CN111137919A - 掺杂铌酸钛与电池 - Google Patents
掺杂铌酸钛与电池 Download PDFInfo
- Publication number
- CN111137919A CN111137919A CN201910956006.9A CN201910956006A CN111137919A CN 111137919 A CN111137919 A CN 111137919A CN 201910956006 A CN201910956006 A CN 201910956006A CN 111137919 A CN111137919 A CN 111137919A
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- Prior art keywords
- titanium niobate
- doped titanium
- oxide
- equal
- fluoride
- 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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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 239000010936 titanium Substances 0.000 title claims abstract description 165
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 134
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 47
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 38
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 229910052799 carbon Inorganic materials 0.000 claims description 38
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 36
- 239000011148 porous material Substances 0.000 claims description 29
- 239000002131 composite material Substances 0.000 claims description 23
- -1 oxide Chemical compound 0.000 claims description 23
- 239000011164 primary particle Substances 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 18
- 229910002785 ReO3 Inorganic materials 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 description 80
- 239000000843 powder Substances 0.000 description 38
- 239000002243 precursor Substances 0.000 description 38
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 32
- 239000011737 fluorine Substances 0.000 description 32
- 239000010955 niobium Substances 0.000 description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 238000005245 sintering Methods 0.000 description 24
- 210000004027 cell Anatomy 0.000 description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 19
