Tuning effect of vanadium substitution on the structural and electronic properties of potassium hollandite surfaces

Kingan, Arun; King, Steven T.; Abraham, Alyson; Le, Thanh; Guo, Haoyue; Marschilok, Amy C.; Takeuchi, Esther S.; Takeuchi, Kenneth J.; Liu, Ping

doi:10.1063/5.0299913

Tuning effect of vanadium substitution on the structural and electronic properties of potassium hollandite surfaces

Journal Article · Mon Nov 24 00:00:00 EST 2025 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0299913· OSTI ID:3008060

Kingan, Arun ^[1]; ^[1]; Abraham, Alyson ^[1]; Le, Thanh ^[1]; ^[2]; ^[3]; ^[3]; ^[3]; ^[3]

Stony Brook Univ., NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Stony Brook Univ., NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Metal oxide surfaces possess unique properties that are crucial for a wide variety of applications. Herein, density functional theory calculations are performed to study surfaces of potassium hollandite, KMn₈O₁₆, a promising cathode material for electrochemical energy storage, and the vanadium-substituted analog KMn₇VO₁₆. The results show that there is a clear increase in the stability of KMn₈O₁₆ with (001) < (110) < (100) or (010), apt to adopt an elongated rod-like morphology. The vanadium (V)-substitution lowers the crystal symmetry and prefers to occupy the surface sites, resulting in electron redistribution and selective tuning of surface energy depending on the surface structures. In particular, the higher stability of substituted V⁴⁺ compared with Mn⁴⁺ ions leads to stabilization of the (001) surface due to the direct interaction of reduced Mn^δ+ ions on the surface, while such tuning effect decreases with the increase in surface stability, (110) > (100) and (010). As a result, the KMnO₁₆ rod is shortened upon V-substitution as observed experimentally, effectively facilitating the ion transport during discharge. The V substituents also introduce stabilization to the defect surfaces resulting from Mn²⁺ dissolution during cycling, thereby hindering further structural decay. In conclusion, our study demonstrates the potential tuning effect of V-substitution to promote the ion transport and mitigate the capacity degradation of α-MnO₂-based materials.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012673; SC0012704

OSTI ID:: 3008060

Report Number(s):: BNL--229190-2025-JAAM

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 20 Vol. 163; ISSN 1089-7690; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (56)

