层状LiNi_（1/3）Co_（1/3）Mn_（1/3）O_2锂离子电池正极材料的制备及其表征
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摘要
层状Li(Ni_((1-x)/2)Co_xMn_((1-x)/2))O_2材料被认为是最有可能替代LiCoO_2的正极材料。本论文以x=1/3的层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2为研究目标,采用溶胶凝胶法和湿法球磨两种工艺合成了性能优良的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2电极材料;运用XRD、SEM、恒电流充/放电等技术对该材料的组织结构和电化学性能进行了系统研究。
采用溶胶凝胶法制备了单一、均匀的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2固溶体材料。该材料晶体结构层状特征好,充放电容量较高,循环性能优良。用柠檬酸作为螯合剂,通过不同柠檬酸量制备样品的结构与性能比较研究表明,柠檬酸与金属离子比为0.8时,合成材料性能较优。不同烧结工艺制得的LiNi_(1/3_Co_(1/3)Mn_(1/3)O_2固溶体材料的结构与性能研究表明:随烧结温度提高,时间延长,所得产物的结晶越完整,层状结构越明显,同时晶粒长大。950℃烧结8h热处理工艺合成LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料的电化学性能最好,在2.75-4.3V之间以0.1C充放电,首次充放电比容量为191.3/163.8 mAh·g~(-1),效率为85.6%,循环性能良好。不同锂源合成的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的结构和电化学性能表明,以氢氧化锂作为锂源,同时加入氨水合成的材料,电化学容量较高,循环性能稳定,但是振实密度较低。
以柠檬酸为分散剂和燃料,六水合硝酸盐、电解二氧化锰为原料,采用球磨活化获得混合均匀、反应活性高的前驱体,高温合成工艺制备了锂离子二次电池用的具有层状结构的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料。该材料为单相的层状嵌锂氧化物,具有α-NaFeO_2结构,属六方晶系,空间群为R(?)m;材料为团聚态颗粒,一次粒子细小,呈多边形,尺寸约200-300nm,结晶化程度高。通过计算反应方程的化学计量系数φ_e,初步确定柠檬酸与金属离子比值范围;对不同柠檬酸与金属离子比值下合成LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料进行比较研究,确定比值为0.7时,合成材料性能较好。对前驱体的预烧处理工艺进行研究,确定了低温分步烧结的工艺。参考溶胶凝胶法合成工艺的热处理优化参数,采用950℃烧结10h高温热处理工艺合成的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料,在2.75-4.3V电压区间,以0.1C恒电流充放电,首次充/放电容量为184.3/156.7 mAh·g~(-1),充/放电效率为85.0%。0.5C倍率下充放电,材料首次放电容量为151.3mAh·g~(-1),经过30次循环后容量保持在150.8mAh·g~(-1)左右,循环性能优异。比较研究了碳酸锂、氢氧化锂、硝酸锂为锂盐原料,制备的层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的结构性能表明:硝酸锂为锂盐原料所制备的材料结构性能较好。
Recently,Layered Li[Ni_((1-x)/2)Co_xMn_((1-x)/2)]O_2 is considered to be one of the best candidates to replace LiCoO_2.In this paper,Layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was selected to be the object of our research and Layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was synthesized by the sol-gel method and ball-milling activation route.The studies of XRD,SEM,charge-discharge at constant current were introduced to characterize the structure, micro-morphology and electrochemical properties of the as-prepared materials.
The lithium nickel cobalt manganese oxide LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was synthesized using citric acid as a chelating agent by a sol-gel method.It has good crystal structure,high theoretical capacity,well cycle performance.The effect of varying the acid to metal ion ratio R on the structural and electrochemical properties of the synthesized compound were studied.An acid to metal ion ratio R=0.8 got the best result.The effect of varying high temperature synthesizing conditions on the structural and electrochemical properties of the synthesized compound was studied.With Raising synthesizing temperature and prolonging sintering period appropriately,it could improve the crystallinity and the layered structure of the as-prepared materials.However,it also might result in the increase of particle size.The electrochemical test in 2.75-4.3V delivered the initial charge and discharge specific capacity of 191.3 and 163.8 mAh·g~(-1) at a 0.1C rate,respectively,with the initial charge/discharge efficiency of 85.6%,and good cycling stability for layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 prepared in the optimized condition of acid to metal ion ratio R=0.8,and sintering for 8h at 950℃.LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was prepared using different lithium raw materials.The results showed that LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was prepared using lithium hydroxide as lithium raw materials with ammonia controlling the PH,which has high theoretical capacity,good cycle performance,but low tap density.
The layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode materials with hexagonal structure were successfully synthesized by ball-milling activation followed with combustion method and high temperature sintering in air. The sample has a phase-pure hexagonalα-NaFeO_2 structure with a space group of R(?)m,and uniform particle size of 200-300nm.With ball-milling activation,uniform precursor with high reacting activity was obtained. The elemental stoichiometric coefficientφ_e of the specific formulas was calculated to ascertain the range of the acid to metal ion ratio K.The effect of varying the acid to metal ion ratio R on the structural and electrochemical properties of the synthesized compound were studied.An acid to metal ion ratio K=0.7 got the best result.The pretreatment temperature process was investigated.The electrochemical test in 2.75-4.3V delivered the initial charge and discharge specific capacity of 184.3 and 156.7 mAh·g~(-1) at a 0.1C rate,respectively,with the initial charge/discharge efficiency of 85.0%,and the discapacity of 150.8mAh·g~(-1) on the 30~(th) cycle at a 0.5C rate for layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 prepared in the condition of sintering for 10h at 950℃.LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was prepared using lithium carbonate、lithium hydroxide、lithium nitrate as raw materials respectively.The results showed that LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 that prepared using lithium nitrate as lithium raw materials has good structural and electrochemical properties.