- 229910000484 niobium oxide Inorganic materials 0.000 description 18
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 239000011651 chromium Substances 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 12
- 238000000498 ball milling Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000007873 sieving Methods 0.000 description 9
- 238000001694 spray drying Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052758 niobium Inorganic materials 0.000 description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910010379 TiNb2O7 Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012073 inactive phase Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- PSVBHJWAIYBPRO-UHFFFAOYSA-N lithium;niobium(5+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[Nb+5] PSVBHJWAIYBPRO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound 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
- 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
- 229910011956 Li4Ti5 Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920006373 Solef Polymers 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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Abstract
一种掺杂铌酸钛,其化学结构为Ti(1‑x)M1xNb(2‑y)M2yO(7‑z)Qz或Ti(2‑x’)M1x,Nb(10‑y’)M2y’O(29‑z’)Qz’,其中M1为Li、Mg或上述的组合;M2为Fe、Mn、V、Ni、Cr或上述的组合;Q为F、Cl、Br、I、S或上述的组合;0≤x≤0.15;0≤y≤0.15;0.01≤z≤2;0≤x′≤0.3;0≤y′≤0.9;以及0.01≤z’≤8。
Description
技术领域
本发明涉及电池,更特别涉及电池的负极组成。
背景技术
现今主流的碳负极材料虽具有不错的电容量(~350mAh/g),但在循环寿命、安全性、可快充等特性仍有瓶颈。而钛酸锂(Li4Ti5O12)具有长寿命、高安全的快充负极材料,但电容量较低(~165mAh/g)。铌酸钛(TiNb2O7,TNO)具有更高的理论电容量(~380mAh/g),其1.6V的工作电位可防止锂枝晶生成,安全性与循环寿命良好,振实密度也较高,适合作为下一代快充负极。目前锂电池能量密度高,但充电速率较差(<5C,充入50%)。钛酸锂电池虽然充电速度快(>5C,充入80%以上),但能量密度低。由于铌酸钛的电容量和密度明显优于钛酸锂,可大幅增加快充锂电池的能量密度,而拥有更大的应用范围,比如提升电动车的续航力与充电速度、储能系统的储能密度,甚至减少消费型电子产品的充电时间。此外,铌酸钛的低温性能良好,可适应各种恶劣环境。然而铌酸钛的导电性质不佳,如需用于动力锂电池,则需进一步对材料改性以得到更好性能。
发明内容
