CN111276742A - 一种含有环三磷腈环的锂离子电池阻燃电解质的制备方法 - Google Patents
一种含有环三磷腈环的锂离子电池阻燃电解质的制备方法 Download PDFInfo
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- CN111276742A CN111276742A CN202010028552.9A CN202010028552A CN111276742A CN 111276742 A CN111276742 A CN 111276742A CN 202010028552 A CN202010028552 A CN 202010028552A CN 111276742 A CN111276742 A CN 111276742A
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- ion battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 50
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- 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 title claims abstract description 40
- 239000003063 flame retardant Substances 0.000 title claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical group N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- -1 cyclotriphosphazene lithium triphosphate Chemical compound 0.000 claims abstract description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 17
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 12
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 9
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 claims abstract description 8
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 5
- 150000008301 phosphite esters Chemical class 0.000 claims abstract description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000013329 compounding Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 claims description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- OIIYIFJVTVSNLY-UHFFFAOYSA-A octadecalithium hexaphosphate Chemical compound P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+] OIIYIFJVTVSNLY-UHFFFAOYSA-A 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002000 Electrolyte additive Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 2
- 230000008020 evaporation Effects 0.000 claims 2
- 229910052723 transition metal Inorganic materials 0.000 claims 2
- 150000003624 transition metals Chemical class 0.000 claims 2
- WHZLCOICKHIPRL-SREVYHEPSA-N (z)-4-anilino-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)NC1=CC=CC=C1 WHZLCOICKHIPRL-SREVYHEPSA-N 0.000 claims 1
