锂离子电池正极材料LiNi_（1/3）Co_（1/3）Mn_（1/3）O_2的合成及性能研究
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摘要
目前商业化的锂离子电池正极材料仍以LiCoO_2为主,由于钴价格逐年上涨以及LiCoO_2材料自身的缺陷,科研工作者一直在努力寻找其替代材料。层状结构材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2具有高比容量、高循环性能、低成本和环保等优点,有望成为新一代锂离子电池正极材料。本文综述了锂离子电池研究进展后,采用共沉淀法合成LiNi_(1/3)Mn_(1/3)Co_(1/3)O_2正极材料,对合成过程中各工艺参数对材料结构和性能的影响进行研究,利用电化学测试手段,结合ICP-OES、XRD和SEM等分析技术,优化了合成工艺,探讨了TiO_2表面包覆改性对材料性能影响。
用数学建模对氢氧化物共沉淀体系Me~(2+) (Me = Ni, Co, Mn)-NH_3-OH--H_2O进行热力学分析的结果表明,共沉淀法合成前驱体Ni_(1/3)Co_(1/3)Mn_(1/3)(OH)_2的最佳pH值为11,最佳氨水浓度为0.1～0.5 mol·L~(-1)。在此基础上研究了共沉淀剂种类、pH值和氨水浓度对前驱体性能的影响,得到前驱体合成的最佳工艺条件:以NaOH + NH_3·H_2O为共沉淀剂,控制pH值为10.5～11,氨水浓度为0.24 mol·L~(-1)。在氢氧化物共沉淀过程中由于Mn(OH)_2易被氧化,通过加入适量水合肼能有效抑制锰的氧化,提高制备过程的可重复操作性及材料的电化学性能,适宜的水合肼量为0.48 mol·L~(-1)。
研究适宜配锂量及最佳焙烧工艺条件对材料结构和性能的影响,即前驱体在500℃下预烧4 h,然后按Li (LiOH·H_2O) / Me (Me= Ni_(1/3)Co_(1/3)Mn_(1/3)) = 1.05 / 1配比充分混合,物料在马弗炉中分两阶段焙烧处理,确定最佳焙烧条件为:先低温500℃下焙烧5 h,然后高温950℃焙烧12 h。上述最佳工艺条件下合成的层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料在2.5～4.6 V电压范围、0.1 C和1 C倍率下的首次充放电比容量分别为193.2 mAh·g~(-1)和174.8 mAh·g~(-1),1 C下30次循环后材料的容量保持率达94.16 %。循环伏安测试表明,LiNi_(1/3)Mn_(1/3)Co_(1/3)O_2材料曲线上存在一对明显的氧化还原峰,对应于Ni~(2+) / Ni~(4+)的氧化还原反应。
为了改善LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2的循环性能,对其进行TiO_2表面包覆改性,研究表明少量包覆不会改变材料层状结构和振实密度。当包覆量为2.0 %时改性效果最好,在2.5～4.6 V电压范围内,1 C倍率下经30次循环后,材料容量保持率达95.74 %。
LiCoO_2 has been widely used as a cathode material in commercial lithium ion battery production at present. Due to the high cost and its own disadvantages of LiCoO_2, many efforts have been made to replace it. Layered structure LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 composite compound has been considered as a promising candidate of new-generation cathode materials for rechargeable lithium ion batteries due to its higher capacity, longer cycle life, lower cost and no harm to environment. The research development of lithium ion battery was summarized in this paper. Based on this, a co-precipitation method was applied to obtain a new type of cathode material LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2, and the synthesis technological condition and parameters were investigated systematically and optimized. And then the electrochemical characteristics, ICP-OES, XRD and SEM of the prepared LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 samples were investigated, and TiO_2 modified LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was prepared and characterized.
Thermodynamic analysis of the Me~(2+) (Me = Ni, Co, Mn) - NH_3 - OH~- - H_2O co-precipitation system was carried out. The thermodynamic analysis results show that the optimal pH value and ammonia concentration range for the precursor synthesis are 10.5～11 and 0.1～0.5 mol·L~(-1), respectively. The effects of several factors such as precipitating agent, pH value and ammonia concentration on precursors were investigated. On this basis, the optimal synthesis technological parameters were obtained, i. e. , NaOH + NH_3·H_2O as precipitating agent, controlling pH value of the solution as 10.5～11, the ammonia concentration as 0.24 mol·L~(-1). Considering of Mn(OH)2 being easily oxydated during the synthesis process, small amount of hydrazine hydrate was added in the precursor co-precipitation process. Hydrazine hydrate can inhibit effectively the oxidation reaction of manganese and the enhance operation reproducibility of preparation process and the electrochemical performance of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 material with the optimal amout 0.48 mol·L~(-1) for hydrazine hydrate.
The effects of different calcination temperature, calcination time and ratio of Li (LiOH·H2O) / Me (Me = Ni_(1/3)Co_(1/3)Mn_(1/3)) on the structure and performance of the synthesized layered cathode material were investigated. On this basis, the optimal synthesis conditions were obtained, i. e., precursor was calcined at 500℃for 4 h, and then LiOH·H2O and precursors were mixed with 1.05 / 1 of Li / Me, the mixed materials were calcined at 500℃for 5 h and then calcined at 950℃for 12 h. Based on the above optimal conditions, the initial discharge capacities are 193.2 mAh·g~(-1) and 174.8 mAh·g~(-1), respectively, with a density of 0.1 C and 1 C at the potential range of 2.5～4.6 V, and the capacity retention maintains 94.16 % after 30 charge discharge cycles at the density of 1C. Cycle voltammetry test shows that one pair of redox peaks was corresponding to the redox process of Ni~(2+) / Ni~(4+) couple.
