CN106252623B - A kind of carbon-nitrogen doped lithium titanate electrode material, preparation method and application - Google Patents
A kind of carbon-nitrogen doped lithium titanate electrode material, preparation method and application Download PDFInfo
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- CN106252623B CN106252623B CN201610740948.XA CN201610740948A CN106252623B CN 106252623 B CN106252623 B CN 106252623B CN 201610740948 A CN201610740948 A CN 201610740948A CN 106252623 B CN106252623 B CN 106252623B
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- lithium titanate
- lithium
- preparation
- electrode material
- carbon
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 136
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 239000007772 electrode material Substances 0.000 title claims abstract description 51
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 150
- 239000000463 material Substances 0.000 claims abstract description 87
- 239000002131 composite material Substances 0.000 claims abstract description 63
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 46
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- -1 nitrogenous compound Chemical class 0.000 claims abstract description 16
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 15
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 15
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 15
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 12
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 239000002657 fibrous material Substances 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 4
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 4
- 125000005456 glyceride group Chemical group 0.000 claims description 4
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 229950008882 polysorbate Drugs 0.000 claims description 3
- 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 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 2
- 230000003068 static effect Effects 0.000 claims 2
- SZWMYRXPLPUQQB-UHFFFAOYSA-N C(#N)NC(=O)N.N1=C(N)N=C(N)N=C1N Chemical compound C(#N)NC(=O)N.N1=C(N)N=C(N)N=C1N SZWMYRXPLPUQQB-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000003599 detergent Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229920000137 polyphosphoric acid Polymers 0.000 claims 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 50
- 239000002041 carbon nanotube Substances 0.000 abstract description 24
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 21
- 238000010041 electrostatic spinning Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 229910052799 carbon Inorganic materials 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000003756 stirring Methods 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229920001214 Polysorbate 60 Polymers 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 238000005213 imbibition Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical group CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical group [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 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
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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 discloses a kind of carbon-nitrogen doped lithium titanate electrode materials, preparation method and application, belong to lithium battery material preparation technical field.The preparation process of the electrode material are as follows: first surfactant, catalyst, nitrogenous compound and titanium dioxide are dissolved in polymethyl methacrylate, pass through the titanic oxide material of chemical vapor deposition for carbon nanotubes and N doping after drying, it is dissolved in polyvinylpyrrolidone solvent together with lithium source, sodium fluoride again, the lithium titanate composite material of threadiness is prepared by electrostatic spinning technique and high-temperature sintering process, and further modification obtains electrode material.The material has the characteristics that conductivity is high, good with compatibility of electrolyte, can significantly improve the cycle performance and high rate performance of lithium titanate battery.
Description
Technical field
The present invention relates to a kind of carbon-nitrogen doped lithium titanate electrode material, also relate to the electrode material preparation method and
Using belonging to lithium battery material preparation technical field.
Background technique
It is well known that cathode material of lithium ion battery is mainly based on graphite type material.And graphite type material is at big times
Charge and discharge easily cause negative terminal surface to analyse lithium under the conditions of rate, bring security risk.The interlamellar spacing of graphite type material is smaller simultaneously, charge and discharge
Lithium ion is embedding in electric process goes out to will cause the destruction of graphite-structure, causes the decaying of cycle performance of battery, thus its application by
Larger limitation.But the lithium titanate of spinel structure compares conventional graphite and just has the advantage that 1) intercalation potential is high (about
1.55V vsLi/Li+), Li dendrite will not be precipitated in charge and discharge process, have a safety feature, lithium-ion electric can be eliminated from material
The security risk in pond；2) material result hardly happens any variation in charge and discharge process, is a kind of " zero strain " material, circulation
Performance is good；3) lithium electron chemistry diffusion coefficient an order of magnitude higher than graphite, diffusion coefficient is 2 × 10 at 25 DEG C-8cm2/ s is fitted
Close fast charging and discharging；4) charging/discharging voltage is steady, and platform voltage capacity is more than the 90% of total capacity.Currently, lithium titanate anode material
Material is increasingly becoming one of the selection of energy-storage system and hybrid-electric car.But the material there is also electric conductivities poor, electrolyte
The problems such as poor compatibility, conductivity are about 10-13S/cm belongs to insulator, and is also easy to produce gas in chemical conversion constant volume process,
Cause the decline of battery overall performance.Therefore, if it is desired to which lithium titanate is applied in high rate charge-discharge, it is necessary to material
It itself is modified or is modified.
The patent of invention of publication No. CN105129844A discloses a kind of preparation method of graphite-doping lithium titanate anode material, leads to
It crosses and covers phenolic resin and nanometer tin in lithium titanate bread, obtain carbon-coated lithium titanate through high-temperature process.Lithium titanate is compared, it should
The capacity of negative electrode material is big, and stability when charge and discharge is high, but its surface-active is also relatively strong, the poor compatibility with electrolyte,
Cycle performance is not good enough.The clad structure of carbon coated is unstable simultaneously, and conductivity increase rate is relatively limited.In addition, publication No.