- GATVHFQKUCJQGI-UHFFFAOYSA-N 1-(7-acetylthianthren-2-yl)ethanone Chemical compound CC(=O)C1=CC=C2SC3=CC(C(=O)C)=CC=C3SC2=C1 GATVHFQKUCJQGI-UHFFFAOYSA-N 0.000 claims 1
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 claims 1
- DSVGFKBFFICWLZ-UHFFFAOYSA-N 1-fluoro-4-isocyanatobenzene Chemical compound FC1=CC=C(N=C=O)C=C1 DSVGFKBFFICWLZ-UHFFFAOYSA-N 0.000 claims 1
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- BZWQNMUGNDAMBX-UHFFFAOYSA-N butyl butane-1-sulfonate Chemical compound CCCCOS(=O)(=O)CCCC BZWQNMUGNDAMBX-UHFFFAOYSA-N 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 229910001386 lithium phosphate Inorganic materials 0.000 claims 1
- 230000000269 nucleophilic effect Effects 0.000 claims 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims 1
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 claims 1
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 claims 1
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 14
- 159000000002 lithium salts Chemical class 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052744 lithium Inorganic materials 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 206010016766 flatulence Diseases 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940034982 antineoplastic agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- FBSFTJQYCLLGKH-UHFFFAOYSA-N cyclohexylphosphonic acid Chemical compound OP(O)(=O)C1CCCCC1 FBSFTJQYCLLGKH-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- C07F9/547—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
- C07F9/6581—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
发明了一种含有环三磷腈环的锂离子电池阻燃电解质的制备方法,电解质采用新结构的有环三磷腈环三膦酸锂盐(LiTHP),其结构式为:
Description
技术领域
本发明涉及一种用于锂电池阻燃电解质的制备。该电解质的电导率高,具有阻燃功能对于提高锂离子电池的安全性能具有重要作用。可用于锂离子电池、锂氧电池、锂硫电池。
技术背景
锂离子电池是一种二次电池(充电电池),它是通过锂离子在正极和负极之间的移动来进行工作的。在充放电过程中,Li+在正、负电极之间往返嵌入和脱嵌:充电时,Li+从正极脱嵌,经过电解质嵌入负极,负极处于富锂状态;放电时则相反。电解质在锂电池充放电过程中起着非常重要的媒介作用,电解质作为锂离子电池的重要组成部分,对于电池电压的稳定输出、工作温度范围调控、循环和安全性能等方面有着重要的影响。而锂盐作为液体电解质(电解液)的重要组分,是决定电解液性能的主要因素。锂盐的种类以及在电解液中的溶剂化状态会对电极/电解液界面的成膜和Li+的移动产生重要影响,从而影响电解液的电化学性能。
