CN116040686A - 一种钛铁铌氧化物电极的制备方法 - Google Patents
一种钛铁铌氧化物电极的制备方法 Download PDFInfo
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- 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 title claims abstract description 21
- 229910000484 niobium oxide Inorganic materials 0.000 title claims abstract description 20
- 229910001200 Ferrotitanium Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010955 niobium Substances 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 239000007772 electrode material Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- -1 titanium-iron-niobium-oxide Chemical compound 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229960004887 ferric hydroxide Drugs 0.000 claims description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 claims description 2
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 claims description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 2
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 claims description 2
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- OBOYOXRQUWVUFU-UHFFFAOYSA-N [O-2].[Ti+4].[Nb+5] Chemical compound [O-2].[Ti+4].[Nb+5] OBOYOXRQUWVUFU-UHFFFAOYSA-N 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 7
- 229910010340 TiFe Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
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- 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
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Abstract
本发明公开了一种钛铁铌氧化物电极的制备方法，包括以下步骤：S1、钛源、铁源和铌源按比例进行混合，得到悬浊液；S2、将悬浊液干燥得到粉末后进行高温退火处理；S3、进行自然冷却得到钛铁铌氧化物电极材料。在该氧化物中，钛、铁、铌三种元素随机占据八面体中心，八面体以共顶点或共边相连，形成的空间可以可逆嵌/脱锂离子。该材料与传统的钛铌氧化物相比，表现出更优的倍率性能和循环性能。根据本发明，解决了氧化铌和钛铌氧化物固有的电子和离子导电性差的问题，能够明显提升材料整体电子电导率和锂离子的扩散速率。
Description
技术领域
本发明涉及材料学的技术领域，特别涉及一种钛铁铌氧化物电极的制备方法。
背景技术
当今社会，由于传统燃油车造成了大量的环境污染，纯电动汽车(EV)和混合动力汽车(HEV)被广泛的开发和研究。其中，锂离子电池(LIB)被认为是最有前景的纯电动汽车和混合动力汽车的电化学储能系统。然而，使用石墨负极的LIB在实际应用中并不能满足高功率密度和安全性的要求，因为锂嵌入碳负极会形成固体电解质界面(SEI)层，从而产生了不可逆的初始容量与较差的倍率性能。此外，在快速充放电过程中，容易形成锂枝晶，可能会导致内部短路，从而大大降低其安全性。
