A monoclinic polymorph of sodium birnessite for ultrafast and ultrastable sodium ion storage

Hui Xia (), Xiaohui Zhu, Jizi Liu, Qi Liu, Si Lan, Qinghua Zhang, Xinyu Liu, Joon Kyo Seo, Tingting Chen, Lin Gu () and Ying Shirley Meng ()
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Hui Xia: Nanjing University of Science and Technology
Xiaohui Zhu: Nanjing University of Science and Technology
Jizi Liu: Nanjing University of Science and Technology
Qi Liu: City University of Hong Kong
Si Lan: Nanjing University of Science and Technology
Qinghua Zhang: Chinese Academy of Sciences
Xinyu Liu: Chinese Academy of Sciences
Joon Kyo Seo: University of California San Diego
Tingting Chen: Nanjing University of Science and Technology
Lin Gu: Chinese Academy of Sciences
Ying Shirley Meng: University of California San Diego

Nature Communications, 2018, vol. 9, issue 1, 1-10

Abstract: Abstract Sodium transition metal oxides with layered structures are attractive cathode materials for sodium-ion batteries due to their large theoretical specific capacities. However, these layered oxides suffer from poor cyclability and low rate performance because of structural instability and sluggish electrode kinetics. In the present work, we show the sodiation reaction of Mn3O4 to yield crystal water free NaMnO2−y−δ(OH)2y, a monoclinic polymorph of sodium birnessite bearing Na/Mn(OH)8 hexahedra and Na/MnO6 octahedra. With the new polymorph, NaMnO2−y−δ(OH)2y exhibits an enlarged interlayer distance of about 7 Å, which is in favor of fast sodium ion migration and good structural stability. In combination of the favorable nanosheet morphology, NaMn2−y−δ(OH)2y cathode delivers large specific capacity up to 211.9 mAh g–1, excellent cycle performance (94.6% capacity retention after 1000 cycles), and outstanding rate capability (156.0 mAh g–1 at 50 C). This study demonstrates an effective approach in tailoring the structural and electrochemical properties of birnessite towards superior cathode performance in sodium-ion batteries.

Date: 2018
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DOI: 10.1038/s41467-018-07595-y

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