锂离子电池正极材料镍钴酸锂的制备及改性研究
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摘要
本论文采用传统固相法和液相法制备了锂离子二次电池用的具有层状结构的LiNi_(0.7)Co_(0.3)O_2正极材料和LiNi_(0.7)Co_(0.3-x)Al_xO_2材料；利用X射线衍射法、扫描电镜、微电极循环伏安法及恒电流充放电测试等，研究了合成材料的结构和电化学性能，得出以下结论：
1．比较了固相法和液相法制得的LiNi_(0.7)Co_(0.3)O_2正极材料的结构和电化学性能发现，采用液相法更易于制得纯相得LiNi_(0.7)Co_(0.3)O_2固溶体材料，阳离子有序度及充放电容量、循环性能均要优于固相法所得的LiNi_(0.7)Co_(0.3)O_2材料。
2．对不同热处理工艺制得的LiNi_(0.7)Co_(0.3)O_2固溶体的结构及电化学性能进行研究发现，热处理温度越高、烧结时间越长，产物的晶型越趋完整，层状结构越明显，但电化学性能并不一定好；对固相法而言，800℃附近热处理20小时左右为比较合适的工艺；对液相法而言，考虑到成本和生产效率，在750℃附近热处理20小时左右为宜。
3．对比研究了三种液相法所制备LiNi_(0.7)Co_(0.3)O_2正极材料的结构和电化学性能发现，以均匀沉淀法所制样品电化学性能最好；以金属镍粉为原料所制样品晶体结构虽好，但放电容量偏低，这可能与金属镍粉的活性有关；而共沉淀法所得样品性能虽好，但工艺较为复杂，pH值不易控制，加大了工业生产的难度。
4．固相法制备的LiNi_(0.7)Co_(0.3-x)Al_xO_2样品具有与层状结构LiNiO_2
摘要
相同的晶体结构，属于三方晶系六方晶胞。研究发现，铿镍钻化合
物中掺铝虽可稳定化合物的结构，但掺入量不宜太多，认为掺入量x
应小于0.10;800℃是最合适的合成温度，这个温度下制备的样品的
I、。。3，/l、，。4，的比值比较大，阳离子有序度高，结构稳定，但电化学
性能尚未得到显著提高，有待于进一步深入的研究。
Layered structral LiNio.7Coo.3O2 positive materials and LiNio.7Coo.3=xAlxO2 materials for rechargable lithium-ion batteries were prepared by traditional solid phase and liquid methods. Measurements such as XRD. SEM. microelectrode cyclic voltammetry. galvamostative charge/discharge test were introduced to study the crystal structures and electrochemical performances of the materials prepared. We arrived the conclusions as following:
1 .After comparision of the structures and electromechical properties of LiNi0.7Coo.3O2 positive materials prepared by solid and liquid phase methods espectively, we came to realize that, it was more easier to get pure LiNio.7Co0.33O2 materials by liquid methods, and the charge/discharge capacity . cyclic performances are superial to that materials prepared by solid phase methods.
2.Comparing the structrues and electrochemical properties of LiNio.7Co0.33O2 solid solutions under different heat treatment processes, we could see that, with the rising of the sintering temperature and the extension of the sintering period, the crystal of the products appeared more and more perfect, but the electrochemical performances were't determined to be good. As to solid phase method, 800 癈 for about 20 hours was the optimum heat treatment process, and about 20 hours under
750 for liquid methods considering of the cost and efficiency.
3. The structrues and electrochemical properties of LiNi0.7.7Co0.3O2 positive materials prepared by three kinds of liquid methods were studied, and samples prepared by homogeneous precipitation were proved to have the best electrochemical properties. Samples introducing nickel powder to be Ni source had perfect crystal structures, but the discharge capacity was far from satisfaction. Materials prepared by simultaneous precipitation had excellent combination properties, while the technology was more complex than others, and it was not convinent to control the pH value, which would bring inconvinences to industrial process.
4. LiNio.7Co.3-AlO2 prepared by solid phase method had the same crystal structures with layered LiNiO. It was revealed that doping Al to LiNioCooO compounds will stablize the layered structure, but the value of 'x' should be less than 0.10. 80C was the optimum synthesis temperature, and materials generated under the condition had larger ratio value of I and higher degree of order of cation, which leading to stable structures. But the electrochemical properties didn't have dramatic elevation, and further investigations were expected.