The Role of Tunnel‐Structured Hollandite Material Family for Advancing Energy Storage Applications Zeng, Xuemei; He, Kun; Li, Xiaomei Advanced Functional Materials, Vol. 35, Issue 39 https://doi.org/10.1002/adfm.202503135	journal	April 2025
Adjusting the Coordination Environment of Mn Enhances Supercapacitor Performance of MnO ₂ Zhang, Anqi; Zhao, Rui; Hu, Lingyuan Advanced Energy Materials, Vol. 11, Issue 32 https://doi.org/10.1002/aenm.202101412	journal	July 2021
Revealing the Dominance of the Dissolution‐Deposition Mechanism in Aqueous Zn−MnO₂ Batteries Li, Yadong; Li, Yuhao; Liu, Qingshan Angewandte Chemie, Vol. 136, Issue 6 https://doi.org/10.1002/ange.202318444	journal	January 2024
Rechargeable Zn−MnO₂ Batteries: Progress, Challenges, Rational Design, and Perspectives Meng, Linghui; Zhu, Yanzhe; Lu, Yile ChemElectroChem, Vol. 11, Issue 3 https://doi.org/10.1002/celc.202300495	journal	December 2023
Basics and Advances of Manganese‐Based Cathode Materials for Aqueous Zinc‐Ion Batteries Hashem Abdelmohsen, Ahmed; El‐khodary, Sherif A.; Ismail, Nahla Chemistry – A European Journal, Vol. 31, Issue 4 https://doi.org/10.1002/chem.202403425	journal	November 2024
Computational Screening of Doped α-MnO ₂ Catalysts for the Oxygen Evolution Reaction Tripkovic, Vladimir; Hansen, Heine Anton; Vegge, Tejs ChemSusChem, Vol. 11, Issue 3 https://doi.org/10.1002/cssc.201701659	journal	January 2018
Reversible Intercalation of Multivalent Al ³⁺ Ions into Potassium‐Rich Cryptomelane Nanowires for Aqueous Rechargeable Al‐Ion Batteries Joseph, Jickson; Nerkar, Jawahar; Tang, Cheng ChemSusChem, Vol. 12, Issue 16 https://doi.org/10.1002/cssc.201902126	journal	July 2019
Recent Progress and Regulation Strategies of Layered Materials as Cathode of Aqueous Zinc‐Ion Batteries Yuan, Yuan; Wu, Si; Song, Xiaoxue ENERGY & ENVIRONMENTAL MATERIALS, Vol. 7, Issue 3 https://doi.org/10.1002/eem2.12632	journal	May 2023
Rational optimization of substituted α‐MnO₂ cathode for aqueous zinc‐ion battery Le, Thanh; Takeuchi, Esther S.; Takeuchi, Kenneth J. Energy Storage, Vol. 6, Issue 4 https://doi.org/10.1002/est2.633	journal	May 2024
Revisiting the Charging Mechanism of α‐MnO₂ in Mildly Acidic Aqueous Zinc Electrolytes Wu, LangYuan; Li, ZhiWei; Xiang, YuXuan Small, Vol. 20, Issue 45 https://doi.org/10.1002/smll.202404583	journal	July 2024
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Nanostructured MnO2 for Li batteries Sugantha, M. International Journal of Hydrogen Energy, Vol. 28, Issue 6 https://doi.org/10.1016/S0360-3199(02)00148-9	journal	June 2003
Mechanism of surface effect and selective catalytic performance of MnO 2 nanorod: DFT+U study Chen, Zheng; Li, Guifa; Zheng, Haizhong Applied Surface Science, Vol. 420 https://doi.org/10.1016/j.apsusc.2017.05.141	journal	October 2017
Tailoring aqueous electrolytes based on M = Li, Na and K for the α-MnO2 electrode and its applications for energy storage devices: A DFT approach Delesma, Cornelio; Celaya, Christian A.; Jiménez-Juárez, Jesús A. Applied Surface Science, Vol. 686 https://doi.org/10.1016/j.apsusc.2024.162141	journal	March 2025
Arsenic adsorption on α-MnO2 nanofibers and the significance of (1 0 0) facet as compared with (1 1 0) Luo, Jinming; Meng, Xiaoyang; Crittenden, John Chemical Engineering Journal, Vol. 331 https://doi.org/10.1016/j.cej.2017.08.123	journal	January 2018