目前,商用的锂离子电池电解液一般由锂盐和有机溶剂组成,所使用的溶剂由于具有高活性、高挥发性和易燃性,使电池泄漏时易发生燃烧甚至爆炸。锂电池主要使用的电解质有高氯酸锂、六氟磷酸锂等。而高氯酸锂制成的电池不仅低温效果不好,而且有爆炸的危险;LiPF6具有较高的离子电导率、氧化稳定性以及对环境污染较小,成为使用广泛的锂盐电解质,但LiPF6受热易分解对高温效果不好且对水比较敏感,这使得生产工艺复杂化,生产成本提高。因此,在电解液的生产过程中需加入一定的阻燃添加剂提高其安全性,但会使电解液中Li+浓度下降,不利于离子在正、负极之间的传导。例如专利文献CN201610193164.X李永坤等公开的聚合物电解液可直接在电解液中引入可溶聚合物,不需要使用单体和引发剂。不用暴露在空气中,生产成本低,使聚合物在电解液中溶解并混合均匀,随着电解液的消耗聚合物能够进行物理交联缠绕形成凝胶态。因此,提高锂离子电池电解液安全性的思路为:(1)对锂盐进行改性:锂盐中的阴离子对电解质的性质和性能会产生非常重要的影响;(2)使用合适的添加剂:主要有阻燃添加剂和过充保护添加剂,其他还包括锂枝晶抑制剂、SEI膜稳定剂等添加剂;(3)复合溶剂的选择:主要通过降低溶剂的挥发性、可燃性,改善工作温度范围和对锂盐的溶解性等策略。
锂离子电池使用的阻燃剂大致可分为含磷阻燃剂、含氟阻燃剂、含氮阻燃剂和复合阻燃剂。含磷阻燃剂以自由基捕捉机理为主,阻燃效果较好。六氯环三磷腈是一种磷、氮键交替排列形成的无机化合物,含有的磷氯键非常活泼,容易发生取代反应,使氯原子被其他基团取代,得到一系列的磷腈化合物。它可被用作杀虫剂、肥料、抗肿瘤药物、相转移催化剂、自由基聚合引发剂、光稳定剂、抗氧化剂、阻燃剂等。例如专利文献CN 201610593034.5袁立新公开的超支化聚磷腈具有良好的阻燃效果和热稳定性;专利文献CN201310430183.6郭强等公开的通过六氯环三磷腈经过一系列反应制备的磺化聚苯硫醚及其磷腈衍生物同样具有良好的阻燃作用。磷腈化合物分子中含有可以起到阻燃效果的磷、氮两种元素,两者可以共同发挥作用,相互促进且磷腈可吸热降解生成含大量磷元素且稳定存在的磷酸盐,偏磷酸盐和多聚磷酸盐及不可燃性气体,在燃烧材料表面形成非挥发性的致密保护膜避免与空气接触,从而起到阻燃的作用。
发明内容:
将一定量六氯环三磷腈(HCCP)加入过量的亚磷酸三乙酯中,80~130℃下反应4~8h,停止反应冷却后,加入适量石油醚(除去过量亚磷酸三乙酯)洗涤2~3次后,放入干燥箱中,90~120℃烘干,得到(1,3,5,2λ5,4λ5,6λ5-三氮杂三嗪-2,2,4,4,6,6-己基)六(磷酸乙酯)(ETHP);将得到的(1,3,5,2λ5,4λ5,6λ5-三氮杂三嗪-2,2,4,4,6,6-己基)六(磷酸酯)加入适量的HCl进行水解,120~140℃下反应70~96h,反应结束后在120℃下进行浓缩,浓缩至一定量时,加入适量乙酸乙酯萃取2~3次(除去未水解完全的乙氧基),放入烘箱80~140℃烘干,得到(1,3,5,2λ5,4λ5,6λ5-三氮杂吖嗪-2,2,4,4,6,6-己基)六(膦酸(THP)。
锂盐制备:首先取制备得(1,3,5,2λ5,4λ5,6λ5-三氮杂吖嗪-2,2,4,4,6,6-己基)六(磷酸(THP)粘稠透明凝胶6.21g溶于40ml超纯水中至完全溶解;再逐滴加入60mL 1mol/L的氢氧化锂溶液得黄色澄清溶液;100℃加热浓缩,静置冷却过夜,溶液中产生白色沉淀,抽滤得到白色固体粗产品,用水与乙醇的混合液进行重结晶得到纯品,在100℃下真空干燥,得LiTHP白色固体7.25g。
溶解性能测试:室温下,在等体积比的二甲基亚砜/N-甲基吡咯烷酮(DMSO/NMP)混合溶剂中的溶解度为60g/L;在碳酸乙酯、碳酸乙烯酯等的混合液中溶解度为80g/L,在醚类溶剂四氢呋喃中的溶解度为33g/L。
电导率测试:室温下,DMSO/NMP溶液的电导率为2.26μS/cm;LiOH的DMSO/NMP饱和溶液的电导率为7.70μS/cm;65g/L的LiTHP的碳酸乙酯/碳酸乙烯酯/DMSO/NMP混合溶剂的溶液的电导率为13.8~56mS/cm。
新型阻燃电解质的优点:
本发明提供了一种用于锂电池电解质,环三磷腈环的六磷酸十二锂盐的制备方法。本发明的环三磷腈环的六磷酸十二锂(LiTHP)能溶于有机溶剂,且一个分子中含12个锂离子,而且含有阻燃的环三磷腈环和磷酸基团;锂离子电池电解质中加入LiTHP不但可以提高锂离子的电导率,而且有很好的阻燃性能;用LiTHP与其酯类(RTHP)与其它锂离子电池电解质添加剂复配,能得到新型阻燃电解质。LiTHP在水中具有很好的溶解性能,溶解度可以达到75~98g/L,对水稳定,见水不发生分解,不会产生胀气现象。
