新型锂离子电池负极材料钛酸锂的研究
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摘要
Li_4Ti_5O_(12)具有尖晶石结构,是“零应变”材料。它是一种理想的嵌入型电极材料,具有充电次数多、充电过程快、安全等特点,这使其成为研究新型锂离子电池负极材料的热点。本文基于提升Li_4Ti_5O_(12)高倍率充放电性能的目的,采用水热法分别合成了纳米颗粒和纳米片形貌的锂离子电池负极材料Li_4Ti_5O_(12),并采用XRD、SEM、TG等方法对材料进行了表征,同时采用了室温恒流充放电、交流阻抗、循环伏安等测试方法进行了电化学性能分析。
采用水热法合成了纳米颗粒形貌的Li_4Ti_5O_(12)材料,颗粒粒径在20nm左右,考察了水热法制备Li_4Ti_5O_(12)材料的工艺条件的影响。实验结果表明:热处理温度为500℃时得到的材料性能最佳,制备得到的Li_4Ti_5O_(12)纳米颗粒具有极佳的倍率性能和循环性能,在8C倍率下的放电容量可保持134.9mAh/g的较高容量,而在1C倍率下充放电100次后仍能保持160.3mAh/g的放电容量,与材料的理论容量非常接近。
采用水热法合成了纳米片形貌的Li_4Ti_5O_(12)材料,宽度为200～400nm,厚度小于5nm,比表面积为104.3m2/g。制得的Li_4Ti_5O_(12)纳米片具有良好的高倍率充放电性能,在10C、20C、30C、40C、50C下分别充放电50次,连续循环250次后,在50C倍率下的充放电比容量仍保持在95mAh/g左右。
Li_4Ti_5O_(12) has spinel structure and exhibits no structural change (so called“zero strain”material). It has advantages in reversibility, kinetic of charge-discharge process and safety performance, and becomes the hotspot of research in anode material. In this article, in order to improve the high-rate performance, Li_4Ti_5O_(12) nanoparticles and nanosheets were synthesized through hydrothermal method. The structure and morphology characteristics of the composite were investigated by XRD, SEM, TG et al. Meanwhile, electrochemical properties were analyzed through CV, EIS and charge-discharge test.
Li_4Ti_5O_(12) nanoparticles with particle size around 20nm were synthesized through hydrothermal method. The infection of the synthesis condition of Li_4Ti_5O_(12) prepared with hydrothermal method was investigated. The results demonstrated that materials achieved best electrochemical property when calcined at 500℃. The prepared Li_4Ti_5O_(12) nanoparticles had good rate performance and cycling performance. It exhibited a discharging capacity of 134.9mAh/g at a high rate of 8C. The capacity at 1C after 100 cycles could also attained 160.3mAh/g, close to the theory capacity of Li_4Ti_5O_(12) material.
Spinel Li_4Ti_5O_(12) nanosheets were synthesized by hydrothermal process. The size was around 200-400nm and thickness was less than 5nm. The Brunauer-Emmett-Teller specific surface area of the sample was 104.3m2/g. The prepared Li_4Ti_5O_(12) nanosheets had fine rate charge-discharge performance. When being cycled at 10C, 20C, 30C, 40C, 50C for 50 cycles separately, it maintained a specific capacity of 95mAh/g at 50C after 250 cycles.
采用水热法合成了纳米颗粒形貌的Li_4Ti_5O_(12)材料,颗粒粒径在20nm左右,考察了水热法制备Li_4Ti_5O_(12)材料的工艺条件的影响。实验结果表明:热处理温度为500℃时得到的材料性能最佳,制备得到的Li_4Ti_5O_(12)纳米颗粒具有极佳的倍率性能和循环性能,在8C倍率下的放电容量可保持134.9mAh/g的较高容量,而在1C倍率下充放电100次后仍能保持160.3mAh/g的放电容量,与材料的理论容量非常接近。
采用水热法合成了纳米片形貌的Li_4Ti_5O_(12)材料,宽度为200～400nm,厚度小于5nm,比表面积为104.3m2/g。制得的Li_4Ti_5O_(12)纳米片具有良好的高倍率充放电性能,在10C、20C、30C、40C、50C下分别充放电50次,连续循环250次后,在50C倍率下的充放电比容量仍保持在95mAh/g左右。
Li_4Ti_5O_(12) has spinel structure and exhibits no structural change (so called“zero strain”material). It has advantages in reversibility, kinetic of charge-discharge process and safety performance, and becomes the hotspot of research in anode material. In this article, in order to improve the high-rate performance, Li_4Ti_5O_(12) nanoparticles and nanosheets were synthesized through hydrothermal method. The structure and morphology characteristics of the composite were investigated by XRD, SEM, TG et al. Meanwhile, electrochemical properties were analyzed through CV, EIS and charge-discharge test.
