluorooxalate phosphate, and the sulfo-silicon-based compound contains a sulfo-cyano group or a sulfo-isocyanate group;
in a non-aqueous solvent, mixing tetrafluoro oxalate phosphate with a sulfo-silicon-based compound for substitution reaction to obtain an oxalate derivative, wherein the structural general formula of the oxalate derivative is shown as the formula (I):
wherein M is Li, Na or K, R 1 、R 2 、R 3 、R 4 Are each selected from F, thiocyano or thioisocyanate, and R 1 、R 2 、R 3 And R 4 Not simultaneously F.
According to the preparation method of the oxalate phosphate derivative, the tetrafluoro oxalate phosphate and the sulfo-silicon-based compound are subjected to substitution reaction, so that at least one fluorine in the tetrafluoro oxalate phosphate is substituted by the sulfo-cyano group or the sulfo-isocyanate group in the sulfo-silicon-based compound, and various oxalate phosphate derivatives can be quickly prepared through a one-step method. More importantly, the preparation process provided by the invention is carried out in a non-aqueous solvent environment, so the oxalic acid phosphate derivative with high purity can be obtained by concentration and drying, and the problems of higher concentration of chloride ions and higher free acid are avoided.
In another aspect of the present invention, an electrolyte solution is provided, which includes a solvent, an electrolyte salt, and an additive, wherein the additive includes the oxalate phosphate derivative according to the present invention or the oxalate phosphate derivative prepared by the preparation method according to the present invention.
According to the invention, the oxalic acid phosphate derivative provided by the invention is added into the electrolyte, so that the increase of the moisture and the acidity of the electrolyte in the storage process can be effectively inhibited, and the method has important significance for improving the stability and the safety of the electrolyte.
In a final aspect of the invention, a secondary battery is provided comprising the electrolyte of the invention.
In the secondary battery provided by the invention, the electrolyte contains the oxalic acid phosphate derivative provided by the invention, so that the electrolyte can effectively improve the safety and stability of the obtained secondary battery. Experiments prove that the secondary battery provided by the invention has good cycle performance and storage performance at normal temperature and high temperature, and is longer in service life.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without making any creative effort in combination with the embodiments of the present invention belong to the protection scope of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, the term "and/or" describing an association relationship of associated objects means that there may be three relationships, for example, a and/or B, may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the description of the present invention, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a. b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple respectively.
It should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In addition, unless the context clearly uses otherwise, an expression of a word in the singular is to be understood as including the plural of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
The embodiment of the invention provides an oxalate phosphate derivative, which has a structural general formula shown in a formula (I):
wherein M is Li, Na or K, R 1 、R 2 、R 3 、R 4 Are each selected from F, thiocyano or thioisocyanate groups, and R 1 、R 2 、R 3 And R 4 Not simultaneously F.
The oxalate phosphate derivative provided by the embodiment of the invention is a series of new compounds derived from oxalate phosphate, and the series of compounds have better thermal stability and higher ionic conductivity, and have wide application prospects.
In some embodiments, the oxalato phosphate derivative is obtained by substituting at least one fluorine in tetrafluorooxalato phosphate with a thiocyano group or a thioisocyanate group. The obtained oxalic acid phosphate derivative comprises at least one of oxalic acid thiocyano trifluoro phosphate, oxalic acid dithiocyano difluoro phosphate, oxalic acid trithiocyano fluorophosphate, oxalic acid tetrathiocyano phosphate, oxalic acid thioisocyanate trifluoro phosphate, oxalic acid dithioisocyanate difluoro phosphate, oxalic acid trithioisocyanate fluorophosphate and oxalic acid tetrathioisocyanate phosphate. Wherein, the structural formulas of oxalic acid thiocyano trifluoro phosphate, oxalic acid dithiocyano difluorophosphate, oxalic acid trithiocyano fluorophosphate, oxalic acid tetrathiocyano phosphate, oxalic acid thioisocyanate trifluoro phosphate, oxalic acid dithioisocyanate difluorophosphate, oxalic acid trithioisocyanate fluorophosphate and oxalic acid tetrathioisocyanate phosphate are sequentially shown in formulas (II) to (IX), wherein M is Li, Na or K:
the oxalic acid phosphate derivative provided by the embodiment of the invention can be prepared by the following preparation method.
Correspondingly, the embodiment of the invention provides a preparation method of the oxalate derivative, which comprises the following steps:
s1, providing tetrafluoro oxalic acid phosphate, a sulfo-silicon-based compound and a non-aqueous solvent, wherein the tetrafluoro oxalic acid phosphate is at least one selected from the group consisting of lithium tetrafluoro oxalic acid phosphate, sodium tetrafluoro oxalic acid phosphate and potassium tetrafluoro oxalic acid phosphate, and the sulfo-silicon-based compound contains sulfo-cyano groups or sulfo-isocyanate groups;
s2, mixing tetrafluoro oxalate phosphate with a sulfo-silicon-based compound in a non-aqueous solvent to carry out substitution reaction to obtain oxalate phosphate derivatives; the structural general formula of the obtained oxalic acid phosphate derivative is shown as the formula (I):
wherein M is Li, Na or K, R 1 、R 2 、R 3 、R 4 Are each selected from F, thiocyano or thioisocyanate groups, and R 1 、R 2 、R 3 And R 4 Not being F at the same time.
According to the preparation method of the oxalate phosphate derivative provided by the embodiment of the invention, the tetrafluoro oxalate phosphate and the sulfo-silicon-based compound are subjected to substitution reaction, so that at least one fluorine in the tetrafluoro oxalate phosphate is substituted by the sulfo-cyano group or the sulfo-isocyanate group in the sulfo-silicon-based compound, and various oxalate phosphate derivatives can be rapidly prepared by a one-step method. More importantly, the preparation process provided by the embodiment of the invention is carried out in a non-aqueous solvent environment, so that the oxalic acid phosphate derivative with high purity can be obtained by concentration and drying, and the problems of high chloride ion concentration and high free acid are avoided.
In some embodiments, the resulting oxalate phosphate derivative includes at least one of oxalate thiocyano trifluorophosphate, oxalate dithiocyano difluorophosphate, oxalate trithiocyano fluorophosphate, oxalate tetrathiocyano phosphate, oxalate thioisocyanate trifluorophosphate, oxalate dithioisocyanate difluorophosphate, oxalate trithioisocyanate fluorophosphate, oxalate tetrathioisocyanate phosphate, oxalate thiocyano trifluorophosphate, the structural formulas of oxalic acid dithiocyano difluorophosphate, oxalic acid trithiocyano fluorophosphate, oxalic acid tetrathiocyanophosphate, oxalic acid thioisocyanate trifluorophosphate, oxalic acid dithioisocyanate difluorophosphate, oxalic acid trithioisocyanate fluorophosphate and oxalic acid tetrathioisocyanate phosphate are sequentially shown in formulas (II) to (IX), wherein M is Li, Na or K:
specifically, in S1, tetrafluoro oxalic acid phosphate (mofpf) is one of the reaction materials in the embodiment of the present invention, and its structural formula is shown in formula (X), where M is Li, Na or K:
in some embodiments, to reduce the moisture of the reaction system, and to reduce the free acid, a tetrafluoro oxalate phosphate having a moisture content of 100ppm or less is selected.
The thiosilicon-based compound is still another reaction raw material in the embodiment of the present invention, which contains a thiocyano group or a thioisocyanate group for providing the thiocyano group or the thioisocyanate group in the subsequent reaction process. When the sulfo-silicon-based compound contains a sulfo-cyano group, the obtained oxalic acid phosphate derivative is at least one of oxalic acid thiocyano trifluoro phosphate, oxalic acid dithiocyano difluoro phosphate, oxalic acid trithiocyano fluorophosphate and oxalic acid tetrathiocyano phosphate; when the sulfo-silicon-based compound contains sulfo-isocyanate groups, the obtained oxalic acid phosphate derivative is at least one of oxalic acid sulfo-isocyanate trifluoro-phosphate, oxalic acid dithioisocyanate difluoro-phosphate, oxalic acid trithioisocyanate fluorophosphate and oxalic acid tetrasulfo-isocyanate phosphate. In some embodiments, the thiosilicon-based compound has a structural formula as shown in formula (XI) or formula (XII):
wherein R is 5 、R 6 、R 7 、R 8 、R 9 、R 10 Each independently selected from one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an aromatic group having 6 to 20 carbon atoms. In some embodiments, R 5 、R 6 、R 7 、R 8 、R 9 、R 10 Preferably methyl, in which case the thiosilyl compound is trimethylsilyl thiocyanide (Me) 3 SiSCN) or trimethylsilyl thioisocyanate (Me) 3 SiNCS), has an advantage of low cost. If the price factor is not considered, R 5 、R 6 、R 7 、R 8 、R 9 、R 10 Groups such as tert-butyl, phenyl and the like can be selected, and when the groups are selected, the stability of the sulfo-silicon-based compound and the yield of the oxalic acid phosphate derivative are improved. When R is 5 、R 6 、R 7 、R 8 、R 9 、R 10 The amino group-containing group is selected to advantageously reduce the moisture content of the thiosilicon-based compound and the acidity of the oxalate phosphate derivative.
The non-aqueous solvent is a non-aqueous solvent. Since the aqueous solution of oxalic acid phosphate is prepared by using an aqueous solvent, it is difficult to separate out oxalic acid phosphate with high purity by crystallization, and there are problems that the concentration of chloride ions and the concentration of free acid are high, embodiments of the present invention use a non-aqueous solvent to overcome the above problems. In some embodiments, the non-aqueous solvent is selected from the group consisting of acetonitrile, propionitrile, 1, 3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2, 5-dimethyltetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N, at least one of N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, hexaethylphosphoric triamide, dimethyl sulfoxide, diethyl sulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, N-hexane, N-heptane, cyclohexane, benzene, toluene, and xylene.
In S2, the substitution reaction of the tetrafluoro oxalic acid phosphate and the sulfo-silicon-based compound is carried out in a non-aqueous solvent system. In some embodiments, in order to facilitate control of the amount of the added reactants and the occurrence of a reaction, the tetrafluoro oxalate phosphate may be mixed with a non-aqueous solvent to obtain a tetrafluoro oxalate phosphate non-aqueous solution, the thiosilicon-based compound may be mixed with a non-aqueous solvent to obtain a thiosilicon-based compound non-aqueous solution, and then the tetrafluoro oxalate phosphate non-aqueous solution and the thiosilicon-based compound non-aqueous solution may be mixed to perform a substitution reaction in which a thiocyano group or a thioisocyanate group in the thiosilicon-based compound substitutes for at least one fluorine in the tetrafluoro oxalate phosphate. In some embodiments, when the tetrafluoro oxalate phosphate is mixed with a non-aqueous solvent to obtain a tetrafluoro oxalate phosphate non-aqueous solution, the temperature is controlled to be-20 ℃ to 20 ℃, and the mixing time is 0.5h to 3 h; when the sulfo-silicon-based compound is mixed with the non-aqueous solvent to obtain the non-aqueous solution of the sulfo-silicon-based compound, the temperature is controlled to be-20 ℃ to 20 ℃, and the mixing time is 0.5h to 3 h.
