Oxide Acidity Modulates Structural Transformations in Hydrogen Titanates during Electrochemical Li-Ion Insertion
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- North Carolina State University, Raleigh, NC (United States)
- North Carolina State University, Raleigh, NC (United States); Helmholtz Institute Ulm (HIU) for Electrochemical Energy Storage (Germany); Karlsruhe Institute of Technology (Germany)
- Ames Laboratory, and Iowa State University, Ames, IA (United States)
- Helmholtz Institute Ulm (HIU) for Electrochemical Energy Storage (Germany); Karlsruhe Institute of Technology (Germany)
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Vanderbilt University, Nashville, TN (United States)
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. Here, this behavior is an example of electrochemical electron transfer to a nonmetal element in a metal oxide host, in analogy to anion redox.
- Research Organization:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- Grant/Contract Number:
- AC05-00OR22725; AC02-76SF00515; AC02-07CH11358
- OSTI ID:
- 2474722
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 42 Vol. 146; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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