1．比较了固相法和液相法制得的LiNi_(0.7)Co_(0.3)O_2正极材料的结构和电化学性能发现，采用液相法更易于制得纯相得LiNi_(0.7)Co_(0.3)O_2固溶体材料，阳离子有序度及充放电容量、循环性能均要优于固相法所得的LiNi_(0.7)Co_(0.3)O_2材料。
2．对不同热处理工艺制得的LiNi_(0.7)Co_(0.3)O_2固溶体的结构及电化学性能进行研究发现，热处理温度越高、烧结时间越长，产物的晶型越趋完整，层状结构越明显，但电化学性能并不一定好；对固相法而言，800℃附近热处理20小时左右为比较合适的工艺；对液相法而言，考虑到成本和生产效率，在750℃附近热处理20小时左右为宜。
3．对比研究了三种液相法所制备LiNi_(0.7)Co_(0.3)O_2正极材料的结构和电化学性能发现，以均匀沉淀法所制样品电化学性能最好；以金属镍粉为原料所制样品晶体结构虽好，但放电容量偏低，这可能与金属镍粉的活性有关；而共沉淀法所得样品性能虽好，但工艺较为复杂，pH值不易控制，加大了工业生产的难度。
4．固相法制备的LiNi_(0.7)Co_(0.3-x)Al_xO_2样品具有与层状结构LiNiO_2
摘要
相同的晶体结构，属于三方晶系六方晶胞。研究发现，铿镍钻化合
物中掺铝虽可稳定化合物的结构，但掺入量不宜太多，认为掺入量x
应小于0.10;800℃是最合适的合成温度，这个温度下制备的样品的
I、。。3，/l、，。4，的比值比较大，阳离子有序度高，结构稳定，但电化学
性能尚未得到显著提高，有待于进一步深入的研究。
Layered structral LiNio.7Coo.3O2 positive materials and LiNio.7Coo.3=xAlxO2 materials for rechargable lithium-ion batteries were prepared by traditional solid phase and liquid methods. Measurements such as XRD. SEM. microelectrode cyclic voltammetry. galvamostative charge/discharge test were introduced to study the crystal structures and electrochemical performances of the materials prepared. We arrived the conclusions as following:
1 .After comparision of the structures and electromechical properties of LiNi0.7Coo.3O2 positive materials prepared by solid and liquid phase methods espectively, we came to realize that, it was more easier to get pure LiNio.7Co0.33O2 materials by liquid methods, and the charge/discharge capacity . cyclic performances are superial to that materials prepared by solid phase methods.
2.Comparing the structrues and electrochemical properties of LiNio.7Co0.33O2 solid solutions under different heat treatment processes, we could see that, with the rising of the sintering temperature and the extension of the sintering period, the crystal of the products appeared more and more perfect, but the electrochemical performances were't determined to be good. As to solid phase method, 800 癈 for about 20 hours was the optimum heat treatment process, and about 20 hours under
750 for liquid methods considering of the cost and efficiency.
3. The structrues and electrochemical properties of LiNi0.7.7Co0.3O2 positive materials prepared by three kinds of liquid methods were studied, and samples prepared by homogeneous precipitation were proved to have the best electrochemical properties. Samples introducing nickel powder to be Ni source had perfect crystal structures, but the discharge capacity was far from satisfaction. Materials prepared by simultaneous precipitation had excellent combination properties, while the technology was more complex than others, and it was not convinent to control the pH value, which would bring inconvinences to industrial process.
4. LiNio.7Co.3-AlO2 prepared by solid phase method had the same crystal structures with layered LiNiO. It was revealed that doping Al to LiNioCooO compounds will stablize the layered structure, but the value of 'x' should be less than 0.10. 80C was the optimum synthesis temperature, and materials generated under the condition had larger ratio value of I and higher degree of order of cation, which leading to stable structures. But the electrochemical properties didn't have dramatic elevation, and further investigations were expected.
引文
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[2]．胡晓红，嵌锂正极材料的制备及其应用，武汉大学博士学位论文，1998
[3]. Armand M., in materials for advance batteries, D.W. Murphy, Broodhead J. and Steele B.C.H. editors, P145, Plenum press, New York(1980)
[4]. Semkov K.W. and Sammels A.F. Secondary solid-state SPE cells. J.Electrochem. Soc., 1987,134:766
[5]. D.W.Murphy and J.N.Carides, Equilibrium properties of lithium/niobium selenide, nonaqueous secondary cells, J.Electrochem.Soc. 1979, 126:349
[6]. Auborn J.J. and Barberio Y.L., Lithium intercalation cells without metallic lithium MoO_2/LiCoO_2 and WO_2/LiCoO_2. J.Electrochem.Soc.,1987.134:63
[7]．李振垣编《元素化学性质数据手册》，河北人们出版社，1985
[8]. Tsutomu Ohzuku. Lithium Batteries. Chapter 6, Pressed by Elsevier Science BV, the Netherlands, 1994
[9]．雷永泉，万群，石永康，新能源材料，天津大学出版社，2000
[10].Mizushima K, Jones P C, Wiseman P J, et al Li_xCoO_2(0
[12].Mizushima K. et al. Mat. Res. Bull. 1980,15,783
[13].Reimers J.N. et al. J. Electrochem. Soc. 1992,139(8),2091
[14].XIA Xi. Dianchi(Battery Bimonthly), 1998,28(6),251
[15].WU Guo-Liang. et al. Dianchi(Battery Bimonthly), 1998,28(6),258
[16].Gummow. R.J. et al. Mat. Res. Bull. 1992,27,327
[17].Hench. L. L. et al. Chem. Rev.1990,90,33
[18].Liu R M, Yang X H, Wiseman P J, et al Mechanism of Li_(1+x)CoO_2 snthesis and the influence of x values on Performance Proceeding of 12th International Conference on solid State Ionics, 1999(in Press)
[19].Desilvestro J, Haas. O. J.Electrochem. Soc., 1990,137:5C-22C
[20].Arai Hajime, Okada Shegeto, Sakurai Yoji, et al. Solid State
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