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The interplay between thermodynamics and kinetics in the solid-state synthesis of layered oxides.

  • Bianchini, Matteo
  • Wang, Jingyang
  • Clément, Raphaële J
  • Ouyang, Bin
  • Xiao, Penghao
  • Kitchaev, Daniil
  • Shi, Tan
  • Zhang, Yaqian
  • Wang, Yan
  • Kim, Haegyeom
  • Zhang, Mingjian
  • Bai, Jianming
  • Wang, Feng
  • Sun, Wenhao
  • Ceder, Gerbrand
Publication Date
May 18, 2020
eScholarship - University of California
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In the synthesis of inorganic materials, reactions often yield non-equilibrium kinetic byproducts instead of the thermodynamic equilibrium phase. Understanding the competition between thermodynamics and kinetics is a fundamental step towards the rational synthesis of target materials. Here, we use in situ synchrotron X-ray diffraction to investigate the multistage crystallization pathways of the important two-layer (P2) sodium oxides Na0.67MO2 (M = Co, Mn). We observe a series of fast non-equilibrium phase transformations through metastable three-layer O3, O3' and P3 phases before formation of the equilibrium two-layer P2 polymorph. We present a theoretical framework to rationalize the observed phase progression, demonstrating that even though P2 is the equilibrium phase, compositionally unconstrained reactions between powder precursors favour the formation of non-equilibrium three-layered intermediates. These insights can guide the choice of precursors and parameters employed in the solid-state synthesis of ceramic materials, and constitutes a step forward in unravelling the complex interplay between thermodynamics and kinetics during materials synthesis.

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