Oxide Acidity Modulates Structural Transformations in Hydrogen Titanates during Electrochemical Li-Ion InsertionClick to copy article linkArticle link copied!
- Saeed SaeedSaeed SaeedDepartment of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27606, United StatesMore by Saeed Saeed
- Simon FleischmannSimon FleischmannDepartment of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27606, United StatesHelmholtz Institute Ulm (HIU) for Electrochemical Energy Storage, 89081 Ulm, GermanyKarlsruhe Institute of Technology, 76021 Karlsruhe, GermanyMore by Simon Fleischmann
- Takeshi KobayashiTakeshi KobayashiU.S. DoE Ames National Laboratory, Iowa State University, Ames, Iowa 50011, United StatesMore by Takeshi Kobayashi
- Zenonas JusysZenonas JusysHelmholtz Institute Ulm (HIU) for Electrochemical Energy Storage, 89081 Ulm, GermanyKarlsruhe Institute of Technology, 76021 Karlsruhe, GermanyMore by Zenonas Jusys
- Eugene MamontovEugene MamontovNeutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United StatesMore by Eugene Mamontov
- Naresh C. OstiNaresh C. OstiNeutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United StatesMore by Naresh C. Osti
- Noah P. HolzapfelNoah P. HolzapfelDepartment of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27606, United StatesMore by Noah P. Holzapfel
- Haohong SongHaohong SongInterdisciplinary Materials Science Program, Vanderbilt University, Nashville, Tennessee 37235, United StatesMore by Haohong Song
- Tao WangTao WangChemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United StatesMore by Tao Wang
- Sheng DaiSheng DaiChemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United StatesMore by Sheng Dai
- De-en JiangDe-en JiangInterdisciplinary Materials Science Program, Vanderbilt University, Nashville, Tennessee 37235, United StatesDepartment of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, Tennessee 37235, United StatesMore by De-en Jiang
- Veronica Augustyn*Veronica Augustyn*Email: [email protected]Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27606, United StatesMore by Veronica Augustyn
Abstract
Hydrogen titanates (HTOs) form a diverse group of metastable, layered titanium oxides with an interlayer containing both water molecules and structural protons. We investigated how the chemistry of this interlayer environment influenced electrochemical Li+-insertion in a series of HTOs, H2TiyO2y+1·nH2O (y = 3, 4, and 5). We correlated the electrochemical response with the physical and chemical properties of HTOs using operando X-ray diffraction, in situ differential electrochemical mass spectroscopy, solid-state proton nuclear magnetic resonance, and quasi-elastic neutron scattering. We found that the potential for the first reduction reaction trended with the relative acidity of the structural protons. This mechanism was supported with first-principles density functional theory (DFT) calculations. We propose that the electrochemical reaction involves reduction of the structural protons to yield hydrogen gas and formation of a lithiated hydrogen titanate (H2–xLixTiyO2y+1). The hydrogen gas is confined within the HTO lattice until the titanate structure expands upon subsequent oxidation. Our work has implications for the electrochemical behavior of insertion hosts containing hydrogen and structural water molecules, where hydrogen evolution is expected at potentials below the hydrogen reduction potential and in the absence of electrolyte proton donors. This behavior is an example of electrochemical electron transfer to a nonmetal element in a metal oxide host, in analogy to anion redox.
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This article is cited by 2 publications.
- Mennatalla Elmanzalawy, Haohong Song, Maciej Tobis, Robert Leiter, Jaehoon Choi, Hyein Moon, Wan‐Yu Tsai, De‐en Jiang, Simon Fleischmann. Nanoconfinement‐Induced Electrochemical Ion‐Solvent Cointercalation in Pillared Titanate Host Materials. Angewandte Chemie International Edition 2025, https://doi.org/10.1002/anie.202423593
- Mennatalla Elmanzalawy, Haohong Song, Maciej Tobis, Robert Leiter, Jaehoon Choi, Hyein Moon, Wan‐Yu Tsai, De‐en Jiang, Simon Fleischmann. Nanoconfinement‐Induced Electrochemical Ion‐Solvent Cointercalation in Pillared Titanate Host Materials. Angewandte Chemie 2025, https://doi.org/10.1002/ange.202423593
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