硼摻雜鎳酸鋰的改性研究

張寧; 厲英; 倪培遠

doi:10.13374/j.issn2095-9389.2020.11.30.004

硼摻雜鎳酸鋰的改性研究

doi: 10.13374/j.issn2095-9389.2020.11.30.004

張寧^{1, 2},
厲英^{1, 2, ,},
倪培遠^{1, 2}

1.
東北大學冶金學院，沈陽 110819
2.
遼寧省冶金傳感器及技術重點實驗室，沈陽 110819

基金項目: 國家自然科學基金資助項目（51834004，51774076，51704062）

詳細信息

通訊作者:
E-mail：liying@mail.neu.edu.cn

中圖分類號: TM912.9
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- 文章訪問數: 1701
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- 被引次數: 0
出版歷程
- 收稿日期: 2020-11-30
- 網絡出版日期: 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: 采用共沉淀法制備了Ni(OH)₂前驅體材料，通過高溫固相法制備了LiNiO₂和B摻雜LiNiO₂（B的摩爾分數為1%），利用X射線衍射（XRD）、里特維爾德（Rietveld）精修、掃描電子顯微鏡（SEM）、恒流充放電測試、循環伏安（CV）和電化學阻抗譜（EIS）對材料的晶體結構、表面形貌和電化學性能進行了系統性表征。XRD和Rietveld精修結果表明，LiNiO₂和B摻雜LiNiO₂均具有良好的層狀結構，B因為占據在過渡金屬層和鋰層的四面體間隙位而導致摻雜后略微增大材料的晶格參數和晶胞體積，同時增大了LiO₆八面體的間距，進而促進鋰離子運輸。由于摻雜的B的摩爾分數僅為1%，LiNiO₂和B摻雜LiNiO₂均表現為直徑10 μm左右的多晶二次顆粒，且一次顆粒晶粒尺寸沒有明顯區別。長循環數據表明B摻雜可以有效提高材料的循環容量保持率，經100次循環后，B摻雜樣品在40 mA·g^?1 電流下的容量保持率為77.5%，優于未摻雜樣品（相同條件下容量保持率為66.6%）。微分容量曲線和EIS分析表明B摻雜可以有效抑制循環過程中的阻抗增長。
- 硼 /
- 摻雜 /
- 鎳酸鋰 /
- 正極材料 /
- 鋰離子電池
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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圖 1 LiNiO₂和B摻雜LiNiO₂的XRD圖譜和精修圖譜

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

下載: 全尺寸圖片幻燈片

圖 2 掃描電鏡照片。（a）LiNiO₂；（b）B摻雜LiNiO₂

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

下載: 全尺寸圖片幻燈片

圖 3 LiNiO₂和B摻雜LiNiO₂的（a）比容量曲線，（b）微分容量曲線，（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

下載: 全尺寸圖片幻燈片

圖 4 LiNiO₂和B摻雜LiNiO₂的在30 ℃，3.0～4.3 V的循環壽命曲線

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

下載: 全尺寸圖片幻燈片

圖 5 （a）LiNiO₂，（b）B摻雜LiNiO₂在第2、第54，和第106次循環的微分容量曲線變化；（c）LiNiO₂和B摻雜LiNiO₂在第106次循環的微分容量曲線的對比圖；（d）循環前后EIS圖譜

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

下載: 全尺寸圖片幻燈片

表 1 用Rietica得到的晶格參數信息

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

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表 2 用ZView擬合得到的循環前后的阻抗值

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

下載: 導出CSV

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