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

Han, Sang-Don; Kim, Soojeong; Li, Dongguo; Petkov, Valeri; Yoo, Hyun Deog; Phillips, Patrick J.; Wang, Hao; Kim, Jae Jin; More, Karren L.; Key, Baris; Klie, Robert F.; Cabana, Jordi; Stamenkovic, Vojislav R.; Fister, Timothy T.; Markovic, Nenad M.; Burrell, Anthony K.; Tepavcevic, Sanja; Vaughey, John T.

doi:10.1021/acs.chemmater.7b00852

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

Journal Article · Fri May 19 00:00:00 EDT 2017 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.7b00852· OSTI ID:1371698

; Kim, Soojeong; Li, Dongguo; ; Yoo, Hyun Deog; Phillips, Patrick J.; Wang, Hao; ; More, Karren L.; Key, Baris; Klie, Robert F.; ; Stamenkovic, Vojislav R.; Fister, Timothy T.; Markovic, Nenad M.; Burrell, Anthony K.; Tepavcevic, Sanja;

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. Several examples of these systems support the use of a Zn metal anode, and reversible intercalation cathodes have been reported. This study utilizes a combination of analytical tools to probe the chemistry of a nanostructured delta-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. Numerous factors affecting capacity fade and issues associated with the second phase formation including Mn dissolution in heavily cycled Zn/delta-MnO2 cells are presented including dramatic mechanistic differences in the storage mechanism of this couple when compared to similar aqueous electrolytes are noted.

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1371698

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 11 Vol. 29; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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