Controlling ion transport and topotactic phase transition processes in oxide thin films
EMSL Project ID
50084
Abstract
The overarching goal of this proposal is to understand, predict, and ultimately control ion transport and topotactic phase transition (TPT) processes occurring in structurally ordered transition metal oxide (TMO) thin films. The fundamental science we propose is highly relevant to energy conversion and storage technologies, as such fundamental processes govern the mass-transport properties and failure mechanisms of widely used electrode and electrolyte materials. TPTs occurring at the forefront of many catalytic reactions and electrode/electrolyte interfaces are often responsible for many of the challenges (e.g., safety concern due to volume expansion and capacity decrease after cycling due to loss of desired structure/phase) found in lithium ion batteries and solid oxide fuel cells. We will investigate structurally and compositionally well-defined complex oxide films and thin-film based devices that will enable the facile intercalation of either small cations (e.g., Li+, Na+, and Ca2+) or oxygen anions (O2-). Our team will bring together 1) state-of-the-art synthesis of oxide thin film heterostructures and devices; 2) detailed in situ/in operando characterization of the superstructures, film/substrate, film/film, film/vacuum, and film/solvent interfaces, and their evolution as a function of interfacial strain, doping level, and processing conditions; and 3) ab initio modeling of defect formation, structural ordering, and phase transition pathways and kinetics within the studied materials. The specific aims of this research are to: 1) correlate atomic-scale structural evolution, mesoscale topotactic phase transition, and macroscopic mass transport characteristics as TPTs occur; 2) understand how doping and interfacial strain can be used to modify the onset (e.g., temperature, electrochemical potential), dynamics, intermediate states, and trajectories of TPTs.
The unique and powerful synthesis, characterization, and high performance computing capabilities in EMSL will allow us to establish defensible structure-stability-property relationships. By controlling the onset and trajectories of the TPTs, metastable phases with desired functional properties can be designed, synthesized, stabilized, and harnessed for technological benefits. This project is well aligned with EMSL’s “Molecular Transformations” thrust of investigating the “dynamic transformation mechanisms and physical and chemical properties at critical interfaces in catalysts and energy materials needed to design new materials and systems for sustainable energy applications.”
Project Details
Start Date
2017-10-13
End Date
2018-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
Fister T.T., Y. Du, Z. Feng, H. Iddir, L.A. Curtiss, and P. Fenter. 2018. "Strain-driven Mn-reorganization in over-lithiated Li2Mn2O4 epitaxial thin-film electrodes." Applied Energy Materials 1, no. 6:2526–2535. PNNL-SA-132780. doi:10.1021/acsaem.8b00270
Guo L., Z. Yang, K. Marcus, Z. Li, B. Luo, L. Zhou, and X. Wang, et al. 2018. "MoS2/TiO2 Heterostructures as Nonmetal Plasmonic Photocatalysts for Highly Efficient Hydrogen Evolution." Energy & Environmental Science 11, no. 1:106-114. PNNL-SA-129523. doi:10.1039/C7EE02464A
