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

doi:10.1038/s41563-020-0688-6

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

Journal Article · Mon May 18 00:00:00 EDT 2020 · Nature Materials

DOI:https://doi.org/10.1038/s41563-020-0688-6· OSTI ID:1633027

^[1]; Wang, Jingyang ^[2]; Clément, Raphaële J. ^[3]; Ouyang, Bin ^[2]; Xiao, Penghao ^[2]; Kitchaev, Daniil ^[4]; Shi, Tan ^[2]; Zhang, Yaqian ^[2];

^[5];

^[2];

^[6];

^[7];

^[2]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Karlsruhe Inst. of Technology (KIT) (Germany)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Univ. of California, Santa Barbara, CA (United States)
Univ. of California, Santa Barbara, CA (United States)
Samsung Research America, Burlington, MA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Michigan, Ann Arbor, MI (United States)

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. In this work, 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.

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Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials Design (CNGMD); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Samsung Advanced Institute of Technology; National Science Foundation (NSF)

Grant/Contract Number:: SC0012704; UGA-0-41029-16/ER392000; DMR-1332208; AC02-06CH11357; AC02-05CH11231

OSTI ID:: 1633027

Alternate ID(s):: OSTI ID: 1633290

Report Number(s):: BNL-216004-2020-JAAM

Journal Information:: Nature Materials, Vol. 19, Issue 10; ISSN 1476-1122

Publisher:: Springer Nature - Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 79 works

Citation information provided by
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