硼掺杂镍酸锂的改性研究

张宁; 厉英; 倪培远

doi:10.13374/j.issn2095-9389.2020.11.30.004

硼掺杂镍酸锂的改性研究

doi: 10.13374/j.issn2095-9389.2020.11.30.004

张宁^{1, 2},
厉英^{1, 2, ,},
倪培远^{1, 2}

1.
东北大学冶金学院，沈阳 110819
2.
辽宁省冶金传感器及技术重点实验室，沈阳 110819

基金项目: 国家自然科学基金资助项目（51834004，51774076，51704062）

详细信息

通讯作者:
E-mail：liying@mail.neu.edu.cn

中图分类号: TM912.9
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- 被引次数: 0
出版历程
- 收稿日期: 2020-11-30
- 网络出版日期: 2021-03-05
- 刊出日期: 2021-08-25

Enhanced electrochemical performance of LiNiO₂ by B doping

ZHANG Ning^{1, 2},
LI Ying^{1, 2
, ,},
NI Pei-yuan^{1, 2}

1.
School of Metallurgy, Northeastern University, Shenyang 110819, China
2.
Liaoning Key Laboratory for Metallurgical Sensor and Technology, Shenyang 110819, China

More Information

Corresponding author: E-mail: liying@mail.neu.edu.cn

摘要

摘要: 采用共沉淀法制备了Ni(OH)₂前驱体材料，通过高温固相法制备了LiNiO₂和B掺杂LiNiO₂（B的摩尔分数为1%），利用X射线衍射（XRD）、里特维尔德（Rietveld）精修、扫描电子显微镜（SEM）、恒流充放电测试、循环伏安（CV）和电化学阻抗谱（EIS）对材料的晶体结构、表面形貌和电化学性能进行了系统性表征。XRD和Rietveld精修结果表明，LiNiO₂和B掺杂LiNiO₂均具有良好的层状结构，B因为占据在过渡金属层和锂层的四面体间隙位而导致掺杂后略微增大材料的晶格参数和晶胞体积，同时增大了LiO₆八面体的间距，进而促进锂离子运输。由于掺杂的B的摩尔分数仅为1%，LiNiO₂和B掺杂LiNiO₂均表现为直径10 µm左右的多晶二次颗粒，且一次颗粒晶粒尺寸没有明显区别。长循环数据表明B掺杂可以有效提高材料的循环容量保持率，经100次循环后，B掺杂样品在40 mA·g⁻¹ 电流下的容量保持率为77.5%，优于未掺杂样品（相同条件下容量保持率为66.6%）。微分容量曲线和EIS分析表明B掺杂可以有效抑制循环过程中的阻抗增长。
- 硼 /
- 掺杂 /
- 镍酸锂 /
- 正极材料 /
- 锂离子电池
Abstract: The application markets for portable electronics, battery-operated electric vehicles, and large-scale energy-storage grids have been expanding rapidly for the past ten years, which has attracted massive attention to the investigation and development of batteries with high energy density, long cycle life, high safety, and low cost. A commonly used lithium-ion battery consists of intercalation-type materials, such as LiCoO₂ as cathode and graphite as an anode. Owing to technical difficulties, including high cost, low stability, and the poor safety of Li, the large-scale application of the high-energy Li anode is still premature. A more common strategy than the one mentioned above for improving the energy density of Li-ion batteries is to develop a cathode material with high specific capacity and low cost, such as LiNi_1–x–yCo_xMn_yO₂ (NCM) and LiNi_1–x–yCo_xAl_yO₂ (NCA). Among the NCMs and NCAs, Co is more expensive and less abundant than Ni, Mn, and Al. Presently, high-nickel, low-cobalt NCMs, and NCAs have attracted huge attention as suitable cathodes for both academic and industrial purposes. LNiO₂ can be regarded as the Ni content increasing to 100% for NMCs and NCAs, which stood as the “holy grail” of layered cathodes. This study aims to investigate the structural and electrochemical stability of LiNiO₂ and B-doped LiNiO₂. In this study, Ni(OH)₂ was synthesized by a coprecipitation method using a continuous stirred tank reactor (CSTR). LiNiO₂ and B-doped LiNiO₂ were synthesized by high-temperature solid-state sintering. The crystal structure, surface morphology, and electrochemical performance were investigated by X-ray diffraction (XRD), Rietveld refinement, scanning electron microscopy (SEM), constant current charge–discharge, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). XRD and Rietveld refinement results indicate that B-doping could slightly increase the lattice parameters and unit cell volume due to the occupancy of B in the tetrahedral site. Meanwhile, the LiO₆ slab distance increases, consequently favoring the transportation of Li⁺ during (de)-intercalation. SEM images suggest that LiNiO₂ and B-doped LiNiO₂ consist of primary grains with a similar size, and the secondary particle in both samples has an average size of 10 µm. Long-term cycling data show that B-doping could improve capacity retention. The capacity retention at 40 mA·g⁻¹ is 77.5% for the B-doped sample, whereas a value of 66.6% is obtained for LiNiO₂. The dQ/dV vs V curves and EIS results suggest the suppression of impedance growth by B-doping.
- boron /
- doping /
- LiNiO₂ /
- positive electrode material /
- lithium-ion batteries