采用溶胶凝胶法制备了单一、均匀的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2固溶体材料。该材料晶体结构层状特征好,充放电容量较高,循环性能优良。用柠檬酸作为螯合剂,通过不同柠檬酸量制备样品的结构与性能比较研究表明,柠檬酸与金属离子比为0.8时,合成材料性能较优。不同烧结工艺制得的LiNi_(1/3_Co_(1/3)Mn_(1/3)O_2固溶体材料的结构与性能研究表明:随烧结温度提高,时间延长,所得产物的结晶越完整,层状结构越明显,同时晶粒长大。950℃烧结8h热处理工艺合成LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料的电化学性能最好,在2.75-4.3V之间以0.1C充放电,首次充放电比容量为191.3/163.8 mAh·g~(-1),效率为85.6%,循环性能良好。不同锂源合成的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的结构和电化学性能表明,以氢氧化锂作为锂源,同时加入氨水合成的材料,电化学容量较高,循环性能稳定,但是振实密度较低。
以柠檬酸为分散剂和燃料,六水合硝酸盐、电解二氧化锰为原料,采用球磨活化获得混合均匀、反应活性高的前驱体,高温合成工艺制备了锂离子二次电池用的具有层状结构的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料。该材料为单相的层状嵌锂氧化物,具有α-NaFeO_2结构,属六方晶系,空间群为R(?)m;材料为团聚态颗粒,一次粒子细小,呈多边形,尺寸约200-300nm,结晶化程度高。通过计算反应方程的化学计量系数φ_e,初步确定柠檬酸与金属离子比值范围;对不同柠檬酸与金属离子比值下合成LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料进行比较研究,确定比值为0.7时,合成材料性能较好。对前驱体的预烧处理工艺进行研究,确定了低温分步烧结的工艺。参考溶胶凝胶法合成工艺的热处理优化参数,采用950℃烧结10h高温热处理工艺合成的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料,在2.75-4.3V电压区间,以0.1C恒电流充放电,首次充/放电容量为184.3/156.7 mAh·g~(-1),充/放电效率为85.0%。0.5C倍率下充放电,材料首次放电容量为151.3mAh·g~(-1),经过30次循环后容量保持在150.8mAh·g~(-1)左右,循环性能优异。比较研究了碳酸锂、氢氧化锂、硝酸锂为锂盐原料,制备的层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2正极材料的结构性能表明:硝酸锂为锂盐原料所制备的材料结构性能较好。
Recently,Layered Li[Ni_((1-x)/2)Co_xMn_((1-x)/2)]O_2 is considered to be one of the best candidates to replace LiCoO_2.In this paper,Layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was selected to be the object of our research and Layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was synthesized by the sol-gel method and ball-milling activation route.The studies of XRD,SEM,charge-discharge at constant current were introduced to characterize the structure, micro-morphology and electrochemical properties of the as-prepared materials.
The lithium nickel cobalt manganese oxide LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was synthesized using citric acid as a chelating agent by a sol-gel method.It has good crystal structure,high theoretical capacity,well cycle performance.The effect of varying the acid to metal ion ratio R on the structural and electrochemical properties of the synthesized compound were studied.An acid to metal ion ratio R=0.8 got the best result.The effect of varying high temperature synthesizing conditions on the structural and electrochemical properties of the synthesized compound was studied.With Raising synthesizing temperature and prolonging sintering period appropriately,it could improve the crystallinity and the layered structure of the as-prepared materials.However,it also might result in the increase of particle size.The electrochemical test in 2.75-4.3V delivered the initial charge and discharge specific capacity of 191.3 and 163.8 mAh·g~(-1) at a 0.1C rate,respectively,with the initial charge/discharge efficiency of 85.6%,and good cycling stability for layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 prepared in the optimized condition of acid to metal ion ratio R=0.8,and sintering for 8h at 950℃.LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was prepared using different lithium raw materials.The results showed that LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was prepared using lithium hydroxide as lithium raw materials with ammonia controlling the PH,which has high theoretical capacity,good cycle performance,but low tap density.
The layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode materials with hexagonal structure were successfully synthesized by ball-milling activation followed with combustion method and high temperature sintering in air. The sample has a phase-pure hexagonalα-NaFeO_2 structure with a space group of R(?)m,and uniform particle size of 200-300nm.With ball-milling activation,uniform precursor with high reacting activity was obtained. The elemental stoichiometric coefficientφ_e of the specific formulas was calculated to ascertain the range of the acid to metal ion ratio K.The effect of varying the acid to metal ion ratio R on the structural and electrochemical properties of the synthesized compound were studied.An acid to metal ion ratio K=0.7 got the best result.The pretreatment temperature process was investigated.The electrochemical test in 2.75-4.3V delivered the initial charge and discharge specific capacity of 184.3 and 156.7 mAh·g~(-1) at a 0.1C rate,respectively,with the initial charge/discharge efficiency of 85.0%,and the discapacity of 150.8mAh·g~(-1) on the 30~(th) cycle at a 0.5C rate for layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 prepared in the condition of sintering for 10h at 950℃.LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was prepared using lithium carbonate、lithium hydroxide、lithium nitrate as raw materials respectively.The results showed that LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 that prepared using lithium nitrate as lithium raw materials has good structural and electrochemical properties.
引文
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