CN111925389B - Trisilyl-containing propinyl phosphate compound and preparation method and application thereof - Google Patents
Trisilyl-containing propinyl phosphate compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN111925389B CN111925389B CN202010963799.XA CN202010963799A CN111925389B CN 111925389 B CN111925389 B CN 111925389B CN 202010963799 A CN202010963799 A CN 202010963799A CN 111925389 B CN111925389 B CN 111925389B
- Authority
- CN
- China
- Prior art keywords
- trimethylsilyl
- lithium
- electrolyte
- triethylamine
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 32
- 239000010452 phosphate Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 phosphate compound Chemical class 0.000 title claims description 72
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 90
- 239000003792 electrolyte Substances 0.000 claims description 52
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 50
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 30
- 239000000654 additive Substances 0.000 claims description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 16
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 5
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 claims description 5
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 3
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- JSPNHQNTROWEKK-UHFFFAOYSA-N C[Si](C)(C)CC#COP(O)(O)=O Chemical compound C[Si](C)(C)CC#COP(O)(O)=O JSPNHQNTROWEKK-UHFFFAOYSA-N 0.000 claims description 2
- NONFLFDSOSZQHR-UHFFFAOYSA-N 3-(trimethylsilyl)propionic acid Chemical compound C[Si](C)(C)CCC(O)=O NONFLFDSOSZQHR-UHFFFAOYSA-N 0.000 claims 1
- 101100537779 Homo sapiens TPM2 gene Proteins 0.000 claims 1
- 229910010941 LiFSI Inorganic materials 0.000 claims 1
- 102100036471 Tropomyosin beta chain Human genes 0.000 claims 1
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 9
- 125000003118 aryl group Chemical group 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 125000004429 atom Chemical group 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 229910013872 LiPF Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- ZBQQCALTKUXQCV-UHFFFAOYSA-N Trimethylsilylpropargyl alcohol Chemical compound C[Si](C)(C)C(O)C#C ZBQQCALTKUXQCV-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000004076 pyridyl group Chemical group 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000004502 1,2,3-oxadiazolyl group Chemical group 0.000 description 2
- 125000004529 1,2,3-triazinyl group Chemical group N1=NN=C(C=C1)* 0.000 description 2
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 2
- 125000004504 1,2,4-oxadiazolyl group Chemical group 0.000 description 2
- 125000004530 1,2,4-triazinyl group Chemical group N1=NC(=NC=C1)* 0.000 description 2
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 description 2
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- GZPPANJXLZUWHT-UHFFFAOYSA-N 1h-naphtho[2,1-e]benzimidazole Chemical compound C1=CC2=CC=CC=C2C2=C1C(N=CN1)=C1C=C2 GZPPANJXLZUWHT-UHFFFAOYSA-N 0.000 description 2
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 2
- HCCNHYWZYYIOFM-UHFFFAOYSA-N 3h-benzo[e]benzimidazole Chemical compound C1=CC=C2C(N=CN3)=C3C=CC2=C1 HCCNHYWZYYIOFM-UHFFFAOYSA-N 0.000 description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910008284 Si—F Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical compound C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 2
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000005956 isoquinolyl group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JAUCCASEHMVMPM-UHFFFAOYSA-N naphtho[2,1-e][1,3]benzoxazole Chemical compound C1=CC2=CC=CC=C2C2=C1C(N=CO1)=C1C=C2 JAUCCASEHMVMPM-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
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- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
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- 239000007774 positive electrode material Substances 0.000 description 1
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- OSOBRNLAUDAQKA-UHFFFAOYSA-N prop-1-ynyl dihydrogen phosphate Chemical compound CC#COP(O)(O)=O OSOBRNLAUDAQKA-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Images
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 Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
- C07F9/092—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl substituted by B, Si or a metal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
The invention relates to a compound containing trimethylsilyl propinyl phosphate and a preparation method and application thereof, wherein the structural general formula of the compound containing trimethylsilyl propinyl phosphate is as follows:wherein R1 and R2 are selected from one of compounds containing Si atoms, alkyl, aryl or heteroaryl.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a compound containing trimethylsilyl and propinyl phosphate and a preparation method and application thereof.