In some embodiments, when the tetrafluoro oxalic acid phosphate and the sulfo-silicon-based compound are mixed for substitution reaction, the molar ratio of the tetrafluoro oxalic acid phosphate to the sulfo-silicon-based compound is 1 (1-4). Different molar ratios of the tetrafluoro oxalate phosphate to the thio-silicon-based compound also result in different products. Therefore, the embodiment of the application can control the types of the obtained products by adjusting the molar ratio of the tetrafluoro oxalic acid phosphate to the sulfo-silicon-based compound. In particular, typical but non-limiting molar ratios between the tetrafluoro oxalato phosphate salt and the thiosilicon-based compound are 1:1, 1:2, 1:3, 1: 4.
The following thiosilyl compounds are Me 3 SiSCN or Me 3 SiNCS to show the chemical combination of different tetrafluoro oxalate phosphates with sulfo-siliconThe chemical reaction formula for the molar ratio of the compounds does not represent a limitation to the specific choice of the thiosilyl compound.
In some embodiments, when the thiosilyl compound is Me 3 SiSCN, and when the molar ratio of the tetrafluoro oxalate phosphate to the sulfo-silicon-based compound is 1:1, the obtained reaction product is oxalatothiocyano trifluoro phosphate, and the reaction formula is shown as follows, wherein M is Li, Na or K:
in some embodiments, when the thiosilyl compound is Me 3 SiSCN, and when the molar ratio of the tetrafluoro oxalate phosphate to the sulfo-silicon-based compound is 1:2, the obtained reaction product is oxalyldithiocarbonyl difluorophosphate, and the reaction formula is shown as follows, wherein M is Li, Na or K:
in some embodiments, when the thiosilyl compound is Me 3 SiSCN, and when the molar ratio of the tetrafluoro oxalic acid phosphate to the sulfo-silicon-based compound is 1:3, the obtained reaction product is oxalic acid trithiocyano fluorophosphate, and the reaction formula is shown as follows, wherein M is Li, Na or K:
in some embodiments, when the thiosilyl compound is Me 3 SiSCN, and when the molar ratio of the tetrafluoro oxalate phosphate to the sulfo-silicon-based compound is 1:4, the obtained reaction product is oxalic acid tetrathiacyano fluorophosphate, and the reaction formula is shown as follows, wherein M is Li, Na or K:
in some embodiments, when the thiosilyl compound is Me 3 SiNCS, wherein when the molar ratio of the tetrafluoro oxalic acid phosphate to the sulfo-silicon-based compound is 1:1, the obtained reaction product is oxalic acid sulfo-isocyanate trifluoro-phosphate, and the reaction formula is shown as follows, wherein M is Li, Na or K:
in some embodiments, when the thiosilyl compound is Me 3 SiNCS, wherein when the molar ratio of the tetrafluoro oxalic acid phosphate to the sulfo-silicon-based compound is 1:2, the obtained reaction product is oxalic acid dithio-isocyanate difluorophosphate, and the reaction formula is shown as follows, wherein M is Li, Na or K:
in some embodiments, when the thiosilyl compound is Me 3 SiNCS, wherein when the molar ratio of the tetrafluoro oxalic acid phosphate to the sulfo-silicon-based compound is 1:3, the obtained reaction product is oxalic acid trithio isocyanate fluorophosphate, and the reaction formula is shown as follows, wherein M is Li, Na or K:
in some embodiments, when the thiosilyl compound is Me 3 SiNCS, wherein when the molar ratio of the tetrafluoro oxalate phosphate to the sulfo-silicon-based compound is 1:4, the obtained reaction product is oxalic acid tetrathioisocyanate phosphate, and the reaction formula is shown as follows, wherein M is Li, Na or K:
in some embodiments, when the tetrafluoro oxalate phosphate and the sulfo-silicon-based compound are mixed for substitution reaction, the reaction temperature is controlled to be-20 ℃ to 80 ℃, and the reaction time is 1h to 6 h. Specifically, typical but not limiting reaction temperatures are 20 ℃, -15 ℃, -10 ℃, -5 ℃, 0 ℃,5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃; typical but not limiting reaction times are 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6 h.
Further, when the tetrafluoro oxalate phosphate non-aqueous solution and the thio-silicon based compound non-aqueous solution are mixed, in order to avoid the reaction from being too violent, the thio-silicon based compound non-aqueous solution is preferably added into the tetrafluoro oxalate phosphate non-aqueous solution by a dropping method, and the stirring is kept in the whole adding process, and the temperature is controlled to be-20 ℃ to 20 ℃, so that the over-violent reaction is avoided, and the heat released by the reaction is absorbed (it is emphasized that the method of dropping the tetrafluoro oxalate phosphate non-aqueous solution into the thio-silicon based compound non-aqueous solution is not suitable for the reaction in the embodiment of the invention. When the nonaqueous solution of the sulfo-silicon-based compound is completely dripped, the obtained solution system is colorless and transparent, and then the system is heated to 40-80 ℃ to react for 1-3 h, so as to improve the reaction rate and promote the reaction to be complete. In addition, a by-product gas generated during the reaction (e.g., Me is the thiosilyl compound) 3 SiSCN or Me 3 In the case of SiNCS, the by-product gas is Me 3 SiF) can be absorbed by aqueous inorganic base solutions. In some embodiments, the inorganic base in the aqueous solution of inorganic base for absorbing the byproduct gas is at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and potassium carbonate, preferably a saturated aqueous solution of sodium hydroxide, which has the advantages of low cost, easily available raw materials and complete absorption.
Since the oxalate derivative obtained after the substitution reaction is carried out by mixing the tetrafluoro oxalate with the thiosilicon-based compound is in a non-aqueous liquid state, in some embodiments, in order to improve the purity of the oxalate derivative, a step of concentrating and drying the non-aqueous solution of the oxalate derivative is further included. In some embodiments, the step of concentrating and drying the solution comprises: firstly, carrying out reduced pressure concentration on the oxalic acid phosphate derivative non-aqueous solution at room temperature to obtain a light yellow or white solid, then recrystallizing the light yellow or white solid by using a non-aqueous solvent to obtain a colorless crystal, and then drying the white crystal in vacuum to obtain the oxalic acid phosphate derivative.
Further, the temperature of vacuum drying is controlled to be 20-100 ℃, preferably 40-80 ℃, and the vacuum drying time is 1-8 h, preferably 3-5 h, so as to improve the efficiency of vacuum drying and fully dry the crystal. Specifically, typical but not limiting vacuum drying temperature is 20 degrees, 25 degrees, 30 degrees, 35 degrees, 40 degrees, 45 degrees, 50 degrees, 55 degrees, 60 degrees, 65 degrees, 70 degrees, 75 degrees, 80 degrees, 85 degrees, 90 degrees, 95 degrees, 100 degrees; typical, but not limiting, vacuum drying times are 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8 h.
Correspondingly, the embodiment of the invention also provides an electrolyte, which comprises a solvent, an electrolyte salt and an additive, wherein the additive comprises the oxalic acid phosphate derivative provided by the embodiment of the invention or the oxalic acid phosphate derivative prepared by the preparation method provided by the embodiment of the invention.
According to the embodiment of the invention, the oxalic acid phosphate derivative provided by the invention is added into the electrolyte, so that the increase of the moisture and the acidity of the electrolyte in the storage process can be effectively inhibited, and the method has important significance for improving the stability and the safety of the electrolyte.
In some embodiments, the mass of the oxalic acid phosphate derivative provided by the embodiments of the present invention accounts for 0.1% to 2% of the total mass of the electrolyte, based on 100% of the total mass of the electrolyte. By adding the oxalic acid phosphate derivative with the content, the function complementation effect with other components in the electrolyte can be realized, the stability and the safety of the electrolyte can be improved, and the electrochemical performance of the electrolyte can not be greatly influenced. Specifically, typical but not limiting mass contents of the oxalate phosphate derivative are 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%.
In some embodiments, the electrolyte salt in the electrolyte is used in combination with the oxalic acid phosphate derivative, which is beneficial to further improving the performance of the obtained electrolyte. In some embodiments, the electrolyte salt is selected from LiPF 6 、LiBF 4 、LiClO 4 、LiSbF 6 、LiAsF 6 、LiN(SO 2 C 2 F 5 ) 2 、LiN(SO 2 CF 3 ) 2 、LiN(SO 3 C 2 F 5 ) 2 、LiN(SO 2 F) 2 、LiN(SO 2 C 6 F 5 ) 2 、LiN(SO 3 C 6 F 5 ) 2 、LiSO 3 CF 3 、LiSO 3 C 2 F 5 、LiSO 3 C 4 F 9 、LiSO 3 C 6 H 5 、LiSO 3 C 6 F 5 At least one of (1).
In some embodiments, the solvent in the electrolyte is a non-aqueous solvent, such as a carbonate-based solvent, wherein the carbonate is a linear or cyclic carbonate. In some embodiments, the cyclic ester is selected from at least one of Ethylene Carbonate (EC), propylene carbonate (VC), γ -butyrolactone, 1, 3-Propane Sultone (PS), ethylene sulfate (DTD); the chain ester is at least one selected from dimethyl carbonate (DMC), butylene carbonate, diethyl carbonate (DEC), dipropyl carbonate, Ethyl Methyl Carbonate (EMC), methyl propyl carbonate, ethyl propyl carbonate, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and propyl propionate.
Correspondingly, the embodiment of the invention also provides a secondary battery, which comprises the electrolyte.
In the secondary battery provided by the embodiment of the invention, the electrolyte contains the oxalic acid phosphate derivative provided by the embodiment of the invention, so that the electrolyte can effectively improve the safety and stability of the obtained secondary battery. Experiments prove that the secondary battery provided by the embodiment of the invention has good cycle performance and storage performance at normal temperature and high temperature, and has longer service life.