The patent of invention of CN104269546A discloses a kind of carbon coating nitridation lithium titanate material of aluminum phosphate cladding, preparation step
Are as follows: 1) titanium dioxide and lithium titanate are mixed, is calcined in vacuum or protective atmosphere, it is cooling, obtain lithium titanate powder；2) by carbon
Source and lithium titanate powder mix, and calcine in vacuum or protective atmosphere, cooling, obtain carbon coating lithium titanate；3) by nitrogen source and carbon
It coats lithium titanate to mix, be calcined in vacuum or protective atmosphere, the nitrogen on lithium titanate surface and titanium elements is made to form titanium nitridation
Key is learned, it is cooling, obtain carbon-coated nitridation lithium titanate Li4Ti5O12/TiN；4) carbon-coated nitridation lithium titanate particle is uniformly divided
It is scattered in alcoholic solution, aluminium salt and phosphate is added, the aluminum phosphate for generating reaction is evenly coated at carbon-coated nitridation lithium titanate
Particle surface is isolated product, is calcined in vacuum or protective atmosphere, cooling, obtains the carbon coating titanium nitride of aluminum phosphate cladding
Sour lithium；Wherein carbon source is selected from pitch, starch, glucose, maltose, citric acid etc.；Nitrogen source is selected from urea, acetonitrile, cyanamide, two
Poly cyanamid etc., aluminium salt are selected from aluminum sulfate, aluminum nitrate or aluminum acetate.The material has gram volume height, circulating ratio performance, safety
Can be good the advantages that, but preparation process is complex.
Summary of the invention
The object of the present invention is to provide a kind of conductivity height and the good carbon-nitrogen doped metatitanic acid lithium electrode materials of compatibility of electrolyte
Material.
Meanwhile the present invention also provides a kind of preparation method of carbon-nitrogen doped lithium titanate electrode material, simple process, operation letters
Just.
Finally, the present invention provides a kind of above-mentioned electrode material again is preparing the application in lithium titanate battery.
In order to achieve the goal above, the technical scheme adopted by the invention is that:
Carbon-nitrogen doped lithium titanate electrode material is prepared by the following steps to obtain:
1) preparation of titanium dioxide precursor material
Surfactant, polymethyl methacrylate, catalyst, nitrogenous compound and titanium dioxide are uniformly mixed, done
It is dry to get；
2) preparation of the composite titania material of carbon nanotube and N doping
In inert atmosphere, titanium dioxide precursor material is heated to 200~400 DEG C, 1~3h of heat preservation is subsequent of continuing rising
Temperature changes logical 1~5h of hydrogen to 600~1200 DEG C, then keeps the temperature 1~3h and (decompose carboritride sufficiently, and be doped to titanium dioxide
In titanium material), be passed through 1~5h of carbon-source gas, cooled down in inert atmosphere to get；
3) preparation of the lithium titanate composite material of carbon nanotube and N doping
Composite titania material, lithium source, sodium fluoride are uniformly mixed with polyvinylpyrrolidone, gained slurry is using quiet
Fibrous material is made in Electrospinning, is warming up to 600~1000 DEG C, and keeps the temperature 1~3h, it is cooling to get；
4) preparation of lithium titanate electrode material
Lithium titanate composite material, potassium hydroxide and sodium hydroxide are uniformly mixed, are warming up to 800~900 under inert atmosphere
DEG C, and keep the temperature 1~3h, it is cooling to get.
The quality of surfactant, polymethyl methacrylate, catalyst, nitrogenous compound, titanium dioxide in step 1)
Than for 1~3:100:1~3:1~5:10~20.Wherein, surfactant is neopelex, P123 (PEO-PPO-
PEO, EO20PO70EO20), polyacrylamide, octadecyltrimethylammonium chloride, glycerin monostearate (monoglyceride), fat
Any one in acid glyceride, polysorbate (polyoxyethylene sorbitan monoleate).Catalyst is Nanoscale Iron, nanometer cobalt, appointing in nano nickel
It anticipates one kind, partial size is 50~500nm.Nitrogenous compound is melamine cyanurate, pentaerythrite melamine phosphate
Salt, ammonium polyphosphate, melamine pyrophosphate, any one in melamine phosphate (melamine phosphate).
Nitrogen or argon atmosphere can be used in inert atmosphere in step 2).
The rate to heat up twice in step 2) is 1~5 DEG C/min.
The flow that is passed through of hydrogen is 10~50cm in step 2)3/min。
Carbon-source gas is methane, acetylene, any one in natural gas in step 2), and flow is 10~50cm3/min。
Composite titania material in step 3), lithium source, sodium fluoride, polyvinylpyrrolidone amount ratio be 40g:15~
30g:0.5~2g:500mL.Wherein, lithium source is lithium carbonate, lithium hydroxide, any one in lithium metaaluminate.