Background
Since the industrial revolution, fossil energy such as petroleum, coal, natural gas and the like occupies an indispensable position in daily production and life of people, however, the storage capacity of fossil energy on the earth is gradually reduced along with the mass exploitation and use of people, so that the problem of energy shortage becomes one of two problems which have to be faced in the world today, and therefore, the development and utilization of renewable energy and new energy are increasingly regarded as important. Renewable energy sources such as solar energy, wind energy, geothermal energy and the like are easily restricted by natural environment and climate and cannot be efficiently applied to production and life of people, and lithium ion batteries are widely applied to portable equipment such as mobile phones, calculators, MP3 and tablet personal computers due to the advantages of high voltage, high specific energy, long cycle life, no pollution and the like, and have wide application prospects on large-scale equipment such as new energy Electric Vehicles (EVs), aerospace and aviation and power grid energy storage.
The lithium ion battery consists of a positive electrode, an electrolyte, a diaphragm, a negative electrode and the like, wherein the electrolyte is used as 'blood' of the lithium ion battery and is responsible for transmitting lithium ions, and the properties of the electrolyte, such as liquid process, viscosity, dielectric constant and the like, are closely related to the safety and electrochemical performance of the lithium ions.
At present, the research on the electrolyte mainly focuses on the additives, and the additives are mainly classified into: 1) A negative electrode film forming additive; 2) A positive electrode interface film forming additive; 3) A flame retardant additive; 4) An anti-overcharge additive; 5) A lithium salt stabilizing additive.
Generally, different additives are combined according to the use requirements of commercial electrolyte so as to meet the performance requirements. The existing additives basically aim at a single problem, and different additive combinations are required according to the use requirements so as to achieve the required performance. When the additive is added in a large amount, the cost is high, and the conductivity of the electrolyte is affected.
Disclosure of Invention
The embodiment of the invention provides a compound containing trimethylsilyl propinyl phosphate and a preparation method and application thereof, wherein the compound contains unsaturated bonds which can be polymerized into polymers, and contains a silyl functional group which can eliminate HF and H 2 And O and the P-containing element are combined with hydroxyl radicals generated by thermal decomposition of the electrolyte to block a reaction chain and inhibit thermal runaway. The compound containing the trimethylsilyl-propynyl phosphate ester is used as an electrolyte additive, so that the storage and cycle performance of the battery can be improved, and a certain effect of reducing the interface impedance is achieved.
In a first aspect, the embodiment of the present invention provides a trisilyl-propynyl phosphate-containing compound, which has a structural formula as follows:
wherein R1 and R2 are selected from one of compounds containing Si atoms, alkyl, aryl or heteroaryl.
Preferably, the Si atom-containing compound includes any one of an alkane silicon compound, an aryl group-containing silicon compound, or a fluorine-containing silicon compound;
said alkyl radical-C m H 2m+1 Wherein m is more than or equal to 1 and less than or equal to 6;
the aryl group includes any one of phenyl, anthracyl, naphthyl or biphenyl;
the carbon atom number of the heteroaryl is 3 to 20, and the heteroaryl comprises 1 to 3 heteroatoms of O, S, P and N; the heteroaryl group specifically includes any of pyridyl, indolyl, pyrrolyl, imidazolyl, thienyl, furyl, 1, 2-thiazolyl, 1, 3-thiazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, thiadiazolyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, pyridyl, pyrazinyl, pyrimidinyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, indole, isoindole, benzimidazole, naphthoimidazole, phenanthroimidazole, benzotriazole, benzoxazole, naphthoxazole, phenanthrooxazole, benzothiadiazolyl, benzotriazolyl, quinolyl, isoquinolyl, benzopyrazinyl, benzothiophenyl, benzofuryl, benzopyrryl, carbazolyl, naphthothiadiazolyl.
Preferably, the trisilylpropynyl phosphate-containing compound specifically includes:
In a second aspect, the present invention provides a preparation method of the trisilyl propynyl phosphate-containing compound described in the first aspect, the preparation method including:
under an inert environment, firstly introducing tetrahydrofuran, and then introducing trimethylsilylproparganol and triethylamine into a reactor;
keeping the temperature of the reaction system at 0-5 ℃, slowly adding phosphorus trichloride or phosphorus oxychloride with continuous stirring, continuously stirring at room temperature for a period of time, and filtering to remove white precipitate of triethylamine hydrochloride;
and (3) distilling under reduced pressure for multiple times to remove low-boiling triethylamine, trimethylsilyl propiolic alcohol and tetrahydrofuran in the filtrate, and washing to obtain the trimethylsilyl-propiolic phosphate-containing compound.
