Stabilization of the surface and lattice structure for LiNi0.83Co0.12Mn0.05O2via B2O3 atomic layer deposition and post-annealing†

IF 3.2 Q2 CHEMISTRY, PHYSICAL Energy advances Pub Date : 2024-05-22 DOI:10.1039/D4YA00206G
Jiawei Li, Junren Xiang, Ge Yi, Zhijia Hu, Xiao Liu and Rong Chen
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Abstract

The Ni-rich LiNixCoyMn1−xyO2 cathode (x ≥ 0.6) shows weak rate capability due to its deleterious surface lithium impurities and lattice defects. Herein, uniform ultrathin B2O3 coatings built by atomic layer deposition (ALD) are utilized to construct a B3+ doped single-crystal LiNi0.83Co0.12Mn0.05O2 (SC83) via post-annealing. LiOH is consumed due to reacting with B2O3 during the B2O3 ALD process, and then B2O3 is transformed into B3+ doping accompanied by the reduction of Li2CO3 during the post-annealing. Surface and bulk characterization results show that B3+ tends to diffuse into the bulk of the SC83 during the post-annealing, which expands the a and c axes and reduces the Li+/Ni2+ mixing of the SC83. When the B3+ content exceeds 0.54 wt%, B3+ segregation occurs on the surface of the SC83, which decreases the electronic conductivity of the SC83. B3+ doping at the content of 0.54 wt% gives the highest capacity of 177.6 mA h g−1 at 1C rate. The B2O3 ALD coupled with post-annealing builds a highly electronic and Li+ conductive surface and bulk for the SC83, which is the key to the improvement of the rate capability.

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通过 B2O3 原子层沉积和后退火稳定 LiNi0.83Co0.12Mn0.05O2 的表面和晶格结构
富含镍的 LiNixCoyMn1-x-yO2 正极(x ≥ 0.6)因其有害的表面锂杂质和晶格缺陷而显示出较低的速率能力。在这里,利用原子层沉积(ALD)技术形成的均匀超薄 B2O3 涂层,通过后退火构建了掺杂 B3+ 的单晶 LiNi0.83Co0.12Mn0.05O2 (SC83)。在 B2O3 ALD 过程中,LiOH 与 B2O3 反应而被还原,然后在后退火过程中,B2O3 与 Li2CO3 的还原一起转化为 B3+掺杂。表面和块体表征显示,在后退火过程中,B3+趋向于扩散到 SC83 的块体中,从而扩大了 a 轴和 c 轴,降低了 SC83 的 Li+/Ni2+ 混合程度。当 B3+ 含量超过 0.54 wt.‰时,B3+ 会在 SC83 表面发生偏析,从而降低 SC83 的电子电导率。B3+ 掺杂含量为 0.54 重量.‰时,在 1C 速率下的容量最高,为 177.6 mAh/g。B2O3 ALD 与后退火相结合,为 SC83 构建了一个高电子和 Li+ 导电的表面和块体,这是提高速率能力的关键。
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