锂离子电池负极材料Li_4Ti_5O_（12）的制备及性能研究
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摘要
本研究采用溶胶凝胶法和高温固相法两种方法制备了Li_4Ti_5O_(12)负极材料,通过TG-DTA测试确定材料的烧结温度,XRD测试确定产物的物理组成和晶体结构,通过SEM研究颗粒的表面形貌和颗粒尺寸范围,用恒流充放电、循环伏安、交流阻抗测试方式来研究材料的电化学性能。
采用溶胶凝胶法,以钛酸四丁酯和Li_2CO_3为原料、柠檬酸为络合剂,将前驱体在650℃烧结8h冷却研磨后再在850℃烧结16h制备了Li_4Ti_5O_(12)负极材料。通过对柠檬酸与Ti(Ⅳ)的摩尔比R的研究,发现当R = 1∶2时得到产物的性能最好,首次放电容量为148.65mAh/g,100次循环后保持在116.82mAh/g,容量保持率为78.59%。
用LiAc代替Li_2CO_3作为锂源时,制得的Li_4Ti_5O_(12)负极材料颗粒致密性更好,电化学性能也更好,首次放电比容量为153.61mAh/g,100个循环之后放电比容量为124.37mAh/g,容量保持率为80.96%。
采用高温固相法,以无定形TiO2和Li_2CO_3为原料制备了Li_4Ti_5O_(12)负极材料。通过研究各种条件对产物性能的影响,得到最优工艺条件:采用两步煅烧法,在650℃烧结8h再在850℃烧结16h后得到产物的性能最好,首次放电容量为159.16mAh/g,放电平台较长,100次循环后保持在143mAh/g左右,容量保持率约89.9%。
尝试用葡萄糖对Li_4Ti_5O_(12)进行碳包覆,在预烧后加入葡萄糖混合充分,包覆质量百分比为20%产物的性能最好,首次放电比容量为172.94mAh/g,100次循环后放电比容量为135.93mAh/g,葡萄糖含量为10%的产物性能有一定的改进,30%的样品电化学性能反而下降。
In this paper, Lithium Titannate was synthesized by sol-gel method and solid-state reaction respectively. In addition, Thermogravimetry-Differential Thermoanalysia(TG-DTA) was used to fix the sinter temperature, X-Ray Diffraction(XRD) to analyze micro-structure, Scanning Electron Microscope(SEM) to observe superficial morphology. Galvanostatic charge-discharge test, Cycle Voltammagram(CV) and Electrochemical Impedanc Spectroscopy(EIS) were used to study specific capacity and cyclic behavior.
Anode material Li_4Ti_5O_(12) for lithium ion batteries had been prepared by a sol-gel method with Tetra-n-butyl Titanate and Li_2CO_3 as starting materials and citric acid as a chelating agent. Citric acid can complex with Ti and Li at the same time to realize more uniform distribution of ions and smaller particle size in the solution. The effect of amount of chelating agent on electochemical properties of product was investigated. In our study, the sample synthesized at 650℃for 8h and 850℃for 16h with citric acid to titanium molar ratio R = 1∶2 showed the best discharge capacity of 148.65mAh/g and 116.82mAh/g for the first cycle and the 100th cycle respectively. The capacity retention was 78.59%。
Anode material Li_4Ti_5O_(12) using LiAc as Li source had smaller paricle distance and contacted each other closer. The material had better electochemical properties than the former using Li_2CO_3. It had a first discharge capacity of 153.61mAh/g and obtained 143mAh/g with a capacity retention of 80.96% after 100 cycles.
Li_4Ti_5O_(12) materials synthesized by solid-state reaction were prepared with amorphism TiO2 and Li_2CO_3 as the raw materials. The results demonstrated that the materials of best performance were sintered by two-step method, the raw materials were pre-sintered at 650℃for 8h then were treated at 850℃for 16h. The Li_4Ti_5O_(12) as the anode materials for lithium ion battery had a first discharge capacity of 159.16mAh/g, and a long platform around the voltage of 1.55V. The sample obtained a capacity of 143mAh/g with a capacity retention of 89.9% after 100 cycles. The materials showed fine cycling properties.