发明内容
针对现有技术中存在的不足之处，本发明的目的是提供一种钛铁铌氧化物电极的制备方法，解决了氧化铌和钛铌氧化物固有的电子和离子导电性差的问题，能够明显提升材料整体电子电导率和锂离子的扩散速率。为了实现根据本发明的上述目的和其他优点，提供了一种钛铁铌氧化物电极的制备方法，包括：
S1、钛源、铁源和铌源按比例进行混合，得到悬浊液；
S2、将悬浊液干燥得到粉末后进行高温退火处理；
S3、进行自然冷却得到钛铁铌氧化物电极材料。
优选的，步骤S1中钛源可为偏钛酸、金红石型二氧化钛、锐钛矿型二氧化钛、P25型二氧化钛中的一种或几种；或为含钛的固态有机醇、酸或酯类化合物。
优选的，步骤S1中铁源可为三氧化二铁、四氧化三铁、氧化亚铁、氯化铁、氟化铁、硫酸铁、硫化铁、硫化亚铁、碳酸铁、氢氧化铁、氢氧化亚铁的其中一种。
优选的，步骤S1中铌源可为氧化铌、五氯化铌、五氟化铌、乙醇铌的其中一种。
优选的，钛铁铌氧化物以TixFeyNbzO(4x+3y+5z)/2来表示，比例为x:y＝1:0.5～1:2，y:z＝1:10～1:1，x:z＝1:0.01～1:100。
优选的，步骤S2中将得到的悬浊液放于100℃鼓风干燥箱中干燥12h，得到的粉末经过研磨后放入通氮气的管式炉中900-1400℃煅烧10h。
优选的，步骤S2中在退火气氛中进行高温退火，所述退火气氛为空气、氧气、氩气，氮气，氦气，氩气与氢气的混合气体、或氮气与氢气的混合气体中的任意一种，所述混合气体中氢气的体积百分比含量为10％～40％。
TiFeNb10O28.5-δ材料组装半电池的方法，包括以下步骤：
(1)将制备的材料与7wt％的粘结剂和8wt％的导电剂混合，搅拌均匀后涂覆在铜箔上，放入烘箱中在60～80℃烘干；
(2)再用直径10～16mm的冲头冲成极片，放入真空烘箱中在60～120℃下干燥4～12h，然后转移到充满氩气的手套箱中；
(3)以金属锂为对电极，电解液溶剂采用乙基碳酸酯(EC):二甲基碳酸酯(DMC)＝1:1，含1％LiPF6的电解质，组装成CR2032扣式电池。
本发明与现有技术相比，其有益效果是：该材料具有剪切ReO3型晶体结构，保证了嵌/脱锂过程的结构稳定性。与具有类似结构的氧化铌和钛铌氧化物相比，三价的铁离子促使四价钛离子和五价铌离子向它们各自的还原态转变，因而产生更多的氧空穴，提升了材料本征电子和离子电导率，因而能够表现出更快速的嵌/脱锂离子的能力，和更稳定的循环性能。适合高功率型锂离子电池负极材料的应用。
附图说明
图1为根据本发明的钛铁铌氧化物电极的制备方法的钛铁铌氧化物的X射线衍射光谱图；
图2为根据本发明的钛铁铌氧化物电极的制备方法的钛铁铌氧化物在1C倍率下1-3V电位区间的充放电曲线图；
图3为根据本发明的钛铁铌氧化物电极的制备方法的钛铁铌氧化物的扫描电镜图；
图4为根据本发明的钛铁铌氧化物电极的制备方法的钛铁铌氧化物在1C倍率下1-3V电位区间的充放电曲线图；
图5为根据本发明的钛铁铌氧化物电极的制备方法的钛铁铌氧化物电极材料的倍率性能图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
参照图1-5，一种钛铁铌氧化物电极的制备方法，包括：
实施例1
TiFeNb10O28.5-δ材料的合成、结构表征及其电化学性能测试。
按照制备0.01mol的TiFeNb10O28.5的化学计量比将0.8g锐钛矿型二氧化钛，0.8g三氧化二铁和10.9g五氧化二铌分散于无水乙醇中，转移至100mL氧化锆球磨罐中，按照球料比5:1的比例，将混合物在500rmp的速度下球磨5h，使其充分混合，将得到的悬浊液放于70℃鼓风干燥箱中干燥12h，得到的粉末经过研磨后放入马弗炉中在空气中1000℃煅烧10h，自然冷却后得到TiFeNb10O28.5-δ(由于Ti和Nb有部分还原，因此在分子式中的氧原子后面减去“δ”)。
TiFeNb10O28.5-δ电极材料的X射线衍射光谱如图1所示，图1中样品的衍射峰属于单斜相Wadsley-Roth空间结构(PDF#13-0317)。将实施例1制得的TiFeNb10O28.5-δ材料按照下述步骤组装半电池：将制备的材料与7wt％的粘结剂(4wt％PVDF的NMP溶液)和8wt％的导电剂(Super P导电碳黑)混合，搅拌均匀后涂覆在铜箔上，放入烘箱中在60～80℃烘干。再用直径10～16mm的冲头冲成极片，放入真空烘箱中在60～120℃下干燥4～12h，然后转移到充满氩气的手套箱中。以金属锂为对电极，电解液溶剂采用乙基碳酸酯(EC):二甲基碳酸酯(DMC)＝1:1，含1％LiPF6的电解质，组装成CR2032扣式电池，在LAND电池测试系统(武汉金诺电子有限公司提供)上进行恒流充放电性能测试，充放电截止电压相对于Li/Li+为1-3V。1C倍率下的充放电测试如图2所示，在1C倍率(充放电时间各为1h)下放电容量达到172mAhg-1。
