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

Matteo Bianchini; Jingyang Wang; Raphaële J Clément; Bin Ouyang; Penghao Xiao; Daniil Kitchaev; Tan Shi; Yaqian Zhang; Yan Wang; Haegyeom Kim; Mingjian Zhang; Jianming Bai; Feng Wang; Wenhao Sun; Gerbrand Ceder

doi:10.1038/s41563-020-0688-6

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

Nat Mater. 2020 Oct;19(10):1088-1095. doi: 10.1038/s41563-020-0688-6. Epub 2020 May 18.

Authors

Matteo Bianchini^#^{1

2

3}, Jingyang Wang^#^{1

2}, Raphaële J Clément^{2

4}, Bin Ouyang^{1

2}, Penghao Xiao^{1

2}, Daniil Kitchaev⁴, Tan Shi^{1

2}, Yaqian Zhang^{1

2}, Yan Wang⁵, Haegyeom Kim^{1

2}, Mingjian Zhang⁶, Jianming Bai⁶, Feng Wang⁶, Wenhao Sun^{7

8}, Gerbrand Ceder^{9

10}

Affiliations

¹ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
² Department of Materials Science and Engineering, University of California, Berkeley, CA, USA.
³ Battery and Electrochemistry Laboratory, Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Germany.
⁴ Materials Department, University of California Santa Barbara, Santa Barbara, CA, USA.
⁵ Samsung Research America, Burlington, MA, USA.
⁶ Brookhaven National Laboratory, Upton, NY, USA.
⁷ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. whsun@umich.edu.
⁸ Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI, USA. whsun@umich.edu.
⁹ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. gceder@berkeley.edu.
¹⁰ Department of Materials Science and Engineering, University of California, Berkeley, CA, USA. gceder@berkeley.edu.

^# Contributed equally.

PMID: 32424371
DOI: 10.1038/s41563-020-0688-6

Abstract

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 Na_0.67MO₂ (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.