It is understood that, when the secondary battery is a lithium secondary battery, M in the oxalate phosphate derivative provided by the embodiment of the present invention added to the electrolyte is preferably Li; when the secondary battery is a sodium secondary battery, M in the oxalic acid phosphate derivative provided by the embodiment of the invention is preferably added into the electrolyte and is Na; when the secondary battery is a potassium secondary battery, M in the oxalic acid phosphate derivative provided by the embodiment of the invention added to the electrolyte is preferably K.
In some embodiments, a secondary battery includes a positive electrode including a positive electrode current collector and a positive electrode active material layer on a surface thereof, a negative electrode including a negative electrode current collector and a negative electrode active material layer on a surface thereof, an electrolyte, and a separator. In some specific embodiments, the material forming the positive electrode current collector may be a material conventional in the art, including, but not limited to, aluminum or aluminum alloys, and the like; the material forming the negative electrode current collector may be a conventional material in the art, including but not limited to copper or copper alloy, etc., and both the positive electrode current collector and the negative electrode current collector may be in the form of foil (foil) or mesh (mesh).
It should be noted that the positive electrode current collector (or the negative electrode current collector) and the positive electrode active material layer (or the negative electrode active material layer) only provide a common positional relationship, that is, the positive electrode active slurry (or the negative electrode active slurry) is coated on the surface of the positive electrode current collector (or the negative electrode current collector) to form the positive electrode active material layer (or the negative electrode active material layer), and should not be construed as a limitation to the secondary battery provided in the embodiment of the present invention. According to actual conditions, the current collector and the active material can be changed according to requirements on battery performance, such as various ways of filling the mixed powder of the positive electrode active material (or the negative electrode active material) and the auxiliary agent in the hollow positive electrode current collector (or the hollow negative electrode current collector).
In some embodiments, the components of the positive active slurry used to prepare the positive active material layer include a positive active material, which may be a positive active material conventional in the art, a positive conductive agent, and a positive binder. In some embodimentsThe positive electrode active material is selected from Li a CoO 2 (0.5<a<1.3)、Li a NiO 2 (0.5<a<1.3)、Li a MnO 2 (0.5<a<1.3)、Li a Mn 2 O 4 (0.5<a<1.3)、Li a (Ni x Co y Mn z )O 2 (0.5<a<1.3，0<x<1，0<y<1，0<z<1，x+y+z＝1)、Li a Ni 1-x Co x O 2 (0.5<a<1.3，0<x<1)、Li a Co 1-x Mn x O 2 (0.5<a<1.3，0≤x<1)、Li a Ni 1-x Mn x O 2 (0.5<a<1.3，0≤x<1)、Li a (Ni x Co y Mn z )O 4 (0.5<a<1.3，0<x<2，0<y<2，0<z<2，x+y+z＝2)、Li a Mn 2- x N x O 4 (0.5<a<1.3，0<x<2)、Li a Mn 2-x N x O 4 (0.5<a<1.3，0<y<2)、Li a NPO 4 (0.5<a<1.3, N is at least one selected from Fe, Ni, Co, Mn, Zn, Al, Cr, Mg, Zr, Mo, W, V, Ti, B, F and Y), Li a (Ni x Co y Mn z )O 2 (0.90≤a≤1.10，0.3≤x≤0.9，0.05≤y<0.5，0.05≤z<0.5, and x + y + z ═ 1), Li (Ni) x Co y Mn z )O 2 (0.3≤x≤0.9，0.05≤y<0.5，0.05≤z<0.5, and x + y + z ═ 1); LiNi is preferred 0.6 Co 0.2 Mn 0.2 O 2 、LiNi 0.5 Co 0.2 Mn 0.3 O 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 At least one of (1). The mass of the positive electrode active material accounts for 88-98% of the mass of the positive electrode active slurry.
In some embodiments, the components of the anode active slurry used to prepare the anode active material layer include an anode active material capable of intercalating and deintercalating lithium ions, an anode conductive agent, an anode binder, and an anode thickener. In some embodiments, the anode active material may be selected from at least one of a carbon material (such as crystalline carbon, amorphous carbon, carbon composite, and carbon fiber), lithium metal, and an alloy of lithium and other elements. Among them, crystalline carbon includes, but is not limited to, graphite-based materials such as artificial graphite, natural graphite, graphitized coke, graphitized mesophase carbon microspheres, graphitized mesophase pitch-based carbon fibers, and the like. Amorphous carbon includes, but is not limited to, soft carbon (low temperature-fired carbon), hard carbon, coke, mesocarbon microbeads (MCMB), mesophase pitch-based carbon fibers (MPCF), and the like. Other elements that form alloys with lithium metal include at least one of aluminum, zinc, bismuth, cadmium, antimony, silicon, lead, tin, gallium, or indium. The mass of the negative electrode active material accounts for 90-96% of the mass of the negative electrode active slurry.
Further, a solvent, which serves to disperse the electrode active material, the binder, the conductive agent, etc., and may be a non-aqueous solvent or an aqueous solvent, is added when preparing the positive electrode active slurry and the negative electrode active slurry. Wherein, when the solvent is high-purity deionized water, the conductivity of the high-purity deionized water is less than or equal to 3 us/cm; when the solvent is a non-aqueous solvent, the solvent is at least one selected from N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, N-dimethylaminopropylamine, ethylene oxide and tetrahydrofuran, and the water content is less than or equal to 100 ppm.
Further, the positive and negative electrode conductive agents can improve the conductivity of the material, and any material that does not undergo chemical reaction in the battery system and is an electron conductor can be used as the conductive agent. In some embodiments, the positive and negative electrode conductive agents are selected from graphite-based conductive agents, carbon black-based conductive agents, metal-based or metal compound-based conductive agents. Among them, the graphite-based conductive agent includes, but is not limited to, artificial graphite, natural graphite, etc.; the carbon black-based conductive agent includes, but is not limited to, acetylene black, ketjen black (ketjen black), superconducting acetylene black (denka black), thermal black (thermal black), channel black (channel black), and the like; metal-based or metal compound-based conductive agents include, but are not limited to, tin oxide, tin phosphate, titanium oxide, potassium titanate, perovskite materials, such as LaSrCoO 3 Or LaSrMnO 3 And the like. Positive and negative electrode leadThe mass of the electrolyte accounts for 0.1-6% of the mass of the positive and negative active slurry respectively. When the mass ratio of the conductive agent is less than 0.1%, deterioration of electrochemical performance may be caused; when the content is more than 6%, the content of the positive and negative electrode active materials is reduced, resulting in a low energy density of the battery.
Further, the positive and negative electrode binders are selected from at least one of polyvinylidene fluoride (PVDF), polyhexafluoropropylene-polyvinylidene fluoride (HFP/PVDF) copolymer, polyvinyl acetate, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, polyvinyl ether, polymethyl methacrylate, polyethylacrylate, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinyl pyridine, styrene-butadiene rubber, acrylonitrile-butadiene rubber. The mass of the positive and negative binders accounts for 1-6% of the mass of the positive and negative active slurry respectively. The content of the binder is too low, and the bonding strength between the positive and negative electrode active materials and the current collector is insufficient; the content of the binder is too high, so that the bonding strength is enhanced, but the content of the positive and negative electrode active materials is reduced, and the energy density of the battery is not improved.
Further, the anode thickener is used to adjust the viscosity of the anode active material slurry. In some specific embodiments, the negative electrode thickener is at least one selected from hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, and accounts for 1-4% of the mass of the negative electrode active slurry.
In some embodiments, the separator mainly provides an ion channel for lithium ions, sodium ions, and/or potassium ions while separating the positive and negative electrodes from a short circuit between the positive and negative electrodes, and olefin polymer films (e.g., polypropylene, polyethylene/polypropylene/polyethylene, and polypropylene/polyethylene/polypropylene) or multi-layer films (multiple-film), microporous films, and woven and nonwoven fabrics thereof are generally used. In some embodiments, a three-layer composite membrane is used, with a thickness of 12-36 μm and a porosity of 30-70%. In order to improve the thermal stability of the separator, a resin or ceramic having structural stability may be coated on the surface of the separator.
The shape of the secondary battery according to the embodiment of the present invention is not particularly limited, and includes, but is not limited to, a square, cylindrical, or pouch battery.
