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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. 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.


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. Fri . "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_1371698,
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. 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.},
doi = {10.1021/acs.chemmater.7b00852},
journal = {Chemistry of Materials},
number = 11,
volume = 29,
place = {United States},
year = {Fri May 19 00:00:00 EDT 2017},
month = {Fri May 19 00:00:00 EDT 2017}
}
  • 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 withmore » 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 electrolytes are noted.« 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.
  • Cited by 15
  • A Bi 2O 3 in β-MnO 2 composite cathode material has been synthesized using a simple hydrothermal method and cycled in a mixed KOH–LiOH electrolyte with a range of concentrations. We show that, at a KOH:LiOH molar ratio of 1:3, both proton insertion and lithium insertion occur, allowing access to a higher fraction of the theoretical capacity of the MnO 2 while preventing the formation of ZnMn 2O 4. This enables a capacity of 360 mAh/g for over 60 cycles, with cycling limited more by anode properties than traditional cathodic failure mechanisms. The structural changes occurring during cycling are characterizedmore » using electron microscopy and in situ synchrotron energy-dispersive X-ray diffraction (EDXRD) techniques. This mixed electrolyte shows exceptional cyclability and capacity and can be used as a drop-in replacement for current alkaline batteries, potentially drastically improving their cycle life and creating a wide range of new applications for this energy storage technology.« less
  • A Bi 2O 3 in β-MnO 2 composite cathode material has been synthesized using a simple hydrothermal method and cycled in a mixed KOH–LiOH electrolyte with a range of concentrations. We show that, at a KOH:LiOH molar ratio of 1:3, both proton insertion and lithium insertion occur, allowing access to a higher fraction of the theoretical capacity of the MnO 2 while preventing the formation of ZnMn 2O 4. This enables a capacity of 360 mAh/g for over 60 cycles, with cycling limited more by anode properties than traditional cathodic failure mechanisms. The structural changes occurring during cycling are characterizedmore » using electron microscopy and in situ synchrotron energy-dispersive X-ray diffraction (EDXRD) techniques. This mixed electrolyte shows exceptional cyclability and capacity and can be used as a drop-in replacement for current alkaline batteries, potentially drastically improving their cycle life and creating a wide range of new applications for this energy storage technology.« less