The parameter of electrostatic spinning technique in step 3) are as follows: receive 10~20cm of distance, 10~20kV of voltage, spinning solution injection
0.01~0.1mL/min of speed, 10~50r/min of revolving speed of roller reception device.
The rate to heat up in step 3) is 1~10 DEG C/min.
Lithium titanate composite material in step 4), potassium hydroxide, sodium hydroxide mass ratio be 50:50~100:50~100.
The rate to heat up in step 4) is 5~10 DEG C/min.
The preparation method of carbon-nitrogen doped lithium titanate electrode material, comprising the following steps:
1) preparation of titanium dioxide precursor material
Surfactant, polymethyl methacrylate, catalyst, nitrogenous compound and titanium dioxide are uniformly mixed, done
It is dry to get；
2) preparation of the composite titania material of carbon nanotube and N doping
In inert atmosphere, titanium dioxide precursor material is heated to 200~400 DEG C, 1~3h of heat preservation is subsequent of continuing rising
Temperature changes logical 1~5h of hydrogen to 600~1200 DEG C, then keeps the temperature 1~3h, is passed through 1~5h of carbon-source gas, cools down in inert atmosphere, i.e.,
?；
3) preparation of the lithium titanate composite material of carbon nanotube and N doping
Composite titania material, lithium source, sodium fluoride are uniformly mixed with polyvinylpyrrolidone, gained slurry is using quiet
Fibrous material is made in Electrospinning, is warming up to 600~1000 DEG C, and keeps the temperature 1~3h, it is cooling to get；
4) preparation of lithium titanate electrode material
Lithium titanate composite material, potassium hydroxide and sodium hydroxide are uniformly mixed, are warming up to 800~900 under inert atmosphere
DEG C, and keep the temperature 1~3h, it is cooling to get.
The quality of surfactant, polymethyl methacrylate, catalyst, nitrogenous compound, titanium dioxide in step 1)
Than for 1~3:100:1~3:1~5:10~20.Wherein, surfactant is neopelex, P123 (PEO-PPO-
PEO, EO20PO70EO20), polyacrylamide, octadecyltrimethylammonium chloride, glycerin monostearate (monoglyceride), fat
Any one in acid glyceride, polysorbate (polyoxyethylene sorbitan monoleate).Catalyst is Nanoscale Iron, nanometer cobalt, appointing in nano nickel
It anticipates one kind, partial size is 50~500nm.Nitrogenous compound is melamine cyanurate, pentaerythrite melamine phosphate
Salt, ammonium polyphosphate, melamine pyrophosphate, any one in melamine phosphate (melamine phosphate).
Nitrogen or argon atmosphere can be used in inert atmosphere in step 2).
The rate to heat up twice in step 2) is 1~5 DEG C/min.
The flow that is passed through of hydrogen is 10~50cm in step 2)3/min。
Carbon-source gas is methane, acetylene, any one in natural gas in step 2), and flow is 10~50cm3/min。
Composite titania material in step 3), lithium source, sodium fluoride, polyvinylpyrrolidone amount ratio be 40g:15~
30g:0.5~2g:500mL.Wherein, lithium source is lithium carbonate, lithium hydroxide, any one in lithium metaaluminate.
The parameter of electrostatic spinning technique in step 3) are as follows: receive 10~20cm of distance, 10~20kV of voltage, spinning solution injection
0.01~0.1mL/min of speed, 10~50r/min of revolving speed of roller reception device.
The rate to heat up in step 3) is 1~10 DEG C/min.
Lithium titanate composite material in step 4), potassium hydroxide, sodium hydroxide mass ratio be 1:1~2:1~2.
The rate to heat up in step 4) is 5~10 DEG C/min.
Above-mentioned carbon-nitrogen doped lithium titanate electrode material is preparing the application in lithium titanate battery.
Beneficial effects of the present invention:
The preparation process of carbon-nitrogen doped lithium titanate electrode material in the present invention are as follows: first by surfactant, catalyst, nitrogenous
Compound and titanium dioxide are dissolved in polymethyl methacrylate, it is dry after by chemical vapor deposition for carbon nanotubes and
The titanic oxide material of N doping, then it is dissolved in polyvinylpyrrolidone solvent together with lithium source, sodium fluoride, pass through electrostatic
Spining technology and high-temperature sintering process prepare the lithium titanate composite material of threadiness, and further modification obtains electrode material.
Present invention Uniform Doped carbon nanotube in lithium titanate, using the reticular structure of carbon nanotube, by polymethyl
The carbon formed after sour methyl esters charing is fixed by carbon net, improves the structural stability of its clad.In addition carbon nanotube mechanics is strong
The characteristics such as big, the specific surface area height of degree, further increase the imbibition liquid-keeping property and electric conductivity of material.Nitrogen-atoms is in the periodic table of elements
In be in the ortho position of carbon atom, radius is close, but its electronegativity is higher than carbon, therefore adulterates nitrogen-atoms and can keep the lattice knot of carbon
Structure and duct, and the additional lone pair electrons of nitrogen-atoms can provide negative electrical charge to carbon skeleton extended system, to effectively improve carbon
Surface polarity, enhance the transmission performance of electronics and the chemical reactivity of material, so enhance lithium titanate electric conductivity and
Electrochemical reaction performance.