In order to make the details and operation of the above-mentioned embodiments of the present invention clearly understood by those skilled in the art and to make the progress of the oxalic acid phosphate derivatives, the preparation method thereof, the electrolyte, and the secondary battery of the embodiments of the present invention remarkably manifest, the above-mentioned technical solutions are exemplified by a plurality of examples below. To enable parallel comparisons to enable more intuitive comparisons of the preparation of the products, the thiosilyl compound used in the examples of the invention was trimethylsilyl thiocyanide (Me) 3 SiSCN) or trimethylsilyl thioisocyanate (Me) 3 SiNCS)。
Example 1
The embodiment provides a preparation method of lithium sulfocyano trifluorophosphate, which comprises the following specific steps:
into a 250ml two-necked flask were charged 20.2g (0.1mol) of lithium tetrafluoro-oxalato-phosphate and 50ml of dimethyl carbonate, and the solid was completely dissolved with stirring at room temperature, and then 13.1g of Me was dissolved 3 50ml of a dimethyl carbonate solution of SiSCN (0.1mol) is added into a two-mouth bottle through a dropping funnel, the dropping speed is controlled to be 1 drop/second, gas is released during the dropping process, the solution is colorless and transparent, after all the dropping is finished, the stirring is continued for 3 hours at room temperature, and then the temperature is raised to 40 ℃ for reaction for 1 hour. Standing at room temperature and filtering at normal pressure to remove suspended solid impurities to obtain a colorless transparent solution, concentrating at room temperature under reduced pressure to obtain a white solid, recrystallizing the white solid by using 30ml of dimethyl carbonate, and then drying in vacuum at 60 ℃ for 3h to obtain 22.2g of the target product lithium sulfocyano trifluorophosphate, wherein the yield is 92%. The gas generated by the reaction is absorbed by a saturated aqueous solution of sodium hydroxide. In a glove box, 5mg of the obtained white powdery solid was taken, added to 2ml of anhydrous acetonitrile to be completely dissolved, suspended matters were removed by filtration using an organic filter, a small amount of the filtrate was injected using a syringe and analyzed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis result showed LC-MS (ESI) [ C ] 2 O 4 PF 3 SCN] - 234.12, it was confirmed that the resulting white powdery solid was lithium oxalatothiocyanatotrifluorophosphate. The water content and acidity were measured by a Karl-type moisture meter and a potentiometric titrator to be 15ppm25ppm, and the chloride ion concentration was 2 ppm. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 2
This example provides a method for preparing sodium sulfocyano trifluoroacetate. This example is substantially the same as example 1 except that 21.8g (0.1mol) of sodium tetrafluorooxalate phosphate was used in place of the lithium tetrafluorooxalate phosphate in example 1, and 23.9g of sodium sulfooxalatotrifluorophosphate was obtained in a yield of 93%. The analysis was performed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis showed LC-MS (ESI) [ C ] 2 O 4 PF 3 SCN] - 234.14, the resulting white powdery solid was confirmed to be sodium sulfocyano trifluoroacetate oxalate. The water content was 14ppm, the acidity was 30ppm and the chloride ion concentration was 2ppm as measured by a Karl moisture meter and a potentiometric titrator. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 3
This example provides a method for preparing potassium sulfocyano trifluoroacetate oxalate. This example is substantially the same as example 1 except that 23.4g (0.1mol) of potassium tetrafluorooxalate was used in place of the lithium tetrafluorooxalate phosphate in example 1, and 25.1g of potassium sulfooxalato trifluoroacetate was obtained in a yield of 92%. The analysis was performed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis showed LC-MS (ESI) [ C ] 2 O 4 PF 3 SCN] - 234.15, it was confirmed that the resulting white powdery solid was potassium sulfocyano trifluoroacetate oxalate. The water content was measured by means of a Karl moisture meter and a potentiometric titrator to be 16ppm, the acidity to be 28ppm and the chloride ion concentration to be 1.5 ppm. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 4
The embodiment provides a preparation method of lithium oxalyldithiocarbocyanodifluorophosphate, which comprises the following specific steps:
into a 250ml two-necked flask were charged 20.2g (0.1mol) of lithium tetrafluorooxalate phosphate and 50ml of dimethyl carbonate, and the solid was completely dissolved with stirring at room temperature, and then 26.2g of Me was dissolved 3 SiSCN (0.2mol) in 50ml of dimethyl carbonate was added via droppingThe funnel is added into a two-mouth bottle, the dropping speed is controlled to be 1 drop/second, gas is released in the dropping process, the solution is colorless and transparent, and after all dropping is completed, the stirring is continued for 3 hours at room temperature and then the temperature is raised to 40 ℃ for reaction for 1 hour. Standing at room temperature and filtering at normal pressure to remove suspended solid impurities to obtain a colorless transparent solution, concentrating at room temperature under reduced pressure to obtain a white solid, recrystallizing the white solid by using 30ml of dimethyl carbonate, and then drying at 60 ℃ for 3h in vacuum to obtain 25.8g of the target product lithium dithiocyano oxalate difluorophosphate with the yield of 92%. The gas generated by the reaction is absorbed by a saturated aqueous solution of sodium hydroxide. In a glove box, 5mg of the obtained white powdery solid was taken, added to 2ml of anhydrous acetonitrile to be completely dissolved, suspended matters were removed by filtration using an organic filter, a small amount of the filtrate was injected using a syringe and analyzed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis result showed LC-MS (ESI) [ C ] 2 O 4 PF 2 S 2 C 2 N 2 ] - 273.08, it was confirmed that the resulting white powdery solid was lithium oxalyldithiocyanodifluorophosphate. The water content was determined to be 13ppm, the acidity 23ppm and the chloride ion concentration 2.5ppm by Karl moisture meter and potentiometric titrator. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 5
The embodiment provides a preparation method of sodium oxalyldithiocarbonate difluorosodium phosphate. This example is substantially the same as example 4 except that it replaces lithium tetrafluoro oxalate phosphate in example 4 with 21.8g (0.1mol) of sodium tetrafluoro oxalate phosphate and obtains 27.2g of sodium dithiocyano difluorophosphate as a product with a yield of 92%. Analysis by liquid chromatography-mass spectrometry (Thermo Fisher Scientific) showed LC-MS (ESI) [ C ] 2 O 4 PF 2 S 2 C 2 N 2 ] - 273.22, the resulting white powdery solid was confirmed to be sodium oxalyldithiocyanodifluorophosphate. The water content, acidity and chloride ion concentration were measured by 17ppm, 31ppm and 2ppm, respectively, using a Karl-type moisture meter and a potentiometric titrator. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 6
This exampleProvides a preparation method of potassium oxalyldithiocarbamoyldifluorophosphate. This example is substantially the same as example 4 except that 23.4g (0.1mol) of potassium tetrafluorooxalate was used in place of the lithium tetrafluorooxalate phosphate in example 4, and 29.0g of potassium oxalyldithiocyanodifluorophosphate was obtained in a yield of 93%. Analysis by liquid chromatography-mass spectrometry (Thermo Fisher Scientific) showed LC-MS (ESI) [ C ] 2 O 4 PF 2 S 2 C 2 N 2 ] - 273.20, it was confirmed that the resulting white powdery solid was potassium oxalyldithiocyanodifluorophosphate. The water content was 16ppm, the acidity was 30ppm and the chloride ion concentration was 2ppm as measured by a Karl moisture meter and a potentiometric titrator. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 7
The embodiment provides a preparation method of lithium trithiocyano fluorophosphate, which comprises the following specific steps:
into a 250ml two-necked flask were charged 20.2g (0.1mol) of lithium tetrafluoro-oxalato-phosphate and 50ml of dimethyl carbonate, and the solid was completely dissolved with stirring at room temperature, and then 39.3g of Me was dissolved 3 50ml of a dimethyl carbonate solution of SiSCN (0.3mol) is added into a two-mouth bottle through a dropping funnel, the dropping speed is controlled to be 1 drop/second, gas is released during the dropping process, the solution is colorless and transparent, after all the dropping is finished, the stirring is continued for 3 hours at room temperature, and then the temperature is raised to 40 ℃ for reaction for 1 hour. Standing at room temperature and filtering under normal pressure to remove suspended solid impurities to obtain a colorless transparent solution, concentrating at room temperature under reduced pressure to obtain a white solid, recrystallizing the white solid by using 30ml of dimethyl carbonate, and then drying in vacuum at 60 ℃ for 3h to obtain 29.4g of the target product lithium trithiocyano fluorophosphate with the yield of 92%. The gas generated by the reaction is absorbed by a saturated aqueous solution of sodium hydroxide. In a glove box, 5mg of the obtained white powdery solid was taken, added to 2ml of anhydrous acetonitrile to be completely dissolved, suspended matters were removed by filtration using an organic filter, a small amount of the filtrate was injected using a syringe and analyzed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis result showed LC-MS (ESI) [ C ] 2 O 4 PFS 3 C 3 N 3 ] - 312.21, proving the white powder obtainedThe solid is lithium oxalate trithiocyano fluorophosphate. The water content was 12ppm, the acidity was 20ppm and the chloride ion concentration was 1.5ppm as determined by Karl moisture meter and potentiometric titrator. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 8
The embodiment provides a preparation method of sodium trithiocyano fluorophosphate oxalate. This example is substantially the same as example 7 except that 21.8g (0.1mol) of sodium tetrafluorooxalate phosphate was used in place of the lithium tetrafluorooxalate phosphate in example 7, and 30.8g of sodium trithiocyano sodium fluorooxalate phosphate was obtained in a yield of 92%. The analysis was performed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis showed LC-MS (ESI) [ C ] 2 O 4 PFS 3 C 3 N 3 ] - 312.24, the resulting white powdery solid was confirmed to be sodium oxalato trithiocyano fluorophosphate. The water content was 14ppm, the acidity was 29ppm and the chloride ion concentration was 2ppm as determined by Karl moisture meter and potentiometric titrator. The product purity was greater than 99% as determined by Ion Chromatography (IC).
Example 9
This example provides a method for preparing potassium trithiocyano potassium fluorophosphate oxalate. This example is substantially the same as example 7 except that 23.4g (0.1mol) of potassium tetrafluorooxalate was used in this example instead of lithium tetrafluorooxalate in example 7, and the resulting product was 32.7g of potassium trithiocyano fluorophosphate oxalate at a yield of 93%. Analysis by liquid chromatography-mass spectrometry (Thermo Fisher Scientific) showed LC-MS (ESI) [ C ] 2 O 4 PFS 3 C 3 N 3 ] - 312.32, the white powdery solid obtained was confirmed to be potassium oxalato trithiocyano fluorophosphate. The water content was measured by means of a Karl-type moisture meter and a potentiometric titrator to be 16ppm, the acidity to be 25ppm and the chloride ion concentration to be 2 ppm. The product purity was greater than 99% as determined by Ion Chromatography (IC).
Example 10
The embodiment provides a preparation method of lithium tetrasulfocyano phosphate oxalate, which comprises the following specific steps:
adding tetrafluoro oxalic acid phosphoric acid into a 250ml two-mouth bottleLithium 20.2g (0.1mol) and 50ml dimethyl carbonate, the solid was completely dissolved with stirring at room temperature, and then 53g Me were dissolved 3 A50 ml dimethyl carbonate solution of SiSCN (0.4mol) is added into a two-mouth bottle through a dropping funnel, the dropping speed is controlled to be 1 drop/second, gas is released in the dropping process, the solution is colorless and transparent, after all dropping is finished, the stirring is continued for 3 hours at room temperature, and then the temperature is raised to 40 ℃ for reaction for 1 hour. Standing at room temperature and filtering at normal pressure to remove suspended solid impurities to obtain a colorless transparent solution, concentrating at room temperature under reduced pressure to obtain a white solid, recrystallizing the white solid by using 30ml of dimethyl carbonate, and then drying in vacuum at 60 ℃ for 3h to obtain 33.7g of the target product lithium tetrasulfamoyl phosphate with the yield of 94%. The gas generated by the reaction is absorbed by a saturated aqueous solution of sodium hydroxide. In a glove box, 5mg of the obtained white powdery solid was taken, added to 2ml of anhydrous acetonitrile to be completely dissolved, suspended matters were removed by filtration using an organic filter, a small amount of the filtrate was injected using a syringe, and analyzed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), the analysis result showed LC-MS (ESI) [ C ] 2 O 4 PS 4 C 4 N 4 ] - 351.33, it was confirmed that the resulting white powdery solid was lithium tetrasulfanocyanophosphate oxalate. The water content was 11ppm, the acidity was 18ppm and the chloride ion concentration was 1ppm as determined by Karl moisture meter and potentiometric titrator. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 11
The embodiment provides a preparation method of sodium tetrasulfanocyano oxalate phosphate. This example is substantially the same as example 10 except that 21.8g (0.1mol) of sodium tetrafluorooxalate phosphate was used in place of the lithium tetrafluorooxalate phosphate in example 10, and 34.8g of sodium tetrasulfanocyano oxalate phosphate was obtained in a yield of 93%. Analysis by liquid chromatography-mass spectrometry (Thermo Fisher Scientific) showed LC-MS (ESI) [ C ] 2 O 4 PS 4 C 4 N 4 ] - 351.38, the resulting white powdery solid was confirmed to be sodium tetrasulfanocyano oxalate phosphate. The water content, acidity and chloride ion concentration were measured by a Karl moisture meter and a potentiometric titrator, respectively, to be 11ppm, 23ppm and 1.5ppm, respectively. High product purity by Ion Chromatography (IC)At a rate of 99%.
