skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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 Zn 2+ 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-MnO 2 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-MnO 2 cells are presented including dramatic mechanistic differences in the storage mechanism of this couple when compared to similar aqueous electrolytesmore » are noted.« less

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2];  [3];  [3];  [1]; ORCiD logo [1]; ORCiD logo [4];  [1];  [3]; ORCiD logo [3];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]
  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:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1376620
Grant/Contract Number:
AC05-00OR22725; AC02-06CH11357; SC0006877
Resource Type:
Journal Article: 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

Citation Formats

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, and Vaughey, John T.. Mechanism of Zn Insertion into Nanostructured δ-MnO 2 : A Nonaqueous Rechargeable Zn Metal Battery. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b00852.
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.. Mechanism of Zn Insertion into Nanostructured δ-MnO 2 : A Nonaqueous Rechargeable Zn Metal Battery. United States. doi:10.1021/acs.chemmater.7b00852.
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, and Vaughey, John T.. 2017. "Mechanism of Zn Insertion into Nanostructured δ-MnO 2 : A Nonaqueous Rechargeable Zn Metal Battery". United States. doi:10.1021/acs.chemmater.7b00852.
@article{osti_1376620,
title = {Mechanism of Zn Insertion into Nanostructured δ-MnO 2 : A Nonaqueous Rechargeable Zn Metal Battery},
author = {Han, Sang-Don and Kim, Soojeong and Li, Dongguo and Petkov, Valeri and Yoo, Hyun Deog and Phillips, Patrick J. and Wang, Hao and Kim, Jae Jin and More, Karren L. and Key, Baris and Klie, Robert F. and Cabana, Jordi and Stamenkovic, Vojislav R. and Fister, Timothy T. and Markovic, Nenad M. and Burrell, Anthony K. and Tepavcevic, Sanja and Vaughey, John T.},
abstractNote = {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.},
doi = {10.1021/acs.chemmater.7b00852},
journal = {Chemistry of Materials},
number = 11,
volume = 29,
place = {United States},
year = 2017,
month = 5
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on May 8, 2018
Publisher's Version of Record

Save / Share:
  • 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) electrolytemore » 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.« less
  • A nonaqueous coprecipitation process has been developed to prepare controlled stoichiometry lithium cobalt oxide precipitates. The process involved mixing a methanolic LiCo-(NO{sub 3}){sub 3} solution with a methanolic solution containing tetramethylammonium oxalate as a precipitating agent. The resulting oxalates were readily converted to phase-pure lithium cobalt oxide at 800 C under an oxygen atmosphere. The various starting solutions, oxalate precipitates, and the resulting oxides have been extensively characterized using a variety of techniques, including multinuclear NMR, TGA/DTA, EPR, and XRD analyses. Results indicate that the strong interaction between the metals (Li and Co) that occurred in solution was maintained duringmore » precipitation. The calcined precipitate revealed that the desired LiCoO{sub 2} phase was formed at 800 C under an O{sub 2} atmosphere. When electrochemically cycled, the material exhibited an initial capacity of {approximately}133 (mA h)/g with a fade of 0.02% in capacity per cycle.« less
  • A beyond Li-ion battery based on Zn metal, aprotic electrolyte, and a hydrated bilayered V2O5 cathode with a large gallery spacing of 11–13 Å is introduced. The battery exhibits high 20 C rate capability with good specific capacity of 130 mA h g-1. This work provides some design rules for Zn intercalation behavior in host electrodes in a nonaqueous environment.
  • The aligned nanorods of Co{sub 3}O{sub 4} and nanoporous hollow spheres (NHS) of SnO{sub 2} and Mn{sub 2}O{sub 3} were investigated as the anodes for Li-ion rechargeable batteries. The Co{sub 3}O{sub 4} nanorods demonstrated 1433 mAh/g reversible capacity. The NHS of SnO{sub 2} and Mn{sub 2}O{sub 3} delivered 400 mAh/g and 250 mAh/g capacities respectively in multiple galvonastatic discharge-charge cycles. It was found that high capacity of NHS of metal oxides is sustainable attributed to their unique structure that maintains material integrity during cycling. The nanostructured metal oxides exhibit great potential as the new anode materials for Li-ion rechargeable batteriesmore » with high energy density, low cost and inherent safety.« less