本发明一实施例提供的掺杂铌酸钛,其化学结构为Ti(1-x)M1xNb(2-y)M2yO(7-z)Qz或Ti(2-x′)M1x,Nb(10-y’)M2y′O(29-z′)Qz′,其中M1为Li、Mg或上述的组合;M2为Fe、Mn、V、Ni、Cr或上述的组合;Q为F、Cl、Br、I、S或上述的组合;0≤x≤0.15;0≤y≤0.15;0.01≤z≤2;0≤x’≤0.3;0≤y’≤0.9;以及0.01≤z’≤8。
在一些实施例中,Ti(1-x)M1xNb(2-y)M2yO(7-z)Qz的晶格为单斜晶,而Ti(2-x,)M1x,Nb(10-y’)M2y’O(29-z’)Qz,的晶格为ReO3型晶格。
在一些实施例中,掺杂铌酸钛为多个一次粒子组成的多孔结构。
在一些实施例中,多孔结构的粒径中位数(d50)介于0.3微米至60微米之间,一次粒子的粒径中位数(d50)介于0.01微米至5微米之间,且多孔结构的孔径介于50纳米至1微米之间。
在一些实施例中,掺杂铌酸钛,其为非多孔结构。
在一些实施例中,非多孔结构的粒径中位数介于0.01微米至10微米之间。
在一些实施例中,掺杂铌酸钛还与钛酸锂混合形成复合材料,其中掺杂铌酸钛与钛酸锂的重量比例介于90∶10至10∶90之间。
在一些实施例中,钛酸锂的表面包覆碳、氧化物或氟化物,且碳、氧化物或氟化物与钛酸锂的重量比例大于0且小于或等于5%。
在一些实施例中,复合材料的表面包覆碳、氧化物或氟化物,且碳、氧化物或氟化物与该复合材料的重量比例大于0且小于或等于5%。
在一些实施例中,掺杂铌酸钛其表面包覆碳、氧化物或氟化物,且碳、氧化物或氟化物与掺杂铌酸钛的重量比例大于0且小于或等于5%。
本发明一实施例提供的电池,包括:负极;正极;以及电解质,位于负极与正极之间,其中负极包括掺杂铌酸钛,其化学结构为:Ti(1-x)M1xNb(2-y)M2yO(7-z)Qz或Ti(2-x′)M1x,Nb(10-y,)M2y,O(29-z′)Qz′,其中M1为Li、Mg或上述的组合;M2为Fe、Mn、V、Ni、Cr或上述的组合;Q为F、Cl、Br、I、S或上述的组合;0≤x≤0.15;0≤y≤0.15;0.01≤z≤2;0≤x’≤0.3;0≤y’≤0.9;以及0.01≤z’≤8。
在一些实施例中,Ti(1-x)M1xNb(2-y)M2yO(7-z)Qz的晶格为单斜晶,而Ti(2-x,)M1x,Nb(10-y’)M2y’O(29-z’)Qz,的晶格为ReO3型晶格。
在一些实施例中,负极还包括钛酸锂,掺杂铌酸钛与钛酸锂混合形成复合材料,且掺杂铌酸钛与钛酸锂的重量比例介于90∶10至10∶90之间。
在一些实施例中,钛酸锂的表面包覆碳、氧化物或氟化物,且碳、氧化物或氟化物与钛酸锂的重量比例大于0且小于或等于5%。
在一些实施例中,复合材料的表面包覆碳、氧化物或氟化物,且碳、氧化物或氟化物与该复合材料的重量比例大于0且小于或等于5%。
在一些实施例中,掺杂铌酸钛的表面包覆碳、氧化物或氟化物,且碳、氧化物或氟化物与掺杂铌酸钛的重量比例大于0且小于或等于5%。
附图说明
图1为本发明实施例1中,掺杂氟的铌酸钛材料属于一次粒子组成的孔洞结构的扫描电子显微镜照片;
图2为本发明实施例1中,电池对不同充放电速率的电容量对电压的曲线图;
图3为本发明比较例1中,电池对不同充放电速率的电容量对电压的曲线图。
具体实施方式
本发明一实施例提供的掺杂铌酸钛,其化学结构为:Ti(1-x)M1xNb(2-y)M2yO(7-z)Qz或Ti(2-x’)M1x,Nb(10-y’)M2y’O(29-z’)Qz,。M1为Li、Mg或上述的组合;M2为Fe、Mn、V、Ni、Cr或上述的组合;而Q为F、Cl、Br、I、S或上述的组合。0≤x≤0.15,0≤y≤0.15,0.01≤z≤2,0≤x’≤0.3,0≤y’≤0.9,且0.01≤z’≤8。在一实施例中,0≤x≤0.05。在一实施例中,0.05≤x≤0.15。在一实施例中,0≤y≤0.03。在一实施例中,0.03≤y≤0.1。在一实施例中,0.1≤y≤0.15。在一实施例中,0≤y’≤0.25。在一实施例中,0.25≤y’≤0.9。若x、y、x’或y’的比例过高,则可能会生成杂相(非活性相),导致克电容量及倍率性能下降。在一实施例中,0.01≤z≤0.25。在一实施例中,0.25≤z≤0.75。在一实施例中,0.75≤z≤1。在一实施例中,1≤z≤2。在一实施例中,0.01≤z’≤4。在一实施例中,4≤z’≤8。若z或z’的比例过低,则与未掺杂Q的铌酸钛性质类似。若z的比例过高,则可能会生成杂相(非活性相),导致克电容量及倍率性能下降。明显地,本发明实施例的铌酸钛主体为TiNb2O7与Ti2Nb10O29,Ti可视情况掺杂M1,Nb可视情况掺杂M2,而O必须掺杂Q。不同原子比例的铌酸钛可能具有完全不同的晶格结构与对应性质,不应视作可轻易置换。
