锂离子电池电极材料LiTi2(PO4)3的纤维模板法制备、微结构和电化学性能研究
李淑瑜1，周晓亮1，马 林1，严铮洸1*，韩晓东1，张 泽1，2
(1. 北京工业大学固体微结构与性能研究所, 北京市固体微结构与性能重点实验室，北京100124；2. 浙江大学电子显微镜中心，材料科学与工程学院，硅材料国家重点实验室，浙江 杭州 310027)
摘 要：使用丝绸等纤维织物为模板结合溶胶凝胶法，利用管式炉控制气氛（惰性气体、氧气氛混合气体）合成了LiTi2(PO4)3 (LTP，磷酸钛锂)/碳复合材料，可作为锂离子电池电极材料。利用X射线衍射(XRD)，红外光谱(FT-IR)，扫描电子显微镜(SEM)和透射电子显微镜(TEM)对所得材料的成分、物相、微观结构进行了表征。结果表明，所得材料具有和所用的纤维模板相同的形貌特征，其中主体部分单根纤维直径为微米级别。将所得材料作为锂离子电池的正极材料，以金属锂为负极，制成半电池，以循环伏安、充放电等方法测试其电化学性能，结果表明，所得材料的首次充放电容量达到109 mAh/g，在0.1C倍率下充放电100次后容量保持率为63.3%。
关键词：磷酸钛锂；丝绸；电化学性能；锂离子电池
中图分类号：TM911；TG115.21+5.3 文献标识码：A doi:10.3969/j.issn.1000-6281.2015.05.005
Synthesis, microstructure and electrochemical properties of LiTi2(PO4)3 using silk fiber as template
LI Shu-yu1, ZHOU Xiao-liang1, MA Lin1, YAN Zheng-guang1*, HAN Xiao-dong1, ZHANG Ze1,2
(1.Institute of Microstructure and Properties of Advanced Materials, Beijing University of Technology, Beijing 100124；2.Department of Materials Science，Zhejiang University，Hangzhou Zhejiang 310027，China)
Abstruct：Using the template of silk cloth and other commercial fabrics combined with sol-gel method, LiTi2(PO4)3 ( LTP, lithium titanium phosphate) / carbon composite material was synthesized by controlling the atmosphere in the tube furnace (adjusting the ratio of inert gas to oxygen gas) . The prepared material could be directly used as lithium-ion battery electrode materials without using binder or conductive agents. The composition, phase, microstructure of the resulting material were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) methods.The results show that the resulting material presents the same morphology with the silk fiber used, and the single fiber in the main body portion is at micron scale.Using the obtained material as the cathode material and lithium metal foil as the anode material, the coin cell was prepared. The coin cells were tested by CHI 1140A and BTS. Thecyclic voltammetry and charge-discharge curves show that the prepared LTP/carbon composite exhibits an initial discharge capacity of 109 mAh/g at 0.1C, and after 100 cycles, still 63.3% of the initial capacity isretained.
Keywords: lithium titanium phosphate；silk cloth；electrochemical performance；lithium-ion batteries
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[1] Young H R，Kiyoshi K. Fabrication of all solid-state rechargeable lithium battery and its electrochemical properties[J]. Power Sources，2006，158：1436-1441.
[2] Liu Li，Zhou Meng，Wang Guo，et al. Synthesis and characterization of LiTi2(PO4)3/C nanocomposite as lithium intercalation electrode materials [J]. Electrochim Acta，2012，70：136-141.
[3] Mariappan C R，Galven C，Crosnier-Lopez M P，et al. Synthesis of nanostructured LiTi2(PO4)3 powder by a pechini-type polymerizable complex method [J]. Solid State Chem，2006，179：450-456.
[4] Delmas C，Nadiri A，Souberoux J L. The nasicon-type titanium phosphates LiTi2(PO4)3, NaTi2(PO4)3as electrode materials[J]. Solide State Ionics，1988，28-30：419-423.
[5] Wang G X，Bradhurst D H，Dou S X，et al. LiTi2(PO4)3 with NASICON-type structure as lithium-storage materials[J]. Power Sources，2003，124：231-236.
[6] Wessells C，Martia F L，Yi Cui，et al. Synthesis and electrochemical performance of a lithium titanium phosphate anode for aqueous lithium-ion batteries[J]. Electrochem Soc，2011，158（3）：A352-355.
[7] Aono H，Sugimoto E，Sadaoka Y，et al. Ionic-conductivity of solid electrolytes based on lithium titanium phosphate[J]. Electrochem Soc，1990，137:1023-1027.
[8] Luo J Y，Cui W J，He P，et al. Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte[J]. NCHEM，2010，2（9）：760-765.
[9] Luo J Y，Xia Y Y. Aqueous lithium-ion battery LiTi2(PO4)3/LiMn2O4 with high power and energy densities as well as superior cycling stability[J]. Adv Func Mater，2007，17(18)：3877.
[10] Zygmunt J，Krumeich F，Muhr H J，et al. Silica nanotubes-template-assisted syntheses and characterisation[J]. Anorg Allg Chem，2002，628: 2189-2189.
[11] He J H，Ichinose I，Kunitake T，et al. Facile fabrication of Ag-Pd bimetallic nanoparticles in ultrathin TiO2-gel films: Nanoparticle morphology and catalytic activity[J]. Am Chem Soc，2003，125: 11034-11040.
[12] Shin Y，Liu J，Chang J H，et al. Hierarchically ordered ceramics through surfactant-templated sol-gel mineralization of biological cellular structures[J]. Adv Mater，2001，13(10): 728.
[13] Shin Y，Li X H S，Wang C M，et al. Synthesis of hierarchical titanium carbide from titania-coated cellulose paper[J]. Adv Mater，2004，16(14): 1212.
[14] Nam K T，Kim D W，Yoo P J，et al. Virus-enabled synthesis and assembly of nanowires for lithium ion battery electrodes[J]. Science，2006，312(5775): 885-888.
[15] Lee Y J，Yi H，Kim W J，et al. Fabricating genetically engineered high-power lithium-ion batteries using multiple virus genes[J]. Science，2009，324(5930): 1051-1055.
[16] Bao L H，Li X D. Towards textile energy storage from cotton T-shirts[J]. Adv Mater，2012，24：3246-3252.
[17] Hu L B，Wu H，La Mantia Fabio，et al. Thin，flexible secondary Li-ion paper batteries[J]. ACS Nano，2010，4: 5843- 5848.
[18] Koo M，Park K I，Lee S H，et al. Bendable inorganic thin-film battery for fully flexible electronic systems[J]. Nano Letters，2012，2: 4810-4816.
[19] 周晓亮. 磷酸钛锂，碳/铜复合微球等电极材料的可控制备、结构及性能研究[D]. 北京：北京工业大学，2014.
[20] 李淑瑜，严铮洸，周晓亮，等. 丝绸模板制备磷酸钛锂纤维[J]. 电子显微学报，2014，(增刊)：101.
[21] 彭丽聪，赵倪婕，陈晓，等. 透射电镜表征中锂-氧气电池放电产物的辐照损伤研究[J]. 电子显微学报，2015，34（1）：7-13.
