High-Energy and Stable Subfreezing Aqueous Zn–MnO2 Batteries with Selective and Pseudocapacitive Zn-Ion Insertion in MnO2
Abstract
Abstract One major challenge of aqueous Zn–MnO 2 batteries for practical applications is their unacceptable performance below freezing temperatures. Here the use of simple Zn(ClO 4 ) 2 aqueous electrolytes is described for all‐weather Zn–MnO 2 batteries even down to −60 °C. The symmetric, bulky ClO 4 − anion effectively disrupts hydrogen bonds between water molecules and provides intrinsic ion diffusion even while frozen, and enables ≈260 mAh g −1 on MnO 2 cathodes at −30 °C . It is identified that subfreezing cycling shifts the reaction mechanism on the MnO 2 cathode from unstable H + insertion to predominantly pseudocapacitive Zn 2+ insertion, which converts MnO 2 nanofibers into complicated zincated MnO x that are largely disordered and appeared as crumpled paper sheets. The Zn 2+ insertion at −30 °C is faster and much more stable than at 20 °C, and delivers ≈80% capacity retention for 1000 cycles without Mn 2+ additives. In addition, simple Zn(ClO 4 ) 2 electrolyte also enables a nearly fully reversible and dendrite‐free Zn anode at −30 °C with ≈98% Coulombic efficiency. Zn–MnO 2 prototypes with an experimentally verified unit energy density of 148 Wh kg −1 at a negative‐to‐positive ratio of 1.5 and an electrolyte‐to‐capacity ratio of 2.0more »
- Authors:
-
[4]
- Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States). Applied Materials Division
- Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States). Applied Materials Division
- Univ. of Connecticut, Storrs, CT (United States)
- Northern Illinois Univ., DeKalb, IL (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Sources
- Argonne National Lab. (ANL), Lemont, IL (United States). Center for Nanoscale Materials
- Argonne National Lab. (ANL), Lemont, IL (United States). Applied Materials Division
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- Northern Illinois University; USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1910031
- Alternate Identifier(s):
- OSTI ID: 1865493
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Materials
- Additional Journal Information:
- Journal Volume: 34; Journal Issue: 21; Journal ID: ISSN 0935-9648
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Zn-MnO2 batteries; Subfreezing aqueous batteries; Pseudocapacitive; Selective Zn2+ insertion
Citation Formats
Gao, Siyuan, Li, Bomin, Tan, Haiyan, Xia, Fan, Dahunsi, Olusola, Xu, Wenqian, Liu, Yuzi, Wang, Rongyue, and Cheng, Yingwen. High-Energy and Stable Subfreezing Aqueous Zn–MnO2 Batteries with Selective and Pseudocapacitive Zn-Ion Insertion in MnO2. United States: N. p., 2022.
Web. doi:10.1002/adma.202201510.
Gao, Siyuan, Li, Bomin, Tan, Haiyan, Xia, Fan, Dahunsi, Olusola, Xu, Wenqian, Liu, Yuzi, Wang, Rongyue, & Cheng, Yingwen. High-Energy and Stable Subfreezing Aqueous Zn–MnO2 Batteries with Selective and Pseudocapacitive Zn-Ion Insertion in MnO2. United States. https://doi.org/10.1002/adma.202201510
Gao, Siyuan, Li, Bomin, Tan, Haiyan, Xia, Fan, Dahunsi, Olusola, Xu, Wenqian, Liu, Yuzi, Wang, Rongyue, and Cheng, Yingwen. Fri .
"High-Energy and Stable Subfreezing Aqueous Zn–MnO2 Batteries with Selective and Pseudocapacitive Zn-Ion Insertion in MnO2". United States. https://doi.org/10.1002/adma.202201510. https://www.osti.gov/servlets/purl/1910031.
@article{osti_1910031,
title = {High-Energy and Stable Subfreezing Aqueous Zn–MnO2 Batteries with Selective and Pseudocapacitive Zn-Ion Insertion in MnO2},
author = {Gao, Siyuan and Li, Bomin and Tan, Haiyan and Xia, Fan and Dahunsi, Olusola and Xu, Wenqian and Liu, Yuzi and Wang, Rongyue and Cheng, Yingwen},
abstractNote = {Abstract One major challenge of aqueous Zn–MnO 2 batteries for practical applications is their unacceptable performance below freezing temperatures. Here the use of simple Zn(ClO 4 ) 2 aqueous electrolytes is described for all‐weather Zn–MnO 2 batteries even down to −60 °C. The symmetric, bulky ClO 4 − anion effectively disrupts hydrogen bonds between water molecules and provides intrinsic ion diffusion even while frozen, and enables ≈260 mAh g −1 on MnO 2 cathodes at −30 °C . It is identified that subfreezing cycling shifts the reaction mechanism on the MnO 2 cathode from unstable H + insertion to predominantly pseudocapacitive Zn 2+ insertion, which converts MnO 2 nanofibers into complicated zincated MnO x that are largely disordered and appeared as crumpled paper sheets. The Zn 2+ insertion at −30 °C is faster and much more stable than at 20 °C, and delivers ≈80% capacity retention for 1000 cycles without Mn 2+ additives. In addition, simple Zn(ClO 4 ) 2 electrolyte also enables a nearly fully reversible and dendrite‐free Zn anode at −30 °C with ≈98% Coulombic efficiency. Zn–MnO 2 prototypes with an experimentally verified unit energy density of 148 Wh kg −1 at a negative‐to‐positive ratio of 1.5 and an electrolyte‐to‐capacity ratio of 2.0 are further demonstrated.},
doi = {10.1002/adma.202201510},
journal = {Advanced Materials},
number = 21,
volume = 34,
place = {United States},
year = {Fri Mar 25 00:00:00 EDT 2022},
month = {Fri Mar 25 00:00:00 EDT 2022}
}
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