Co-Mn比例调控对LiNi0.8Co0.10-y Mn0.05+y Al0.05O2材料性能影响探究

doi:10.11949/0438-1157.20220692

摘要/Abstract

摘要：

采用共沉淀法，以草酸为沉淀剂，过渡金属锰作为钴的替代元素，制备了系列不同钴锰比例的镍钴锰铝锂（LiNi_0.8Co_0.10-_y Mn_0.05+_y Al_0.05O₂，y=0.01，0.02，0.03，0.04）四元材料，研究锰对钴的逐步取代对镍钴锰铝锂四元材料的性能产生的影响。实验结果表明，当y=0.02时的LiNi_0.8Co_0.08Mn_0.07Al_0.05O₂材料具有最好的形貌、结构发育程度以及电化学性能。钴锰共掺杂对合成的LiNi_0.8Co_0.10-_y Mn_0.05+_y Al_0.05O₂材料产生了协同作用，且锰掺杂比例低于钴时可以提升材料电化学容量，当锰掺杂比例超过钴时容量开始下降，说明掺杂比例过多的锰对合成的高镍四元材料的电化学性能提升没有助益。

关键词: 电化学, 锂离子电池, 高镍四元材料, 合成, 纳米材料

Abstract:

A series of LiNi_0.8Co_0.10-_y Mn_0.05+_y Al_0.05O₂ (y=0.01,0.02,0.03,0.04) materials with different cobalt-manganese ratios were prepared by co-precipitation method with oxalic acid as precipitant and transition metal manganese as cobalt replacement element, and the effect of gradual substitution of manganese for cobalt on the properties of Ni-rich quaternary materials was studied. The experimental results show that the LiNi_0.8Co_0.08Mn_0.07Al_0.05O₂ material had the best morphology, structural development and electrochemical performance. The co-doping of cobalt and manganese has a synergistic effect on the synthesized LiNi_0.8Co_0.10-_y Mn_0.05+_y Al_0.05O₂ material, and the electrochemical capacity can be improved when the ratio of manganese doping is lower than that of cobalt. When the doping ratio of manganese exceeds that of cobalt, the capacity begins to decrease, indicating that the excessive doping ratio of manganese is not helpful for the improvement of the electrochemical performance of the synthesized high-nickel quaternary materials.

Key words: electrochemistry, Li-ion battery, high-nickel quaternary materials, synthesis, nanomaterials

中图分类号:

TM 912

杨伟, 王昱杰, 方凯斌, 邹汉波, 陈胜洲, 刘自力. Co-Mn比例调控对LiNi_0.8Co_0.10-_y Mn_0.05+_y Al_0.05O₂材料性能影响探究[J]. 化工学报, 2022, 73(12): 5615-5624.

Wei YANG, Yujie WANG, Kaibin FANG, Hanbo ZOU, Shengzhou CHEN, Zili LIU. Influence of cobalt-manganese ratio adjustment on the properties of LiNi_0.8Co_0.10-_y Mn_0.05+_y Al_0.05O₂ materials[J]. CIESC Journal, 2022, 73(12): 5615-5624.

图/表 8

图1 LiNi0.8Co0.10–y Mn0.05+y Al0.05O2(y=0.01,0.02,0.03,0.04)样品的X射线衍射全谱图(a)， (003)峰区域扩展谱图(b)，(101)、(006)/(012)峰区域扩展谱图(c)和(018)/(110)峰区域扩展谱图(d)

Fig.1 Full XRD patterns (a), expanded views of (003) peaks (b), expanded views of (101), (006)/(012) peaks (c) and expanded views of (018)/(110) peaks (d) of LiNi0.8Co0.10-y Mn0.05+y Al0.05O2 (y=0.01,0.02,0.03,0.04)

表1 LiNi0.8Co0.10–y Mn0.05+y Al0.05O2（y=0.01，0.02，0.03，0.04）样品的晶胞参数

Table 1 Cell parameter of LiNi0.8Co0.10–y Mn0.05+y Al0.05O2 （y=0.01，0.02，0.03，0.04） samples

样品	a/Å	c/Å	c/a	v/Å³	I₍₀₀₃₎/I₍₁₀₄₎
LiNi_0.8Co_0.09Mn_0.06Al_0.05O₂	2.8717	14.1813	4.9383	101.28	1.5408
LiNi_0.8Co_0.08Mn_0.07Al_0.05O₂	2.8748	14.1944	4.9376	101.59	1.5674
LiNi_0.8Co_0.07Mn_0.08Al_0.05O₂	2.8743	14.1844	4.9349	101.49	1.4205
LiNi_0.8Co_0.06Mn_0.09Al_0.05O₂	2.8735	14.1910	4.9385	101.48	1.3298