在一实施例中,Ti(1-x)M1xNb(2-y)M2yO(7-z)Qz的晶格为单斜晶,而Ti(2-x’)M1x,Nb(10-y’)M2y’O(29-z’)Qz,的晶格为ReO3型晶格。其他晶格结构或非晶结构的铌酸钛可能不适于作为锂电池的负极材料。
在一些实施例中,上述掺杂铌酸钛为多个一次粒子组成的多孔结构。举例来说,多孔结构的粒径中位数(d50)介于0.3微米至60微米之间,一次粒子的粒径中位数介于0.01微米至5微米之间,且多孔结构的孔径介于50纳米至1微米之间。若多孔结构的粒径过大或过小,则可能造成极板密度降低。若一次粒子的粒径过大,将增加电子与锂离子传导路径,增加传导的时间而降低倍率能力。若一次粒子的粒径过小,则会提升材料的比表面积,造成混浆工艺分散不易,降低极板密度与均匀性。若多孔结构的孔径过大,则造成极板密度降低。若多孔结构的孔径过小,则过于致密使得电解液不易渗入内部而导致电化学反应面积变小。
在其他实施例中,掺杂铌酸钛为非多孔结构,且非多孔结构的粒径中位数介于0.01微米至10微米之间。若非多孔结构的粒径过大,则降低极板密度、增加电子与锂离子传导路径及增加传导的时间而降低倍率能力。若非多孔结构的粒径过小,则会增加材料的比表面积,造成混浆工艺分散不易,降低极板密度与均匀性。
上述多孔结构或非多孔结构的形貌主要来自于工艺差异。举例来说,可取氧化铌、氧化钛、视情况采用的M1源、视情况采用的M2源与Q源加入已具有分散剂的溶剂中,充分混合8至24小时后得到均匀分散的浆料,再以喷雾干燥(spray drying)的方式造粒得到前驱物粉体。在一实施例中,合适的分散剂可为聚乙烯醇(PVA)或市售的BYK190。在一实施例中,合适的溶剂可为去离子水。前驱物粉体经900℃至1200℃烧结8小时至15小时后,即可得到多孔结构的掺杂Q的钛酸铌(可视情况掺杂M1和/或M2)。
另一方面,可取氧化铌、氧化钛、视情况采用的M1源、视情况采用的M2源与Q源加入已具有分散剂的溶剂中,经球磨分散8至24小时后,得到前驱物粉体。前驱物粉体经900℃至1200℃烧结8小时至15小时后,即可得到非多孔结构的掺杂Q的钛酸铌(可视情况掺杂M1和/或M2)。
此外,可取氧化铌、氧化钛、视情况采用的M1源与视情况采用的M2源加入已具有分散剂的溶剂中,充分混合8至24小时后得到均匀分散的浆料,再以喷雾干燥的方式造粒得到前驱物粉体。前驱物粉体经900℃至1200℃烧结8小时至15小时后,即可得到钛酸铌(可视情况掺杂M1和/或M2)。接着将上述钛酸铌与Q源混合均匀,经350℃至750℃烧结2小时至5小时后,即可得多孔结构的掺杂Q的钛酸铌(可视情况掺杂M1和/或M2)。
另一方面,可取氧化铌、氧化钛、视情况采用的M1源、视情况采用的M2源与Q源加入已具有分散剂的溶剂中,经球磨分散8至24小时后,得到前驱物粉体。前驱物粉体经900℃至1200℃烧结8小时至15小时后,即可得到钛酸铌(可视情况掺杂M1和/或M2)。接着将上述钛酸铌与Q源混合均匀,经350℃至750℃烧结2小时至5小时后,即可得非多孔结构的掺杂Q的钛酸铌(可视情况掺杂M1和/或M2)。
在一些实施例中,掺杂铌酸钛的表面可进一步包覆碳、氧化物或氟化物,以抑制产气反应。在一些实施例中,“碳、氧化物或氟化物”与“掺杂铌酸钛”的重量比例,可大于0且小于或等于5%。若碳、氧化物或氟化物的比例过高,则形成过厚的包覆层,反而阻碍锂离子嵌出嵌入。
在另一实施例中,掺杂铌酸钛可与钛酸锂(掺杂或未掺杂皆可)混合形成复合材料,以提升负极倍率性能及降低成本。在一些实施例中,掺杂铌酸钛与钛酸锂的重量比例介于90∶10至10∶90之间。若钛酸锂的比例过低,则与无钛酸锂的效果类似。若钛酸锂的比例过高,则导致此复合材料的克电容量下降过多。举例来说,未掺杂的钛酸锂的化学结构为Li4Ti5Oa,且8≤a≤12。
在一些实施例中,钛酸锂的表面可进一步包覆碳、氧化物或氟化物,以抑制产气反应。在一些实施例中,“碳、氧化物或氟化物”与“钛酸锂”的重量比例大于0且小于或等于5%。若碳、氧化物或氟化物的比例过高,则形成过厚的包覆层,反而阻碍锂离子嵌出嵌入。
在一些实施例中,复合材料的表面包覆碳、氧化物或氟化物,以抑制产气反应。举例来说,氧化物可为氧化铝、氧化镁或氧化锌,而氟化物可为氟化铝。在一些实施例中,“碳、氧化物或氟化物”与“复合材料”的重量比例大于0且小于或等于5%。若碳、氧化物或氟化物的比例过高,则形成过厚的包覆层,反而阻碍锂离子嵌出嵌入。
