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High-Energy and Stable Subfreezing Aqueous Zn–MnO2 Batteries with Selective and Pseudocapacitive Zn-Ion Insertion in MnO2

Journal Article · · Advanced Materials
 [1];  [1];  [2];  [3];  [3];  [4];  [5];  [6];  [3]
  1. Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States). Applied Materials Division
  2. Univ. of Connecticut, Storrs, CT (United States)
  3. Northern Illinois Univ., DeKalb, IL (United States)
  4. Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Sources
  5. Argonne National Lab. (ANL), Lemont, IL (United States). Center for Nanoscale Materials
  6. Argonne National Lab. (ANL), Lemont, IL (United States). Applied Materials Division
+ Show Author Affiliations
One major challenge of aqueous Zn–MnO2 batteries for practical applications is their unacceptable performance below freezing temperatures. Here, in this study, the use of simple Zn(ClO4)2 aqueous electrolytes is described for all-weather Zn–MnO2 batteries even down to -60 °C. The symmetric, bulky ClO4- anion effectively disrupts hydrogen bonds between water molecules and provides intrinsic ion diffusion even while frozen, and enables ≈260 mAh g-1 on MnO2 cathodes at -30 °C . It is identified that subfreezing cycling shifts the reaction mechanism on the MnO2 cathode from unstable H+ insertion to predominantly pseudocapacitive Zn2+ insertion, which converts MnO2 nanofibers into complicated zincated MnOx that are largely disordered and appeared as crumpled paper sheets. The Zn2+ insertion at -30 °C is faster and much more stable than at 20 °C, and delivers ≈80% capacity retention for 1000 cycles without Mn2+ additives. In addition, simple Zn(ClO4)2 electrolyte also enables a nearly fully reversible and dendrite-free Zn anode at -30 °C with ≈98% Coulombic efficiency. Zn–MnO2 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.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
Northern Illinois University; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1910031
Alternate ID(s):
OSTI ID: 1865493
Journal Information:
Advanced Materials, Journal Name: Advanced Materials Journal Issue: 21 Vol. 34; ISSN 0935-9648
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

25 ENERGY STORAGE
Pseudocapacitive
Selective Zn2+ insertion
Subfreezing aqueous batteries
Zn-MnO2 batteries