The present invention using electrostatic spinning technique preparation fibrous carbonic acid lithium composite material have higher conductivity height and
Bigger specific surface area can improve the imbibition liquid-keeping property and electric conductivity of electrode material, so as to improve battery cycle performance and
High rate performance.Meanwhile using potassium hydroxide and sodium hydroxide modified active lithium titanate composite material, lithium titanate on the one hand can be reduced
And its active site of enveloped carbon nanometer tube, its compatibility with electrolyte is improved, the occurrence probability of side reaction is reduced, on the other hand
The specific surface area that carbon nanotube in clad can also be increased enhances its ability for adsorbing electronics, to improve the electricity of electrode material
Sub- transmission capacity and chemical property.
The preparation process of carbon-nitrogen doped lithium titanate electrode material is simple in the present invention, easy to operate, high production efficiency, preparation
Obtained lithium titanate electrode material consistency is higher.
Detailed description of the invention
Fig. 1 is the SEM figure of carbon-nitrogen doped lithium titanate electrode material in embodiment 1；
Fig. 2 is discharge curve of lithium titanate soft-package battery under the conditions of different multiplying in embodiment 1.
Specific embodiment
Only invention is further described in detail for following embodiments, but does not constitute any limitation of the invention.
Embodiment 1
Carbon-nitrogen doped lithium titanate electrode material is prepared by the following steps to obtain:
1) preparation of titanium dioxide precursor material
2g neopelex (surfactant) is dissolved in 100g polymethyl methacrylate (analysis is pure), is stirred
2g Nanoscale Iron (partial size 200nm) is added after mixing uniformly, after stirring 1h, adds 3g melamine cyanurate, is eventually adding 15g
Titanium dioxide obtains titanium dioxide mixed sols after mixing evenly, dry, obtains the titanium dioxide precursor material of the iron containing catalyst
Material；
2) preparation of the composite titania material of carbon nanotube and N doping
Titanium dioxide precursor material is transferred in tube furnace, is heated up under protection of argon gas, first with the heating of 3 DEG C/min
Rate rises to 250 DEG C, and keeps the temperature 2h at such a temperature, then rises to 850 DEG C with the heating rate of 3 DEG C/min, changes logical hydrogen 3h (stream
Fast 30cm3/ min), then 2h is kept the temperature, it is passed through methane gas 3h (flow velocity 30cm3/ min), it is finally cooled to room under protection of argon gas
Temperature obtains composite titania material；
3) preparation of the lithium titanate composite material of carbon nanotube and N doping
40g composite titania material, 20g lithium carbonate, 1g sodium fluoride (additive) are added to 500mL polyvinyl pyrrole
In alkanone solvent, uniformly (revolving speed 30rpm disperses 2h), gained slurry (receives distance using electrostatic spinning technique to high speed dispersion
15cm, voltage 15kV, spinning solution injection rate 0.05mL/min, roller reception device revolving speed 30r/min) fibrous material is made
Material, material is moved in tube furnace, 800 DEG C is risen to the heating rate of 5 DEG C/min, and keep the temperature 2h, naturally cools to room later
Temperature obtains lithium titanate composite material；
4) modification of lithium titanate composite material
50g lithium titanate composite material is uniformly mixed with 80g potassium hydroxide, 80g sodium hydroxide powder (using three-dimensional hybrid
Machine), and be transferred in ceramic boat, then be placed in the ceramic tube of horizontal pipe furnace, under nitrogen protection, with the heating of 8 DEG C/min
Rate rises to 840 DEG C, and keeps the temperature 2h, and cooled to room temperature is later to get carbon-nitrogen doped lithium titanate electrode material.
Lithium titanate button cell takes the above-mentioned carbon-nitrogen doped lithium titanate electrode material of 9g, 0.5g conductive agent SP, 0.5g to gather inclined fluorine
Ethylene (binder) is uniformly mixed with 220mL N-Methyl pyrrolidone, and film is in being made diaphragm on copper foil, using lithium piece as cathode,
Celegard 2400 is diaphragm, 1mol/L LiPF6/ EC+DMC (volume ratio 1:1) is electrolyte (EC, that is, ethylene carbonate, DMC
That is diethyl carbonate), button cell is assembled in the glove box that oxygen and water content are below 0.1ppm.
Lithium titanate soft-package battery (7Ah), using the carbon-nitrogen doped lithium titanate of above-mentioned preparation as negative electrode material, LiNi1/3Co1/ 3Mn1/3O2Ternary material is positive electrode, and celegard 2400 is diaphragm, 1.3mol/L LiPF6/ EC+DEC (volume ratio 1:1)
For electrolyte preparation.
