Strain-Driven Mn-Reorganization in Overlithiated LixMn2O4 Epitaxial Thin-Film Electrodes

Chen, Xiao; Vörös, Márton; Garcia, Juan C.; Fister, Tim T.; Buchholz, D. Bruce; Franklin, Joseph; Du, Yingge; Droubay, Timothy C.; Feng, Zhenxing; Iddir, Hakim; Curtiss, Larry A.; Bedzyk, Michael J.; Fenter, Paul

doi:10.1021/acsaem.8b00270

Title: Strain-Driven Mn-Reorganization in Overlithiated Li_xMn₂O₄ Epitaxial Thin-Film Electrodes

Journal Article · 23 May 2018 · ACS Applied Energy Materials

DOI: https://doi.org/10.1021/acsaem.8b00270 · OSTI ID:1473685

Chen, Xiao ^[1];

^[2];

^[2]; Buchholz, D. Bruce ^[3]; Franklin, Joseph ^[4];

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^[2];

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Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. College London, London (United Kingdom)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Oregon State Univ., Corvallis, OR (United States)

Here, lithium manganate Li_xMn₂O₄ (LMO) is a lithium ion cathode that suffers from the widely observed but poorly understood phenomenon of capacity loss due to Mn dissolution during electrochemical cycling. Here, operando X-ray reflectivity (low- and high-angle) is used to study the structure and morphology of epitaxial LMO (111) thin film cathodes undergoing lithium insertion and extraction to understand the inter-relationships between biaxial strain and Mn-dissolution. The initially strain-relieved LiMn₂O₄ films generate in-plane tensile and compressive strains for delithiated (x < 1) and overlithiated (x > 1) charge states, respectively. The results reveal reversible Li insertion into LMO with no measurable Mn-loss for 0 < x < 1, as expected. In contrast, deeper discharge (x > 1) reveals Mn loss from LMO along with dramatic changes in the intensity of the (111) Bragg peak that cannot be explained by Li stoichiometry. These results reveal a partially reversible site reorganization of Mn ions ithin the LMO film that is not seen in bulk reactions and indicates a transition in Mn-layer toichiometry from 3:1 to 2:2 in alternating cation planes. Density functional theory calculations confirm that compressive strains (at x = 2) stabilize LMO structures with 2:2 Mn site distributions, therefore providing new insights into the role of lattice strain in the stability of LMO.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-76RL01830; AC02-06CH11357

OSTI ID:: 1473685

Alternate ID(s):: OSTI ID: 1843219

Report Number(s):: PNNL-SA-132780

Journal Information:: ACS Applied Energy Materials, Vol. 1, Issue 6; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 14 works

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