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Synthesis of Cation and Water Free Cryptomelane Type OMS-2 Cathode Materials: The Impact of Tunnel Water on Electrochemistry

Published online by Cambridge University Press:  20 January 2017

Altug S. Poyraz ,
Jianping Huang ,
Bingjie Zhang ,
Amy C. Marschilok ,
Kenneth J. Takeuchi  and
Esther S. Takeuchi
Altug S. Poyraz
Affiliation:
Energy Sciences Directorate, Brookhaven National Laboratory, Upton, NY 11973, USA.
Jianping Huang
Affiliation:
Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA.
Bingjie Zhang
Affiliation:
Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA.
Amy C. Marschilok*
Affiliation:
Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA. Department of Materials Science and Engineering, Stony Brook University, Stony Brook, NY 11794, USA.
Kenneth J. Takeuchi*
Affiliation:
Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA. Department of Materials Science and Engineering, Stony Brook University, Stony Brook, NY 11794, USA.
Esther S. Takeuchi*
Affiliation:
Energy Sciences Directorate, Brookhaven National Laboratory, Upton, NY 11973, USA. Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA. Department of Materials Science and Engineering, Stony Brook University, Stony Brook, NY 11794, USA.
*
* corresponding authors: (ACM) amy.marschilok@stonybrook.edu, (KJT) kenneth.takeuchi.1@stonybrook.edu, (EST) esther.takeuchi@stonybrook.edu
* corresponding authors: (ACM) amy.marschilok@stonybrook.edu, (KJT) kenneth.takeuchi.1@stonybrook.edu, (EST) esther.takeuchi@stonybrook.edu
* corresponding authors: (ACM) amy.marschilok@stonybrook.edu, (KJT) kenneth.takeuchi.1@stonybrook.edu, (EST) esther.takeuchi@stonybrook.edu
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Abstract

Cryptomelane type manganese dioxides (α-MnO2, OMS-2) are interesting potential cathode materials due to the ability of their one dimensional (1D) tunnels to reversibly host various cations including Li+ and an accessible stable 3+/4+ redox couple. Here, we synthesized metal cation free OMS-2 materials where the tunnels were occupied by only water and hydronium ions. Water was subsequently removed from the tunnels. Cation free OMS-2 and Dry-OMS-2 were used as cathodes in Li based batteries to investigate the role of tunnel water on their electrochemistry. The initial discharge capacity was higher for Dry-OMS-2 (252 mAh/g) compared to OMS-2 (194 mAh/g), however, after 100 cycles Dry-OMS-2 and OMS-2 delivered 137 mAh/g and 134 mAh/g, respectively. Li+ ion diffusion was more facile for Dry-OMS as evidenced by rate capability, at 400 mA/g. Dry-OMS-2 delivered 135mAh/g whereas OMS-2 delivered ∼115 mAh/g. This first report of the impact of tunnel water on the electrochemistry of OMS-2 type materials demonstrates that the presence of tunnel water in OMS-2 type materials negatively impacts the electrochemistry.

Keywords

energy storageLiMn
Type
Articles
Information
MRS Advances , Volume 2 , Issue 7: Electrochemistry , 2017 , pp. 407 - 412
Copyright
Copyright © Materials Research Society 2017 

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