Unlocking the critical role of Mg doping in α-MnO2 cathode for aqueous zinc ion batteries Li, Qiongguang; Wang, Cun; Zhu, Yue Chemical Engineering Journal, Vol. 485 https://doi.org/10.1016/j.cej.2024.150077	journal	April 2024
Experimental and theoretical studies on NO selective catalytic oxidation over α-MnO2 Hao, Xingguang; Yang, Jie; Sun, Xin Journal of Environmental Sciences, Vol. 126 https://doi.org/10.1016/j.jes.2022.04.006	journal	April 2023
A comprehensive review of strategies to augment the performance of MnO2 cathode by structural modifications for aqueous zinc ion battery Azmi, Zarina; Senapati, Krushna C.; Goswami, Arpan K. Journal of Power Sources, Vol. 613 https://doi.org/10.1016/j.jpowsour.2024.234816	journal	September 2024
Elucidating the diffusion and interaction mechanisms of Zn2+ and H+ in MnO2 for aqueous zinc-ion batteries: A DFT study Zheng, Yichun; Chen, Diancheng; Zhao, Yuling Journal of Power Sources, Vol. 625 https://doi.org/10.1016/j.jpowsour.2024.235658	journal	January 2025
The effects of vanadium substitution on one-dimensional tunnel structures of cryptomelane: Combined TEM and DFT study Yang, Shi-Ze; Tallman, Killian R.; Liu, Ping Nano Energy, Vol. 71 https://doi.org/10.1016/j.nanoen.2020.104571	journal	May 2020
Synthesis and electrochemical behavior of hollandite MnO2/acetylene black composite cathode for secondary Mg-ion batteries Rasul, Shahid; Suzuki, Shinya; Yamaguchi, Shu Solid State Ionics, Vol. 225 https://doi.org/10.1016/j.ssi.2012.01.019	journal	October 2012
Investigation of α-MnO ₂ Tunneled Structures as Model Cation Hosts for Energy Storage Housel, Lisa M.; Wang, Lei; Abraham, Alyson Accounts of Chemical Research, Vol. 51, Issue 3 https://doi.org/10.1021/acs.accounts.7b00478	journal	February 2018
Reaction Mechanisms and Improvement of α-MnO₂ Cathode in Aqueous Zn-Ion Battery Hwang, Taesoon; Bergschneider, Matthew; Kong, Fantai Chemistry of Materials, Vol. 37, Issue 3 https://doi.org/10.1021/acs.chemmater.4c03176	journal	January 2025
Local and Bulk Probe of Vanadium-Substituted α-Manganese Oxide (α-K_xV_yMn_8–yO₁₆) Lithium Electrochemistry Lutz, Diana M.; Dunkin, Mikaela R.; Tallman, Killian R. Inorganic Chemistry, Vol. 60, Issue 14, p. 10398-10414 https://doi.org/10.1021/acs.inorgchem.1c00954	journal	July 2021
Vanadium-Substituted Tunnel Structured Silver Hollandite (Ag _1.2 V _x Mn _{8– x} O ₁₆ ): Impact on Morphology and Electrochemistry Smith, Paul F.; Wang, Lei; Bock, David C. Inorganic Chemistry, Vol. 59, Issue 6 https://doi.org/10.1021/acs.inorgchem.9b03443	journal	March 2020
Tuning Discharge Behavior of Hollandite α-MnO₂ in Hydrated Zinc Ion Battery by Transition Metal Substitution Le, Thanh; Takeuchi, Esther S.; Takeuchi, Kenneth J. The Journal of Physical Chemistry C, Vol. 127, Issue 2 https://doi.org/10.1021/acs.jpcc.2c06851	journal	January 2023
Transition Metal Substitution of Hollandite α-MnO ₂ : Enhanced Potential and Structural Stability on Lithiation from First-Principles Calculation Brady, Alexander B.; Tallman, Killian R.; Takeuchi, Esther S. The Journal of Physical Chemistry C, Vol. 123, Issue 41 https://doi.org/10.1021/acs.jpcc.9b05376	journal	September 2019
Discharging Behavior of Hollandite α-MnO ₂ in a Hydrated Zinc-Ion Battery Le, Thanh; Sadique, Nahian; Housel, Lisa M. ACS Applied Materials & Interfaces, Vol. 13, Issue 50 https://doi.org/10.1021/acsami.1c18849	journal	December 2021
