Cationic and transition metal co-substitution strategy of O3-type NaCrO2 cathode for high-energy sodium-ion batteries
- Authors
- Lee, Indeok; Oh, Gwangeon; Lee, Seulgi; Yu, Tae-Yeon; Alfaruqi, Muhammad Hilmy; Mathew, Vinod; Sambandam, Balaji; Sun, Yang-Kook; Hwang, Jang-Yeon; Kim, Jaekook
- Issue Date
- Oct-2021
- Publisher
- ELSEVIER
- Keywords
- High energy; High voltage; O3-type cathode; Thermal Stability; Water stability
- Citation
- ENERGY STORAGE MATERIALS, v.41, pp.183 - 195
- Indexed
- SCIE
SCOPUS
- Journal Title
- ENERGY STORAGE MATERIALS
- Volume
- 41
- Start Page
- 183
- End Page
- 195
- URI
- https://scholarworks.bwise.kr/hanyang/handle/2021.sw.hanyang/133917
- DOI
- 10.1016/j.ensm.2021.05.046
- ISSN
- 2405-8297
- Abstract
- The development of advanced cathode materials with high operational voltage and high reversible capacity is crucial for facilitating the practical realization of sodium-ion battery (SIB) technology. Herein, O3-type Na0.9Ca0.035Cr0.97Ti0.03O2 is designed by co-substitution of Ca and Ti into O3-type NaCrO2, and proposed as a new cathode material for high-energy and practical SIBs. On the basis of the stoichiometry, alkali earth metal ions successfully incorporate into the NaO6 octahedron of NaCrO2 by substituting a single Ca2+ per two Na+, while Ti4+ ions are substituted with Cr3+ ions into the CrO6 octahedral site, resulting in formation of Na+ vacancies in the Na+ layer for the charge compensation. This co-substitution strategy reinforces the structural stability of the O3-type Na0.9Ca0.035Cr0.97Ti0.03O2 cathode, induced by the stronger Ti–O bond than Cr–O bond and presence of immobile Ca2+ ions between the CrO6 slabs. These structural features suppress the irreversible phase transition and provide excellent Na+ ion-diffusion kinetics in a wide operation voltage window of 1.5–3.8 V, allowing the cathode to deliver the high initial Coulombic efficiency of 95% and retain the 90% of its initial capacity after 1000 cycles at a 10 C rate. Moreover, the cathode guarantees the practical applicability with long-term cycling in a pouch-type full cell using a hard carbon anode, as well as with durability against water.
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