Rational optimization of substituted α–MnO2 cathode for aqueous zinc–ion battery

Le, Thanh; Takeuchi, Esther S.; Takeuchi, Kenneth J.; Marschilok, Amy C.; Liu, Ping

doi:10.1002/est2.633

Rational optimization of substituted α–MnO₂ cathode for aqueous zinc–ion battery

Journal Article · Wed May 22 00:00:00 EDT 2024 · Energy Storage (Online)

DOI:https://doi.org/10.1002/est2.633· OSTI ID:2382639

Le, Thanh ^[1]; Takeuchi, Esther S. ^[2]; Takeuchi, Kenneth J. ^[2]; Marschilok, Amy C. ^[2]; ^[2]

State Univ. of New York (SUNY) at Stony Brook, NY (United States)
State Univ. of New York (SUNY) at Stony Brook, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Density functional theory (DFT) is utilized to explore the effects of increasing concentrations of vanadium (V) and chromium (Cr) substitution on the discharge of α-MnO₂ cathode in hydrated zinc-ion batteries (ZIBs). During H⁺-intercalation and Zn²⁺-intercalation, Cr-substitution proves to be more effective than V-substitution in promoting discharge behaviors. Transitioning from Mn_0.875Cr_0.125O₂, Mn_0.75Cr_0.25O₂ to Mn_0.625Cr_0.375O₂ is found to consistently enhance the discharge voltage, along with improved tunnel structure retention and volume expansion suppression. In comparison, the promoting effect of increasing V-substitution is relatively small at initial discharge stages and leads to degradation at later stages, primarily due to an increased concentration of unstable Mn²⁺ ion. The superior effect of Cr-substitution is attributed to the unique atomic and electronic structures of substituted Cr⁴⁺ and reduced Cr³⁺ ions during discharge. These ions serve as active electron acceptors to limit the formation of Mn³⁺ and Mn²⁺ ions, and as anchors to stabilize the α-MnO² framework and intercalated H⁺/Zn²⁺ ions, respectively. Finally, our study highlights fine-tuning through substitution to enhance the performance of α-MnO²-based cathode materials in ZIBs.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012673; SC0012704

OSTI ID:: 2382639

Report Number(s):: BNL--225760-2024-JAAM

Journal Information:: Energy Storage (Online), Journal Name: Energy Storage (Online) Journal Issue: 4 Vol. 6; ISSN 2578-4862

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Rational optimization of substituted α–MnO2 cathode for aqueous zinc–ion battery

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