Title: Mechanism of Zn Insertion into Nanostructured δ-MnO ₂ : A Nonaqueous Rechargeable Zn Metal Battery

Abstract

Unlike the more established lithium-ion based energy storage chemistries, the complex intercalation chemistry of multivalent cations in a host lattice is not well understood, especially the relationship between the intercalating species solution chemistry and the prevalence and type of side reactions. Among multivalent metals, a promising model system can be based on nonaqueous Zn²⁺ ion chemistry. There are several examples of these systems support the use of a Zn metal anode, and reversible intercalation cathodes have been reported. Our study utilizes a combination of analytical tools to probe the chemistry of a nanostructured δ-MnO₂ cathode in association with a nonaqueous acetonitrile–Zn(TFSI)₂ electrolyte and a Zn metal anode. As many of the issues related to understanding a multivalent battery relate to the electrolyte–electrode interface, the high surface area of a nanostructured cathode provides a significant interface between the electrolyte and cathode host that maximizes the spectroscopic signal of any side reactions or minor mechanistic pathways. There are numerous factors affecting capacity fade and issues associated with the second phase formation including Mn dissolution in heavily cycled Zn/δ-MnO₂ cells are presented including dramatic mechanistic differences in the storage mechanism of this couple when compared to similar aqueous electrolytes are noted.

Authors:

Han, Sang-Don  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-2931-659X"

Kim, Soojeong ^[1]; Li, Dongguo ^[1]; Petkov, Valeri  ^[2];

• Search DOE PAGES for author "Petkov, Valeri"
• Search DOE PAGES for ORCID "0000-0002-6392-7589"

Yoo, Hyun Deog ^[3]; Phillips, Patrick J. ^[3]; Wang, Hao ^[1]; Kim, Jae Jin  ^[1];

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• Search DOE PAGES for ORCID "0000-0001-7709-3530"

More, Karren L.  ^[4];

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• Search DOE PAGES for ORCID "0000-0001-5223-9097"

Key, Baris ^[1]; Klie, Robert F. ^[3]; Cabana, Jordi  ^[3];

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• Search DOE PAGES for ORCID "0000-0002-2353-5986"

Stamenkovic, Vojislav R. ^[1]; Fister, Timothy T. ^[1]; Markovic, Nenad M. ^[1]; Burrell, Anthony K. ^[1]; Tepavcevic, Sanja ^[1]; Vaughey, John T.  ^[1]

• Search DOE PAGES for author "Vaughey, John T."
• Search DOE PAGES for ORCID "0000-0002-2556-6129"

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+ Show Author Affiliations

1. Argonne National Lab. (ANL), Argonne, IL (United States)
2. Central Michigan Univ., Mount Pleasant, MI (United States)
3. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Illinois, Chicago, IL (United States)
4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Publication Date:

Mon May 08 00:00:00 EDT 2017

Research Org.:

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1376620

Grant/Contract Number:  

AC05-00OR22725; AC02-06CH11357; SC0006877

Resource Type:

Accepted Manuscript

Journal Name:

Chemistry of Materials

Additional Journal Information:

Journal Volume: 29; Journal Issue: 11; Journal ID: ISSN 0897-4756

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

25 ENERGY STORAGE