层状LiNi_（0.8）Co_（0.2）O_2正极材料掺杂研究
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摘要
目前,已大规模商业化的层状锂离子电池正极材料有LiCoO_2,但因为钴价格昂贵和毒性等问题,研究者一直致力于寻找其他替代材料。钴和镍的各种性质非常相近,能以任意比例形成固溶体,同时LiNi_(1-y)Co_yO_2体系兼有钴酸锂和镍酸锂两者的优点而受到了人们的广泛研究。在LiNi_(1-y)Co_yO_2体系中,LiNi_(0.8)Co_(0.2)O_2的前景被看好。
通过对共沉淀法制备前驱体、前驱体预处理和高温固相反应过程各种影响因素进行分析和优化,确定了合成LiNi_(0.8)Co_(0.2)O_2正极材料的较优的工艺条件:以镍钴混合液为原液、碳酸氢钠为沉淀剂、氨水为络合剂调节溶液pH值8附近制备前躯体,锂盐过量5%、750℃烧结15小时,在空气气氛中较成功地合成了具有较好层状结构和电化学性能的LiNi_(0.8)Co_(0.2)O_2正极材料。在2.7-4.3V范围,以0.1C放电,首次放电容量达179.2mAh·g~(-1)。循环10次后容量变为167 mAh·g~(-1),容量保持率为93.2 %。以0.2C充电、0.5C放电,第一次循环后容量为159.7 mAh·g~(-1),循环30次后容量衰减到112.3 mAh·g~(-1),容量保持率为70.3%。
本文对LiNi_(0.8)Co_(0.2)O_2进行了掺杂改性研究,探讨了Fe、Al、Mg等掺杂离子的影响。得到了Li(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)O_2,Li[(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)]_(1-x)Fe_xO_2(x=0.02, 0.05, 0.1, 0.2),Li[(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)]_(1-x)Mg_xO_2(x=0.02, 0.05)正极材料中以Li(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)O_2正极材料的性能最好,以0.1C充放电,Li(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)O_2的比容量达到155.7 mAh·g~(-1),前10次循环容量保持率达到98.3%。以0.2C充电、0.5C放电时。在前30次循环中,Li(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)O_2的比容量从142.8 mAh·g~(-1)下降到131.8 mAh·g~(-1),容量保持率达到92.3%。而Fe、Mg掺杂均导致材料性能变差。
LiCoO_2 has been widely used as a cathode material in commercial lithium ion battery layed .But due to the high cost and toxicity of Co , many efforts have been made to replace it. In practice, it is regularly argued that LiNi_(0.8)Co_(0.2)O_2 is a promising cathode materials to replace LiCoO_2, because it possess the merit of LiCoO_2 and LiNiO_2.
The reaction conditions in co-precipitation process, pretreatment process and calcination process were analyzed and optimized. The precussor was prepared by control the pH value about 8、the ammonia concentration. Layered LiNo_(0.8)Co_(0.2)O_2 was synthesized with 5 % excess lithium under 750℃for 15h in atmosphere. The results of LiNo_(0.8)Co_(0.2)O_2 indicated that the LiNo_(0.8)Co_(0.2)O_2 delivered 179.2 mAh·g~(-1)at the rate of 0.1C during the voltage range of 2.7-4.3V.The capacity retention rateswas 93.2% after 10 cycles. The material shows an initial discharge capacity of 159.7 mAh·g~(-1)at the rate of 0.2C charge and 0.5C discharge during the voltage range of 2.7-4.3V. The capacity retention rates were 70.3% after 30 cycles.
Doped LiNi_(0.8)Co_(0.2)O_2 were studied. The effect of Fe、Mg、Al on the performance of LiNi_(0.8)Co_(0.2)O_2 were explored. in Li (Ni_(0.8)Co_(0.2)) _(0.95)Al_(0.05)O_2、Li[(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)]_(1-x)Fe_xO_2(x=0.02, 0.05, 0.1, 0.2)、Li[(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)]_(1-x)Mg_xO_2(x=0.02, 0.05). The performance of Li (Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)O_2 was the best. The prepared Li (Ni_(0.8)Co_(0.2)) _(0.95)Al_(0.05)O_2 delivered the intial capacity of 155.7 mAh·g~(-1) at 0.1C. The capacity retention rate was 98.3% after 10 cycles at the rate of 0.1C. it delivered the intial capacity of 142.8 mAh·g~(-1) at the rate of 0.2C charge and 0.5C discharge during the voltage range of 2.7-4.3V. The capacity retention rate was 92.3% after 30 cycles.The doping of Fe and Mg deteriorates the performance of Li (Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)O_2.
