Nanocomposite Engineering of a High‐Capacity Partially Ordered Cathode for Li‐Ion Batteries. Issue 13 (7th February 2023)

• Record Type: Journal Article
• Authors: Lee, Eunryeol; Wi, Tae‐Ung; Park, Jaehyun; Park, Sang‐Wook; Kim, Min‐Ho; Lee, Dae‐Hyung; Park, Byung‐Chun; Jo, Chiho; Malik, Rahul; Lee, Jong Hoon; Shin, Tae Joo; Kang, Seok Ju; Lee, Hyun‐Wook; Lee, Jinhyuk; Seo, Dong‐Hwa
• Is Part Of: Advanced materials. Volume 35:Issue 13(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-02-07
• Subjects: cation‐disordered cathode materials -- DFT calculations -- high‐energy Li‐ion battereis -- local cation order -- nanocomposite nature; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adma.202208423
• Languages: English
• ISSNs: 0935-9648

Abstract

Abstract: Understanding the local cation order in the crystal structure and its correlation with electrochemical performances has advanced the development of high‐energy Mn‐rich cathode materials for Li‐ion batteries, notably Li‐ and Mn‐rich layered cathodes (LMR, e.g., Li1.2 Ni0.13 Mn0.54 Co0.13 O2 ) that are considered as nanocomposite layered materials with C2/m Li2 MnO3 ‐type medium‐range order (MRO). Moreover, the Li‐transport rate in high‐capacity Mn‐based disordered rock‐salt (DRX) cathodes (e.g., Li1.2 Mn0.4 Ti0.4 O2 ) is found to be influenced by the short‐range order of cations, underlining the importance of engineering the local cation order in designing high‐energy materials. Herein, the nanocomposite is revealed, with a heterogeneous nature (like MRO found in LMR) of ultrahigh‐capacity partially ordered cathodes (e.g., Li1.68 Mn1.6 O3.7 F0.3 ) made of distinct domains of spinel‐, DRX‐ and layered‐like phases, contrary to conventional single‐phase DRX cathodes. This multi‐scale understanding of ordering informs engineering the nanocomposite material via Ti doping, altering the intra‐particle characteristics to increase the content of the rock‐salt phase and heterogeneity within a particle. This strategy markedly improves the reversibility of both Mn‐ and O‐redox processes to enhance the cycling stability of the partially ordered DRX cathodes (nearly ≈30% improvement of capacity retention). This work sheds light on the importance of nanocomposite engineering to develop ultrahigh‐performance, low‐cost Li‐ion cathode materials. Abstract : The multi‐phase heterogeneous nature of ultrahigh‐energy Mn‐based partially disordered cathodes is revealed by combined experimental and computational studies. This fundamental understanding enables the novel nanocomposite design, which controls a phase fraction within a single particle. Consequently, T30 cathode via a nanocomposite engineering shows more reversible redox properties and a superior cycle retention, showing new insights into developing advanced Mn‐based cathodes.