The carbon modification using dextrose as carbon source was researched. The results showed that 20%wt was the best carbon doping quantity, the materials had a first discharge of 172.94 mAh·g-1. The sample with 10%wt carbon had a little improvement in cyclic stability and diacharge capacity. However, the 30%wt carbon doped sample’s electrochemical properties were weakened.
采用溶胶凝胶法,以钛酸四丁酯和Li_2CO_3为原料、柠檬酸为络合剂,将前驱体在650℃烧结8h冷却研磨后再在850℃烧结16h制备了Li_4Ti_5O_(12)负极材料。通过对柠檬酸与Ti(Ⅳ)的摩尔比R的研究,发现当R = 1∶2时得到产物的性能最好,首次放电容量为148.65mAh/g,100次循环后保持在116.82mAh/g,容量保持率为78.59%。
用LiAc代替Li_2CO_3作为锂源时,制得的Li_4Ti_5O_(12)负极材料颗粒致密性更好,电化学性能也更好,首次放电比容量为153.61mAh/g,100个循环之后放电比容量为124.37mAh/g,容量保持率为80.96%。
采用高温固相法,以无定形TiO2和Li_2CO_3为原料制备了Li_4Ti_5O_(12)负极材料。通过研究各种条件对产物性能的影响,得到最优工艺条件:采用两步煅烧法,在650℃烧结8h再在850℃烧结16h后得到产物的性能最好,首次放电容量为159.16mAh/g,放电平台较长,100次循环后保持在143mAh/g左右,容量保持率约89.9%。
尝试用葡萄糖对Li_4Ti_5O_(12)进行碳包覆,在预烧后加入葡萄糖混合充分,包覆质量百分比为20%产物的性能最好,首次放电比容量为172.94mAh/g,100次循环后放电比容量为135.93mAh/g,葡萄糖含量为10%的产物性能有一定的改进,30%的样品电化学性能反而下降。
In this paper, Lithium Titannate was synthesized by sol-gel method and solid-state reaction respectively. In addition, Thermogravimetry-Differential Thermoanalysia(TG-DTA) was used to fix the sinter temperature, X-Ray Diffraction(XRD) to analyze micro-structure, Scanning Electron Microscope(SEM) to observe superficial morphology. Galvanostatic charge-discharge test, Cycle Voltammagram(CV) and Electrochemical Impedanc Spectroscopy(EIS) were used to study specific capacity and cyclic behavior.
Anode material Li_4Ti_5O_(12) for lithium ion batteries had been prepared by a sol-gel method with Tetra-n-butyl Titanate and Li_2CO_3 as starting materials and citric acid as a chelating agent. Citric acid can complex with Ti and Li at the same time to realize more uniform distribution of ions and smaller particle size in the solution. The effect of amount of chelating agent on electochemical properties of product was investigated. In our study, the sample synthesized at 650℃for 8h and 850℃for 16h with citric acid to titanium molar ratio R = 1∶2 showed the best discharge capacity of 148.65mAh/g and 116.82mAh/g for the first cycle and the 100th cycle respectively. The capacity retention was 78.59%。
Anode material Li_4Ti_5O_(12) using LiAc as Li source had smaller paricle distance and contacted each other closer. The material had better electochemical properties than the former using Li_2CO_3. It had a first discharge capacity of 153.61mAh/g and obtained 143mAh/g with a capacity retention of 80.96% after 100 cycles.
Li_4Ti_5O_(12) materials synthesized by solid-state reaction were prepared with amorphism TiO2 and Li_2CO_3 as the raw materials. The results demonstrated that the materials of best performance were sintered by two-step method, the raw materials were pre-sintered at 650℃for 8h then were treated at 850℃for 16h. The Li_4Ti_5O_(12) as the anode materials for lithium ion battery had a first discharge capacity of 159.16mAh/g, and a long platform around the voltage of 1.55V. The sample obtained a capacity of 143mAh/g with a capacity retention of 89.9% after 100 cycles. The materials showed fine cycling properties.
The carbon modification using dextrose as carbon source was researched. The results showed that 20%wt was the best carbon doping quantity, the materials had a first discharge of 172.94 mAh·g-1. The sample with 10%wt carbon had a little improvement in cyclic stability and diacharge capacity. However, the 30%wt carbon doped sample’s electrochemical properties were weakened.