通过对共沉淀法制备前驱体、前驱体预处理和高温固相反应过程各种影响因素进行分析和优化,确定了合成LiNi_(0.8)Co_(0.2)O_2正极材料的较优的工艺条件:以镍钴混合液为原液、碳酸氢钠为沉淀剂、氨水为络合剂调节溶液pH值8附近制备前躯体,锂盐过量5%、750℃烧结15小时,在空气气氛中较成功地合成了具有较好层状结构和电化学性能的LiNi_(0.8)Co_(0.2)O_2正极材料。在2.7-4.3V范围,以0.1C放电,首次放电容量达179.2mAh·g~(-1)。循环10次后容量变为167 mAh·g~(-1),容量保持率为93.2 %。以0.2C充电、0.5C放电,第一次循环后容量为159.7 mAh·g~(-1),循环30次后容量衰减到112.3 mAh·g~(-1),容量保持率为70.3%。
本文对LiNi_(0.8)Co_(0.2)O_2进行了掺杂改性研究,探讨了Fe、Al、Mg等掺杂离子的影响。得到了Li(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)O_2,Li[(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)]_(1-x)Fe_xO_2(x=0.02, 0.05, 0.1, 0.2),Li[(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)]_(1-x)Mg_xO_2(x=0.02, 0.05)正极材料中以Li(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)O_2正极材料的性能最好,以0.1C充放电,Li(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)O_2的比容量达到155.7 mAh·g~(-1),前10次循环容量保持率达到98.3%。以0.2C充电、0.5C放电时。在前30次循环中,Li(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)O_2的比容量从142.8 mAh·g~(-1)下降到131.8 mAh·g~(-1),容量保持率达到92.3%。而Fe、Mg掺杂均导致材料性能变差。
LiCoO_2 has been widely used as a cathode material in commercial lithium ion battery layed .But due to the high cost and toxicity of Co , many efforts have been made to replace it. In practice, it is regularly argued that LiNi_(0.8)Co_(0.2)O_2 is a promising cathode materials to replace LiCoO_2, because it possess the merit of LiCoO_2 and LiNiO_2.
The reaction conditions in co-precipitation process, pretreatment process and calcination process were analyzed and optimized. The precussor was prepared by control the pH value about 8、the ammonia concentration. Layered LiNo_(0.8)Co_(0.2)O_2 was synthesized with 5 % excess lithium under 750℃for 15h in atmosphere. The results of LiNo_(0.8)Co_(0.2)O_2 indicated that the LiNo_(0.8)Co_(0.2)O_2 delivered 179.2 mAh·g~(-1)at the rate of 0.1C during the voltage range of 2.7-4.3V.The capacity retention rateswas 93.2% after 10 cycles. The material shows an initial discharge capacity of 159.7 mAh·g~(-1)at the rate of 0.2C charge and 0.5C discharge during the voltage range of 2.7-4.3V. The capacity retention rates were 70.3% after 30 cycles.
Doped LiNi_(0.8)Co_(0.2)O_2 were studied. The effect of Fe、Mg、Al on the performance of LiNi_(0.8)Co_(0.2)O_2 were explored. in Li (Ni_(0.8)Co_(0.2)) _(0.95)Al_(0.05)O_2、Li[(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)]_(1-x)Fe_xO_2(x=0.02, 0.05, 0.1, 0.2)、Li[(Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)]_(1-x)Mg_xO_2(x=0.02, 0.05). The performance of Li (Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)O_2 was the best. The prepared Li (Ni_(0.8)Co_(0.2)) _(0.95)Al_(0.05)O_2 delivered the intial capacity of 155.7 mAh·g~(-1) at 0.1C. The capacity retention rate was 98.3% after 10 cycles at the rate of 0.1C. it delivered the intial capacity of 142.8 mAh·g~(-1) at the rate of 0.2C charge and 0.5C discharge during the voltage range of 2.7-4.3V. The capacity retention rate was 92.3% after 30 cycles.The doping of Fe and Mg deteriorates the performance of Li (Ni_(0.8)Co_(0.2))_(0.95)Al_(0.05)O_2.
引文
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