Preferably, before the reactor is firstly filled with tetrahydrofuran and then with the trimethylsilylpropynyl alcohol and the triethylamine, the method further comprises the following steps:
and respectively pretreating the tetrahydrofuran, the trimethylsilyl propiolic alcohol, the triethylamine and the phosphorus trichloride or the phosphorus oxychloride.
Preferably, the pretreatment specifically comprises:
heating and distilling the tetrahydrofuran, and simultaneously drying and removing water by using metal sodium to ensure that the purity of the tetrahydrofuran is more than 99.9 percent and the water content is reduced to below 50ppm;
heating and fractionating the triethylamine to obtain a colorless and transparent triethylamine solution, and then adding an activated 4A molecular sieve to ensure that the water content of the triethylamine is lower than 50ppm;
and respectively adding the trimethylsilyl propiolic alcohol, the phosphorus trichloride or the phosphorus oxychloride into the activated 4A molecular sieve, so that the moisture content of the trimethylsilyl propiolic alcohol, the phosphorus trichloride or the phosphorus oxychloride is respectively lower than 50ppm.
In a third aspect, an embodiment of the present invention provides an electrolyte, where the electrolyte includes the trimethylsilyl-propynyl-containing phosphate compound described in the first aspect.
Preferably, the electrolyte further comprises: lithium salt electrolyte, organic solvent and auxiliary additive; the adding amount of the trimethylsilyl-containing propynyl phosphate ester compound accounts for 0.1-2 wt% of the total mass of the electrolyte.
Preferably, the lithium salt electrolyte includes: one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorophosphate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis (trifluoromethylsulfonimide) and lithium bis (fluorosulfonimide);
the organic solvent includes: a mixture of one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, 1, 4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, and halogenated derivatives thereof;
the auxiliary additive comprises: one or more of fluoroethylene carbonate FCE, lithium difluorosulfonimide LiFSI, vinyl sulfate DTD, tris (trimethylsilyl) borate TMSB and tris (trimethylsilyl) phosphate TMSP.
In a fourth aspect, an embodiment of the present invention provides a lithium battery, including the electrolyte according to the third aspect.
The compound containing trimethylsilyl propinyl phosphate provided by the embodiment of the invention has the advantages of simple synthesis method, easily obtained raw materials and large-scale production; the additive is multifunctional, and contains silicon-based functional group, unsaturated polymer and sulfur-containing functional group, in which the unsaturated bond can be condensed and polymerized into conductive polymer film, and the silicon-based can consume HF and H 2 And O, so that the corrosion of HF to an electrode is reduced, the P-containing element is combined with hydroxyl radicals thermally decomposed by the electrolyte, a reaction chain is blocked, and thermal runaway is inhibited.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
FIG. 1 is a flow chart of a method for preparing a trisilylpropynyl phosphate-containing compound according to an embodiment of the present invention;
FIG. 2 shows superconducting nuclear magnetic resonance spectroscopy (NMR) analysis of a trimethylsilyl-propynyl-phosphate-containing compound provided in example 1 of the present invention 1 H spectrum carries on the test result picture of the structural characterization;
FIG. 3 shows superconducting nuclear magnetic resonance spectroscopy (NMR) analysis of the trimethylsilyl-propynyl-phosphate-containing compound provided in example 2 of the present invention 1 H spectrum is used for carrying out structural characterization.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it will be understood that these examples are given solely for the purpose of illustration and are not to be construed as limiting the invention in any way, i.e., not as limiting the scope of the invention.
The compound contains silicon base, unsaturated polymer and sulfur-containing functional group, and the general structural formula is as follows:
wherein R1 and R2 are selected from one of compounds containing Si atoms, alkyl, aryl or heteroaryl.
