Synthesis and performance improvement mechanism of high-efficiency B doped LiNi0.5Co0.2Mn0.3O2 cathode materials for Li-ion batteries

doi:10.11949/0438-1157.20200836

Abstract

Abstract:

High-efficiency doping of strong-bonding energy heteroatoms is an effective strategy to stabilize high-voltage LiNi_0.5Co_0.2Mn_0.3O₂ (NCM) ternary cathode materials and improve their electrochemical performance. Herein, a strategy with boron-containing precursor surface enrichment and diffusion-reinforcement by high-temperature calcination is proposed to construct high-efficiency B-doped LiNi_0.5Co_0.2Mn_0.3O₂ cathode material (NCM-B). The high B—O bond energy (809 kJ·mol^-1) greatly inhibits the evolution of oxygen atoms, hence steadying the oxygen ion framework. Moreover, the LiO₂-B₂O₃ coating layer with high Li⁺ conductivity can stabilize the electrode-electrolyte interface. Compared with pure NCM, the NCM-B exhibits a high reversible capacity of 193.7 mA·h·g^-1 within 3.0—4.5 V and delivers a superior high-rate performance of 120 mA·h·g^-1 at 10 C (only 78.2 mA·h·g^-1 for NCM). Furthermore, the capacity retention after 100 cycles at 1 C can be improved from 73% to 90%. The present surface-enrichment and diffusion-reinforcement strategy is expected to realize high-efficiency doping of other cathode materials.

Key words: LiNi_0.5Co_0.2Mn_0.3O₂, high voltage, B doping, Li-ion batteries

摘要：

高键能异质原子的高效掺杂是稳定高电压LiNi_0.5Co_0.2Mn_0.3O₂（NCM）三元正极材料并提升其电化学性能的有效策略。借助含硼前体在二次颗粒表面富集及随后高温煅烧强化B³⁺体相扩散的策略，构建了硼离子高效掺杂NCM正极材料（NCM-B）。引入B—O键（键能：809 kJ·mol^-1）抑制了电化学反应过程中晶格氧析出，进而稳定材料的氧离子框架；此外，表面残余的高锂离子导体Li₂O-B₂O₃包覆层可以在一定程度上稳定电极-电解液界面。与改性前NCM相比，改性后的NCM-B正极材料在3.0~4.5 V电压区间的可逆比电容量可以达到193.7 mA·h·g^-1，在10 C大功率下，比电容量仍保持120 mA·h·g^-1（NCM仅为78.2 mA·h·g^-1）。1 C下连续循环100圈后，比电容量保持率从73%提升到90%。表面富集和扩散强化的思想也有望实现其他正极材料的高效掺杂。

关键词: LiNi_0.5Co_0.2Mn_0.3O₂, 高电压, 硼掺杂, 锂离子电池

CLC Number:

TM 912.9

ZHU Huawei, YU Haifeng, JIANG Qianqian, YANG Zhaofeng, JIANG Hao, LI Chunzhong. Synthesis and performance improvement mechanism of high-efficiency B doped LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials for Li-ion batteries[J]. CIESC Journal, 2021, 72(1): 609-618.

朱华威, 余海峰, 江仟仟, 杨兆峰, 江浩, 李春忠. 硼高效掺杂LiNi_0.5Co_0.2Mn_0.3O₂正极材料及其性能提升机制[J]. 化工学报, 2021, 72(1): 609-618.

Figures/Tables 7

Fig.1 Schematic illustration for the preparation of NCM-B (a); SEM (b), and TEM [(c)，(d)] images of the NCM; SEM (e) and TEM [(f)，(g)] images of the B-coated NCM; SEM (h) and TEM [(i)，(j)] images of the NCM-B; XPS survey spectra (k), O 1s (l) and B 1s (m) XPS spectra of the NCM-B with different etching depth

Fig.2 XRD Rietveld refinement patterns of the NCM-B (a) and NCM (b); Ni 2p3/2 XPS patterns of the NCM-B (c) and NCM (d)

Table 1 Lattice constants of the NCM-B and NCM calculated from X-ray Rietveld refinement

Sample	a/?	c/?	Volume/?³	c/a	R_wp/%
NCM-B	2.8703	14.2502	101.674	4.9620	14.68
NCM	2.8670	14.2289	101.291	4.9630	12.56

Fig.3 Rate capability (a), cycling stability (b) and the corresponding charge-discharge curves [(c),(d)] of the NCM-B and the NCM for 100 cycles

Fig.4 The calculated dQ/dV profiles [(a),(b)], the initial three CV curves at 0.2 mV·s-1 [(c),(d)] of the NCM-B and the NCM；Linear relationship between the anodic/cathodic peak current (ip) and the square root of the scan rate (v1/2) of the NCM-B and the NCM [(e),(f)], respectively

Fig.5 XRD patterns [(a),(b)] and SEM images [(c),(d)] of the NCM-B and the NCM after 100 cycles at 1 C

Fig.6 XPS spectra of C 1s [(a)，(c)] and O 1s [(b)，(d)] regions for the NCM-B and the NCM after 100 cycles at 1 C

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Synthesis and performance improvement mechanism of high-efficiency B doped LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials for Li-ion batteries

硼高效掺杂LiNi_0.5Co_0.2Mn_0.3O₂正极材料及其性能提升机制

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