LiNi1-x-yCoxMnyO2正极材料的制备与电化学性能

朱余银; 李晶

doi:10.11884/HPLPB201931.180352

LiNi_1-x-yCo_xMn_yO₂正极材料的制备与电化学性能

doi: 10.11884/HPLPB201931.180352

朱余银^1,,
李晶^2, ,

1.
西南科技大学环境与资源学院, 四川绵阳 621010
2.
西南科技大学材料科学与工程学院, 四川绵阳 621010

基金项目:

国家高技术发展计划项目 2013AA0509

西南科技大学博士基金项目 18zx712201

西南科技大学学科建设软科学研究项目 18sxb08501

详细信息

作者简介:
朱余银(1977-)，男，博士，讲师，主要从事矿物材料研究; jsjyzyy@126.com

通讯作者:
李晶(1975-)，男，博士，教授，主要从事锂离子电池与超级电容器研究; xy13787103391@126.com

中图分类号: TQ152
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- 被引次数: 0
出版历程
- 收稿日期: 2018-12-24
- 修回日期: 2019-03-11
- 刊出日期: 2019-05-15

Preparation and electrochemical performances of ternary LiNi_1-x-yCo_xMn_yO₂ cathode material

Zhu Yuyin^1
,,
Li Jing^{2
, ,}

1.
School of Environment and Resources, Southwest University of Science and Technology, Mianyang 621010, China
2.
School of Material Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, China

摘要

摘要: LiNi_1-x-yCo_xMn_yO₂正极材料作为最有商业化前途的锂离子电池正极材料，近年来成为研究者关注的焦点。但目前针对该材料合成工艺的研究还较少。对LiNi_0.8Co_0.15Mn_0.05O₂开展了不同的烧结工艺研究，并对制备出的正极材料进行了表征和性能测试。研究发现在0.1C (电池容量额定值)倍率下充放电比容量为200 mA·h·g^-1左右，在1C倍率循环100次下，480 ℃@3 h + 780 ℃@5 h和500 ℃@5 h + 780 ℃@10 h两种烧结工艺下容量保持率分别为94%和86%，说明用这两种工艺制备的正极材料的综合性能最优。
- 三元正极材料 /
- 烧结工艺 /
- 电化学性能 /
- 锂离子电池
Abstract: As the most promising commercial lithium-ion battery, the LiNi_1-x-yCo_xMn_yO₂ cathode have become the focus of researchers in recent years. However, there are less researches on the synthetic process of this material. This paper discusses various sintering processes of LiNi_0.8Co_0.15Mn_0.05O₂, and the characterization and electrochemical performances testing of the prepared cathode materials. The research shows that the material has higher specific capacity (about 200 mA·h·g^-1) at 0.1C (C is battery capacity rating value) charging-discharging rate. At 1C and 100 times of charging-discharging, the capacity retention ratios of 480 ℃@3 h + 780 ℃@5 h and 500 ℃@5 h + 780 ℃@10 h sintering processes are 94% and 86%, respectively, which illustrates the synthetical properties of the cathode materials prepared by these two processes are optimal.
- ternary cathode material /
- sintering process /
- electrochemical performance /
- lithium-ion battery

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图 1 不同烧结工艺下的正极材料SEM图

Figure 1. SEM images of cathode material under different sintering processes

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图 2 不同烧结工艺下正极材料的XRD图谱

Figure 2. XRD spectra of cathode material under different sintering processes

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图 3 不同烧结工艺下正极材料在0.1C下的首次充放电曲线

Figure 3. The first charging and discharging curve at 0.1C of cathode material under different sintering processes

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图 4 不同烧结工艺下正极材料在1C下的循环充放电曲线

Figure 4. The charging-discharging cycles at 1C of cathode material under different sintering processes

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图 5 不同烧结工艺下正极材料的倍率性能曲线

Figure 5. The rate capability curve of cathode material under different sintering processes

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图 6 不同烧结工艺下材料组装电池的EIS曲线

Figure 6. The EIS curve of the battery of cathode material under different sintering processes

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图 7 循环3周/100周后各材料所装电池的循环伏安曲线

Figure 7. cyclic voltammetry curve of the battery loaded by each material after 3 cycles /100 cycles

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表 1 正极材料LiNi_0.8Co_0.15Mn_0.05O₂的烧结工艺

Table 1. Sintering process of cathode material LiNi_0.8Co_0.15Mn_0.05O₂

No	presintering temperature/℃	presintering time/h	calcination temperature/℃	calcination time/h	remarks
1	20→480(120 min)	3	480→780 (60 min)	5	cooling
2	20→480(120 min)	5	480→780(60 min)	10	cooling
3	20→480(120 min)	3	480→800(64 min)	5	cooling
4	20→480(120 min)	5	480→800(64 min)	10	cooling
5	20→500(124 min)	3	500→780(56 min)	5	cooling
6	20→500(124 min)	5	500→780(56 min)	10	cooling
7	20→500(124 min)	3	500→800(60 min)	5	cooling
8	20→500(124 min)	5	500→800(60 min)	10	cooling