Specifically, the Si atom-containing compound includes any of an alkane silicon compound, an aryl group-containing silicon compound, or a fluorine-containing silicon compound;
alkyl radical-C m H 2m+1 Wherein m is more than or equal to 1 and less than or equal to 6;
the aryl group includes any one of phenyl, anthracyl, naphthyl or biphenyl;
the carbon atom number of the heteroaryl is 3 to 20, and the heteroaryl comprises 1 to 3 heteroatoms of O, S, P and N; heteroaryl specifically includes any of pyridyl, indolyl, pyrrolyl, imidazolyl, thienyl, furyl, 1, 2-thiazolyl, 1, 3-thiazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, thiadiazolyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, pyridyl, pyrazinyl, pyrimidinyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, indole, isoindole, benzimidazole, naphthoimidazole, phenanthroimidazole, benzotriazole, benzoxazole, naphthooxazole, phenanthrooxazole, benzothiadiazolyl, benzotriazolyl, quinolyl, isoquinolyl, benzopyrazinyl, benzothiophenyl, benzofuranyl, benzopyrolyl, carbazolyl, naphthothiadiazolyl.
The compound containing the trimethylsilyl-propynyl phosphate can be obtained by the preparation method shown in the flow chart of the figure 1, and the main steps comprise:
Specifically, heating and distilling the tetrahydrofuran, and simultaneously drying and removing water by using metal sodium to ensure that the purity of the tetrahydrofuran is more than 99.9 percent and the water content is reduced to below 50ppm;
heating and fractionating triethylamine to obtain a colorless and transparent triethylamine solution, and then adding an activated 4A molecular sieve to ensure that the water content of the triethylamine is lower than 50ppm;
adding trimethylsilyl propargyl alcohol, phosphorus trichloride or phosphorus oxychloride into the activated 4A molecular sieve respectively to ensure that the moisture content of the trimethylsilyl propargyl alcohol, the phosphorus trichloride or the phosphorus oxychloride is respectively lower than 50ppm.
and 140, carrying out reduced pressure distillation for many times to remove low-boiling triethylamine, trimethylsilyl propiolic alcohol and tetrahydrofuran in the filtrate, and washing to obtain the trimethylsilyl-containing propiolic phosphate compound.
The trimethylsilyl-containing propinyl phosphate compound provided by the invention can be used in electrolyte, and preferably, the addition amount of the trimethylsilyl-containing propinyl phosphate compound accounts for 0.1-2 wt% of the total mass of the electrolyte.
The electrolyte also comprises: lithium salt electrolyte, organic solvent and auxiliary additive; wherein the lithium salt electrolyte may include: one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorophosphate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis (trifluoromethylsulfonimide) and lithium bis (fluorosulfonimide); the organic solvent may include: one or more mixtures of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, 1, 4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, and halogenated derivatives thereof; the auxiliary additives may include: one or more of fluoro ethylene carbonate (FCE), lithium bis (fluorosulfonyl) imide (LiFSI), vinyl sulfate (DTD), tris (trimethylsilyl) borate (TMSB), and tris (trimethylsilyl) phosphate (TMSP).
The electrolyte containing the trimethylsilyl propinyl phosphate compound provided by the embodiment of the invention is used for a lithium battery.
Because of H in the electrolyte 2 O causes a fluorine-containing lithium salt (e.g., lithium hexafluorophosphate LiPF) 6 ) The decomposition of (2) to generate HF, which causes corrosion of the positive electrode and deterioration of the battery performance, and the Si group in the trimethylsilyl-containing propinyl phosphate compound and the compound derived from LiPF due to the higher binding energy of the Si-F bond 6 F of (A) - React to form a-Si-F containing product, and the silicon group can react with H 2 O forms a-Si-OH containing product. That is, the silyl group containing the trisilylpropynyl phosphate compound may react with HF and H in the electrolyte 2 And (4) O reaction, which reduces the content of HF in the electrolyte and inhibits the corrosion of HF on the anode.
The electrolyte contains unsaturated bonds, can be generally polymerized, can be polymerized at the positive electrode and the negative electrode to form polymer films, effectively prevents the positive electrode from contacting with the electrolyte, inhibits the side reaction of high-valence transition metal ions and the electrolyte, and can stabilize the electrode structure, inhibit the corrosion of HF to the electrode, and reduce the dissolution of the transition metal ions and the damage of the HF to SEI.