实施例2
TiFe0.1Nb1.9O7-δ材料的合成、形貌表征及其电化学性能测试。
按照制备0.02mol的TiFe0.1Nb1.9O7-δ的化学计量比将1.96g偏钛酸，0.21g氢氧化铁和10.28g五氯化铌分散于水中，磁力搅拌2h后，将得到的悬浊液放于100℃鼓风干燥箱中干燥12h，得到的粉末经过研磨后放入通氮气的管式炉中1300℃煅烧10h，自然冷却后得到TiFe0.1Nb1.9O7-δ(由于Ti和Nb有部分还原，因此在分子式中的氧原子后面减去“δ”)。
TiFe0.1Nb1.9O7-δ电极材料的扫描电镜图如图3所示呈现宽度约为2-5微米的块状。将实施例2制得的TiFe0.1Nb1.9O7-δ材料按照实施例1的步骤组装半电池，之后在LAND电池测试系统(武汉金诺电子有限公司提供)上进行恒流充放电性能测试，充放电截止电压相对于Li/Li+为1-3V。充放电电流密度为100mA g-1下的充放电测试如图4所示放电容量达到205mAh g-1。倍率性能如图5所示，在5A g-1的电流密度下，放电容量保持80mAh g-1。并且在回复到100mA g-1电流密度后，容量可以恢复到200mAh g-1。
实施例3～实施例5
按以上实验参数参照实施例1或例2的方法即可获得钛铁铌氧化物电极材料。
综上所述，本发明涉及的钛铁铌氧化物不仅具有稳定Li+脱嵌结构，并且由于过渡金属中有三价的铁、四价的钛和五价的铌，可以平衡过渡金属价态，在结构中引入氧空穴，能够明显提升材料整体电子电导率和锂离子的扩散速率，提升作为电极材料的电化学性能。这一进步的发明解决了氧化铌和钛铌氧化物固有的电子和离子导电性差的问题。
这里说明的设备数量和处理规模是用来简化本发明的说明的，对本发明的应用、修改和变化对本领域的技术人员来说是显而易见的。
尽管本发明的实施方案已公开如上，但其并不仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节和这里示出与描述的图例。
Claims (8)
1.一种钛铁铌氧化物电极的制备方法，其特征在于，包括以下步骤：
S1、钛源、铁源和铌源按比例进行混合，得到悬浊液；
S2、将悬浊液干燥得到粉末后进行高温退火处理；
S3、进行自然冷却得到钛铁铌氧化物电极材料。
2.如权利要求1所述的一种钛铁铌氧化物电极的制备方法，其特征在于，步骤S1中钛源可为偏钛酸、金红石型二氧化钛、锐钛矿型二氧化钛、P25型二氧化钛中的一种或几种；或为含钛的固态有机醇、酸或酯类化合物。
3.如权利要求2所述的一种钛铁铌氧化物电极的制备方法，其特征在于，步骤S1中铁源可为三氧化二铁、四氧化三铁、氧化亚铁、氯化铁、氟化铁、硫酸铁、硫化铁、硫化亚铁、碳酸铁、氢氧化铁、氢氧化亚铁的其中一种。
4.如权利要求3所述的一种钛铁铌氧化物电极的制备方法，其特征在于，步骤S1中铌源可为氧化铌、五氯化铌、五氟化铌、乙醇铌的其中一种。
5.如权利要求1所述的一种钛铁铌氧化物电极的制备方法，其特征在于，钛铁铌氧化物以TixFeyNbzO(4x+3y+5z)/2来表示，比例为x:y=1:0.5~1:2，y:z=1:10~1:1，x:z=1:0.01~1:100。
6.如权利要求5所述的一种钛铁铌氧化物电极的制备方法，其特征在于，步骤S2中将得到的悬浊液放于100℃鼓风干燥箱中干燥12h，得到的粉末经过研磨后放入通氮气的管式炉中900-1400℃煅烧10h。
7.如权利要求1所述的一种钛铁铌氧化物电极的制备方法，其特征在于，步骤S2中在退火气氛中进行高温退火，所述退火气氛为空气、氧气、氩气，氮气，氦气，氩气与氢气的混合气体、或氮气与氢气的混合气体中的任意一种，所述混合气体中氢气的体积百分比含量为10%~40%。
8.将权利要求1制备的TiFeNb10O28.5-δ材料组装半电池的方法，其特征在于，包括以下步骤：
（1）将制备的材料与7wt%的粘结剂和8 wt%的导电剂混合，搅拌均匀后涂覆在铜箔上，放入烘箱中在60～80℃烘干；
（2）再用直径10～16 mm的冲头冲成极片，放入真空烘箱中在60～120℃下干燥4～12h，然后转移到充满氩气的手套箱中；
（3）以金属锂为对电极，电解液溶剂采用乙基碳酸酯（EC）:二甲基碳酸酯（DMC）=1:1，含1% LiPF6 的电解质，组装成CR2032扣式电池。
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