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表 2 不同烧结工艺下正极材料的NCM晶格参数

Table 2. NCM lattice parameters of cathode material under different sintering processes

sample	a/nm	c/nm	c/a	I₍₀₀₃₎	I₍₁₀₄₎	R=I₍₀₀₃₎/I₍₁₀₄₎
480 ℃@3 h+780 ℃@5 h	0.250 74	1.409 47	5.621 2	100	54.2	1.845 0
480 ℃@3 h+800 ℃@5 h	0.250 48	1.410 10	5.629 6	100	51.0	1.960 8
500℃@3 h+780 ℃@5 h	0.286 45	1.410 94	4.925 6	100	57.4	1.742 2
500℃@3 h+800 ℃@5 h	0.286 38	1.407 10	4.913 4	100	58.9	1.697 8
480 ℃@5 h+780 ℃@10 h	0.250 39	1.410 24	5.632 2	100	54.9	1.821 5
480 ℃@5 h+800 ℃@10 h	0.250 56	1.409 18	5.624 1	100	63.1	1.584 8
500℃@5 h+780 ℃@10 h	0.286 20	1.407 21	4.916 9	100	47.6	2.100 8
500℃@5 h+800 ℃@10 h	0.286 37	1.411 11	4.927 6	100	57.5	1.739 1

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表 3 不同烧结工艺下正极材料EIS拟合结果

Table 3. EIS fitting results of cathode material under different sintering processes

sample	electrolyte resistivity/Ω	R_SEI/Ω	resistency/Ω	R_ct/Ω
480 ℃@3 h+780 ℃@5 h	135.40	171.70	211.50	366.20
480 ℃@3 h+800 ℃@5 h	153.50	310.60	146.60	44.84
500℃@3 h+780 ℃@5 h	90.93	43.19	100.30	293.60
500℃@3 h+800 ℃@5 h	0.001 253	237.40	218.50	111.10
480 ℃@5 h+780 ℃@10 h	3.933	271.00	86.11	20.65
480 ℃@5 h+800 ℃@10 h	0.544 1	31.76	134.50	460.50
500℃@5 h+780 ℃@10 h	17.00	36.86	360.60	80.89
500℃@5 h+800 ℃@10 h	27.21	312.7	47.51	276.70

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表 4 各材料CV曲线对应的主要氧化还原峰电位及电位差

Table 4. Main REDOX peak potential and PD corresponding to CV curve of each material

sample	oxidation peak potential/V		reduction peak potential/V		potential_{(oxidation peak-reduction peak)}/V
sample	3 cycles	100 cycles	3 cycles	100 cycles	3 cycles	100 cycles
480 ℃@3 h+780 ℃@5 h	3.733	3.767	3.699	3.669	0.034	0.098
480 ℃@3 h+800 ℃@5 h	3.760	3.872	3.682	3.628	0.078	0.244
500℃@3 h+780 ℃@5 h	3.784	3.846	3.670	3.639	0.114	0.207
500℃@3 h+800 ℃@5 h	3.732	3.817	3.667	3.592	0.065	0.225
480 ℃@5 h+780 ℃@10 h	3.776	3.859	3.681	3.653	0.095	0.206
480 ℃@5 h+800 ℃@10 h	3.769	3.828	3.680	3.626	0.089	0.202
500℃@5 h+780 ℃@10 h	3.794	3.859	3.679	3.644	0.115	0.215
500℃@5 h+800 ℃@10 h	3.780	3.823	3.680	3.652	0.100	0.171

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表 5 三元正极材料电化学性能对比表

Table 5. Properties comparison of ternary layered oxide cathode materials

ternary anode material	initial charge-discharge specific capacity at 0.1C magnification/(mA·h·g^-1)	capacity retention ratio after 100 cycles at 1C/%	ref.
LiNi_0.6Co_0.2Mn_0.2O₂	173.0	89.7	[23]
LiNi_0.5Co_0.2Mn_0.3O₂	167.4	89.7	[24]
LiNi_1/3Co_1/3Mn_1/3O₂	152.3	85.8	[25]
LiNi_0.4Co_0.2Mn_0.4O₂	180.7	90.3	[26]
LiNi_1-x-yCo_xAl_yO₂	172.7	92.1	[27]
LiNi_0.8Co_0.15Mn_0.05O₂	200.0	94.0

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