Vanadium-Substituted Tunnel Structured Silver Hollandite (Ag1.2VxMn8–xO16): Impact on Morphology and Electrochemistry

Smith, Paul F.; Wang, Lei; Bock, David C.; Brady, Alexander B.; Lutz, Diana M.; Yang, Shize; Hu, Xiaobing; Wu, Lijun; Zhu, Yimei; Marschilok, Amy C.; Takeuchi, Esther S.; Takeuchi, Kenneth J.

doi:10.1021/acs.inorgchem.9b03443

Title: Vanadium-Substituted Tunnel Structured Silver Hollandite (Ag_1.2V_xMn_8–xO₁₆): Impact on Morphology and Electrochemistry

Journal Article · Wed Mar 04 00:00:00 EST 2020 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.9b03443· OSTI ID:1633605

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^[2]; Brady, Alexander B. ^[3];

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^[2]; Hu, Xiaobing ^[2]; Wu, Lijun ^[2];

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Stony Brook Univ., NY (United States); Valparaiso Univ., IN (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Stony Brook Univ., NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)

A series of tunnel structured vanadium-substituted silver hollandite (Ag_1.2V_xMn_{8- x}O₁₆, V = 0 – 1.4) samples is prepared and characterized through a combination of synchrotron Xray diffraction, synchrotron X-ray absorption spectroscopy, laboratory Raman spectroscopy and electron diffraction measurements. The oxidation states of the individual transition metals are characterized using V and Mn K-edge XAS data indicating the vanadium centers exist as V⁵⁺, and the Mn oxidation states decrease with increased V substitution to balance the charge. Scanning transmission electron microscopy of reduced materials shows reduction-displacement of silver metal at high levels of lithiation. In lithium batteries the V-substituted tunneled manganese oxide materials reveal previously unseen reversible non-aqueous Ag electrochemistry and exhibit up to 2.5x higher Li storage capacity relative to their unsubstituted counterparts. The highest capacity was observed for the Ag_1.2(V_0.8Mn_7.2)O₁₆∙0.8H₂O material with an intermediate level of vanadium substitution, likely due to a combination of the atomic composition, the morphology of the particle, and the homogeneous distribution of the active material within the electrode structure where factors over multiple length scales contribute to the electrochemistry.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Lab. (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1633605

Report Number(s):: BNL-216053-2020-JAAM

Journal Information:: Inorganic Chemistry, Vol. 59, Issue 6; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 3 works

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Title: Vanadium-Substituted Tunnel Structured Silver Hollandite (Ag1.2VxMn8–xO16): Impact on Morphology and Electrochemistry

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Title: Vanadium-Substituted Tunnel Structured Silver Hollandite (Ag_1.2V_xMn_8–xO₁₆): Impact on Morphology and Electrochemistry