首先,以HCCP与亚磷酸酯为原料,在无溶剂、无催化剂条件下,一步在环三磷腈环上引入六个膦酸基,直接合成含环三磷腈环的六磷酸酯(RTHP)。然后,在浓盐酸中对其进行水解,得到含环三磷腈环的六膦酸(THP)。将THP与氢氧化锂、氧化锂或碳酸锂进行反应,即可制备其盐LiTHP。本专利提供的LiTHP的制备工艺具有原料廉价易得、工艺简单、条件温和、产率高和后处理简单等优势。LiTHP可以溶解在大多极性有机溶剂中,可以溶解的溶剂:二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、碳酸甲酯、碳酸乙酯、碳酸丙酯、碳酸乙烯酯、氟代碳酸乙烯等,其纯单一溶剂和两两混合的溶剂对LiTHP的室温下的溶解度达到23~68g/L,其溶液的电导率达到7.6×10-3~5.5×10-2S/cm;另外,LiTHP具有良好的热稳定性能(450℃不发生分解),且具有很好的阻燃功能,复配物阻燃测试极限氧指数LOI达到40,防火等级(UL-94)达到V-0。(可以很好地解决目前锂离子电池所使用的电解质的易燃、易爆的问题。
新型阻燃电解质组装的锂离子电池其耐温性能得到提高,电池可以在70℃工作,过冲性能;针刺后性能;等阻燃效果均高于市售产品。
这样制备的LiTHP,制备方法简便。更重要的是,由于在反应的第一步中,在环三磷腈环上一步引入六个磷酸基团,使THP结构中,每个环三磷腈环上六个磷酸基团,从空间取向上,六个磷酸基在环三磷腈环上平均分布,彼此之间位阻最小,有利于活性基团暴露出来,使其具有良好的锂离子传导性能。
本发明在合成工艺和性能方面具有如下优点:
(1)合成工艺上的优点。本发明提供的含环三磷腈环的六磷酸锂盐的制备工艺,可以在环三磷腈环上一步引入六个磷酸基,所用原料廉价易得,制备工艺简单,条件温和,后处理简便,环境友好,产率高。
(2)环三磷腈环的六磷酸锂盐是新型锂盐,可以溶解在有机溶剂中。其分子中含有十二个锂离子,可以提高锂盐溶液中锂离子的浓度,可以提高溶液的电导率。该盐也可以溶于水,对水不敏感,不会产生胀气现象。
(3)环三磷腈环的六磷酸锂盐分子中含有阻燃的环三磷腈环基团和磷酸基团,锂盐本身就有很好的阻燃性能。
(4)环三磷腈环的六磷酸锂盐的加入,不但可以起到阻燃的效果,而且其加入还可以提高电解质的电导率,提高电池的性能。通常使用的阻燃剂由于其降低了电解质溶液的电导率,使用会大大降低电池性能。
具体实施方式
[实施例1]:ETHP的制备:
将20.9g HCCP(0.06mol)在搅拌下2h内分三批慢慢加入60mL亚磷酸三乙酯(TEP,0.34mol)中,升温至120℃反应6h,冷却后加入石油醚静置过夜,得到的沉淀抽滤得到黄色固体,即环三磷腈基六元磷酸乙酯(ETHP),产率86%。
采用相同反应步骤,以不同亚磷酸酯或在不同条件进行反应的产率汇总如表1所示:
表1不同亚磷酸酯反应制备RTHP的反应条件及产率
[实施例2]:THP的制备:
将46.5g ETHP(0.05mol)加入100mL浓盐酸中,磁力搅拌下回流72h,冷却至50℃,减压蒸去HCl,浓缩至40mL,用90mL乙酸乙酯萃取三次,以除去未水解的TTP。将水相浓缩至近干,在真空干燥箱中120℃下干燥至恒重,得到29.5g白色固体,即六磷酸基环三磷腈(THP,产率:95%)。
采用相同反应步骤,只是用二氯甲烷、苯、甲苯或石油醚萃取,产率分别为89%,85%,87%和82%。
采用相同的反应步骤,在浓盐酸中回流24h,在70℃下减压蒸馏,用乙酸乙酯萃取,产率为71%。
不同酯基的RTHP水解反应结果如表2所示。
表2不同酯基的RTHP水解制备THP的产率
[实施例3]:LiTHP的制备。取18.6g THP(0.03mol)加入20mL去离子水中,室温搅拌30min使其充分溶解。取6.65g碳酸锂(0.09mol)溶于30mL 0.1mol L-1稀盐酸中。将其盐酸溶液滴加到THP的水溶液中,室温搅拌12h,浓缩溶剂,真空干燥至恒重,得到Li THP固体,产率97%。
[实施例4]:Li THP的溶解性能和电导率。
分别用二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、碳酸甲酯、碳酸乙酯、碳酸丙酯、碳酸乙烯酯、氟代碳酸乙烯酯等溶剂测试单一溶剂和两两混合得到的混合溶剂对LiTPT的溶解性能,其LiTHP的室温下的溶解度达到23~68g/L,其溶液的电导率达到7.6×10-3~5.5×10-2S/cm。其电导率大于LiPF6的电导率。由于LiTPT对水稳定,遇水不会产生气体,所以其应用潜力大于LiPF6。
[实施例5]:Li THP与RTHP复配及加入锂离子电池中的性能考察。以LiTHP与RTHP的摩尔比按照6:1的比例进行复配,所用溶剂用二甲基亚砜、碳酸乙酯、碳酸乙烯酯、氟代碳酸乙烯酯等混合溶剂进行复配,添加过冲剂,SEI膜形成添加剂等辅助配料作为新型阻燃电解质组装的锂离子电池性能优于市场购买的电解质,但是其电池的安全性测试均优于市售的产品。