在掺杂铌酸钛、钛酸锂或复合材料的表面上包覆碳、氧化物或氟化物的方法可参考“Journal of Power Sources,Vol.196,Issue 18,2011,P.7763-7766”。在复合材料的实施例中,可在掺杂铌酸钛、钛酸锂或上述两者的表面上包覆碳、氧化物或氟化物,再混合形成复合材料。另一方面,可取掺杂铌酸钛与钛酸锂混合形成复合材料后,在复合材料的表面上包覆碳、氧化物或氟化物。
在一实施例中,上述掺杂铌酸钛或复合材料可用于电池的负极。举例来说,电池可包含负极、正极;以及电解质,位于负极与正极之间,且负极包括上述掺杂铌酸钛或复合材料。此外,负极可进一步包含导电碳黑、粘合剂或其他合适组成。在一些实施例中,正极可包含钴酸锂、镍酸锂、锰酸锂、三元正极材料、磷酸锂铁、磷酸锂铁锰或上述的组合。在一些实施例中,电解质由其形态可分为液态、胶态与固态。液态电解质由锂盐、溶剂或离子液体所组成,常用的锂盐有LiPF6、LiAsF6、LiClO4、LiBF4、LiTFSI或LiCF3SO3等,常用的溶剂有环状碳酸酯(如碳酸乙烯酯、碳酸丙烯酯)、链状碳酸酯(如碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯)或醚类化合物(如二甲醚、1,3-二氧环戊烷)等。固态电解质区分为高分子及玻璃陶瓷等。另一方面,在测量含掺杂铌酸钛的负极性能时,此负极可与锂正极及常见电解液组成半电池。
为让本发明的上述内容和其他目的、特征和优点能更明显易懂,下文特别列举出较佳实施例,并配合所附附图,作详细说明如下:
[实施例]
实施例1
依计量比将氧化铌、氧化钛与氟源(NH4F)加入含分散剂PVA BP-05的去离子水中,充分混合18小时后得到均匀分散的浆料。接着以喷雾干燥的方式造粒得到前驱物粉体。将前驱物粉体置入坩锅,经1150℃烧结12小时后,即得掺杂氟的铌酸钛材料TiNb2O6.75F0.25。掺杂氟的铌酸钛材料TiNb2O6.75F0.25的晶格为单斜晶(经XRD确认)。上述掺杂氟的铌酸钛材料属于一次粒子组成的孔洞结构,其扫描电子显微镜照片如图1所示。一次粒子的中位数粒径介于0.01至5微米之间,孔洞结构的粒径介于0.3至60微米之间,且孔洞结构的孔径介于50纳米至1微米之间。
取85重量份的上述掺杂氟的铌酸钛、6重量份的KS4(购自TIMCAL TIMREX)、4重量份的Super P(购自TIMCAL TIMREX)与5重量份的PVDF(购自Solef)均匀混合配置为浆料。接着将浆料涂布于铝箔基材上,得到厚度小于150微米的涂层。以辗压机将涂层辗至原厚度的65%,以得负极板。将负极板裁切为直径12mm的圆形负极板。取上述圆形负极板、锂金属的正极板、以及电解液组成CR2032半电池,以测试半电池的电化学性质。上述电解液组成为1MLiPF6,EC∶DMC=1∶2(体积比)。此电池对不同充放电速率的电容量对电压的曲线图如图2所示。此电池对不同充放电速率的电容量如表1所示。
实施例2
依计量比将氧化铌与氧化钛加入含分散剂PVA BP-05的去离子水中,充分混合18小时后得到均匀分散的浆料。接着以喷雾干燥的方式造粒得到前驱物粉体。将前驱物粉体置入坩锅,经1150℃烧结12小时后,即得到铌酸钛。接着依计量比将铌酸钛与氟源(NH4F)混合均匀,经450℃烧结5小时后,即得到掺杂氟的铌酸钛材料TiNb2O6.75F0.25。掺杂氟的铌酸钛材料TiNb2O6.75F0.25的晶格为单斜晶(经XRD确认)。上述掺杂氟的铌酸钛材料属于一次粒子组成的孔洞结构,一次粒子的中位数粒径介于0.01至5微米之间,孔洞结构的粒径介于0.3至60微米之间,且孔洞结构的孔径介于50纳米至1微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用实施例2的掺杂氟的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表1所示。
实施例3
依计量比将氧化铌、氧化钛、氧化铁与氟源(NH4F)加入含分散剂PVA BP-05的去离子水中,充分混合18小时后得到均匀分散的浆料。接着以喷雾干燥的方式造粒得到前驱物粉体。将前驱物粉体置入坩锅,经1150℃烧结12小时后,即得掺杂氟与铁的铌酸钛材料TiNb1.9Fe0.1O6.25F0.75。掺杂氟与铁的铌酸钛材料TiNb1.9Fe0.1O6.25F0.75的晶格为单斜晶(经XRD确认)。上述掺杂氟与铁的铌酸钛材料属于一次粒子组成的孔洞结构,一次粒子的中位数粒径介于0.01至5微米之间,孔洞结构的粒径介于0.3至60微米之间,且孔洞结构的孔径介于50纳米至1微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用实施例3的掺杂氟与铁的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表1所示。
