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Title: Water-induced formation of an alkali-ion dimer in cryptomelane nanorods

Abstract

Tunneled metal oxides such as α-Mn8O16 (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K+ ions (which act as structure-stabilizing dopants) and H2O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K+-doped α-Mn8O16 (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H2O displaces K+ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K2+ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li+/Na+ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [1]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [2];  [1]
+ Show Author Affiliations
  1. Department of Condensed Matter Physics and Materials Science, Brookhaven National Laboratory, Upton, USA
  2. Department of Physics and Astronomy, Stony Brook University, Stony Brook, USA, Institute for Advanced Computational Science
  3. Energy Sciences Directorate, Brookhaven National Laboratory, Upton, USA, Department of Chemistry and Biochemistry
  4. School of Physics and Microelectronics, Zhengzhou University, Zhengzhou, China
  5. Energy Sciences Directorate, Brookhaven National Laboratory, Upton, USA, Department of Chemistry
  6. Department of Chemistry, Stony Brook University, Stony Brook, USA, Department of Materials Science and Chemical Engineering
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1616772
Alternate Identifier(s):
OSTI ID: 1635100
Report Number(s):
BNL-216076-2020-JAAM
Journal ID: ISSN 2041-6520; CSHCBM
Grant/Contract Number:  
SC0001137; SC0012704; SC0012673
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 19; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Cheng, Shaobo, Sharma, Vidushi, Poyraz, Altug S., Wu, Lijun, Li, Xing, Marschilok, Amy C., Takeuchi, Esther S., Takeuchi, Kenneth J., Fernández-Serra, Marivi, and Zhu, Yimei. Water-induced formation of an alkali-ion dimer in cryptomelane nanorods. United Kingdom: N. p., 2020. Web. doi:10.1039/D0SC01517B.
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Cheng, Shaobo, Sharma, Vidushi, Poyraz, Altug S., Wu, Lijun, Li, Xing, Marschilok, Amy C., Takeuchi, Esther S., Takeuchi, Kenneth J., Fernández-Serra, Marivi, & Zhu, Yimei. Water-induced formation of an alkali-ion dimer in cryptomelane nanorods. United Kingdom. https://doi.org/10.1039/D0SC01517B
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Cheng, Shaobo, Sharma, Vidushi, Poyraz, Altug S., Wu, Lijun, Li, Xing, Marschilok, Amy C., Takeuchi, Esther S., Takeuchi, Kenneth J., Fernández-Serra, Marivi, and Zhu, Yimei. Wed . "Water-induced formation of an alkali-ion dimer in cryptomelane nanorods". United Kingdom. https://doi.org/10.1039/D0SC01517B.
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@article{osti_1616772,
title = {Water-induced formation of an alkali-ion dimer in cryptomelane nanorods},
author = {Cheng, Shaobo and Sharma, Vidushi and Poyraz, Altug S. and Wu, Lijun and Li, Xing and Marschilok, Amy C. and Takeuchi, Esther S. and Takeuchi, Kenneth J. and Fernández-Serra, Marivi and Zhu, Yimei},
abstractNote = {Tunneled metal oxides such as α-Mn8O16 (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K+ ions (which act as structure-stabilizing dopants) and H2O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K+-doped α-Mn8O16 (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H2O displaces K+ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K2+ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li+/Na+ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.},
doi = {10.1039/D0SC01517B},
journal = {Chemical Science},
number = 19,
volume = 11,
place = {United Kingdom},
year = {Wed May 20 00:00:00 EDT 2020},
month = {Wed May 20 00:00:00 EDT 2020}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1039/D0SC01517B
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Figures / Tables:

Fig. 1 Fig. 1: Structure and microscopy observations of the cryptomelane nanorod. Perspective view of the cryptomelane atomic models from the (a) [001], (b) [104], and (c) [100] projection. Orange, purple, green, and yellow spheres represent K+ at 2b, K+ at 2a, Mn, and O, respectively. The thin black rectangle outlines themore » unit cell. Thick grey and orange lines in (b) and (c) outline the K+(2b)-O2– and K+(2a)-O2– bond, respectively. K+(2b) bonds with 8 surrounding O2– with a bond length of 2.91 Å, while K+(2a) forms bond with 4 surrounding O2– with bonding length of 2.56 Å. The red and blue arrows highlight Mn atoms adjacent to K+(2b) and K+(2a), respectively. (d) Typical high-resolution TEM image of a cryptomelane nanorod from [$1\bar{3}1$] zone axis. The corresponding FFT result is also shown in the inset. (e) Selected area electron diffraction pattern acquired from the same nanorod, which shares the similar streaking feature with the FFT result in (d) due to the 2c ordering. Streaks at 1/2c are indicated by red arrows.« less
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