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Title: The effects of vanadium substitution on one-dimensional tunnel structures of cryptomelane: Combined TEM and DFT study

Abstract

Rational design of energy storage materials requires mechanistic understanding which relies on atomic scale characterization of structure and defects. In this paper we utilize vanadium (V)-substituted one-dimensional cryptomelane as a model material to study structural features critical to electrochemical reversibility of the cathode in lithium-ion batteries. We found the substitution of manganese (Mn) atoms in the tunnel wall with V enhances structural uniformity in the parent KMn8O16 material by inhibiting formation of irregular (2 × 3 and 2 × 1) manganese oxide tunnel structures. Upon lithiation, both transmission electron microscopy (TEM) and density functional theory (DFT) reveal significant structural evolution, eventually resulting in phase separation and formation of highly reduced manganese oxide. During this process, Mn4+ accepts electrons donated by intercalated Li, while the V4+ substituent is not electrochemically reduced but acts to stabilize the tunnel framework structure. As a result, the V substituted material shows higher operating voltage and improved electrochemical reversibility. Our results highlight the benefits of V-substitution in cryptomelane, and the significance of integrating characterization with simulation for understanding and developing design principles for lithium ion battery materials.

Authors:
 [1];  [2];  [1];  [2];  [2];  [1];  [1];  [3];  [3];  [2];  [4]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Stony Brook Univ., NY (United States). Dept. of Chemistry
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States). Dept. of Chemistry
  4. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
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); National Science Foundation (NSF)
OSTI Identifier:
1633871
Alternate Identifier(s):
OSTI ID: 1599463
Report Number(s):
BNL-216062-2020-JAAM
Journal ID: ISSN 2211-2855
Grant/Contract Number:  
SC0012704; SC0012673; 1839287
Resource Type:
Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 71; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Scanning transmission electron microscopy (STEM); In-situ TEM; Battery; Alpha-MnO2; DFT

Citation Formats

Yang, Shi-Ze, Tallman, Killian R., Liu, Ping, Lutz, Diana M., Zhang, Bingjie, Kim, Sung Joo, Wu, Lijun, Marschilok, Amy C., Takeuchi, Esther S., Takeuchi, Kenneth J., and Zhu, Yimei. The effects of vanadium substitution on one-dimensional tunnel structures of cryptomelane: Combined TEM and DFT study. United States: N. p., 2020. Web. doi:10.1016/j.nanoen.2020.104571.
Yang, Shi-Ze, Tallman, Killian R., Liu, Ping, Lutz, Diana M., Zhang, Bingjie, Kim, Sung Joo, Wu, Lijun, Marschilok, Amy C., Takeuchi, Esther S., Takeuchi, Kenneth J., & Zhu, Yimei. The effects of vanadium substitution on one-dimensional tunnel structures of cryptomelane: Combined TEM and DFT study. United States. https://doi.org/10.1016/j.nanoen.2020.104571
Yang, Shi-Ze, Tallman, Killian R., Liu, Ping, Lutz, Diana M., Zhang, Bingjie, Kim, Sung Joo, Wu, Lijun, Marschilok, Amy C., Takeuchi, Esther S., Takeuchi, Kenneth J., and Zhu, Yimei. Tue . "The effects of vanadium substitution on one-dimensional tunnel structures of cryptomelane: Combined TEM and DFT study". United States. https://doi.org/10.1016/j.nanoen.2020.104571. https://www.osti.gov/servlets/purl/1633871.
@article{osti_1633871,
title = {The effects of vanadium substitution on one-dimensional tunnel structures of cryptomelane: Combined TEM and DFT study},
author = {Yang, Shi-Ze and Tallman, Killian R. and Liu, Ping and Lutz, Diana M. and Zhang, Bingjie and Kim, Sung Joo and Wu, Lijun and Marschilok, Amy C. and Takeuchi, Esther S. and Takeuchi, Kenneth J. and Zhu, Yimei},
abstractNote = {Rational design of energy storage materials requires mechanistic understanding which relies on atomic scale characterization of structure and defects. In this paper we utilize vanadium (V)-substituted one-dimensional cryptomelane as a model material to study structural features critical to electrochemical reversibility of the cathode in lithium-ion batteries. We found the substitution of manganese (Mn) atoms in the tunnel wall with V enhances structural uniformity in the parent KMn8O16 material by inhibiting formation of irregular (2 × 3 and 2 × 1) manganese oxide tunnel structures. Upon lithiation, both transmission electron microscopy (TEM) and density functional theory (DFT) reveal significant structural evolution, eventually resulting in phase separation and formation of highly reduced manganese oxide. During this process, Mn4+ accepts electrons donated by intercalated Li, while the V4+ substituent is not electrochemically reduced but acts to stabilize the tunnel framework structure. As a result, the V substituted material shows higher operating voltage and improved electrochemical reversibility. Our results highlight the benefits of V-substitution in cryptomelane, and the significance of integrating characterization with simulation for understanding and developing design principles for lithium ion battery materials.},
doi = {10.1016/j.nanoen.2020.104571},
journal = {Nano Energy},
number = C,
volume = 71,
place = {United States},
year = {Tue Feb 04 00:00:00 EST 2020},
month = {Tue Feb 04 00:00:00 EST 2020}
}

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