实施例4
依计量比将氧化铌、氧化钛与氟源(NH4F)加入乙醇中,球磨分散24小时后过筛,得到前驱物粉体。将前驱物粉体置入坩锅,经1000℃烧结18小时后,即得掺杂氟的铌酸钛材料TiNb2O6F。掺杂氟的铌酸钛材料TiNb2O6F的晶格为单斜晶(经XRD确认)。上述掺杂氟的铌酸钛材料属于非孔洞结构,且非孔洞结构的粒径介于0.01至10微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用实施例4的掺杂氟的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表1所示。
实施例5
依计量比将氧化铌、氧化钛与氟源(NH4F)加入乙醇中,球磨分散24小时后过筛,得到前驱物粉体。将前驱物粉体置入坩锅,经1000℃烧结18小时后,即得掺杂氟的铌酸钛材料TiNb2O6F。掺杂氟的铌酸钛材料TiNb2O6F的晶格为单斜晶(经XRD确认)。上述掺杂氟的铌酸钛材料属于非孔洞结构,且非孔洞结构的粒径介于0.01至10微米之间。取烧结完成的铌酸钛材料20克与葡萄糖0.6克加入去离子水50克搅拌24小时,烘干后再置入坩锅经700℃于氮气气氛下烧结6小时后,接着形成碳膜包覆掺杂氟的铌酸钛材料TiNb2O6F的非孔洞结构。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用实施例5的包覆碳膜的掺杂氟的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表1所示,本处理可抑制锂电池的产气反应。
实施例6
依计量比将氧化铌、氧化钛、氟化镁加入乙醇中,球磨分散24小时后过筛,得到前驱物粉体。将前驱物粉体置入坩锅,经1150℃烧结12小时后,即得掺杂氟与镁的铌酸钛材料Ti0.95Mg0.05Nb2O6.9F0.1。掺杂氟与镁的铌酸钛材料Ti0.95Mg0.05Nb2O6.9F0.1的晶格为单斜晶(经XRD确认)。上述掺杂氟的铌酸钛材料属于非孔洞结构,且非孔洞结构的粒径介于0.01至10微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用实施例6的掺杂氟与镁的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表1所示。
实施例7
依计量比将氧化铌、氧化钛、氧化铬与氟源(NH4F)加入含分散剂PVA BP-05的去离子水中,球磨分散24小时后过筛,得到前驱物粉体。将前驱物粉体置入坩锅,经1150℃烧结12小时后,即得掺杂氟与铬的铌酸钛材料TiNb1.97Cr0.03O6.9F0.1。掺杂氟与铬的铌酸钛材料TiNb1.97Cr0.03O6.9F0.1的晶格为单斜晶(经XRD确认)。上述掺杂氟的铌酸钛材料属于非孔洞结构,且非孔洞结构的粒径介于0.01至10微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用实施例7的掺杂氟与铬的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表1所示。
比较例1
依计量比将氧化铌与氧化钛加入含分散剂PVA BP-05的去离子水中,充分混合18小时后得到均匀分散的浆料。接着以喷雾干燥的方式造粒得到前驱物粉体。将前驱物粉体置入坩锅,经1150℃烧结12小时后,即得到铌酸钛材料TiNb2O7。上述铌酸钛材料属于一次粒子组成的孔洞结构,一次粒子的中位数粒径介于0.01至5微米之间,孔洞结构的粒径介于0.3至60微米之间,且孔洞结构的孔径介于50纳米至1微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用比较例1的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量对电压的曲线图如图3所示。此电池对不同充放电速率的电容量如表1所示。
比较例2