Embodiment 2
Carbon-nitrogen doped lithium titanate electrode material is prepared by the following steps to obtain:
1) preparation of titanium dioxide precursor material
1g polyacrylamide is dissolved in 100g polymethyl methacrylate, 1g Co catalysts (grain is stirring evenly and then adding into
Diameter 50nm), after stirring 1h, 1g pentaerythrite melamine phosphate salt is added, is eventually adding 10g titanium dioxide, stirring is equal
Titanium dioxide mixed sols is obtained after even, it is dry, obtain the titanium dioxide precursor material containing catalyst cobalt；
2) preparation of the composite titania material of carbon nanotube and N doping
Titanium dioxide precursor material is transferred in tube furnace, is heated up under nitrogen protection, first with the heating of 1 DEG C/min
Rate rises to 200 DEG C, and keeps the temperature 3h at such a temperature, then rises to 600 DEG C with the heating rate of 1 DEG C/min, changes logical hydrogen 5h (stream
Fast 10cm3/ min), then 3h is kept the temperature, it is passed through acetylene gas 1h (flow velocity 50cm3/ min), it is finally cooled to room under nitrogen protection
Temperature obtains composite titania material；
3) preparation of the lithium titanate composite material of carbon nanotube and N doping
40g composite titania material, 15g lithium hydroxide, 0.5g sodium fluoride are added to 500mL polyvinylpyrrolidone
In solvent, high speed dispersion uniformly (revolving speed 30rpm, disperse 5h), gained slurry using electrostatic spinning technique (receive distance 10cm,
Voltage 10kV, spinning solution injection rate 0.01mL/min, roller reception device revolving speed 10r/min) fibrous material is made, by material
Material moves in tube furnace, rises to 600 DEG C with the heating rate of 1 DEG C/min, and keep the temperature 3h, cooled to room temperature, obtains later
Lithium titanate composite material；
4) modification of lithium titanate composite material
50g lithium titanate composite material is uniformly mixed with 50g potassium hydroxide, 50g sodium hydroxide powder, and is transferred to ceramics
It in boat, then is placed in the ceramic tube of horizontal pipe furnace, under nitrogen protection, rises to 800 DEG C with the heating rate of 5 DEG C/min, and
3h is kept the temperature, cooled to room temperature is later to get carbon-nitrogen doped lithium titanate electrode material.
The preparation of lithium titanate button cell and soft-package battery is the same as embodiment 1.
Embodiment 3
Carbon-nitrogen doped lithium titanate electrode material is prepared by the following steps to obtain:
1) preparation of titanium dioxide precursor material
3g octadecyltrimethylammonium chloride is dissolved in 100g polymethyl methacrylate, 3g is stirring evenly and then adding into and receives
Rice nickel (partial size 500nm) adds 5g melamine phosphate, is eventually adding 20g titanium dioxide, stirs evenly after stirring 1h
After obtain titanium dioxide mixed sols, it is dry, obtain the titanium dioxide precursor material of the nickel containing catalyst；
2) preparation of the composite titania material of carbon nanotube and N doping
Titanium dioxide precursor material is transferred in tube furnace, is heated up under protection of argon gas, first with the heating of 5 DEG C/min
Rate rises to 400 DEG C, and keeps the temperature 1h at such a temperature, then rises to 1200 DEG C with the heating rate of 5 DEG C/min, changes logical hydrogen 1h
(flow velocity 50cm3/ min), then 1h is kept the temperature, it is passed through natural gas 5h (flow velocity 10cm3/ min), it is finally cooled to room under protection of argon gas
Temperature obtains composite titania material；
3) preparation of the lithium titanate composite material of carbon nanotube and N doping
By 40g composite titania material, 30g lithium metaaluminate, that 2g sodium fluoride is added to 500mL polyvinylpyrrolidone is molten
In agent, uniformly (revolving speed 30rpm disperses 1h), gained slurry (receives distance 20cm, electricity using electrostatic spinning technique to high speed dispersion
Pressure 20kV, spinning solution injection rate 0.1mL/min, roller reception device revolving speed 50r/min) fibrous material is made, by material
It moves in tube furnace, rises to 1000 DEG C with the heating rate of 10 DEG C/min, and keep the temperature 1h, cooled to room temperature, obtains later
Lithium titanate composite material；
4) modification of lithium titanate composite material
50g lithium titanate composite material is uniformly mixed with 100g potassium hydroxide, 100g sodium hydroxide powder, and is transferred to pottery
It in porcelain boat, then is placed in the ceramic tube of horizontal pipe furnace, under nitrogen protection, rises to 900 DEG C with the heating rate of 10 DEG C/min,
And 1h is kept the temperature, cooled to room temperature is later to get carbon-nitrogen doped lithium titanate electrode material.
The preparation of lithium titanate button cell and soft-package battery is the same as embodiment 1.