The P-containing element is combined with hydroxyl radicals generated by thermal decomposition of the electrolyte to play a role of a phosphorus flame retardant additive, block a reaction chain and inhibit thermal runaway. When the lithium ion battery is heated, the phosphorus flame-retardant additive is changed into a gaseous state from a liquid, the gaseous flame-retardant additive releases [ P ]. And finally [ P ]. Is combined with [ H ]. And [ OH ]. And the like, so that the continuous operation of hydroxyl chain reaction is effectively inhibited, and the safety performance of the lithium ion battery is improved.
The trivalent P in the electrolyte can be in a state of three lone pairs of electrons to be easily oxidized into a pentavalent state, and can be in a state of three valence with O in a system 2 Reacting to generate pentavalent P.
The following are specific examples to illustrate the specific preparation of the trimethylsilyl-propynyl-containing phosphate compound provided by the invention and the characteristics of the trimethylsilyl-propynyl-containing phosphate compound applied to the electrolyte.
Example 1
The preparation method has the following specific reaction principle:
the preparation method comprises the following specific steps:
(1) Pretreatment of raw materials: heating and distilling tetrahydrofuran, and simultaneously drying and removing water by using metal sodium to ensure that the purity of the tetrahydrofuran is more than 99.9 percent and the water content is reduced to below 50ppm; heating and fractionating triethylamine to obtain a colorless and transparent triethylamine solution, and then adding an activated 4A molecular sieve to ensure that the water content of triethylamine (Et 3N) is lower than 50ppm; adding the trimethylsilyl propiolic alcohol and the phosphorus oxychloride into the activated 4A molecular sieve respectively to ensure that the moisture content of the trimethylsilyl propiolic alcohol and the phosphorus oxychloride is lower than 50ppm.
(2) The preparation reaction of the embodiment is carried out in an inert atmosphere, and 50mL of tetrahydrofuran is added after the inert gas is filled into the reactor;
(3) Sequentially adding 0.3mol of trimethylsilyl propiolic alcohol and 0.3mol of triethylamine into a reactor;
(4) Keeping the temperature of the reaction system at 0-5 ℃, slowly adding 0.1mol of phosphorus oxychloride while continuously stirring, and continuously stirring for 12 hours at room temperature;
(5) Filtering to remove white precipitate of triethylamine hydrochloride;
(6) And (3) carrying out repeated reduced pressure distillation to remove low-boiling triethylamine, trimethylsilyl propargyl alcohol and tetrahydrofuran in the filtrate, and washing to obtain a compound shown in a formula (3), namely the trimethylsilyl propinyl phosphate-containing compound prepared in the embodiment.
Dissolving the washed product in dimethyl sulfoxide (DMSO) for useGuided nuclear magnetic resonance spectroscopy (NMR) 1 H spectrum, the structure characterization is carried out, and the result is shown in figure 2.
Example 2
The preparation method has the following specific reaction principle:
the preparation method comprises the following specific steps:
(1) Pretreatment of raw materials: heating and distilling tetrahydrofuran, and simultaneously drying and removing water by using metal sodium to ensure that the purity of the tetrahydrofuran is more than 99.9 percent and the water content is reduced to below 50ppm; heating and fractionating triethylamine to obtain a colorless and transparent triethylamine solution, and then adding an activated 4A molecular sieve to ensure that the water content of triethylamine (Et 3N) is lower than 50ppm; adding the trimethylsilyl propiolic alcohol and the phosphorus trichloride into the activated 4A molecular sieve respectively to ensure that the moisture content of the trimethylsilyl propiolic alcohol and the phosphorus trichloride is less than 50ppm.
(2) The preparation reaction of the embodiment is carried out in an inert atmosphere, and 50mL of tetrahydrofuran is added after the inert gas is filled into the reactor;
(3) Sequentially adding 0.3mol of trimethylsilyl propiolic alcohol and 0.3mol of triethylamine into a reactor;
(4) Keeping the temperature of the reaction system at 0-5 ℃, slowly adding 0.1mol of phosphorus trichloride while continuously stirring, and continuously stirring for 12 hours at room temperature;
(5) Filtering to remove white precipitate of triethylamine hydrochloride;
(6) And (3) distilling under reduced pressure for multiple times to remove low-boiling triethylamine, trimethylsilyl propiolic alcohol and tetrahydrofuran in the filtrate, and washing to obtain a compound shown as a formula (4), namely the trimethylsilyl-propinyl phosphate-containing compound prepared in the embodiment.