依计量比将氧化铌与氧化钛加入含分散剂PVA BP-05的去离子水中,充分混合18小时后得到均匀分散的浆料。接着以喷雾干燥的方式造粒得到前驱物粉体。将前驱物粉体置入坩锅,经1150℃烧结12小时后,再经450℃烧结5小时后,即得到铌酸钛材料TiNb2O7。上述铌酸钛材料属于一次粒子组成的孔洞结构,一次粒子的中位数粒径介于0.01至5微米之间,孔洞结构的粒径介于0.3至60微米之间,且孔洞结构的孔径介于50纳米至1微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用比较例2的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表1所示。
比较例3
依计量比将氧化铌、氧化钛与氧化铁加入含分散剂PVABP-05的去离子水中,充分混合18小时后得到均匀分散的浆料。接着以喷雾干燥的方式造粒得到前驱物粉体。将前驱物粉体置入坩锅,经1150℃烧结12小时后,即得到掺杂铁的铌酸钛材料TiNb1.9Fe0.1O7。上述掺杂铁的铌酸钛材料属于一次粒子组成的孔洞结构,一次粒子的中位数粒径介于0.01至5微米之间,孔洞结构的粒径介于0.3至60微米之间,且孔洞结构的孔径介于50纳米至1微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用比较例3的掺杂铁的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表1所示。
比较例4
依计量比将氧化铌与氧化钛加入乙醇中,球磨分散24小时后过筛,得到前驱物粉体。将前驱物粉体置入坩锅,经1150℃烧结12小时后,即得到铌酸钛材料TiNb2O7。上述铌酸钛材料属于非孔洞结构,且非孔洞结构的粒径介于0.01至10微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用比较例4的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表1所示。
表1
由上述可知,掺杂氟的铌酸钛材料在作为电池负极时,可比铌酸钛材料作为电池负极时提供更高的电容量。
比较例5
依计量比将氧化铌与氧化钛加入乙醇中,球磨分散24小时后过筛,得到前驱物粉体。将前驱物粉体置入坩锅,经1100℃烧结16小时后,即得到铌酸钛材料Ti2Nb10O29。上述铌酸钛材料属于非孔洞结构,且非孔洞结构的粒径介于0.1至10微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用比较例5的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表2所示。
实施例8
依计量比将氧化铌、氧化钛与氟源(NH4F)加入含乙醇中,球磨分散24小时后过筛,得到前驱物粉体。将前驱物粉体置入坩锅,经1000℃烧结12小时后,即得到掺杂氟的铌酸钛材料Ti2Nb10O25F4。掺杂氟的铌酸钛材料Ti2Nb10O25F4的晶格为ReO3型晶格(经XRD确认)。上述掺杂氟的铌酸钛材料属于非孔洞结构,且非孔洞结构的粒径介于0.1至10微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用实施例8的掺杂氟的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表2所示。
实施例9
依计量比将氧化铬、氧化铌、氧化钛与氟源(NH4F)加入乙酸中,球磨分散24小时后过筛,得到前驱物粉体。将前驱物粉体置入坩锅,经1200℃烧结10小时后,即得到掺杂氟与铬的铌酸钛材料Ti2Nb9.75Cr0.25O25F4。掺杂氟与铬的铌酸钛材料Ti2Nb9.75Cr0.25O25F4的晶格为ReO3型晶格(经XRD确认)。上述掺杂氟与铬的铌酸钛材料属于非孔洞结构,且非孔洞结构的粒径介于0.1至10微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用实施例9的掺杂氟与铬的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表2所示。
实施例10
依计量比将氧化铁、氧化铌、氧化钛与氟源(NH4F)加入乙酸中,球磨分散24小时后过筛,得到前驱物粉体。将前驱物粉体置入坩锅,经1200℃烧结10小时后,即得到掺杂氟与铁的铌酸钛材料Ti2Nb9.75Fe0.25O25F4。掺杂氟与铁的铌酸钛材料Ti2Nb9.75Fe0.25O25F4的晶格为ReO3型晶格(经XRD确认)。上述掺杂氟与铁的铌酸钛材料属于非孔洞结构,且非孔洞结构的粒径介于0.1至10微米之间。
