Tunnel Structured α-MnO 2 with Different Tunnel Cations (H + , K + , Ag + ) as Cathode Materials in Rechargeable Lithium Batteries: The Role of Tunnel Cation on Electrochemistry

Poyraz, Altug S.; Huang, Jianping; Cheng, Shaobo; Wu, Lijun; Tong, Xiao; Zhu, Yimei; Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S.

doi:10.1149/2.0911709jes

Title: Tunnel Structured α-MnO ₂ with Different Tunnel Cations (H ⁺ , K ⁺ , Ag ⁺ ) as Cathode Materials in Rechargeable Lithium Batteries: The Role of Tunnel Cation on Electrochemistry

Journal Article · Wed Jul 12 00:00:00 EDT 2017 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/2.0911709jes· OSTI ID:1426450

Poyraz, Altug S. ^[1];

^[2]; Cheng, Shaobo ^[3]; Wu, Lijun ^[1]; Tong, Xiao ^[4]; Zhu, Yimei ^[1]; Marschilok, Amy C. ^[5]; Takeuchi, Kenneth J. ^[5]; Takeuchi, Esther S. ^[6]

Brookhaven National Laboratory (BNL), Upton, NY (United States). Energy Sciences Directorate
Stony Brook Univ., NY (United States). Dept. of Chemistry
Brookhaven National Laboratory (BNL), Upton, NY (United States). Energy Sciences Directorate; Tsinghua Univ., Beijing (China). Dept. of Materials Science and Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Stony Brook Univ., NY (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering
Brookhaven National Laboratory (BNL), Upton, NY (United States). Energy Sciences Directorate; Stony Brook Univ., NY (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering

α-MnO₂ type manganese dioxide is an interesting prospective cathode material for reversible lithium insertion owing to its cation accessible tunnels (0.46nm x 0.46nm), high voltage, and low cost. The tunneled structure is synthetically formed by the assistance of cations acting as structure directing agents where the cations may remain in the tunnel. The electrochemistry of this family of materials is strongly dependent on the morphological and physicochemical (i.e. surface area, crystallite size, and average manganese oxidation state) properties as well as tunnel occupancy. For this work, we prepared a set of materials Mn₈O₁₆·0.81H₂O, K_0.81Mn₈O₁₆·0.78H₂O and Ag_1.33Mn₈O₁₆·0.95H₂O with similar nanorod morphology, crystallite size, surface area, and tunnel water content. This set of samples allowed us to investigate the role of tunnel cations in the electrochemistry of α-MnO₂ type manganese dioxide in a lithium based environment while minimizing the effects of the other parameters. The electrochemistry was evaluated using cyclic voltammetry, galvanostatic cycling, rate capability, and galvanostatic intermittent titration type testing. Mn₈O₁₆·0.81H₂O showed higher loaded voltages, improved capacity retention, and higher specific energy relative to K_0.81Mn₈O₁₆·0.78H₂O and Ag_1.33Mn₈O₁₆·0.95H₂O. After 100 cycles, Mn₈O₁₆·0.81H₂O delivered ~200% more capacity than Ag_1.33Mn₈O₁₆·0.95H₂O (64 vs. 129 mAh/g) and ~35% more capacity than K_0.81Mn₈O₁₆·0.78H₂O (85 vs. 129 mAh/g). Mn₈O₁₆·0.81H₂O also showed higher effective lithium diffusion coefficients (DLi+) and higher rate capability compared to K_0.81Mn₈O₁₆·0.78H₂O and Ag_1.33Mn₈O₁₆·0.95H₂O suggesting faster Li+ ion diffusion in the absence of large metal tunnel cations.

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Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: SC0012704; SC0012673; AC02-98CH10886

OSTI ID:: 1426450

Report Number(s):: BNL-203332-2018-JAAM

Journal Information:: Journal of the Electrochemical Society, Vol. 164, Issue 9; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 30 works

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25 ENERGY STORAGE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
Rechargeable
Li Battery
Cryptomelane
Hollandite
Manganese Dioxide
tunnel
cation
battery
energy storage
hollandite

Title: Tunnel Structured α-MnO 2 with Different Tunnel Cations (H + , K + , Ag + ) as Cathode Materials in Rechargeable Lithium Batteries: The Role of Tunnel Cation on Electrochemistry

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Title: Tunnel Structured α-MnO ₂ with Different Tunnel Cations (H ⁺ , K ⁺ , Ag ⁺ ) as Cathode Materials in Rechargeable Lithium Batteries: The Role of Tunnel Cation on Electrochemistry