Li_4Ti_5O_(12) nanoparticles with particle size around 20nm were synthesized through hydrothermal method. The infection of the synthesis condition of Li_4Ti_5O_(12) prepared with hydrothermal method was investigated. The results demonstrated that materials achieved best electrochemical property when calcined at 500℃. The prepared Li_4Ti_5O_(12) nanoparticles had good rate performance and cycling performance. It exhibited a discharging capacity of 134.9mAh/g at a high rate of 8C. The capacity at 1C after 100 cycles could also attained 160.3mAh/g, close to the theory capacity of Li_4Ti_5O_(12) material.
Spinel Li_4Ti_5O_(12) nanosheets were synthesized by hydrothermal process. The size was around 200-400nm and thickness was less than 5nm. The Brunauer-Emmett-Teller specific surface area of the sample was 104.3m2/g. The prepared Li_4Ti_5O_(12) nanosheets had fine rate charge-discharge performance. When being cycled at 10C, 20C, 30C, 40C, 50C for 50 cycles separately, it maintained a specific capacity of 95mAh/g at 50C after 250 cycles.
引文
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[1] Yoo E.J., Kim J., Hosono E., et al. Large reversible Li storage of graphene nanosheet families for use in rechargeable lithium ion batteries[J]. Nano Lett., 2008, 8: 2277-2282.
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[3] Wahihara M. Recent developments in lithium ion batteries[J]. Mater. Sci. Eng., 2001, 33: 109-134.
[4]汪继强.锂离子蓄电池技术进展及市场前景[J].电源技术, 1996, 20(4): 147~151.
[5]米常焕,曹高劭,赵新兵.锂离子蓄电池负极材料最新研究进展[J].电源技术, 2004, 28(3): 180~183.
[6]吴国良,杨新河,阚素荣等.锂离子电池及其电极材料的研制[J].电池, 1998, 28(6): 258~262.
[7] Shi H., Barker J, Saidi M.Y, et al. Structure and lithium intercalation properties of synthetic and natural graphite[J]. J. Electrochem. Soc., 1996, 143(11): 3466-3472.
[8] Pasquier A.D., Plitz I., Menocal S., et al. A comparative study of Li-ion battery, supercapacitor and nonaqueous asymmetric hybrid devices for automotive applications[J]. J. Power Sources, 2003, 115: 171-178.
[9] Zheng T., Zhong Q., Dahn J.R. High capacity carbon prepared from phenolic resin for anodes of lithium-ion batteries[J]. J. Electrochem. Soc., 1995, 142: 211-214.
[10]吴宇平,戴晓兵,马军旗等.锂离子电池——应用与实践.北京:化学工业出版社. 2004, 14: 29-30.
[11] Vincent C.A. Lithium batteries: a 50-year perspective, 1959-2009[J]. Solid State Ionics, 2000, 134: 159-167.
[12]谢维. Al与Al基金属间化合物作为锂离子二次电池负极材料的研究[硕士论文].长沙:中南工业大学, 2005.
[13] Hatchard T.D., Dahn J.R. Study of the electrochemical performance of sputtered Si1-xSnx films[J]. J. Electrochem. soc., 2004, 151(10): A1628-A1635.
[14] Kim B.C., Uono H., Sato T., et al. Cyclic properties of Si-Cu/carbon nano-composite anodes for Li-ion secondary batteries[J]. J. Electrochem. Soc., 2005, 152(3): A523-A526.
[15] Beaulieu L.Y., Hewitt K.C., Turner R.L., et al. The electrochemical reaction of Li with amorphous Si-Sn alloys[J]. J. Electrochem. Soc., 2003, 150(2): A149-A156.
[16] Idota Y., Kubota T., Matsufuji A., et al. Tin-based Amorphous Oxide: A High-capacity Lithium Ion Storage Material[J]. Science, 1997, 276: 1395-1397.
[17] Poizot P., Laruelle S., Grugeon S., et al. Nano-sized transition metal oxides as negative-electrode materials for lithiun-ion batteries[J]. Nature, 2000, 407: 496-499.
[18] Subramanian V., Burke W.W., Zhu H.W., et al. Novel microwave synthesis of nanocrystalline SnO2 and its electrochemical properties[J]. J. Phys. Chem. C., 2008, 112: 4550-4556.
[19] Park M.S., Wang G.X., Kang Y.M., et al. Preparation and electrochemical properties of SnO2 nanowires for application in lithium-ion batteries[J]. Angew. Chem. Intern. Edit., 2007, 46(5): 750-753.
[20] Zheng J. P., The limitations of energy density of battery/double-layer capacitor asymmetric cells[J]. J. Electrochem. Soc., 2003, 150(4): A484-A492.
[21] Yang L.C., Gao Q.S., Zhang Y.H., et al. Tremella-like molybdenum dioxide consisting of nanosheets as an anode material for lithium ion battery[J]. Electrochem. Commun., 2008, 10: 118–122.
[22] Ding N., Feng X., Liu S., et al. High capacity and excellent cyclability of vanadium (IV) oxide in lithium battery applications[J]. Electrochem. Commun., 2009, 11: 538-541.
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