Anionic‐Based Layered Oxide Cathodes with High Electrochemical Performance through Dual‐Site Substitutions for Sodium‐Ion Batteries

Thanwisai, Panya; Yang, Songge; Yao, Zeyi; Meng, Zifei; Hou, Jiahui; Vanaphuti, Panawan; Sultanov, Maksim A.; Wen, Jianguo; Yang, Zhenzhen; Zhong, Yu; Wang, Yan

doi:10.1002/smll.202411928

Anionic‐Based Layered Oxide Cathodes with High Electrochemical Performance through Dual‐Site Substitutions for Sodium‐Ion Batteries

Journal Article · Wed Feb 05 00:00:00 EST 2025 · Small

DOI:https://doi.org/10.1002/smll.202411928· OSTI ID:2572993

Thanwisai, Panya ^[1]; Yang, Songge ^[1]; Yao, Zeyi ^[1]; Meng, Zifei ^[1]; Hou, Jiahui ^[1]; Vanaphuti, Panawan ^[2]; Sultanov, Maksim A. ^[3]; Wen, Jianguo ^[4]; Yang, Zhenzhen ^[5]; Zhong, Yu ^[1]; ^[1]

Worcester Polytechnic Institute, MA (United States)
Chulalongkorn Univ., Bangkok (Thailand)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM); Northern Illinois Univ., DeKalb, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)
Argonne National Laboratory (ANL), Argonne, IL (United States)

Mn-rich layered oxide cathodes with anionic redox promise high energy density for sodium-ion batteries (SIBs) due to ultra-high capacity derived from both Mn and O redox couples. Nevertheless, instability of the reactions that lead to poor electrochemical stability hinders the cathodes from practical applications. Here, the Al and Zn dual-site substitution strategy is proposed to enhance electrochemical performance. Here, the designed cathode, Na_0.73Zn_0.03Li_0.25Mn_0.76Al_0.01O₂ (AlZn), delivers a high discharge capacity of 242 mAh g⁻¹ with an impressive rate capability (162 mAh g⁻¹ at 1000 mA g⁻¹) and excellent capacity retention (89.69% over 150 cycles). In addition, full-cell SIB based on AlZn coupled with hard carbon exhibits a high energy density of 317 Wh kg⁻¹ (based on both cathode and anode mass) and a reasonable capacity retention of 80.8% after 250 cycles. Revealed by advanced investigations, the synergy of robust Al–O in TM layers and O–Zn–O pillars in Na layers helps alleviate severe inactive spinel/rock-salt phase transformation and intragranular cracks in the AlZn cathode. This consequently leads to greatly enhanced electrochemical performance over the pristine cathode. This work provides insight into improving electrochemical properties of anionic-redox-based layered oxides by Al/Zn co-substitutions toward high-energy SIBs.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2572993

Alternate ID(s):: OSTI ID: 2514514

Journal Information:: Small, Journal Name: Small Journal Issue: 11 Vol. 21; ISSN 1613-6810; ISSN 1613-6829

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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