Example 12
This example provides a method for preparing potassium tetrasulfamoyl oxalate. This example is substantially the same as example 10 except that 23.4g (0.1mol) of potassium tetrafluorooxalate was used in place of the lithium tetrafluorooxalate in example 10, and the obtained product was 36.7g of potassium tetrasulfanocyanato oxalate in a yield of 94%. The analysis was performed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis showed LC-MS (ESI) [ C ] 2 O 4 PS 4 C 4 N 4 ] - 351.34, the white powdery solid obtained was confirmed to be potassium tetrasulfanocyano oxalate. The product purity was greater than 99% by Ion Chromatography (IC) with a moisture content of 12ppm, acidity of 20ppm, and chloride ion concentration of 1.5ppm as determined by Kaschin-Betz moisture meter and potentiometric titrator. .
Example 13
The embodiment provides a preparation method of lithium oxalylthioisocyanate trifluoro-phosphate, which comprises the following steps:
into a 250ml two-necked flask were charged 20.2g (0.1mol) of lithium tetrafluoro-oxalato-phosphate and 50ml of dimethyl carbonate, and the solid was completely dissolved with stirring at room temperature, and then 13.1g of Me was dissolved 3 50ml of a SiNCS (0.1mol) dimethyl carbonate solution is added into a two-mouth bottle through a dropping funnel, the dropping speed is controlled to be 1 drop/second, gas is released in the dropping process, the solution is colorless and transparent, after all the dropping is finished, the solution is continuously stirred at room temperature for 3 hours, and then the temperature is raised to 40 ℃ for reaction for 1 hour. Standing at room temperature and filtering at normal pressure to remove suspended solid impurities to obtain a colorless transparent solution, concentrating at room temperature under reduced pressure to obtain a white solid, recrystallizing the white solid by using 30ml of dimethyl carbonate, and then drying in vacuum at 60 ℃ for 3h to obtain 22.3g of the target product lithium oxalato-thioisocyanate trifluorophosphate, wherein the yield is 92%. The gas generated by the reaction is absorbed by a saturated aqueous solution of sodium hydroxide. In a glove box, 5mg of the obtained white powdery solid was taken, added to 2ml of anhydrous acetonitrile to be completely dissolved, suspended matters were removed by filtration using an organic filter, a small amount of the filtrate was injected using a syringe and analyzed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis result showed LC-MS (ESI) [ C ] 2 O 4 PF 3 NCS] - 234.14, the resulting white powdery solid was confirmed to be lithium oxalylthioisocyanate trifluorophosphate. The water content was 23ppm, the acidity was 25ppm and the chloride ion concentration was 3ppm as determined by Karl moisture meter and potentiometric titrator. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 14
This example provides a method for preparing sodium sulfoisocyanate trifluoroacetate oxalate. This example is substantially the same as example 13 except that it replaces lithium tetrafluoro oxalate phosphate in example 13 with 21.8g (0.1mol) of sodium tetrafluoro oxalate phosphate and obtains 23.9g of sodium oxalylthioisocyanate triflate in 93% yield. The analysis was performed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis showed LC-MS (ESI) [ C ] 2 O 4 PF 3 NCS] - 234.12, the white powdery solid obtained was confirmed to be sodium oxalatothioisocyanate trifluorphosphate. The water content was measured by a Karl-type moisture meter and a potentiometric titrator to be 13ppm, the acidity to be 33ppm, and the chloride ion concentration to be 2 ppm. The product purity was greater than 99% as determined by Ion Chromatography (IC).
Example 15
This example provides a process for the preparation of potassium thioisocyanate trifluoroacetate oxalate. This example is substantially the same as example 13 except that 23.4g (0.1mol) of potassium tetrafluorooxalate phosphate was used in place of the lithium tetrafluorooxalate phosphate in example 13, and 25.1g of potassium oxalatothioisocyanate trifluoroacetate was obtained in a yield of 92%. Analysis by liquid chromatography-mass spectrometry (Thermo Fisher Scientific) showed LC-MS (ESI) [ C ] 2 O 4 PF 3 NCS] - 234.14, the white powdery solid obtained was confirmed to be potassium oxalatothioisocyanate trifluoroacetate. The water content was measured by means of a Karl-type moisture meter and a potentiometric titrator to be 16ppm, the acidity to be 28ppm and the chloride ion concentration to be 2 ppm. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 16
The embodiment provides a preparation method of lithium oxalyldithio isocyanate difluorophosphate, which comprises the following specific steps:
into a 250ml two-necked flask were charged 20.2g (0.1mol) of lithium tetrafluorooxalate phosphate and 50ml of dimethyl carbonate, and the solid was completely dissolved with stirring at room temperature, and then 26.2g of Me was dissolved 3 Adding 50ml of a dimethyl carbonate solution of SiNCS (0.2mol) into a two-mouth bottle through a dropping funnel, controlling the dropping speed to be 1 drop/second, releasing gas in the dropping process, enabling the solution to be colorless and transparent, continuously stirring at room temperature for 3 hours after all the dropping is finished, and then heating to 40 ℃ for reaction for 1 hour. Standing at room temperature and filtering at normal pressure to remove suspended solid impurities to obtain a colorless transparent solution, concentrating at room temperature under reduced pressure to obtain a white solid, recrystallizing the white solid by using 30ml of dimethyl carbonate, and then drying in vacuum at 60 ℃ for 3h to obtain 25.8g of the target product lithium dithiooxalate isocyanate difluorophosphate with the yield of 92%. The gas generated by the reaction is absorbed by a saturated aqueous solution of sodium hydroxide. In a glove box, 5mg of the obtained white powdery solid was taken, added to 2ml of anhydrous acetonitrile to be completely dissolved, suspended matters were removed by filtration using an organic filter, a small amount of the filtrate was injected using a syringe and analyzed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis result showed LC-MS (ESI) [ C ] 2 O 4 PF 2 N 2 C 2 S 2 ] - 273.11, it was confirmed that the resulting white powdery solid was lithium oxalyldithio isocyanate difluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 20ppm, the acidity was measured to be 21ppm, and the chloride ion concentration was measured to be 2 ppm. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 17
The embodiment provides a preparation method of sodium oxalyldithio isocyanate difluorophosphate. This example is substantially the same as example 16 except that 21.8g (0.1mol) of sodium tetrafluorooxalate phosphate was used in place of the lithium tetrafluorooxalate phosphate in example 16, and 27.2g of sodium oxalyldithioisocyanate difluorophosphate was obtained in a yield of 92%. Analysis by liquid chromatography-mass spectrometry (Thermo Fisher Scientific) showed LC-MS (ESI) [ C ] 2 O 4 PF 2 N 2 C 2 S 2 ] - 273.16, proving the white powdery solid obtainedIs oxalic acid dithioisocyanate sodium difluorophosphate. The water content was 14ppm, the acidity was 27ppm and the chloride ion concentration was 2ppm as measured by a Karl moisture meter and a potentiometric titrator. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 18
This example provides a method for preparing potassium oxalyldithio isocyanate difluorophosphate. This example is substantially the same as example 16 except that 23.4g (0.1mol) of potassium tetrafluorooxalate was used in place of the lithium tetrafluorooxalate in example 16, and 29.0g of potassium oxalyldithioisocyanate difluorophosphate was obtained in a yield of 93%. Analysis by liquid chromatography-mass spectrometry (Thermo Fisher Scientific) showed LC-MS (ESI) [ C ] 2 O 4 PF 2 N 2 C 2 S 2 ] - 273.20, it was confirmed that the resulting white powdery solid was potassium oxalyldithioisocyanate difluorophosphate. The water content was 14ppm, the acidity was 30ppm and the chloride ion concentration was 2ppm as determined by Karl moisture meter and potentiometric titrator. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 19
The embodiment provides a preparation method of lithium oxalato trithioisocyanate fluorophosphate, which comprises the following specific steps:
into a 250ml two-necked flask were charged 20.2g (0.1mol) of lithium tetrafluoro-oxalato-phosphate and 50ml of dimethyl carbonate, and the solid was completely dissolved with stirring at room temperature, and then 39.3g of Me was dissolved 3 Adding 50ml of a dimethyl carbonate solution of SiNCS (0.3mol) into a two-mouth bottle through a dropping funnel, controlling the dropping speed to be 1 drop/second, releasing gas in the dropping process, enabling the solution to be colorless and transparent, continuously stirring at room temperature for 3 hours after all the dropping is finished, and then heating to 40 ℃ for reaction for 1 hour. Standing at room temperature and filtering under normal pressure to remove suspended solid impurities to obtain a colorless transparent solution, concentrating at room temperature under reduced pressure to obtain a white solid, recrystallizing the white solid by using 30ml of dimethyl carbonate, and then drying in vacuum at 60 ℃ for 3h to obtain 29.4g of the target product lithium trithioisocyanate oxalate fluorophosphate with the yield of 92%. The gas generated by the reaction is absorbed by a saturated aqueous solution of sodium hydroxide. Taking the obtained white in a glove box5mg of a powdery solid was added to 2ml of anhydrous acetonitrile to completely dissolve the solid, suspended matter was removed by filtration using an organic filter, a small amount of the filtrate was injected using a syringe and analyzed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis result showed LC-MS (ESI) [ C ] 2 O 4 PFN 3 C 3 S 3 ] - 312.23, it was confirmed that the resulting white powdery solid was lithium oxalato trithioisocyanate fluorophosphate. The water content was measured by a Karl moisture meter and a potentiometric titrator to be 18ppm, the acidity to be 22ppm and the chloride ion concentration to be 2.5 ppm. The product purity was greater than 99% as determined by Ion Chromatography (IC).