[实施例6]:LiTHP与RTHP其它配比的复配电解质的制备方法与上述方法类似,只是改变其配比即可,其电池性能及安全性能也与实施例5类似。
[实施例7]:LiTHP与RTHP复配及加入锂氧气电池中的性能考察。采用实施例5相同的方法配置电解质溶液用于锂氧电池,其锂氧电池充放电性能优于市售的产品,其安全性能优于市售的产品。
[实施例8]:LiTHP与RTHP复配及加入锂硫电池中的性能考察。采用实施例5相同的方法配置电解质溶液用于锂硫电池,其锂硫电池充放电性能优于市售的产品,其安全性能优于市售的产品。
Claims (4)
1.一种含有环三磷腈环的锂离子电池阻燃电解质的制备方法,其特征在于:电解质采用新结构含有环三磷腈环的磷酸锂离子盐(LiTHP)为主要组份复配而成的新型阻燃电解质;其LiTHP为有环三磷腈环的六磷酸十二锂,可以溶解在有机溶剂中,其溶液可以电离出多个锂离子,所以,溶液的电导率高;分子中含有的环三磷腈环和磷酸基团均属于阻燃性的基团,所以,LiTHP具有很好的阻燃性能;锂离子电池电解液中加入LiTHP不但可以提高电解液的锂离子电导率,而且具有很好的阻燃性能;用LiTHP与环三磷腈基六磷酸酯(RTHP)和其它锂离子电池电解质添加剂复配得到新型添加剂复配物用于锂离子电池、锂-氧电池、锂硫电池阻燃电解质,其具体制备方法如下:
(1)以六氯环三磷腈(HCCP)为原料,HCCP与亚磷酸酯反应,得到环三磷腈基六磷酸酯(RTHP),在浓盐酸中水解得到环三磷腈基六元磷酸(THP),将六元磷酸在水相中与氢氧化锂、氧化锂或碳酸锂反应得到环三磷腈基六元磷酸锂(LiTHP);将HCCP在搅拌下0.5~2h内分批慢慢加入亚磷酸酯中,升温至90~140℃反应6~12h,冷却后加入石油醚中过夜,抽滤得到RTHP;将RTHP在浓盐酸中加热、搅拌、回流反应24~72h,在50℃~70℃下,减压蒸出HCl、醇和水,用水和有机溶剂萃取,将水相浓缩,真空干燥得THP;将THP溶于水,加入氢氧化锂、氧化锂或碳酸锂溶液反应可以得到环三磷腈基六元磷酸锂(LiTHP);
(2)LiTHP与RTHP按照一定比例混合,溶解到合适溶剂中,加入防过充剂、SEI膜形成剂电解质添加剂复配得到锂离子电池阻燃电解质用于锂离子电池、锂-氧电池、锂硫电池。
2.根据权利要求1所述的一种含有环三磷腈环的锂离子电池阻燃电解质的制备方法,其特征在于:制备LiTHP的工艺中,原料HCCP中的磷-氯键非常活泼,卤素容易被亲核基团取代;其亚磷酸酯选用:亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸三丙酯或亚磷酸三异丙酯中的一种或几种的混合物,其特征在于:水解反应生成的醇沸点低,容易被蒸发去除。
3.根据权利要求1所述的一种含有环三磷腈环的锂离子电池阻燃电解质的制备方法,其特征在于:LiTHP与RTHP的摩尔比为8:1~2:1;所用溶剂为:碳酸甲酯、碳酸乙酯、碳酸丙酯、碳酸乙烯酯、氟代碳酸乙烯酯、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮这些溶剂中的一种或几种的混合液作为电解质的溶剂。
4.根据权利要求1所述的一种含有环三磷腈环的锂离子电池阻燃电解质的制备方法,其特征在于:加入的其它添加剂为:防止过充的添加剂,如,二乙酰基二茂铁、二联或三联吡啶的过渡金属配合物、邻菲罗啉的过渡金属配合物、大茴香醚、环己基苯、2,7-二乙酰基噻蒽、N-苯基马来酰胺中的一种或几种的混合物,添加质量比为5%~20%;促进SEI膜生成的添加剂:如,氟代碳酸乙烯酯、氟代碳酸丙烯酯、九氟代丁基乙基醚、丁磺内酯、1,3-丙基磺内酯、乙烯基三甲氧基硅烷、2-苯基咪唑、4-氟苯基异氰酸酯中的一种或几种的混合物为添加剂,添加质量比为3%~15%。
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US20180269531A1 (en) * | 2015-09-25 | 2018-09-20 | Tsinghua University | Electrolyte liquid, method for preparing the same, and lithium sulfur battery using the same |
CN108923066A (zh) * | 2018-06-29 | 2018-11-30 | 南通新宙邦电子材料有限公司 | 一种锂离子电池阻燃电解液 |
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CN106229549A (zh) * | 2016-10-10 | 2016-12-14 | 珠海市赛纬电子材料股份有限公司 | 一种高压锂离子电池的非水电解液 |
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