引文
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2 B. A. Ritchie, C. O. Giwa, J. C. Lee. Future Cathode Materials for Lithium Rechargeable Batteries. Journal of Power Sources. 1999, 80(1-2): 98~102
3 A. G. Ritchie. Recent Developments and Future Prospects for Lithium Rechargeable Batteries. Journal of Power Sources. 2001, 96(1): 1~4
4 J. S. Xue, R D. Wise, X. L. Zhang, et al. Performance Characteristics of Ultralife’s Solid Polymer Rechargeable Batteries. Journal of Power Sources. 1999, 80(1-2):119~127
5 E. A. Cuellar, M. E. Manna, R. D. Wise. Ultralife’s Polymer Electrolyte Rechargeable Lithium-Ion Batteries for Use in the Mobile Electronics Industry. Journal of Power Sources. 2001, 96(1): 184~198
6 J. R. Dahn, U. V. Sacken, M. W. Juzkow. Rechargeable LiNiO2/Carbon Cells. Journal of The Electrochemical Society. 1991, 138(8): 2207-2211
7高文明.钛酸锂的制备与改性研究.天津大学硕士论文. 2007: 1~2
8 M. S. Whittingham. Insertion Eleetrodes as Smart Materials the First 25 Years and Future Promises. Solid State Ionies. 2000. 134(1-2): 169~178
9李阳新等.锂离子电池的研究与开发.第四届中国国际电池技术交流会,北京: 2002: 26~30
10 I. Bloom, A. N. Jansen, D. P. Abraham, et al. Differential Voltage Analyses of High- Power, Lithium-Ion Cells. Technique and application. Journal of Power Sources. 2005, 139(1-2): 2955~303
11 J. Fan, P. S. Fedkiw. Electrochemical Impedance Spectra of Full Cells:Relation to Capacity and Capacity-rate of Rechargeable Li Cells Using LiCoO_2,LiMn_2O_4 and LiNiO_2 Cathodes. Journal of Power Sources. 1998, 72(2): 165~173
12 S. H. Choi, O. A. Shlyakhtin, K. Joosun. Structural and Electrochemical Properties of Li_(1+x)Ni_(0.5)Mn_(0.5)O_2(0≤x≤0.7) Cathode Materials for Lithium-Ion Batteries. Journal of Power Sources. 2005, 140(2): 355~360
13 C. P. Vicente, J. M. Lloris, J. L.Tirado. Understanding the Voltage Profile of Li Insertion into LiNi_(0.5-y)Fe_yMn_(1.5)O_4 in Li Cells. Electrochimica. 2004, 49(12): 1963~ 1967
14 Y. Idemoto, H. Sekina, K. Ui. Crystal Structurl Change during Charge- Discharge Process of LiMn_(1.5)Ni_(0.5)O_4 as Cathode Material for 5V Class Lithium Secondary Battery. Solid State Ionics. 2005, 176(3-4): 299~306
15 K. S. Park, J. T. Son, H. T. Chung, et al. Surface Modification by Silver Coating forImproving Electrochemical Properties of LiFePO4. Solid State communication. 2004, 129(5): 311~314
16陈召勇,肖劲,朱华丽,刘业翔.不同原料对Li-Ni-Mn-O 5V正极材料的结构和性能影响.无机化学学报. 2005, 9(21): 1417
17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.电源技术. 2004, 28(3): 180~183
18 M. Endo, C. Kim, K. N. Shimura,et al. Recent Development of Carbon Material for Lithium Ion Batteries. Carbon. 2000, 38(2): 183~179
19 T. D. Tran. Commerial Carbonaceous Materials as Lithium Intercalation Anodes. Journal of The Electrochemical Society. 1995, 142(10): 3297~3302
20周向阳,胡国荣,彭忠东.锂离子电池碳负极材料的研究进展.电池. 2001, 31(3):146~149
21 H. Fujimoto, A. Mabuchi, K. Tokumitsu. Effect of Crystallite Size on the Chemical Compositions of the Stage Metal-graphite Intercalation Compounds. Carbon. 1994, 32(2):193~202
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