Dissolving the washed product in dimethyl sulfoxide (DMSO) and performing superconducting nuclear magnetic resonance spectroscopy (NMR) 1 H spectrum, the structure characterization, the results are shown in figure 3.
The trisilylpropynyl phosphate-containing compounds obtained in the above examples 1 and 2 were used for the preparation of an electrolyte solution by the following methods:
in a glove box which is filled with argon and has the moisture content of less than 0.1ppm and the oxygen content of less than 0.1ppm, ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) are added according to the mass ratio of 3:2:5, and adding lithium hexafluorophosphate (LiPF) 6 ) The concentration of lithium salt is 1 mol. L -1 Auxiliary additives of fluoroethylene carbonate (FEC), lithium bis (fluorosulfonyl) imide (LiFSI), and vinyl sulfate (DTD) are added in an amount of 1%, and 1% by mass, respectively, based on the total mass of the electrolyte, and the trimethylsilyl-containing propynyl phosphate ester compound obtained in the above examples 1 and 2 is added in an amount of 1wt% by mass, respectively, to obtain an electrolyte a and an electrolyte B.
For comparison, the invention also provides a comparative example for subsequent test comparison.
Comparative example 1
In a glove box which is filled with argon and has the moisture content of less than 0.1ppm and the oxygen content of less than 0.1ppm, ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) are mixed according to the mass ratio of 3:2:5, and adding lithium hexafluorophosphate (LiPF) 6 ) The concentration of lithium salt is 1 mol. L -1 Auxiliary additives of fluoroethylene carbonate (FEC), lithium bis (fluorosulfonyl) imide (LiFSI) and vinyl sulfate (DTD) were added in an amount of 1%, 1% and 1% by mass, respectively, based on the total mass of the electrolyte, to prepare a comparative electrolyte C.
Comparative example 2
In a glove box which is filled with argon and has the moisture content of less than 0.1ppm and the oxygen content of less than 0.1ppm, ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) are added according to the mass ratio of 3:2:5, and adding lithium hexafluorophosphate (LiPF) 6 ) The concentration of lithium salt is 1 mol. L -1 Auxiliary additives VC, liP fluoroethylene carbonate (FEC), lithium bis (fluorosulfonyl) imide (LiFSI), vinyl sulfate (DTD) and tris (trimethyl) are added according to the mass fractions of 1%, 1% and 1% respectivelySilane) Borate (TMSB) to give comparative electrolyte D.
Comparative example 3
In a glove box which is filled with argon and has the moisture content of less than 0.1ppm and the oxygen content of less than 0.1ppm, ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) are mixed according to the mass ratio of 3:2:5, and adding lithium hexafluorophosphate (LiPF) 6 ) The concentration of lithium salt is 1 mol. L -1 And adding auxiliary additives of fluoroethylene carbonate (FEC), lithium bis (fluorosulfonyl) imide (LiFSI), ethylene sulfate (DTD) and tris (trimethylsilyl) phosphate (TMSP) according to the mass fractions of 1%, 1% and 1% respectively to obtain a comparative electrolyte E.
The electrolyte of each of the above specific examples and comparative examples was used for lithium battery preparation and testing, and the lithium battery preparation and testing methods were as follows:
lithium battery preparation
Selecting LiNi 0.5 Co 0.2 Mn 0.3 O 2 A positive electrode material LiNi 0.5 Co 0.2 Mn 0.3 O 2 Carbon Nanotubes (CNTs) and polyvinylidene fluoride (PVDF) were prepared according to 97.4:1.3: and 1.3, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector through an oven, and rolling the aluminum foil current collector on a roller press to obtain the required positive plate.
Selecting artificial graphite as a negative electrode material, and mixing graphite, CMC, a conductive agent Carbon Nano Tube (CNT) and a binder Styrene Butadiene Rubber (SBR) according to a ratio of 95.8:1.4:0.8:2.0, coating the mixture on a copper foil current collector, drying the copper foil current collector by using an oven, and rolling the copper foil current collector on a roller press to obtain the required negative plate.
