Energy &, Environment Directorate Pacific Northwest National Laboratory Richland WA 99352 USA
John A. Paulson School of Engineering and Applied Sciences Harvard University Cambridge MA 02138 USA
Chemistry Division Brookhaven National Laboratory Upton NY 11973 USA
Physical and Computational Sciences Directorate Pacific Northwest National Laboratory Richland WA 99352 USA
Department of Chemistry and Biochemistry Florida State University Tallahassee FL 32306 USA
Department of Chemistry Virginia Tech Blacksburg VA 24061 USA
Environmental Molecular Sciences Laboratory Pacific Northwest National Laboratory Richland WA 99352 USA
Chemical Sciences and Engineering Division Argonne National Laboratory 9700 South Cass Avenue Lemont IL 60439 USA, Materials Science and Engineering Stanford University Stanford CA 94305 USA
Chemical Sciences and Engineering Division Argonne National Laboratory 9700 South Cass Avenue Lemont IL 60439 USA
Manganese‐rich layered oxide materials hold great potential as low‐cost and high‐capacity cathodes for Na‐ion batteries. However, they usually form a P2 phase and suffer from fast capacity fade. In this work, an O3 phase sodium cathode has been developed out of a Li and Mn‐rich layered material by leveraging the creation of transition metal (TM) and oxygen vacancies and the electrochemical exchange of Na and Li. The Mn‐rich layered cathode material remains primarily O3 phase during sodiation/desodiation and can have a full sodiation capacity of ca. 220 mAh g −1 . It delivers ca. 160 mAh g −1 specific capacity between 2–3.8 V with >86 % retention over 250 cycles. The TM and oxygen vacancies pre‐formed in the sodiated material enables a reversible migration of TMs from the TM layer to the tetrahedral sites in the Na layer upon de‐sodiation and sodiation. The migration creates metastable states, leading to increased kinetic barrier that prohibits a complete O3‐P3 phase transition.
@article{osti_1786141,
author = {Xiao, Biwei and Wang, Yichao and Tan, Sha and Song, Miao and Li, Xiang and Zhang, Yuxin and Lin, Feng and Han, Kee Sung and Omenya, Fredrick and Amine, Khalil and others},
title = {Vacancy‐Enabled O3 Phase Stabilization for Manganese‐Rich Layered Sodium Cathodes},
annote = {Abstract Manganese‐rich layered oxide materials hold great potential as low‐cost and high‐capacity cathodes for Na‐ion batteries. However, they usually form a P2 phase and suffer from fast capacity fade. In this work, an O3 phase sodium cathode has been developed out of a Li and Mn‐rich layered material by leveraging the creation of transition metal (TM) and oxygen vacancies and the electrochemical exchange of Na and Li. The Mn‐rich layered cathode material remains primarily O3 phase during sodiation/desodiation and can have a full sodiation capacity of ca. 220 mAh g −1 . It delivers ca. 160 mAh g −1 specific capacity between 2–3.8 V with >86 % retention over 250 cycles. The TM and oxygen vacancies pre‐formed in the sodiated material enables a reversible migration of TMs from the TM layer to the tetrahedral sites in the Na layer upon de‐sodiation and sodiation. The migration creates metastable states, leading to increased kinetic barrier that prohibits a complete O3‐P3 phase transition. },
doi = {10.1002/ange.202016334},
url = {https://www.osti.gov/biblio/1786141},
journal = {Angewandte Chemie},
issn = {ISSN 0044-8249},
number = {15},
volume = {133},
place = {Germany},
publisher = {Wiley Blackwell (John Wiley & Sons)},
year = {2021},
month = {04}}
Kaufman, Jonas L.; Vinckevičiūtė, Julija; Krishna Kolli, Sanjeev
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2152https://doi.org/10.1098/rsta.2019.0020