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

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.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [2]; ORCiD logo [1];  [3];  [3];  [4];  [1]; ORCiD logo [3]; ORCiD logo [4]
  1. Nanjing Univ. of Science and Technology, Nanjing (China)
  2. City Univ. of Hong Kong, Hong Kong (China)
  3. Chinese Academy of Sciences (CAS), Beijing (China)
  4. Univ. of California San Diego, La Jolla, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE
OSTI Identifier:
1543750
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Science & Technology; Other Topics

Citation Formats

Xia, Hui, Zhu, Xiaohui, Liu, Jizi, Liu, Qi, Lan, Si, Zhang, Qinghua, Liu, Xinyu, Seo, Joon Kyo, Chen, Tingting, Gu, Lin, and Meng, Ying Shirley. A monoclinic polymorph of sodium birnessite for ultrafast and ultrastable sodium ion storage. United States: N. p., 2018. Web. doi:10.1038/s41467-018-07595-y.
Xia, Hui, Zhu, Xiaohui, Liu, Jizi, Liu, Qi, Lan, Si, Zhang, Qinghua, Liu, Xinyu, Seo, Joon Kyo, Chen, Tingting, Gu, Lin, & Meng, Ying Shirley. A monoclinic polymorph of sodium birnessite for ultrafast and ultrastable sodium ion storage. United States. doi:10.1038/s41467-018-07595-y.
Xia, Hui, Zhu, Xiaohui, Liu, Jizi, Liu, Qi, Lan, Si, Zhang, Qinghua, Liu, Xinyu, Seo, Joon Kyo, Chen, Tingting, Gu, Lin, and Meng, Ying Shirley. Fri . "A monoclinic polymorph of sodium birnessite for ultrafast and ultrastable sodium ion storage". United States. doi:10.1038/s41467-018-07595-y. https://www.osti.gov/servlets/purl/1543750.
@article{osti_1543750,
title = {A monoclinic polymorph of sodium birnessite for ultrafast and ultrastable sodium ion storage},
author = {Xia, Hui and Zhu, Xiaohui and Liu, Jizi and Liu, Qi and Lan, Si and Zhang, Qinghua and Liu, Xinyu and Seo, Joon Kyo and Chen, Tingting and Gu, Lin and Meng, Ying Shirley},
abstractNote = {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.},
doi = {10.1038/s41467-018-07595-y},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {11}
}

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