He Y., J. Liu, L. Luo, Y. Wang, J. Zhu, Y. Du, and J. Li, et al. 2018. "Size-Dependent Dynamic Structures of Supported Gold Nanoparticles in CO Oxidation Reaction Condition." Proceedings of the National Academy of Sciences of the United States of America 115, no. 30:7700-7705. PNNL-SA-134341. doi:10.1073/pnas.1800262115
Liang K., K. Marcus, Z. Yang, L. Zhou, H. Pan, Y. Bai, and Y. Du, et al. 2018. "Freestanding NiFe Oxyfluoride Holey Film with Ultrahigh Volumetric Capacitance for Flexible Asymmetric Supercapacitors." Small 14, no. 3:Article No. 1702295. PNNL-SA-130019. doi:10.1002/smll.201702295
Li G., Q. Shen, Z. Yang, S. Kou, F. Zhang, W. Zhang, and H. Guo, et al. 2019. "Photocatalytic behaviors of epitaxial BiVO4 (010) thin films." Applied Catalysis. B, Environmental 248. PNNL-SA-136328. doi:10.1016/j.apcatb.2019.02.028
Li X., K. Zhang, D. Mitlin, M. Wang, J. Fei, Y. Huang, and Z. Yang, et al. 2018. "Li-rich Li[Li1/6Fe1/6Ni1/6Mn1/2]O2 (LFNMO) Cathodes: Atomic Scale Insight on the Mechanisms of Cycling Decay and of the Improvement due to Cobalt Phosphate Surface Modification." Small 14, no. 40:Article number 1802570. PNNL-SA-136858. doi:10.1002/smll.201802570
Li X., K. Zhang, Z. Yang, M. Wang, Y. Tang, J. Fei, and Y. Du, et al. 2018. "Fundamental Insight into Zr Modification of Li- and Mn-Rich Cathodes: Combined Transmission Eelctron Microscopy and Electrochemical Impedance Spectroscopy Study." Chemistry of Materials 30, no. 8:2566-2573. PNNL-SA-130227. doi:10.1021/acs.chemmater.7b04861
Ong P., Z. Yang, P. Sushko, and Y. Du. 2018. "Formation, Structural Variety, and Impact of Anti-Phase Boundaries on Li Diffusion in LiCoO2 Thin Film Cathodes." Journal of Physical Chemistry Letters 9, no. 18:5515-5520. PNNL-SA-137774. doi:10.1021/acs.jpclett.8b02185
Qin Y., Z. Yang, J.J. Wang, Z.Y. Xie, M. Cui, C.M. Tian, and Y. Du, et al. 2019. "Epitaxial Growth and Band Alignment of p-NiO/n-Fe2O3 Heterojunction on Al2O3(0001)." Applied Surface Science 464. PNNL-SA-138270. doi:10.1016/j.apsusc.2018.09.106
Wang L., K.A. Stoerzinger, L. Chang, J. Zhao, Y. Li, C. Tang, and X. Yin, et al. 2018. "Tuning Bifunctional Oxygen Electrocatalysts by Changing A-site Rare-Earth Element in Perovskite Nickelates." Advanced Functional Materials. PNNL-SA-135288. doi:10.1002/adfm.201803712
Wang L., K.A. Stoerzinger, L. Chang, X. Yin, Y. Li, C. Tang, and E. Jia, et al. 2019. "Strain Effect on Oxygen Evolution Reaction Activity of Epitaxial NdNiO3 Thin Films." ACS Applied Materials & Interfaces 11, no. 13:12941-12947. PNNL-SA-139978. doi:10.1021/acsami.8b21301
Yang Z., P. Ong, Y. He, L. Wang, M.E. Bowden, W. Xu, and T.C. Droubay, et al. 2018. "Direct Visualization of Li Dendrite Effect on LiCoO2 Cathode by In Situ TEM." Small 14, no. 52:1803108. PNNL-SA-135382. doi:10.1002/smll.201803108
Zhang JY, W Li, RLZ Hoye, JL Macmanus-Driscoll, M Budde, O Bierwagen, L Wang, Y Du, MJ Wahila, LFJ Piper, TL Lee, HJ Edwards, VR Dhanak, and KHL Zhang. 2018. "Electronic and transport properties of Li-doped NiO epitaxial thin films." Journal of Materials Chemistry C 6(9):2275-2282. doi:10.1039/c7tc05331b
Zhang K.L., G. Li, S.R. Spurgeon, L. Wang, P. Yan, Z. Wang, and M. Gu, et al. 2018. "Creation and Ordering of Oxygen Vacancies at WO3-d and Perovskite Interfaces." ACS Applied Materials & Interfaces 10, no. 20:17480–17486. PNNL-SA-132665. doi:10.1021/acsami.8b03278