Example 20
The embodiment provides a preparation method of sodium thioisocyanate oxalate fluorophosphate. This example is substantially the same as example 19 except that 21.8g (0.1mol) of sodium tetrafluorooxalate phosphate was used in place of the lithium tetrafluorooxalate phosphate in example 19, and 30.8g of sodium trithioisocyanate oxalate fluorophosphate was obtained in a yield of 92%. Analysis by liquid chromatography-mass spectrometry (Thermo Fisher Scientific) showed LC-MS (ESI) [ C ] 2 O 4 PFN 3 C 3 S 3 ] - 312.28, the resulting white powdery solid was confirmed to be sodium oxalato trithioisocyanate fluorophosphate. The water content was 12ppm, the acidity was 25ppm and the chloride ion concentration was 2ppm as measured by a Karl moisture meter and a potentiometric titrator. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 21
This example provides a method for preparing potassium oxytetrathio isocyanate fluorophosphate. This example is substantially the same as example 19 except that 23.4g (0.1mol) of potassium tetrafluorooxalate was used in place of the lithium tetrafluorooxalate in example 19, and the resulting product was 32.7g of potassium oxytetrathioisocyanate fluorophosphate in a yield of 93%. Analysis by liquid chromatography-mass spectrometry (Thermo Fisher Scientific) showed LC-MS (ESI) [ C ] 2 O 4 PFN 3 C 3 S 3 ] - 312.30, it was confirmed that the resulting white powdery solid was potassium oxalate trithioisocyanate fluorophosphate.The water content was 14ppm, the acidity was 23ppm and the chloride ion concentration was 2ppm as measured by a Karl moisture meter and a potentiometric titrator. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 22
The embodiment provides a preparation method of lithium oxalate tetrathioisocyanate phosphate, which comprises the following specific steps:
into a 250ml two-necked flask were charged 20.2g (0.1mol) of lithium tetrafluoro-oxalato-phosphate and 50ml of dimethyl carbonate, and the solid was completely dissolved with stirring at room temperature, and then 53g of Me was dissolved 3 Adding 50ml of a dimethyl carbonate solution of SiNCS (0.4mol) into a two-mouth bottle through a dropping funnel, controlling the dropping speed to be 1 drop/second, releasing gas in the dropping process, enabling the solution to be colorless and transparent, continuously stirring at room temperature for 3 hours after all the dropping is finished, and then heating to 40 ℃ for reaction for 1 hour. Standing at room temperature and filtering at normal pressure to remove suspended solid impurities to obtain a colorless transparent solution, concentrating at room temperature under reduced pressure to obtain a white solid, recrystallizing the white solid by using 30ml of dimethyl carbonate, and then drying in vacuum at 60 ℃ for 3h to obtain 33.9g of the target product lithium tetrathioisocyanate oxalate phosphate, wherein the yield is 95%. The gas generated by the reaction is absorbed by a saturated aqueous solution of sodium hydroxide. In a glove box, 5mg of the obtained white powdery solid was taken, added to 2ml of anhydrous acetonitrile to be completely dissolved, suspended matters were removed by filtration using an organic filter, a small amount of the filtrate was injected using a syringe, and analyzed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), the analysis result showed LC-MS (ESI) [ C ] 2 O 4 PN 4 C 4 S 4 ] - 351.31, it was confirmed that the resulting white powdery solid was lithium tetrathioisocyanate oxalate phosphate. The water content was measured by a Karl-type moisture meter and a potentiometric titrator to be 15ppm, the acidity to be 20ppm, and the chloride ion concentration to be 1.5 ppm. The purity of the product was greater than 99% as determined by Ion Chromatography (IC).
Example 23
The embodiment provides a preparation method of sodium tetrathioisocyanate oxalate phosphate. This example is substantially the same as example 22 except that 21.8g (0.1mol) of sodium tetrafluorooxalate phosphate was used in place of the lithium tetrafluorooxalate phosphate in example 22 to obtain a product34.8g of sodium tetrasulfamoyl oxalate phosphate, 93% yield. Analysis by liquid chromatography-mass spectrometry (Thermo Fisher Scientific) showed LC-MS (ESI) [ C ] 2 O 4 PN 4 C 4 S 4 ] - 351.34, the white powdery solid was confirmed to be sodium tetrathioisocyanate oxalate phosphate. The water content was 12ppm, the acidity was 23ppm and the chloride ion concentration was 1.5ppm as measured by a Karl moisture meter and a potentiometric titrator. The product purity was greater than 99% as determined by Ion Chromatography (IC).
Example 24
This example provides a method for preparing potassium oxalate tetrathioisocyanate. This example is substantially the same as example 22 except that 23.4g (0.1mol) of potassium tetrafluorooxalate was used in place of the lithium tetrafluorooxalate in example 22, and 36.7g of potassium tetrathioisocyanate oxalate was obtained in a yield of 94%. The analysis was performed by liquid chromatography-mass spectrometry (Thermo Fisher Scientific), and the analysis showed LC-MS (ESI) [ C ] 2 O 4 PN 4 C 4 S 4 ] - 351.36, the white powdery solid obtained was confirmed to be potassium tetrathioisocyanate oxalate. The water content was 11ppm, the acidity 23ppm and the chloride ion concentration 1.5ppm as determined by Karl moisture meter and potentiometric titrator. The product purity was greater than 99% as determined by Ion Chromatography (IC).
The following provides test results of the lithium salts prepared in the above examples as additives of electrolytes, and the corresponding sodium salts and potassium salts have similar properties, which are not listed here.
Experimental example 1
In an argon atmosphere glove box (glove box H) 2 O、O 2 Content less than 0.1ppm) to prepare a nonaqueous electrolytic solution. Mixing Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) at a mass ratio of 30:50:20 to obtain an electrolyte solution, and adding lithium hexafluorophosphate (LiPF) to the electrolyte solution 6 ) Reacting lithium hexafluorophosphate (LiPF) 6 ) Vinylene Carbonate (VC) and lithium difluorophosphate (LiO) were added to the nonaqueous electrolyte solution at a concentration of 1.0mol/L in an amount of 100% by weight based on the total weight of the nonaqueous electrolyte solution 2 PF 2 ) 1, 3-Propane Sultone (PS) and vinyl sulfate (DTD) with the mass fraction of 1 percent to obtain a reference electrolyte sample with the number of (1);
in an argon atmosphere glove box (glove box H) 2 O、O 2 Content less than 0.1ppm) lithium tetrafluoro oxalate, lithium oxalatothiocyanotrifluorophosphate obtained in example 1, lithium oxalatodithiocyano difluorophosphate obtained in example 4, lithium oxalatotrithiocyano fluorophosphate obtained in example 7, lithium oxalatotetrathiocyanocyanophosphate obtained in example 10, lithium oxalatothioisocyanatotrifluorophosphate obtained in example 13, lithium oxalatodithioisocyanate difluorophosphate obtained in example 16, lithium oxalatotrithioisocyanate fluorophosphate obtained in example 19, and lithium oxalatotetrathioisocyanate phosphate obtained in example 22 were added to control electrolyte samples so that the mass fractions thereof were all 0.5%, and the obtained electrolytes were numbered (2) to (10) in this order. The main components of each electrolyte are shown in table 1.
Table 1 main components of each electrolyte in experimental example 1
The electrolytes (1) to (10) are respectively sealed and stored in a glove box, a small amount of the electrolytes are respectively placed in a fluorinated bottle, after the electrolytes are placed at room temperature for 1 month, the moisture content of the electrolytes is tested by a Karl Fischer moisture meter, and the acidity of the electrolytes is tested by an acid-base titration method. The test results are shown in table 2.
Table 2 results of moisture and acidity tests for each electrolyte
| Electrolyte numbering | Additive component | Moisture (ppm) | Acidity (ppm) |
| (1) | \ | 62 | 121 |
| (2) | Lithium tetrafluoro oxalate phosphate | 58 | 120 |
| (3) | Lithium sulfocyano trifluorophosphate oxalate | 54 | 111 |
| (4) | Lithium oxalyldithiocyanodifluorophosphate | 48 | 102 |
| (5) | Lithium trithiocyano fluorophosphate oxalate | 43 | 95 |
| (6) | Lithium tetrasulfocyano phosphate oxalate | 35 | 86 |
| (7) | Lithium oxalylthioisocyanurate trifluorophosphate | 51 | 108 |
| (8) | Lithium oxalyldithio isocyanate difluorophosphate | 46 | 98 |
| (9) | Lithium Trithio-Oxylisocyanato fluorophosphate | 42 | 90 |
| (10) | Lithium tetra thio isocyanate oxalate phosphate | 33 | 83 |
As can be seen from table 2, when the lithium oxalate phosphate derivative prepared in the embodiment of the present invention is used as an electrolyte additive, the moisture and acidity of the electrolyte can be reduced, which is beneficial to improving the stability of the electrolyte. In addition, the results of examination of the sodium phosphate oxalate derivative and the potassium phosphate oxalate derivative prepared in other examples of the present invention according to the procedure of experimental example 1 were substantially the same as in experimental example 1, and are not shown for economy.
Experimental example 2
1. Preparing a positive pole piece: lithium nickel cobalt manganese (LiNi) 0.8 Co 0.1 Mn 0.1 O 2 NCM811 for short) as a positive electrode active substance, and the positive electrode active slurry is obtained by dissolving 96% of the positive electrode active substance, 2% of PVDF adhesive and 2% of Super P conductive carbon black in a solvent N-methyl pyrrolidone and mixing. Then evenly coating the positive active slurry on a current collector aluminum foil with the coating weight of 280g/m 2 Then drying at 80 deg.CAnd (3) after cold pressing, trimming, cutting and slitting, drying for 4 hours at the temperature of 80 ℃ under a vacuum condition, and welding a tab to obtain the positive plate.
2. Preparing a negative pole piece: taking artificial graphite as a negative active material, mixing 96% of negative active material, 2% of CMC/SBR adhesive and 2% of Super P conductive carbon black according to a mass ratio, adding the mixture into deionized water, and uniformly stirring to obtain the composite material, and then uniformly coating the negative active material on a current collector copper foil with a coating weight of 200g/m 2 And then drying at 85 ℃, performing cold pressing, trimming, cutting and slitting, drying for 4 hours at 110 ℃ under a vacuum condition, and welding tabs to obtain the negative plate.
3. Preparing a soft package lithium ion battery: the positive plate, the negative plate and the PE diaphragm coated with the ceramic are manufactured into a soft package battery core through a lamination process, the soft package battery core is baked for 10 hours at 75 ℃, electrolyte with the number of (1) in the experimental example 1 is used for injecting the soft package battery core, the soft package battery core is kept stand for 24 hours after the electrolyte is injected, and the soft package battery with the number of (A1) is obtained through the working procedures of formation aging, clamping, capacity grading and the like.
Experimental example 3
This experimental example is substantially the same as experimental example 2, except that the electrolyte solution numbered (2) in experimental example 1 was used to fill the pouch cell, and the pouch battery numbered (a2) was obtained.