Embodiment 4
Carbon-nitrogen doped lithium titanate electrode material is prepared by the following steps to obtain:
1) preparation of titanium dioxide precursor material
2.5g P123 is dissolved in 100g polymethyl methacrylate, 1.5g Nanoscale Iron (partial size is stirring evenly and then adding into
400nm), after stirring 1h, 4g ammonium polyphosphate is added, 12g titanium dioxide is eventually adding, obtains titanium dioxide after mixing evenly
Mixed sols, it is dry, obtain the titanium dioxide precursor material of the iron containing catalyst；
2) preparation of the composite titania material of carbon nanotube and N doping
Titanium dioxide precursor material is transferred in tube furnace, is heated up under protection of argon gas, first with the heating of 4 DEG C/min
Rate rises to 350 DEG C, and keeps the temperature 1.5h at such a temperature, then rises to 1000 DEG C with the heating rate of 4 DEG C/min, changes logical hydrogen 4h
(flow velocity 30cm3/ min), then 1.5h is kept the temperature, it is passed through natural gas 2h (flow velocity 30cm3/ min), finally it is cooled under protection of argon gas
Room temperature obtains composite titania material；
3) preparation of the lithium titanate composite material of carbon nanotube and N doping
By 40g composite titania material, 25g lithium carbonate, that 1.5g sodium fluoride is added to 500mL polyvinylpyrrolidone is molten
In agent, uniformly (revolving speed 30rpm disperses 2h), gained slurry (receives distance 18cm, electricity using electrostatic spinning technique to high speed dispersion
Pressure 18kV, spinning solution injection rate 0.08mL/min, roller reception device revolving speed 20r/min) fibrous material is made, by material
It moves in tube furnace, rises to 900 DEG C with the heating rate of 7 DEG C/min, and keep the temperature 1.5h, cooled to room temperature, obtains later
Lithium titanate composite material；
4) modification of lithium titanate composite material
50g lithium titanate composite material is uniformly mixed with 65g potassium hydroxide, 65g sodium hydroxide powder, and is transferred to ceramics
It in boat, then is placed in the ceramic tube of horizontal pipe furnace, under nitrogen protection, rises to 880 DEG C with the heating rate of 6 DEG C/min, and
1.5h is kept the temperature, cooled to room temperature is later to get carbon-nitrogen doped lithium titanate electrode material.
The preparation of lithium titanate button cell and soft-package battery is the same as embodiment 1.
Embodiment 5
Carbon-nitrogen doped lithium titanate electrode material is prepared by the following steps to obtain:
1) preparation of titanium dioxide precursor material
1.5g polyoxyethylene sorbitan monoleate is dissolved in 100g polymethyl methacrylate, 2.5g Co catalysts are stirring evenly and then adding into
(partial size 400nm) adds 2g melamine pyrophosphate, is eventually adding 18g titanium dioxide after stirring 1h, after mixing evenly
It is dry to titanium dioxide mixed sols, obtain the titanium dioxide precursor material containing catalyst cobalt；
2) preparation of the composite titania material of carbon nanotube and N doping
Titanium dioxide precursor material is transferred in tube furnace, is heated up under protection of argon gas, first with the heating of 2 DEG C/min
Rate rises to 250 DEG C, and keeps the temperature 2.5h at such a temperature, then rises to 700 DEG C with the heating rate of 2 DEG C/min, changes logical hydrogen 2h
(flow velocity 30cm3/ min), then 2.5h is kept the temperature, it is passed through natural gas 4h (flow velocity 30cm3/ min), finally it is cooled under protection of argon gas
Room temperature obtains composite titania material；
3) preparation of the lithium titanate composite material of carbon nanotube and N doping
40g composite titania material, 18g lithium metaaluminate, 1.2g sodium fluoride are added to 500mL polyvinylpyrrolidone
In solvent, high speed dispersion uniformly (revolving speed 30rpm, disperse 2h), gained slurry using electrostatic spinning technique (receive distance 13cm,
Voltage 13kV, spinning solution injection rate 0.03mL/min, roller reception device revolving speed 40r/min) fibrous material is made, by material
Material moves in tube furnace, rises to 700 DEG C with the heating rate of 3 DEG C/min, and keep the temperature 2.5h, cooled to room temperature, obtains later
To lithium titanate composite material；
4) modification of lithium titanate composite material
50g lithium titanate composite material is uniformly mixed with 85g potassium hydroxide, 85g sodium hydroxide powder, and is transferred to ceramics
It in boat, then is placed in the ceramic tube of horizontal pipe furnace, under nitrogen protection, rises to 830 DEG C with the heating rate of 9 DEG C/min, and
2.5h is kept the temperature, cooled to room temperature is later to get carbon-nitrogen doped lithium titanate electrode material.
The preparation of lithium titanate button cell and soft-package battery is the same as embodiment 1.