Selecting ceramic-coated Polyethylene (PE) film as isolating film (12 um PE base film +4um Al) 2 O 3 ) And the pole piece is manufactured into a 2Ah small soft package battery by a lamination method and is used for testing the electrolyte.
Wherein, the electrolyte is the electrolyte in the above embodiment. The performance of the electrolyte is measured by testing a small soft package battery, namely, the effect of the compound containing the trimethylsilyl propinyl phosphate is evaluated.
The charge-discharge voltage window under the test condition is 2.75-4.2V; the battery cycling test is carried out at room temperature of 25 ℃ and high temperature of 55 ℃, the high-temperature storage performance test is 60 ℃,100% state of charge (SOC) is stored for 50 days, and the cycling charge-discharge current is 0.5C. The specific results are shown in Table 1 below.
TABLE 1
As can be seen from the data in table 1, compared with comparative electrolytes C, D, and E, the electrolytes a and B provided in this embodiment can significantly improve the cycle life of the lithium battery at room temperature, and also significantly improve the storage performance at high temperature, and the voltage retention ratio, the capacity retention ratio, and the capacity recovery ratio are higher and the dc impedance is lower when the lithium battery is stored at 60 ℃ for 50 days. Therefore, the trimethylsilyl-containing propinyl phosphate compound provided by the embodiment of the invention has good effects on improving the storage and cycle performance and reducing the interface impedance of the battery.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
2. A method for preparing a trisilylpropynyl phosphate-containing compound according to claim 1, which comprises:
under an inert environment, firstly introducing tetrahydrofuran, and then introducing trimethylsilylpropynyl alcohol and triethylamine into a reactor;
keeping the temperature of the reaction system at 0-5 ℃, slowly adding phosphorus trichloride or phosphorus oxychloride with continuous stirring, continuously stirring at room temperature for a period of time, and filtering to remove white precipitate of triethylamine hydrochloride;
and (3) carrying out repeated reduced pressure distillation to remove low-boiling triethylamine, trimethylsilyl propiolic alcohol and tetrahydrofuran in the filtrate, and washing to obtain the trimethylsilyl-containing propiolic phosphate compound.
3. The method according to claim 2, wherein the reactor is first filled with tetrahydrofuran, and then filled with trimethylsilylpropynyl alcohol and triethylamine, and the method further comprises:
and respectively pretreating the tetrahydrofuran, the trimethylsilyl propiolic alcohol, the triethylamine and the phosphorus trichloride or the phosphorus oxychloride.
4. The preparation method according to claim 2, wherein the pretreatment specifically comprises:
heating and distilling the tetrahydrofuran, and simultaneously drying and removing water by using metal sodium to ensure that the purity of the tetrahydrofuran is more than 99.9 percent and the water content is reduced to below 50ppm;
heating and fractionating the triethylamine to obtain a colorless and transparent triethylamine solution, and then adding an activated 4A molecular sieve to ensure that the water content of the triethylamine is lower than 50ppm;
and respectively adding the trimethylsilyl propiolic alcohol, the phosphorus trichloride or the phosphorus oxychloride into the activated 4A molecular sieve, so that the moisture content of the trimethylsilyl propiolic alcohol, the phosphorus trichloride or the phosphorus oxychloride is respectively lower than 50ppm.
5. An electrolyte comprising the trisilylpropynyl phosphate-containing compound according to claim 1.
6. The electrolyte of claim 5, further comprising: the electrolyte comprises a lithium salt electrolyte, an organic solvent and an auxiliary additive, wherein the addition amount of the trimethylsilyl-propynyl phosphate ester-containing compound accounts for 0.1-2 wt% of the total mass of the electrolyte.
7. The electrolyte of claim 6, wherein the lithium salt electrolyte comprises: one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorophosphate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis (trifluoromethylsulfonimide) and lithium bis (fluorosulfonimide);
the organic solvent includes: one or more mixtures of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, 1, 4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, and halogenated derivatives thereof;
the auxiliary additive comprises: one or more of fluoroethylene carbonate FEC, lithium bifluorosulfonylimide LiFSI, vinyl sulfate DTD, tri (trimethylsilyl) borate TMSB and tri (trimethylsilyl) phosphate TMSP.
8. A lithium battery, characterized in that it comprises an electrolyte as claimed in any one of the preceding claims 5 to 7.
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