The washing of cathode active materials (CAMs) for lithium-ion batteries (LIBs) to remove unwanted contaminants is of high importance in industrial CAM manufacturing. Nickel-rich NCMs (LiMO₂, M = Ni, Co, Mn), a family of commercial high-energy CAMs, are known for their detrimental reactivity with liquid/gaseous water; yet, insights on the kinetics of the occurring lithium/proton (Li⁺/H⁺) exchange are still lacking. To assess the Li⁺/H⁺ exchange, a set of five independent techniques is developed and employed to quantify its extent for a nickel-rich NCM (LiNi_0.83Co_0.12Mn_0.05O₂) as a function of the washing parameters. Using titration, prompt-gamma activation analysis, thermogravimetric analysis, temperature-dependent X-ray diffraction, and X-ray photoelectron spectroscopy, the proton content of washed NCM samples is determined, exploring the impact of washing time and water-to-CAM mass ratio. Furthermore, a highly protonated NCM (H_0.25Li_0.75Ni_0.83Co_0.12Mn_0.05O₂) is used to investigate the bulk properties, e.g., the change of lattice parameters and the spatial proton distribution, as well as the thermal decomposition of the protonated phase. The gained knowledge on the mechanism and the kinetics of the Li⁺/H⁺ exchange as well as on the decomposition mechanism of the protonated NCM phase is essential for the successful aqueous processing of nickel-rich CAMs, advancing the sustainable production of LIBs.

中文翻译：

---

洗涤对富镍 NCM 的影响：量化锂/质子交换动力学、插入质子和结构变化的方法


在工业 CAM 制造中，清洗锂离子电池 (LIB) 的阴极活性材料 (CAM) 以去除不需要的污染物非常重要。富镍 NCM（LiMO ₂ ，​​M = Ni、Co、Mn）是商用高能 CAM 家族，因其与液态/气态水的有害反应性而闻名。然而，对发生的锂/质子（Li ⁺ /H ⁺ ）交换动力学的见解仍然缺乏。为了评估Li ⁺ /H ⁺交换，开发并采用了一套五种独立技术来量化富镍NCM (LiNi _0.83 Co _0.12 Mn _0.05 O ₂ ) 的交换程度，作为洗涤参数的函数。使用滴定、瞬发伽马活化分析、热重分析、温度依赖性 X 射线衍射和 X 射线光电子能谱，测定洗涤后的 NCM 样品的质子含量，探索洗涤时间和水与 CAM 质量的影响比率。此外，使用高度质子化的NCM (H _0.25 Li _0.75 Ni _0.83 Co _0.12 Mn _0.05 O ₂ )来研究体特性，例如晶格参数的变化和空间质子分布，以及质子化的热分解。阶段。 所获得的有关Li ⁺ /H ⁺交换机制和动力学以及质子化NCM相分解机制的知识对于富镍CAM的成功水处理、促进LIB的可持续生产至关重要。