In order to improve the cycle performance of layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2, surface modification was carried out using TiO_2 as coating agent. The results show that small TiO_2 modification did not change the layered structure and tap density of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2, and the optimal coating amout was 2.0 %. And its capacity retains 95.74 % after cycling 30 times at the density of 1 C in the potential range of 2.5～4.6 V.
用数学建模对氢氧化物共沉淀体系Me~(2+) (Me = Ni, Co, Mn)-NH_3-OH--H_2O进行热力学分析的结果表明,共沉淀法合成前驱体Ni_(1/3)Co_(1/3)Mn_(1/3)(OH)_2的最佳pH值为11,最佳氨水浓度为0.1～0.5 mol·L~(-1)。在此基础上研究了共沉淀剂种类、pH值和氨水浓度对前驱体性能的影响,得到前驱体合成的最佳工艺条件:以NaOH + NH_3·H_2O为共沉淀剂,控制pH值为10.5～11,氨水浓度为0.24 mol·L~(-1)。在氢氧化物共沉淀过程中由于Mn(OH)_2易被氧化,通过加入适量水合肼能有效抑制锰的氧化,提高制备过程的可重复操作性及材料的电化学性能,适宜的水合肼量为0.48 mol·L~(-1)。
研究适宜配锂量及最佳焙烧工艺条件对材料结构和性能的影响,即前驱体在500℃下预烧4 h,然后按Li (LiOH·H_2O) / Me (Me= Ni_(1/3)Co_(1/3)Mn_(1/3)) = 1.05 / 1配比充分混合,物料在马弗炉中分两阶段焙烧处理,确定最佳焙烧条件为:先低温500℃下焙烧5 h,然后高温950℃焙烧12 h。上述最佳工艺条件下合成的层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料在2.5～4.6 V电压范围、0.1 C和1 C倍率下的首次充放电比容量分别为193.2 mAh·g~(-1)和174.8 mAh·g~(-1),1 C下30次循环后材料的容量保持率达94.16 %。循环伏安测试表明,LiNi_(1/3)Mn_(1/3)Co_(1/3)O_2材料曲线上存在一对明显的氧化还原峰,对应于Ni~(2+) / Ni~(4+)的氧化还原反应。
为了改善LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2的循环性能,对其进行TiO_2表面包覆改性,研究表明少量包覆不会改变材料层状结构和振实密度。当包覆量为2.0 %时改性效果最好,在2.5～4.6 V电压范围内,1 C倍率下经30次循环后,材料容量保持率达95.74 %。
LiCoO_2 has been widely used as a cathode material in commercial lithium ion battery production at present. Due to the high cost and its own disadvantages of LiCoO_2, many efforts have been made to replace it. Layered structure LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 composite compound has been considered as a promising candidate of new-generation cathode materials for rechargeable lithium ion batteries due to its higher capacity, longer cycle life, lower cost and no harm to environment. The research development of lithium ion battery was summarized in this paper. Based on this, a co-precipitation method was applied to obtain a new type of cathode material LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2, and the synthesis technological condition and parameters were investigated systematically and optimized. And then the electrochemical characteristics, ICP-OES, XRD and SEM of the prepared LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 samples were investigated, and TiO_2 modified LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 was prepared and characterized.
Thermodynamic analysis of the Me~(2+) (Me = Ni, Co, Mn) - NH_3 - OH~- - H_2O co-precipitation system was carried out. The thermodynamic analysis results show that the optimal pH value and ammonia concentration range for the precursor synthesis are 10.5～11 and 0.1～0.5 mol·L~(-1), respectively. The effects of several factors such as precipitating agent, pH value and ammonia concentration on precursors were investigated. On this basis, the optimal synthesis technological parameters were obtained, i. e. , NaOH + NH_3·H_2O as precipitating agent, controlling pH value of the solution as 10.5～11, the ammonia concentration as 0.24 mol·L~(-1). Considering of Mn(OH)2 being easily oxydated during the synthesis process, small amount of hydrazine hydrate was added in the precursor co-precipitation process. Hydrazine hydrate can inhibit effectively the oxidation reaction of manganese and the enhance operation reproducibility of preparation process and the electrochemical performance of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 material with the optimal amout 0.48 mol·L~(-1) for hydrazine hydrate.
The effects of different calcination temperature, calcination time and ratio of Li (LiOH·H2O) / Me (Me = Ni_(1/3)Co_(1/3)Mn_(1/3)) on the structure and performance of the synthesized layered cathode material were investigated. On this basis, the optimal synthesis conditions were obtained, i. e., precursor was calcined at 500℃for 4 h, and then LiOH·H2O and precursors were mixed with 1.05 / 1 of Li / Me, the mixed materials were calcined at 500℃for 5 h and then calcined at 950℃for 12 h. Based on the above optimal conditions, the initial discharge capacities are 193.2 mAh·g~(-1) and 174.8 mAh·g~(-1), respectively, with a density of 0.1 C and 1 C at the potential range of 2.5～4.6 V, and the capacity retention maintains 94.16 % after 30 charge discharge cycles at the density of 1C. Cycle voltammetry test shows that one pair of redox peaks was corresponding to the redox process of Ni~(2+) / Ni~(4+) couple.
In order to improve the cycle performance of layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2, surface modification was carried out using TiO_2 as coating agent. The results show that small TiO_2 modification did not change the layered structure and tap density of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2, and the optimal coating amout was 2.0 %. And its capacity retains 95.74 % after cycling 30 times at the density of 1 C in the potential range of 2.5～4.6 V.
引文
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