Experimental example 4
This experimental example is substantially the same as experimental example 2, except that the electrolyte solution numbered (3) in experimental example 1 was used to fill the pouch cell, and the pouch battery numbered (a3) was obtained.
Experimental example 5
This experimental example is substantially the same as experimental example 2, except that the electrolyte solution numbered (4) in experimental example 1 was used to fill the pouch cell, and the pouch battery numbered (a4) was obtained.
Experimental example 6
This experimental example is substantially the same as experimental example 2, except that the electrolyte solution numbered (5) in experimental example 1 was used to fill the pouch cell, and the pouch battery numbered (a5) was obtained.
Experimental example 7
This experimental example is substantially the same as experimental example 2, except that the electrolyte solution numbered (6) in experimental example 1 was used to fill the pouch cell, and the pouch battery numbered (a6) was obtained.
Experimental example 8
This experimental example is substantially the same as experimental example 2, except that the electrolyte solution numbered (7) in experimental example 1 was used to fill the pouch cell, and the pouch battery numbered (a7) was obtained.
Experimental example 9
This experimental example is substantially the same as experimental example 2, except that the electrolyte solution numbered (8) in experimental example 1 was used to fill the pouch cell, and the pouch battery numbered (A8) was obtained.
Experimental example 10
This experimental example is substantially the same as experimental example 2, except that the electrolyte solution numbered (9) in experimental example 1 was used to fill the pouch cell, and the pouch battery numbered (a9) was obtained.
Experimental example 11
This experimental example is substantially the same as experimental example 2, except that the electrolyte solution numbered (10) in experimental example 1 was used to fill the pouch cell, and the pouch battery numbered (a10) was obtained.
Experimental example 12
The experimental example is basically the same as the experimental example 2, except that lithium nickel cobalt manganese oxide (LiNi) is used in the preparation process of the positive pole piece 0.6 Co 0.2 Mn 0.2 O 2 NCM622 for short) ternary material as the positive electrode active material, and the number of the soft package battery is (B1).
Experimental example 13
The experimental example is basically the same as experimental example 3, except that lithium nickel cobalt manganese oxide (LiNi) is used in the preparation process of the positive pole piece 0.6 Co 0.2 Mn 0.2 O 2 NCM622 for short) as the positive electrode active material, and the number of the pouch cell is (B2).
Experimental example 14
The experimental example is basically the same as experimental example 4, except that lithium nickel cobalt manganese oxide (LiNi) is used in the preparation process of the positive pole piece 0.6 Co 0.2 Mn 0.2 O 2 NCM622 for short) as the positive electrode active material, and the number of the pouch cell is (B3).
Experimental example 15
The experimental example is basically the same as the experimental example 5, except that lithium nickel cobalt manganese oxide (LiNi) is used in the preparation process of the positive pole piece 0.6 Co 0.2 Mn 0.2 O 2 NCM622 for short) as the positive electrode active material, and the number of the pouch cell is (B4).
Experimental example 16
The experimental example is basically the same as the experimental example 6, except that lithium nickel cobalt manganese oxide (LiNi) is used in the preparation process of the positive pole piece 0.6 Co 0.2 Mn 0.2 O 2 NCM622 for short) as the positive electrode active material, and the number of the pouch cell is (B5).
Experimental example 17
This example is substantially the same as example 7, except that lithium nickel cobalt manganese oxide (LiNi) was used in the preparation of the positive electrode sheet 0.6 Co 0.2 Mn 0.2 O 2 NCM622 for short) as the positive electrode active material, and the number of the pouch cell is (B6).
Experimental example 18
The experimental example is basically the same as the experimental example 8, except that lithium nickel cobalt manganese oxide (LiNi) is used in the preparation process of the positive pole piece 0.6 Co 0.2 Mn 0.2 O 2 NCM622 for short) as the positive electrode active material, and the number of the pouch cell is (B7).
Experimental example 19
The experimental example is basically the same as the experimental example 9, except that lithium nickel cobalt manganese oxide (LiNi) is used in the preparation process of the positive pole piece 0.6 Co 0.2 Mn 0.2 O 2 NCM622 for short) ternary material as the positive electrode active material, and the number of the soft package battery is (B8).
Experimental example 20
This example is substantially the same as example 10, except that lithium nickel cobalt manganese oxide (LiNi) is used in the preparation of the positive electrode sheet 0.6 Co 0.2 Mn 0.2 O 2 NCM622) ternary material asThe positive electrode active material, pouch cell number (B9).
Experimental example 21
This example is substantially the same as example 11, except that lithium nickel cobalt manganese oxide (LiNi) was used in the preparation of the positive electrode sheet 0.6 Co 0.2 Mn 0.2 O 2 NCM622 for short) as the positive electrode active material, and the number of the pouch cell is (B10).
The following describes a test procedure of the lithium ion battery.
In order to maintain the consistency of the experiment, all the soft package batteries use the same volume of electrolyte, and then the prepared soft package batteries are subjected to a charge and discharge test, and a performance test is performed by using a LAND charge and discharge test system.
In the preparation process of the positive pole piece, nickel cobalt lithium manganate (LiNi) is used 0.8 Co 0.1 Mn 0.1 O 2 NCM811 for short) ternary material as positive electrode active material was tested as follows:
firstly, testing the normal-temperature cycle performance: the battery after formation was placed in an oven at a constant temperature of 25 ℃, charged to a voltage of 4.2V using a 1C constant current and constant voltage (CC CV), and cut off to a current of 0.01C, and then discharged to a voltage of 3.0V using a 1C Constant Current (CC). After N cycles of such charge/discharge, the capacity retention rates after the first and Nth cycles were recorded to evaluate the normal temperature cycle performance.
The calculation formula of the capacity retention rate at 25 ℃ and 1C circulation for N times is as follows:
the nth cycle capacity retention (%) × 100% (nth cycle discharge capacity/first cycle discharge capacity).
II, testing high-temperature cycle performance: the battery after formation was placed in an oven at a constant temperature of 45 ℃, charged to a voltage of 4.2V using a 1C constant current constant voltage (CC CV), cut off to a current of 0.01C, and then discharged to a voltage of 3.0V using a 1C Constant Current (CC). After N cycles of such charge/discharge, the capacity retention rates after the first and Nth cycles were recorded to evaluate the high-temperature cycle performance.
The calculation formula of the capacity retention rate at 45 ℃ and 1C circulation for N times is as follows:
the nth cycle capacity retention (%) × 100% (nth cycle discharge capacity/first cycle discharge capacity).
And thirdly, testing the room temperature storage performance: the formed battery cell is charged to the voltage of 4.2V by using a 1C constant current and constant voltage (CC CV) at normal temperature, the current is cut off to 0.01C, the battery cell is discharged to the voltage of 3.0V by using the 1C Constant Current (CC), the initial discharge capacity of the battery is measured, the battery cell is charged to the voltage of 4.2V by using the 1C constant current and constant voltage (CC CV), the current is cut off to 0.01C, the initial thickness of the battery is measured, the thickness of the battery is measured after the battery is stored for N days at room temperature, the voltage is discharged to the voltage of 3.0V by using the 1C Constant Current (CC), the retention capacity of the battery is measured, the battery cell is charged to the voltage of 4.2V by using the 1C constant current and constant voltage (CC) and the current is cut off to 0.01C, the voltage is discharged to the voltage of 3.0V by using the 1C Constant Current (CC), and the recovery capacity is measured.
The calculation formulas of the capacity retention rate and the capacity recovery rate are as follows:
battery capacity retention (%) — retention capacity/initial capacity × 100%;
the battery capacity recovery (%) — recovery capacity/initial capacity × 100%.
Fourthly, testing the high-temperature storage performance at 60 ℃: the formed battery cell is charged to the voltage of 4.2V by using a 1C constant current and constant voltage (CC CV) at normal temperature, the current is cut off to 0.01C, the battery cell is discharged to the voltage of 3.0V by using the 1C Constant Current (CC), the initial discharge capacity of the battery is measured, the battery cell is charged to the voltage of 4.2V by using the 1C constant current and constant voltage (CC CV), the current is cut off to 0.01C, the thickness of the battery is measured after the battery cell is stored for N days at the temperature of 60 ℃, the voltage of 3.0V is discharged by using the 1C Constant Current (CC), the retention capacity of the battery is measured, the battery cell is charged to the voltage of 4.2V by using the 1C constant current and constant voltage (CC) and the current is cut off to 0.01C, the voltage of 3.0V by using the 1C Constant Current (CC), and the recovery capacity is measured.
The calculation formulas of the capacity retention rate and the capacity recovery rate are as follows:
battery capacity retention (%) — retention capacity/initial capacity × 100%;
the battery capacity recovery ratio (%) — recovery capacity/initial capacity × 100%.
And fifthly, the battery thickness expansion rate after high-temperature storage at 60 ℃: will be transformed intoThe battery cell is charged to 4.2V at a Constant Current (CC) of 1C at normal temperature, then charged to 0.05C at a Constant Voltage (CV) of 4.2V, and the thickness of the lithium ion battery is tested and recorded as h 0 (ii) a Then putting the lithium ion battery into a constant temperature box with the temperature of 60 ℃, storing for N days, taking out, testing the thickness of the lithium ion battery at the moment, and recording as h 1 。
Battery thickness expansion (%) (thickness h after N days) 1 Initial thickness h 0 ) Initial thickness x 100%.
The cell test voltage is 3.0-4.2V, and the capacity retention rate of the battery after 300 weeks of charge-discharge circulation under the conditions of room temperature and 45 ℃ by a Constant Current (CC) of 1C, the capacity retention rate and the recovery rate after 3 months of storage at room temperature and 15 days of storage at 60 ℃ and the volume expansion rate of the cell after 15 days of storage at 60 ℃ are respectively tested.
In the preparation process of the positive pole piece, nickel cobalt lithium manganate (LiNi) is used 0.6 Co 0.2 Mn 0.2 O 2 NCM622 for short) ternary material was used as the positive electrode active material to make a pouch cell test as follows:
sixthly, testing the normal-temperature cycle performance: the formed battery was charged with a 1C constant current and constant voltage (CC CV) to a voltage of 4.3V at 25 ℃, cut off to a current of 0.01C, and then discharged with a 1C Constant Current (CC) to a voltage of 3.0V. After N cycles of charge/discharge, the capacity retention rate after the Nth cycle was calculated to evaluate the normal temperature cycle performance.
The calculation formula of the capacity retention rate at 25 ℃ and 1C circulation for N times is as follows:
the nth cycle capacity retention (%) × 100% (nth cycle discharge capacity/first cycle discharge capacity).