Essential Role of Spinel ZnFe ₂ O ₄ Surfaces during Lithiation Guo, Haoyue; Marschilok, Amy C.; Takeuchi, Kenneth J. ACS Applied Materials & Interfaces, Vol. 10, Issue 41 https://doi.org/10.1021/acsami.8b12869	journal	September 2018
Engineering Crystal Facet of α-MnO ₂ Nanowire for Highly Efficient Catalytic Oxidation of Carcinogenic Airborne Formaldehyde Rong, Shaopeng; Zhang, Pengyi; Liu, Fang ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.8b00456	journal	March 2018
Structural Defects of Silver Hollandite, Ag _x Mn ₈ O _{y ,} Nanorods: Dramatic Impact on Electrochemistry Wu, Lijun; Xu, Feng; Zhu, Yimei ACS Nano, Vol. 9, Issue 8 https://doi.org/10.1021/acsnano.5b03274	journal	July 2015
Theory of Carbon Doping of Titanium Dioxide Di Valentin, Cristiana; Pacchioni, Gianfranco; Selloni, Annabella Chemistry of Materials, Vol. 17, Issue 26 https://doi.org/10.1021/cm051921h	journal	December 2005
Capture Lithium in αMnO ₂ : Insights from First Principles Ling, Chen; Mizuno, Fuminori Chemistry of Materials, Vol. 24, Issue 20 https://doi.org/10.1021/cm302347j	journal	October 2012
Reactivity of Anatase TiO ₂ Nanoparticles: The Role of the Minority (001) Surface Gong, Xue-Qing; Selloni, Annabella The Journal of Physical Chemistry B, Vol. 109, Issue 42 https://doi.org/10.1021/jp055311g	journal	October 2005
First Principles Study of Nitrogen Doping at the Anatase TiO ₂ (101) Surface Finazzi, Emanuele; Di Valentin, Cristiana; Selloni, Annabella The Journal of Physical Chemistry C, Vol. 111, Issue 26 https://doi.org/10.1021/jp071186s	journal	July 2007
Asynchronous Crystal Cell Expansion during Lithiation of K ⁺ -Stabilized α-MnO ₂ Yuan, Yifei; Nie, Anmin; Odegard, Gregory M. Nano Letters, Vol. 15, Issue 5 https://doi.org/10.1021/nl5048913	journal	April 2015
Rechargeable aqueous zinc-manganese dioxide batteries with high energy and power densities Zhang, Ning; Cheng, Fangyi; Liu, Junxiang Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00467-x	journal	September 2017
Cooperative Jahn-Teller effect and engineered long-range strain in manganese oxide/graphene superlattice for aqueous zinc-ion batteries Wang, Shijian; Guo, Xin; Huang, Kun Nature Communications, Vol. 16, Issue 1 https://doi.org/10.1038/s41467-025-60558-y	journal	June 2025
In situ high-energy synchrotron X-ray diffraction studies and first principles modeling of α-MnO ₂ electrodes in Li–O ₂ and Li-ion coin cells Yang, Zhenzhen; Trahey, Lynn; Ren, Yang Journal of Materials Chemistry A, Vol. 3, Issue 14 https://doi.org/10.1039/C4TA06633B	journal	January 2015
Surface properties of α-MnO ₂ : relevance to catalytic and supercapacitor behaviour Tompsett, David A.; Parker, Stephen C.; Islam, M. Saiful J. Mater. Chem. A, Vol. 2, Issue 37 https://doi.org/10.1039/c4ta00952e	journal	January 2014
A first principles study of spinel ZnFe ₂ O ₄ for electrode materials in lithium-ion batteries Guo, Haoyue; Zhang, Yiman; Marschilok, Amy C. Physical Chemistry Chemical Physics, Vol. 19, Issue 38 https://doi.org/10.1039/c7cp04590e	journal	January 2017
Quantitative temporally and spatially resolved X-ray fluorescence microprobe characterization of the manganese dissolution-deposition mechanism in aqueous Zn/α-MnO ₂ batteries Wu, Daren; Housel, Lisa M.; Kim, Sung Joo Energy & Environmental Science, Vol. 13, Issue 11 https://doi.org/10.1039/d0ee02168g	journal	January 2020
Microstructural study of hollandite-type MnO2 nano-fibers Benaissa, M.; José-Yacamán, M.; Xiao, T. D. Applied Physics Letters, Vol. 70, Issue 16 https://doi.org/10.1063/1.119253	journal	April 1997
