Mechanism of Zn Insertion into Nanostructured δ-MnO2: A Nonaqueous Rechargeable Zn Metal Battery

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

doi:10.1021/acs.chemmater.7b00852

Mechanism of Zn Insertion into Nanostructured δ-MnO₂: A Nonaqueous Rechargeable Zn Metal Battery

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

Center for Nanophase Matls Sciences

Research output: Contribution to journal › Article › peer-review

235 Scopus citations

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. 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 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. 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.

Original language	English
Pages (from-to)	4874-4884
Number of pages	11
Journal	Chemistry of Materials
Volume	29
Issue number	11
DOIs	https://doi.org/10.1021/acs.chemmater.7b00852
State	Published - Jun 13 2017

Funding

This work was supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. The submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory ("Argonne"). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DEAC02- 06CH11357. MRCAT (sector 10, APS) operations are supported by the Department of Energy and the MRCAT member institutions. Prof. Valeri Petkov thanks DOE for support via Grant DE-SC0006877 and scientists from Sector 11, APS, for help with high-energy XRD experiments.

Funders	Funder number
U.S. Department of Energy	DE-SC0006877
Office of Science	DEAC02- 06CH11357
Basic Energy Sciences
Argonne National Laboratory	DE-AC02-06CH11357
American Pain Society

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10.1021/acs.chemmater.7b00852

Cite this

Han, S. D., Kim, S., Li, D., Petkov, V., Yoo, H. D., Phillips, P. J., Wang, H., Kim, J. J., More, K. L., Key, B., Klie, R. F., Cabana, J., Stamenkovic, V. R., Fister, T. T., Markovic, N. M., Burrell, A. K., Tepavcevic, S., & Vaughey, J. T. (2017). Mechanism of Zn Insertion into Nanostructured δ-MnO₂: A Nonaqueous Rechargeable Zn Metal Battery. Chemistry of Materials, 29(11), 4874-4884. https://doi.org/10.1021/acs.chemmater.7b00852

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title = "Mechanism of Zn Insertion into Nanostructured δ-MnO2: 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. 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 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. 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.",

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

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Han, SD, Kim, S, Li, D, Petkov, V, Yoo, HD, Phillips, PJ, Wang, H, Kim, JJ, More, KL, Key, B, Klie, RF, Cabana, J, Stamenkovic, VR, Fister, TT, Markovic, NM, Burrell, AK, Tepavcevic, S & Vaughey, JT 2017, 'Mechanism of Zn Insertion into Nanostructured δ-MnO₂: A Nonaqueous Rechargeable Zn Metal Battery', Chemistry of Materials, vol. 29, no. 11, pp. 4874-4884. https://doi.org/10.1021/acs.chemmater.7b00852

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AU - Han, Sang Don

AU - Kim, Soojeong

AU - Li, Dongguo

AU - Petkov, Valeri

AU - Yoo, Hyun Deog

AU - Phillips, Patrick J.

AU - Wang, Hao

AU - Kim, Jae Jin

AU - More, Karren L.

AU - Key, Baris

AU - Klie, Robert F.

AU - Cabana, Jordi

AU - Stamenkovic, Vojislav R.

AU - Fister, Timothy T.

AU - Markovic, Nenad M.

AU - Burrell, Anthony K.

AU - Tepavcevic, Sanja

AU - Vaughey, John T.

PY - 2017/6/13

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N2 - 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 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. 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.

AB - 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 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. 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.

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