接着依实施例1中组成CR2032半电池的方法制备半电池,差异在于采用实施例10的掺杂氟与铁的铌酸钛材料而非实施例1的掺杂氟的铌酸钛材料。此电池对不同充放电速率的电容量如表2所示。
表2
由上述可知,掺杂氟的铌酸钛材料在作为电池负极时,可比铌酸钛材料作为电池负极时提供更高的电容量。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (16)
1.一种掺杂铌酸钛,其化学结构为:
Ti(1-x)M1xNb(2-y)M2yO(7-z)Qz或Ti(2-x’)M1x’Nb(10-y’)M2y’O(29-z’)Qz’,
其中M1为Li、Mg或上述的组合;
M2为Fe、Mn、V、Ni、Cr或上述的组合;
Q为F、Cl、Br、I、S或上述的组合;
0≤x≤0.15;
0≤y≤0.15;
0.01≤z≤2;
0≤x’≤0.3;
0≤y’≤0.9;以及
0.01≤z’≤8。
2.如权利要求1所述的掺杂铌酸钛,其中Ti(1-x)M1xNb(2-y)M2yO(7-z)Qz的晶格为单斜晶,而Ti(2-x’)M1x’Nb(10-y’)M2y’O(29-z’)Qz’的晶格为ReO3型晶格。
3.如权利要求1所述的掺杂铌酸钛,其为多个一次粒子组成的多孔结构。
4.如权利要求3所述的掺杂铌酸钛,其中该多孔结构的粒径中位数介于0.3微米至60微米之间,这些一次粒子的粒径中位数介于0.01微米至5微米之间,且该多孔结构的孔径介于50纳米至1微米之间。
5.如权利要求1所述的掺杂铌酸钛,其为非多孔结构。
6.如权利要求5所述的掺杂铌酸钛,其中该非多孔结构的粒径中位数介于0.01微米至10微米之间。
7.如权利要求1所述的掺杂铌酸钛,还与钛酸锂混合形成一复合材料,其中该掺杂铌酸钛与该钛酸锂的重量比例介于90∶10至10∶90之间。
8.如权利要求7所述的掺杂铌酸钛,其中该钛酸锂的表面包覆碳、氧化物或氟化物,且碳、氧化物或氟化物与该钛酸锂的重量比例大于0且小于或等于5%。
9.如权利要求7所述的掺杂铌酸钛,其中该复合材料的表面包覆碳、氧化物或氟化物,且碳、氧化物或氟化物与该复合材料的重量比例大于0且小于或等于5%。
10.如权利要求1或7所述的该掺杂铌酸钛,其表面包覆碳、氧化物或氟化物,且碳、氧化物或氟化物与该掺杂铌酸钛的重量比例大于0且小于或等于5%。
11.一种电池,包括:
一负极;
一正极;以及
一电解质,位于该负极与该正极之间,
其中该负极包括掺杂铌酸钛,其化学结构为:
Ti(1-x)M1xNb(2-y)M2yO(7-z)Qz或Ti(2-x’)M1x’Nb(10-y’)M2y’O(29-z’)Qz’,
其中M1为Li、Mg或上述的组合;
M2为Fe、Mn、V、Ni、Cr或上述的组合;
Q为F、Cl、Br、I、S或上述的组合;
0≤x≤0.15;
0≤y≤0.15;
0.01≤z≤2;
0≤x’≤0.3;
0≤y’≤0.9;以及
0.01≤z’≤8。
12.如权利要求11所述的电池,其中Ti(1-x)M1xNb(2-y)M2yO(7-z)Qz的晶格为单斜晶,而Ti(2-x’)M1x’Nb(10-y’)M2y’O(29-z’)Qz’的晶格为ReO3型晶格。
13.如权利要求11所述的电池,其中该负极还包括钛酸锂,该掺杂铌酸钛与该钛酸锂混合形成一复合材料,且该掺杂铌酸钛与该钛酸锂的重量比例介于90∶10至10∶90之间。
14.如权利要求13所述的电池,其中该钛酸锂的表面包覆碳、氧化物或氟化物,且碳、氧化物或氟化物与该钛酸锂的重量比例大于0且小于或等于5%。
15.如权利要求13所述的电池,其中该复合材料的表面包覆碳、氧化物或氟化物,且碳、氧化物或氟化物与该复合材料的重量比例大于0且小于或等于5%。
16.如权利要求11或13所述的电池,其中该掺杂铌酸钛的表面包覆碳、氧化物或氟化物,且碳、氧化物或氟化物与该掺杂铌酸钛的重量比例大于0且小于或等于5%。
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CN116040686A (zh) * | 2023-02-14 | 2023-05-02 | 上海理工大学 | 一种钛铁铌氧化物电极的制备方法 |
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