Hollandites’ crystal chemistry, properties, and processing: a review Tumurugoti, Priyatham; Betal, Soutik; Sundaram, S. K. International Materials Reviews, Vol. 66, Issue 3 https://doi.org/10.1080/09506608.2020.1743592	journal	March 2020
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Charge localization and ordering in A 2 Mn 8 O 16 hollandite group oxides: Impact of density functional theory approaches Kaltak, Merzuk; Fernández-Serra, Marivi; Hybertsen, Mark S. Physical Review Materials, Vol. 1, Issue 7 https://doi.org/10.1103/PhysRevMaterials.1.075401	journal	December 2017
Photoexcitation of bulk polarons in rutile TiO2 Tanner, Alex J.; Wen, Bo; Zhang, Yu Physical Review B, Vol. 103, Issue 12 https://doi.org/10.1103/physrevb.103.l121402	journal	March 2021
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/physrevb.54.11169	journal	October 1996
Surface and subsurface oxygen vacancies in anatase TiO 2 and differences with rutile Cheng, Hongzhi; Selloni, Annabella Physical Review B, Vol. 79, Issue 9 https://doi.org/10.1103/physrevb.79.092101	journal	March 2009
Discharge, Relaxation, and Charge Model for the Lithium Trivanadate Electrode: Reactions, Phase Change, and Transport Brady, Nicholas W.; Zhang, Qing; Knehr, K. W. Journal of The Electrochemical Society, Vol. 163, Issue 14 https://doi.org/10.1149/2.0341614jes	journal	January 2016
Capacity Retention for (De)lithiation of Silver Containing α-MnO ₂ : Impact of Structural Distortion and Transition Metal Dissolution Huang, Jianping; Housel, Lisa M.; Quilty, Calvin D. Journal of The Electrochemical Society, Vol. 165, Issue 11 https://doi.org/10.1149/2.0371811jes	journal	January 2018
Recent development in addressing challenges and implementing strategies for manganese dioxide cathodes in aqueous zinc ion batteries Luo, Chi; Lei, Haoyun; Xiao, Yiyang Energy Materials, Vol. 4, Issue 3 https://doi.org/10.20517/energymater.2023.119	journal	April 2024
WulffPack: A Python package for Wulff constructions Rahm, J.; Erhart, Paul Journal of Open Source Software, Vol. 5, Issue 45 https://doi.org/10.21105/joss.01944	journal	January 2020
Cryptomelane-Type KMn8O16 as Potential Cathode Material — for Aqueous Zinc Ion Battery Cui, Jiajie; Wu, Xianwen; Yang, Sinian Frontiers in Chemistry, Vol. 6 https://doi.org/10.3389/fchem.2018.00352	journal	August 2018
Nanostructured MnO₂ as Electrode Materials for Energy Storage Julien, Christian M.; Mauger, Alain Nanomaterials, Vol. 7, Issue 11, p. 396 https://doi.org/10.3390/nano7110396	journal	November 2017

Similar Records

The effects of vanadium substitution on one-dimensional tunnel structures of cryptomelane: Combined TEM and DFT study

Journal Article · Mon Feb 03 19:00:00 EST 2020 · Nano Energy · OSTI ID:1633871

Tuning Discharge Behavior of Hollandite α-MnO₂ in Hydrated Zinc Ion Battery by Transition Metal Substitution

Journal Article · Thu Jan 05 19:00:00 EST 2023 · Journal of Physical Chemistry. C · OSTI ID:1964073

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

Journal Article · Tue Mar 03 19:00:00 EST 2020 · Inorganic Chemistry · OSTI ID:1633605

Related Subjects

25 ENERGY STORAGE
Interfaces
Materials
Surfaces

Tuning effect of vanadium substitution on the structural and electronic properties of potassium hollandite surfaces

Citation Formats

References (56)

Similar Records

Related Subjects