Comparative example
Lithium titanate electrode material is prepared by the following steps to obtain:
1) 15g titanium dioxide, 2g carbon nanotube are added in 100mL polymethyl methacrylate, after mixing evenly,
The lower heating of argon gas protection, first rises to 250 DEG C with the heating rate of 5 DEG C/min, and the 1h that is carbonized at such a temperature, obtains carbon-coated
Titanic oxide material；
2) the carbon-coated titanic oxide material of 40g and 20g lithium carbonate are added to 500mL polyvinylpyrrolidone solvent
In, uniformly (revolving speed 30rpm disperses 2h), gained slurry is transferred in tube furnace high speed dispersion, under nitrogen protection, in temperature 800
DEG C heat preservation 2h, obtain lithium titanate electrode material.
The preparation of lithium titanate button cell and soft-package battery is the same as embodiment 1.
Test example
1) SEM is tested
Carbon-nitrogen doped lithium titanate electrode material carries out SEM test in Example 1.As shown in Figure 1, electrode material is in fiber
Shape is evenly distributed, rationally.
2) button cell performance test
Lithium titanate button cell in Examples 1 to 5 and comparative example is connected on blue electric tester, is filled with the multiplying power of 0.1C
Electric discharge, 1.0~2.8V of voltage range, circulation stop after 3 weeks, and test result see the table below 1.
3) soft-package battery performance test
Lithium titanate soft-package battery in Example 1~3 and comparative example, with the charging of 0.1C multiplying power, constant-current charge to 3.2V, row
The gas generated in charging process out, then with 0.1C multiplying power discharging to 1.0V, it is spare that 2 heel row of charge and discharge cycles go out gas.
Cycle performance test: above-mentioned soft-package battery, 1.5~2.8V of charging/discharging voltage, 25 ± 3 DEG C of temperature, charge and discharge are taken respectively
Cycle performance test (1000 times) are carried out under electric multiplying power 1.0C/1.0C, as a result see the table below 2.
High rate performance test: taking above-mentioned soft-package battery respectively, 25 ± 3 DEG C of 1.65~2.8V of charging/discharging voltage, temperature, with
The charging of 1.0C multiplying power, then respectively with 1.0C, 2.0C, 3.0C, 5.0C, 10.0C, 15.0C, 20.0C multiplying power discharging, capacity retention ratio
It see the table below 3, the discharge curve of soft-package battery is shown in Fig. 2 in embodiment 1.
The performance of button cell compares in 1 embodiment of table and comparative example
As shown in Table 1, the gram volume of lithium titanate electrode material and first charge discharge efficiency are substantially better than comparative example in Examples 1 to 3.
Analyze reason are as follows: compare direct doped carbon nanometer pipe in lithium titanate long carbon nanotube of looking unfamiliar by chemical vapour deposition technique and have
There are structural stability height, uniform doping, the gram volume that can significantly improve battery material plays efficiency.Meanwhile adding fluorine
The reason of structural stability of electrode material can be improved by changing sodium, adulterate nitrogen in addition, can be further improved the conductivity of material, thus
The final gram volume and first charge discharge efficiency for improving material.
The cycle performance of soft-package battery compares in 2 embodiment of table and comparative example
As shown in Table 2, cycle performance of the lithium titanate soft-package battery in each stage of circulation is superior in Examples 1 to 3
Comparative example.Analyze reason are as follows: there is the nitrogen material for improving self structure stability on the surface of lithium titanate electrode material in embodiment, adds
Be evenly distributed by chemical vapour deposition technique in the carbon nanotube that material internal and surface are grown, stable structure, further mention
The high cycle performance of lithium titanate battery.
The high rate performance of soft-package battery compares in 3 embodiment of table and comparative example
As shown in Table 3, the high rate performance of lithium titanate soft-package battery is substantially better than comparative example in Examples 1 to 3.Analyze reason
Are as follows: lithium titanate electrode material is in fibrous structure in embodiment, and it is big to improve battery for specific surface area and conductivity with higher
Charging and discharging capabilities under the conditions of multiplying power.Meanwhile the carbon nanotube for looking unfamiliar long in lithium titanate is firmly combined with lithium titanate, the two is equal
Even doping, and doping nitrogen can further enhance the electric conductivity and electrochemical reaction performance of material, so as to improve lithium titanate battery
High rate performance.
