Photonic Synthesis and Coating of High‐Entropy Oxide on Layered Ni‐Rich Cathode Particles

Yanyan Cui, Yushu Tang, Jing Lin, Junbo Wang, Horst Hahn, B. Breitung, Simon Schweidler, T. Brezesinski, M. Botros
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Abstract

High‐entropy materials have drawn much attention as battery materials due to their distinctive properties. Lithiated high‐entropy oxide (Li0.33(MgCoNiCuZn)0.67O, LiHEO) exhibits both high lithium‐ion and electronic conductivity, making it a potential coating material for layered Ni‐rich oxide cathodes (Li1+x(Ni1−y−zCoyMnz)1−xO2, NCM or NMC) in conventional Li‐ion battery cells; however, high‐temperature synthesis limits its application. Therefore, a photonic curing strategy is used for synthesizing LiHEO and the non‐lithiated form (denoted as high‐entropy oxide [HEO]), and nanoscale coatings are successfully produced on LiNi0.85Co0.1Mn0.05O2 (NCM851005) particles. To one's knowledge, this is the first report on particle coating with high‐entropy materials using photonic curing. NCM851005 with LiHEO‐modified surface shows good cycling stability, with a capacity retention of 97% at 1 C rate after 200 cycles. The improvement in electrochemical performance is attributed to the conformal coating that prevents structural changes caused by the reaction between cathode material and liquid electrolyte. Compared to bare NCM851005, the coated material shows a significantly reduced tendency for intergranular cracking, successfully preventing electrolyte penetration and suppressing side reactions. Overall, photonic curing presents a novel cost‐ and energy‐efficient synthesis and coating procedure that paves the way for surface modification of any heat‐sensitive material for a wide range of applications.

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层状富镍阴极粒子上高熵氧化物的光子合成与涂层
高熵材料作为电池材料因其独特的性能而备受关注。锂化高熵氧化物(Li0.33(MgCoNiCuZn)0.67O,LiHEO)具有很高的锂离子电导率和电子电导率,使其成为传统锂离子电池中富镍层状氧化物正极(Li1+x(Ni1-y-zCoyMnz)1-xO2,NCM 或 NMC)的潜在涂层材料;然而,高温合成限制了其应用。因此,我们采用光子固化策略合成 LiHEO 和非石硫酸化形式(称为高熵氧化物 [HEO]),并在 LiNi0.85Co0.1Mn0.05O2 (NCM851005) 颗粒上成功制备出纳米级涂层。据我们所知,这是首次报道利用光子固化技术为粒子涂覆高熵材料。表面经锂氢氧化物修饰的 NCM851005 具有良好的循环稳定性,在 1 C 速率下循环 200 次后容量保持率为 97%。电化学性能的改善归功于保形涂层,它能防止阴极材料和液态电解质之间的反应引起的结构变化。与裸露的 NCM851005 相比,涂层材料明显减少了晶间开裂的趋势,成功地防止了电解质渗透并抑制了副反应。总之,光子固化技术提供了一种新颖的低成本、高能效合成和涂层程序,为广泛应用于任何热敏材料的表面改性铺平了道路。
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