图2 LiNi0.8Co0.10–y Mn0.05+y Al0.05O2(y=0.01,0.02,0.03,0.04)正极材料的SEM图

Fig.2 SEM images of LiNi0.8Co0.10–y Mn0.05+y Al0.05O2 (y=0.01,0.02,0.03,0.04) cathode materials

表2 LiNi0.8Co0.10-y Mn0.05+y Al0.05O2（y=0.01，0.02，0.03，0.04）正极材料各金属的含量

Table 2 Content of the quaternary metal of as-prepared LiNi0.8Co0.10-y Mn0.05+y Al0.05O2 （y=0.01，0.02，0.03，0.04） samples

样品	含量/% (mol)
样品	Ni(理论含量/实际含量)	Co(理论含量/实际含量)	Mn(理论含量/实际含量)	Al(理论含量/实际含量)
LiNi_0.8Co_0.09Mn_0.06Al_0.05O₂	0.80/0.8028	0.09/0.0851	0.06/0.0572	0.05/0.0549
LiNi_0.8Co_0.08Mn_0.07Al_0.05O₂	0.80/0.8074	0.08/0.0833	0.07/0.0726	0.05/0.0367
LiNi_0.8Co_0.07Mn_0.08Al_0.05O₂	0.80/0.7992	0.07/0.0728	0.08/0.0829	0.05/0.0451
LiNi_0.8Co_0.06Mn_0.09Al_0.05O₂	0.80/0.7927	0.06/0.0624	0.09/0.0909	0.05/0.054

图3 LiNi0.8Co0.10-y Mn0.05+y Al0.05O2（y=0.01，0.02，0.03，0.04）在1C倍率下100圈循环性能（a）和首圈充放电平台（b）； 1C倍率下第4圈和第103圈充放电平台：y=0.01（c），y=0.02（d），y=0.03（e），y=0.04（f）Fig.3 The cycle performance at 1C （a） and the initial charge-discharge curves （b） of LiNi0.8Co0.10-y Mn0.05+y Al0.05O2（y=0.01，0.02，0.03，0.04） cathode materials； the 4th and the 103th charge-discharge curves at 1C： y=0.01（c）， y=0.02（d）， y=0.03（e）， y=0.04（f）

图4 LiNi0.8Co0.10-y Mn0.05+y Al0.05O2(y=0.01,0.02,0.03,0.04)正极材料的倍率性能(a)及对应的倍率放电电压平台曲线： y=0.01(b), y=0.02 (c), y=0.03 (d), y=0.04 (e)

Fig.4 The rate performances of LiNi0.8Co0.10-y Mn0.05+y Al0.05O2 (y=0.01,0.02,0.03,0.04) cathode materials (a) and the corresponding discharge curves： y=0.01 (b), y=0.02 (c), y=0.03 (d), y=0.04 (e)

图5 LiNi0.8Co0.10–y Mn0.05+y Al0.05O2(y=0.01,0.02,0.03,0.04)正极材料在1C倍率下第4圈与第103圈循环的dQ/dV图

Fig.5 dQ/dV plot for the 4th and 103th cycles of LiNi0.8Co0.10–y Mn0.05+y Al0.05O2 (y=0.01,0.02,0.03,0.04) at 1C rate

图6 LiNi0.8Co0.10–y Mn0.05+y Al0.05O2(y=0.01,0.02,0.03,0.04)正极材料在0.1C倍率下首圈循环的Nyquist曲线高频区域图(a)，0.1C倍率下首圈循环的Nyquist曲线(b)，1C倍率下第13圈循环的Nyquist曲线高频区域图(c)，1C倍率下第13圈循环的Nyquist曲线(d)

Fig.6 The high frequency region of the Nyquist plots for the first cycle 0.1C rate (a), Nyquist plots for the first cycle at 0.1C rate (b), the high frequency region of the Nyquist plots for the 13th cycle at 1C rate (c) and Nyquist plots for the 13th cycle at 1C rate (d) of LiNi0.8Co0.10–y Mn0.05+y Al0.05O2 (y=0.01,0.02,0.03,0.04)

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Co-Mn比例调控对LiNi_0.8Co_0.10-_y Mn_0.05+_y Al_0.05O₂材料性能影响探究

Influence of cobalt-manganese ratio adjustment on the properties of LiNi_0.8Co_0.10-_y Mn_0.05+_y Al_0.05O₂ materials

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