High‐Temperature Treatment of Li‐Rich Cathode Materials with Ammonia: Improved Capacity and Mean Voltage Stability during Cycling

• Published in: Advanced energy materials 2017-09, Vol.7 (18), p.n/a
• Main Authors: Erickson, Evan M., Sclar, Hadar, Schipper, Florian, Liu, Jing, Tian, Ruiyuan, Ghanty, Chandan, Burstein, Larisa, Leifer, Nicole, Grinblat, Judith, Talianker, Michael, Shin, Ji‐Yong, Lampert, Jordan K., Markovsky, Boris, Frenkel, Anatoly I., Aurbach, Doron
• Format: Article
• Language: English
• Subjects: Ammonia; ammonia treatment; Cathodes; Cycles; Electric potential; Electrode materials; Electrodes; lithium‐ion batteries; lithium‐rich materials; Photoelectron spectroscopy; Spinel; stabilization; Structural stability; voltage fade; Voltage stability; X-rays
• ISSN: 1614-6832; 1614-6840
• DOI: 10.1002/aenm.201700708

Li‐rich electrode materials of the family xLi2MnO3·(1−x)LiNiaCobMncO2 (a + b + c = 1) suffer a voltage fade upon cycling that limits their utilization in commercial batteries despite their extremely high discharge capacity, ≈250 mA h g−1. Li‐rich, 0.35Li2MnO3·0.65LiNi0.35Mn0.45Co0.20O2, is exposed to NH3 at 400 °C, producing materials with improved characteristics: enhanced electrode capacity and a limited average voltage fade during 100 cycles in half cells versus Li. Three main changes caused by NH3 treatment are established. First, a general bulk reduction of Co and Mn is observed via X‐ray photoelectron spectroscopy and X‐ray absorption near edge structure. Next, a structural rearrangement lowers the coordination number of CoO and MnO bonds, as well as formation of a surface spinel‐like structure. Additionally, Li+ removal from the bulk causes the formation of surface LiOH, Li2CO3, and Li2O. These structural and surface changes can enhance the voltage and capacity stability of the Li‐rich material electrodes after moderate NH3 treatment times of 1–2 h. Li‐rich, xLi2MnO3·(1−x)LiNiaCobMncO2 (a + b + c = 1), Li‐ion battery cathode materials suffer a debilitating voltage fade during cycling that prohibits their commercialization. NH3 treatment of Li‐rich materials is shown herein to limit voltage fading throughout cycling. This is caused by a bulk reduction of the material, subtle surface changes, and extraction of Li‐salts.