Epitaxial single-crystal thin films of Mn Ti1−O2− grown on (rutile)TiO2 substrates with pulsed laser deposition: Experiment and theory

Ilton, Eugene S.; Droubay, Timothy C.; Chaka, Anne M.; Kovařík, Libor; Varga, Tamás; Arey, Bruce W.; Kerisit, Sebastien N.

doi:10.1016/j.susc.2014.10.013

Cited by 9 publications

(7 citation statements)

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“…13−15 Formation of lithiated Mn−Ti solid solutions with the spinel structure has been considered to minimize the capacity loss during cycling of pure lithiated Mn spinel oxide for Li-ion batteries. 16−18 In our own work, epitaxial singlecrystal thin films of Mn x Ti 1−x O 2 with the rutile structure have been synthesized 19 to facilitate the derivation of intrinsic structure−property relationships for energy materials, in particular as it relates to diffusion of inserted lithium ions.…”

Section: ■ Introductionmentioning

confidence: 99%

Shell Model for Atomistic Simulation of Lithium Diffusion in Mixed Mn/Ti Oxides

et al. 2014

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Mixed Mn/Ti oxides present attractive physicochemical properties such as their ability to accommodate Li for application in Li-ion batteries. In this work, atomic parameters for Mn were developed to extend an existing shell model of the Li−Ti−O system and allow simulations of pure and lithiated Mn and mixed Mn/Ti oxide polymorphs. The shell model yielded good agreement with experimentally derived structures (i.e., lattice parameters and interatomic distances) and represented an improvement over existing potential models. The shell model was employed in molecular dynamics (MD) simulations of Li diffusion in the 1 × 1 c-direction channels of Li x Mn 1−y Ti y O 2 with the rutile structure, where 0 ≤ x ≤ 0.25 and 0 ≤ y ≤ 1. In the infinite dilution limit, the arrangement of Mn and Ti ions in the lattice was found to have a significant effect on the activation energy for Li diffusion in the c channels due to the destabilization of half of the interstitial octahedral sites. Anomalous diffusion was demonstrated for Li concentrations as low as x = 0.125, with a single Li ion positioned in every other c channel. Further increase in Li concentration showed not only the substantial effect of Li−Li repulsive interactions on Li mobility but also their influence on the time dependence of Li diffusion. The results of the MD simulations can inform intrinsic structure−property relationships for the rational design of improved electrode materials for Li-ion batteries.

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Section: ■ Introductionmentioning

confidence: 99%

Shell Model for Atomistic Simulation of Lithium Diffusion in Mixed Mn/Ti Oxides

et al. 2014

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“…According to the XAS spectra of Mn L-edge in Figure 5b, the electrochemical reaction is accompanied by the reduction of Mn 4+ in the film (explained in the next paragraph). Because Mn 3+ has a larger ionic radius than Mn 4+ , 43 the existence of Mn 3+ increases the lattice parameters. The change in the lattice parameter of 5 nm film is within the error range owing to the suppression effect of Ti diffusion.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Interfacial Titanium Diffusion Self-Adapting Layer in Ultrathin Epitaxial MnO₂/TiO₂ Heterostructures

Liu

Huang

Jiang

et al. 2020

ACS Appl. Mater. Interfaces

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The electrochemical performance of supercapacitors is suppressed by a large number of defects in the interface of heterostructure due to lattice mismatch. In this paper, the (001) oriented rutile MnO 2 thin films with different thicknesses were grown on rutile TiO 2 substrates. The lattice mismatch between film and substrate was minimized through a Ti diffusion self-adapting layer. The energy-dispersive spectroscopy mappings were used to measure the diffusion range of Ti. The results of high-resolution X-ray diffraction confirmed that the dependence of the out-of-plane lattice parameter on the thickness was consistent with the self-adapting interface model, indicating that Ti diffusion can indeed alleviate the lattice mismatch. In addition, the results of the synchrotron soft X-ray absorption spectrum indicated that the capacitance of the thin films with a large proportion of Ti diffusion increased with electrons involved in the reaction. Although the decrease of carrier density and conductivity of the thinner films depressed the electrochemical activity, it is worth mentioning that the film we designed still has considerable specific capacitance even when it is very thin, which can provide a new idea for the development of thinner and larger capacity potential microsupercapacitors.

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“…The transitions of XPS spectra of MnO compound are strongly dependent on the valence of the manganese (Mn 2+ , Mn 3+ , Mn 4+ ). They are discussed and reported by Ilton [22,23] and Cerato [24,25].…”

Section: Xps Compositional Analysismentioning

confidence: 91%

Spray Pyrolysis Synthesis of Pure and Mg-Doped Manganese Oxide Thin Films

et al. 2021

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Pure and Mg-doped manganese oxide thin films were synthesized on heated glass substrates using the spray pyrolysis technique. The surface chemical composition was investigated by the use of X-ray photoelectron spectroscopy (XPS). Structural and morphological properties were studied by using X-ray diffraction (XRD), scanning electron microscope (SEM) and atomic force microscopy (AFM). Optical properties were characterized by UV-visible spectroscopy. XPS spectra showed typical Mn (2p3/2), (2p1/2) and O (1s) peaks of Mn3O4 with a slight shift attributed to the formation of different chemical states of manganese. XRD analysis revealed the tetragonal phase of Mn3O4 with a preferred (211) growth orientation that improved with Mg-doping; likewise, grain size is observed to increase with the Mg doping. SEM images of Mn3O4 films showed rough surfaces composed of uniformly distributed nanograins whose size decreases with the Mg-doping. The manganese oxide films surface observed in AFM show a textured, rough and porous surface. The combination of transmittance and absorption data in the UV-visible range allowed determining the energy values of the Eg band gap (1.5–2.5 eV). The decrease of the band gap with the Mg-doping increase is attributed to the influence of the greater size of the Mg2+ ion in the manganese oxide lattice.

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Epitaxial single-crystal thin films of Mn Ti1−O2− grown on (rutile)TiO2 substrates with pulsed laser deposition: Experiment and theory

Cited by 9 publications

References 50 publications

Shell Model for Atomistic Simulation of Lithium Diffusion in Mixed Mn/Ti Oxides

Shell Model for Atomistic Simulation of Lithium Diffusion in Mixed Mn/Ti Oxides

Interfacial Titanium Diffusion Self-Adapting Layer in Ultrathin Epitaxial MnO₂/TiO₂ Heterostructures

Spray Pyrolysis Synthesis of Pure and Mg-Doped Manganese Oxide Thin Films

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Epitaxial single-crystal thin films of Mn Ti1−O2− grown on (rutile)TiO2 substrates with pulsed laser deposition: Experiment and theory

Cited by 9 publications

References 50 publications

Shell Model for Atomistic Simulation of Lithium Diffusion in Mixed Mn/Ti Oxides

Shell Model for Atomistic Simulation of Lithium Diffusion in Mixed Mn/Ti Oxides

Interfacial Titanium Diffusion Self-Adapting Layer in Ultrathin Epitaxial MnO2/TiO2 Heterostructures

Spray Pyrolysis Synthesis of Pure and Mg-Doped Manganese Oxide Thin Films

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Interfacial Titanium Diffusion Self-Adapting Layer in Ultrathin Epitaxial MnO₂/TiO₂ Heterostructures