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图 1 LiNiO₂和B掺杂LiNiO₂的XRD图谱和精修图谱

Figure 1. X-ray diffraction patterns and fitting results of LiNiO₂ and B-doped LiNiO₂

下载: 全尺寸图片幻灯片

图 2 扫描电镜照片。（a）LiNiO₂；（b）B掺杂LiNiO₂

Figure 2. SEM images of: (a) LiNiO₂; (b) B doped LiNiO₂

下载: 全尺寸图片幻灯片

图 3 LiNiO₂和B掺杂LiNiO₂的（a）比容量曲线，（b）微分容量曲线，（c）首圈CV，（d）第2圈CV

Figure 3. (a) Voltage vs specific capacity, (b) differential capacity vs cell voltage, (c) CV for the 1^st cycle, and (d) CV for the 2^nd cycles of LiNiO₂ and B-doped LiNiO₂

下载: 全尺寸图片幻灯片

图 4 LiNiO₂和B掺杂LiNiO₂的在30 ℃，3.0～4.3 V的循环寿命曲线

Figure 4. Cycle life of LiNiO₂ and B-doped LiNiO₂ at 30 ℃ at voltage at 3.0–4.3 V

下载: 全尺寸图片幻灯片

图 5 （a）LiNiO₂，（b）B掺杂LiNiO₂在第2、第54，和第106次循环的微分容量曲线变化；（c）LiNiO₂和B掺杂LiNiO₂在第106次循环的微分容量曲线的对比图；（d）循环前后EIS图谱

Figure 5. Differential capacity vs cell voltage of (a) LiNiO₂ and (b) B-doped LiNiO₂ at the 2^nd, 54^th, and 106^th cycles; (c) comparison of differential capacity vs cell voltage at the 106^th cycle; (d) electrochemical impedance spectroscopy before and after the cycling of LiNiO₂ and B-doped LiNiO₂

下载: 全尺寸图片幻灯片

表 1 用Rietica得到的晶格参数信息

Table 1. Lattice parameters and fitting results using Rietica

Sample	a/nm	c/nm	Unit cell volume/nm³	Ni in Li layer/%	LiO₆ slab/nm	NiO₆ slab/nm	I₀₀₃/I₁₀₄	Bragg-factor
LiNiO₂	0.28769	1.41991	0.101773	2.0	0.2567	0.2166	1.15	2.07
B-doped LiNiO₂	0.28773	1.42000	0.101809	2.6	0.2581	0.2153	1.12	1.96

下载: 导出CSV

表 2 用ZView拟合得到的循环前后的阻抗值

Table 2. Electrochemical impedance spectroscopy fitting results using ZView (Ω·cm²)

Condition	Sample	R_s	R_c	R_ct
Before cycles	LiNiO₂	3.7	10.9	20.1
Before cycles	B doped LiNiO₂	4.1	14.4	24.2
After cycles	LiNiO₂	11.6	125.1	378.5
After cycles	B doped LiNiO₂	10.4	116.0	235.2

下载: 导出CSV

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