Claims (10)
1. carbon-nitrogen doped lithium titanate electrode material, it is characterised in that: the electrode material is prepared by the following steps to obtain:
1) preparation of titanium dioxide precursor material
Surfactant, polymethyl methacrylate, catalyst, nitrogenous compound and titanium dioxide are uniformly mixed, it is dry, i.e.,
, the catalyst is Nanoscale Iron, nanometer cobalt, any one in nano nickel；
2) preparation of composite titania material
In inert atmosphere, titanium dioxide precursor material is heated to 200 ~ 400 DEG C, is continuously heating to after keeping the temperature 1 ~ 3h
600 ~ 1200 DEG C, change logical 1 ~ 5h of hydrogen, then keep the temperature 1 ~ 3h, be passed through 1 ~ 5h of carbon-source gas, cooled down in inert atmosphere to get；
3) preparation of lithium titanate composite material
Composite titania material, lithium source, sodium fluoride are uniformly mixed with polyvinylpyrrolidone, gained slurry uses Static Spinning
Fibrous material is made in silk technology, is warming up to 600 ~ 1000 DEG C, and keeps the temperature 1 ~ 3h, it is cooling to get；
4) preparation of lithium titanate electrode material
Lithium titanate composite material, potassium hydroxide and sodium hydroxide are uniformly mixed, are warming up to 800 ~ 900 DEG C under inert atmosphere, and
Keep the temperature 1 ~ 3h, it is cooling to get.
2. electrode material according to claim 1, it is characterised in that: surfactant is detergent alkylate sulphur in step 1)
Sour sodium, P123, polyacrylamide, octadecyltrimethylammonium chloride, glycerin monostearate, fatty glyceride, poly- sorb
Any one in ester, nitrogenous compound are melamine cyanurate, pentaerythrite melamine phosphate salt, polyphosphoric acids
Ammonium, melamine pyrophosphate, any one in melamine phosphate.
3. electrode material according to claim 2, it is characterised in that: the surfactant, polymethyl methacrylate,
Catalyst, nitrogenous compound, titanium dioxide mass ratio be 1 ~ 3:100:1 ~ 3:1 ~ 5:10 ~ 20.
4. electrode material according to claim 1 or 3, it is characterised in that: composite titania material, lithium in step 3)
Source, sodium fluoride, polyvinylpyrrolidone amount ratio be 40g:15 ~ 30g:0.5 ~ 2g:500mL；Lithium source is lithium carbonate, hydroxide
Any one in lithium, lithium metaaluminate.
5. electrode material according to claim 4, it is characterised in that: lithium titanate composite material in step 4), potassium hydroxide,
The mass ratio of sodium hydroxide is 50:50 ~ 100:50 ~ 100.
6. the preparation method of carbon-nitrogen doped lithium titanate electrode material, it is characterised in that: the following steps are included:
1) preparation of titanium dioxide precursor material
Surfactant, polymethyl methacrylate, catalyst, nitrogenous compound and titanium dioxide are uniformly mixed, it is dry, i.e.,
, the catalyst is Nanoscale Iron, nanometer cobalt, any one in nano nickel；
2) preparation of composite titania material
In inert atmosphere, titanium dioxide precursor material is heated to 200 ~ 400 DEG C, is continuously heating to after keeping the temperature 1 ~ 3h
600 ~ 1200 DEG C, change logical 1 ~ 5h of hydrogen, then keep the temperature 1 ~ 3h, be passed through 1 ~ 5h of carbon-source gas, cooled down in inert atmosphere to get；
3) preparation of lithium titanate composite material
Composite titania material, lithium source, sodium fluoride are uniformly mixed with polyvinylpyrrolidone, gained slurry uses Static Spinning
Fibrous material is made in silk technology, is warming up to 600 ~ 1000 DEG C, and keeps the temperature 1 ~ 3h, it is cooling to get；
4) preparation of lithium titanate electrode material
Lithium titanate composite material, potassium hydroxide and sodium hydroxide are uniformly mixed, are warming up to 800 ~ 900 DEG C under inert atmosphere, and
Keep the temperature 1 ~ 3h, it is cooling to get；
Surfactant is neopelex, P123, polyacrylamide, octadecyl trimethyl chlorination in step 1)
Ammonium, glycerin monostearate, fatty glyceride, any one in polysorbate, nitrogenous compound is melamine cyanurea
Hydrochlorate, pentaerythrite melamine phosphate salt, ammonium polyphosphate, melamine pyrophosphate, appointing in melamine phosphate
It anticipates one kind.
7. preparation method according to claim 6, it is characterised in that: surfactant, polymethylacrylic acid in step 1)
Methyl esters, catalyst, nitrogenous compound, titanium dioxide mass ratio be 1 ~ 3:100:1 ~ 3:1 ~ 5:10 ~ 20.
8. preparation method according to claim 6 or 7, it is characterised in that: composite titania material, lithium in step 3)
Source, sodium fluoride, polyvinylpyrrolidone amount ratio be 40g:15 ~ 30g:0.5 ~ 2g:500mL；Lithium source is lithium carbonate, hydroxide
Any one in lithium, lithium metaaluminate.
9. preparation method according to claim 8, it is characterised in that: lithium titanate composite material in step 4), potassium hydroxide,
The mass ratio of sodium hydroxide is 50:50 ~ 100:50 ~ 100.
10. lithium titanate electrode material is preparing the application in lithium titanate battery as described in any one of claim 1 ~ 5.
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| CN107359344A (en) * | 2017-08-01 | 2017-11-17 | 湖北工程学院 | A kind of battery, cell negative electrode material and preparation method thereof |
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