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An Insight from the CALPHAD Approach: How to Control the LaMnO3 Perovskite Formation Via the Molten Salt Synthesis

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Abstract

LiCl-KCl molten salt has been used as a reaction medium to synthesize various perovskite materials from oxide precursors. However, it was observed that temperature, p(O2), precursor mix ratio, etc., greatly affected the perovskite stoichiometry, phase stability, crystal structure, and the formation of various impurities (secondary phases). Thermodynamics and kinetics involved in the synthesis are complicated. Guidance from thermodynamic modeling is thus needed to control the formation of the perovskites. In the present work, for the first time we use the CALculation of PHAse Diagram (CALPHAD) approach to develop a perovskite-molten salt thermodynamic database, which is used to understand the phase equilibrium between the molten salt, precursor oxides, and the resulting LaMnO3 (LMO) perovskite. Especially, the effects of temperature, La2O3 and Mn2O3 precursor ratio, and p(O2) on the LMO phase stability were predicted. Pseudo-ternary isothermal sections were generated, which successfully predicted the coexistence of LaMnO3 and the impurity, LaOCl. Meanwhile, the molten salt thermodynamic experiments were designed and carried out to verify La and Mn's solubilities in LiCl-KCl molten salt and thermodynamic equilibria in the La-Mn-O-Li-K-Cl system. The CALPHAD predictions were in accord with the experimental observations.

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Acknowledgment

This material is based upon work supported by the Department of Energy under Award Number DE- FE0031205. Useful discussions with Steven Markovich and Shailesh Vora at National Energy Technology Laboratory are acknowledged. This paper was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed or represented that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

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Authors and Affiliations

  1. Department of Mechanical Engineering, Worcester Polytechnic Institute, Worcester, MA, 01609, USA

    Yu Zhong, Shadi Darvish, Tauny Tambolleo & Mei Yang

  2. Division of Materials Science and Engineering, Boston University, Boston, MA, 02215, USA

    Benjamin Levitas & Srikanth Gopalan

  3. Department of Mechanical Engineering, Division of Materials Science and Engineering, Boston University, Boston, MA, 02215, USA

    Benjamin Levitas & Srikanth Gopalan

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  1. Yu Zhong
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Correspondence to Yu Zhong.

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Zhong, Y., Darvish, S., Levitas, B. et al. An Insight from the CALPHAD Approach: How to Control the LaMnO3 Perovskite Formation Via the Molten Salt Synthesis. J. Phase Equilib. Diffus. 42, 419–427 (2021). https://doi.org/10.1007/s11669-021-00895-9

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  • DOI: https://doi.org/10.1007/s11669-021-00895-9

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