Seventhly, testing high-temperature cycle performance: the formed battery was charged with a 1C constant current and constant voltage (CC CV) to a voltage of 4.3V at 45C, cut off to a current of 0.01C, and then discharged with a 1C Constant Current (CC) to a voltage of 3.0V. After N cycles of such charge/discharge, the capacity retention rate after the Nth cycle was calculated to evaluate the high-temperature cycle performance.
The calculation formula of the capacity retention rate at 45 ℃ and 1C circulation for N times is as follows:
the nth cycle capacity retention (%) × 100% (nth cycle discharge capacity/first cycle discharge capacity).
Eighthly, testing the room-temperature storage performance: the formed battery cell is charged to the voltage of 4.3V by using a 1C constant current and constant voltage (CC CV) at normal temperature, the current is cut off to 0.01C, the battery cell is discharged to the voltage of 3.0V by using the 1C Constant Current (CC), the initial discharge capacity of the battery is measured, the battery cell is charged to the voltage of 4.3V by using the 1C constant current and constant voltage (CC CV), the current is cut off to 0.01C, the initial thickness of the battery is measured, the thickness of the battery is measured after the battery is stored for N days at room temperature, the voltage is discharged to the voltage of 3.0V by using the 1C Constant Current (CC), the retention capacity of the battery is measured, the battery cell is charged to the voltage of 4.3V by using the 1C constant current and constant voltage (CC) and the current is cut off to 0.01C, the voltage is discharged to the voltage of 3.0V by using the 1C Constant Current (CC), and the recovery capacity is measured.
The calculation formulas of the capacity retention rate and the capacity recovery rate are as follows:
battery capacity retention (%) — retention capacity/initial capacity × 100%;
the battery capacity recovery ratio (%) — recovery capacity/initial capacity × 100%.
Nine, 60 ℃ high-temperature storage performance test: the formed battery cell is charged to a voltage of 4.3V by using a 1C constant current and constant voltage (CC CV) at normal temperature, a cutoff current is 0.01C, the battery cell is discharged to a voltage of 3.0V by using a 1C Constant Current (CC), the initial discharge capacity of the battery is measured, the battery cell is charged to a voltage of 4.3V by using a 1C constant current and constant voltage (CC CV), a cutoff current is 0.01C, the initial thickness of the battery is measured, the battery cell is stored for N days at a temperature of 60 ℃, the thickness of the battery cell is measured, the battery cell is discharged to a voltage of 3.0V by using a 1C Constant Current (CC), the retention capacity of the battery cell is measured, the battery cell is charged to a voltage of 4.3V by using a 1C constant current and constant voltage (CC) until a cutoff current is 0.01C, and the recovery capacity is measured.
The calculation formulas of the capacity retention rate and the capacity recovery rate are as follows:
battery capacity retention (%) — retention capacity/initial capacity × 100%;
the battery capacity recovery (%) — recovery capacity/initial capacity × 100%.
Tenthly, the battery thickness expansion rate of high-temperature storage at 60 ℃ is as follows:charging the formed battery cell at normal temperature by using a 1C Constant Current (CC) until the voltage is 4.3V, then charging by using a 4.3V Constant Voltage (CV) until the current is 0.05C, and testing the thickness of the lithium ion battery and recording the thickness as h 0 (ii) a Then putting the lithium ion battery into a constant temperature box with the temperature of 60 ℃, storing for N days, taking out, testing the thickness of the lithium ion battery at the moment, and recording as h 1 。
Battery thickness swelling ratio (%) (thickness h after N days) 1 Initial thickness h 0 ) Initial thickness x 100%.
The cell test voltage is 3.0-4.3V, the capacity retention rate of the battery is tested after 300 weeks of charge-discharge circulation under the conditions of room temperature and 45 ℃ by a 1C Constant Current (CC), the capacity retention rate and the recovery rate after storage for 3 months at room temperature and storage for 15 days at 60 ℃ and the volume expansion rate of the cell after storage for 15 days at 60 ℃ are tested.
The specific data of the battery performance test results are shown in table 3.
TABLE 3 Battery Performance test results
As can be seen from the test results in table 3, when the oxalic acid phosphate derivative prepared by the embodiment of the invention is used as an additive in an electrolyte, the stability of the electrolyte can be improved. When the electrolyte is applied to the preparation of a secondary battery, the normal-temperature cycle performance, the high-temperature cycle performance, the normal-temperature storage performance and the high-temperature storage performance of the battery are favorably improved, gas generation of the battery can be inhibited, the volume expansion of the battery is reduced, the safety of the battery is improved, and the service life of the battery is prolonged.
Claims (10)
1. An oxalate derivative is characterized in that the structural general formula of the oxalate derivative is shown as formula (I):
wherein M is Li, Na or K, R 1 、R 2 、R 3 、R 4 Are each selected from F, thiocyano or thioisocyanate groups, and R 1 、R 2 、R 3 And R 4 Not being F at the same time.
2. An oxalate phosphate derivative according to claim 1, wherein the oxalate phosphate derivative includes at least one of an oxalate thiocyano trifluorophosphate, an oxalate dithiocyano difluorophosphate, an oxalate trithiocyano fluorophosphate, an oxalate tetrathiocyano phosphate, an oxalate thioisocyanate trifluorophosphate, an oxalate dithioisocyanate difluorophosphate, an oxalate trithioisocyanate fluorophosphate, an oxalate tetrathioisocyanate phosphate, and the structural formulas of the oxalate thiocyano trifluorophosphate, the oxalate dithiocyano difluorophosphate, the oxalate trithiocyano fluorophosphate, the oxalate thioisocyanate trifluorophosphate, the oxalate dithioisocyanate difluorophosphate, the oxalate trithioisocyanate fluorophosphate, and the oxalate tetrathioisocyanate phosphate are shown in the following formulas (II) to (IX), wherein M is Li, Na or K:
3. a preparation method of the oxalic acid phosphate derivative is characterized by comprising the following steps:
providing tetrafluoro oxalate phosphate, a sulfo-silicon-based compound and a non-aqueous solvent, wherein the tetrafluoro oxalate phosphate is selected from at least one of lithium tetrafluorooxalate phosphate, sodium tetrafluorooxalate phosphate and potassium tetrafluorooxalate phosphate, and the sulfo-silicon-based compound contains sulfo-cyano groups or sulfo-isocyanate groups;
mixing the tetrafluoro oxalate phosphate with the sulfo-silicon-based compound in the non-aqueous solvent to carry out substitution reaction to obtain an oxalate phosphate derivative;
the structural general formula of the oxalic acid phosphate derivative is shown as the formula (I):
wherein M is Li, Na or K, R 1 、R 2 、R 3 、R 4 Are each selected from F, thiocyano or thioisocyanate groups, and R 1 、R 2 、R 3 And R 4 Not simultaneously F.
4. The method for preparing an oxalate phosphate derivative according to claim 3, wherein the oxalate phosphate derivative includes at least one of an oxalate thiocyano trifluorophosphate, an oxalate dithiocyano difluorophosphate, an oxalate trithiocyano fluorophosphate, an oxalate tetrathiocyano phosphate, an oxalate thioisocyanate trifluorophosphate, an oxalate dithioisocyanate difluorophosphate, an oxalate trithioisocyanate fluorophosphate, and an oxalate tetrathioisocyanate phosphate, and the structural formulas of the oxalate thiocyano trifluorophosphate, the oxalate dithiocyano difluorophosphate, the oxalate trithiocyano fluorophosphate, the oxalate thioisocyanate trifluorophosphate, the oxalate dithioisocyanate difluorophosphate, the oxalate trithioisocyanate fluorophosphate, and the oxalate tetrathioisocyanate phosphate are shown in the following formulas (II) to (IX), wherein M is Li, Na or K:
5. the method for preparing oxalate phosphate derivatives of claim 3, wherein the thiosilyl compound has a formula represented by formula (XI) or formula (XII), wherein R is 5 、R 6 、R 7 、R 8 、R 9 、R 10 Are respectively and independentlyOne selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 20 carbon atoms;
6. the method for preparing an oxalate phosphate derivative according to claim 3, wherein, in the step of mixing the tetrafluoro-oxalate phosphate with the thiosilicon-based compound to carry out the substitution reaction, the molar ratio of the tetrafluoro-oxalate phosphate to the thiosilicon-based compound is 1 (1-4); and/or
And in the step of mixing the tetrafluoro oxalate phosphate with the sulfo-silicon-based compound for substitution reaction, the reaction temperature of the substitution reaction is-20 ℃ to 80 ℃, and the reaction time is 1h to 6 h.
7. The method for producing an oxalic acid phosphate derivative according to any one of claims 3 to 6, wherein the nonaqueous solvent is selected from acetonitrile, propionitrile, 1, 3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2, 5-dimethyltetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, formamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, hexaethylphosphoric triamide, dimethyl sulfoxide, diethylsulfoxide, dichloromethane, chloroform, diethyl ether, propyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl methyl carbonate, ethyl acetate, ethyl propionate, propyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl acetate, and mixtures thereof, At least one of n-hexane, n-heptane, cyclohexane, benzene, toluene, and xylene; and/or
The water content of the tetrafluoro oxalic acid phosphate is less than or equal to 100 ppm.
8. An electrolyte comprising a solvent, an electrolyte salt and an additive, wherein the additive comprises the oxalic acid phosphate derivative of claim 1 or 2, or the oxalic acid phosphate derivative prepared by the preparation method of any one of claims 3 to 7.
9. The electrolyte according to claim 8, wherein the oxalic acid phosphate derivative is contained in the electrolyte in an amount of 0.1 to 2% by mass.
10. A secondary battery comprising the electrolyte according to claim 8 or 9.
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| US20210013547A1 (en) * | 2019-07-09 | 2021-01-14 | Uchicago Argonne, Llc | Rechargeable non-aqueous sodium-air batteries |
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| JP2008305574A (en) * | 2007-06-05 | 2008-12-18 | Toyota Central R&D Labs Inc | Lithium ion secondary battery |
| CN107851847A (en) * | 2015-08-12 | 2018-03-27 | 中央硝子株式会社 | Non-aqueous electrolyte and use its non-aqueous electrolyte cell |
| CN109155438A (en) * | 2016-07-06 | 2019-01-04 | 中央硝子株式会社 | Non-aqueous electrolyte and the non-aqueous electrolyte cell for using it |
| US20210013547A1 (en) * | 2019-07-09 | 2021-01-14 | Uchicago Argonne, Llc | Rechargeable non-aqueous sodium-air batteries |
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