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

Abstract

Here, lithium manganate LixMn2O4 (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 providingmore » new insights into the role of lattice strain in the stability of LMO.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [3];  [4]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]
  1. Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. College London, London (United Kingdom)
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  6. Oregon State Univ., Corvallis, OR (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1473685
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Energy Materials
Additional Journal Information:
Journal Volume: 1; Journal Issue: 6; Journal ID: ISSN 2574-0962
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 42 ENGINEERING; 25 ENERGY STORAGE; X-ray reflectivity; lithiation; lithium manganese oxide; spinel; strain

Citation Formats

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., and Fenter, Paul. Strain-Driven Mn-Reorganization in Overlithiated LixMn2O4 Epitaxial Thin-Film Electrodes. United States: N. p., 2018. Web. https://doi.org/10.1021/acsaem.8b00270.
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. Strain-Driven Mn-Reorganization in Overlithiated LixMn2O4 Epitaxial Thin-Film Electrodes. United States. https://doi.org/10.1021/acsaem.8b00270
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., and Fenter, Paul. Wed . "Strain-Driven Mn-Reorganization in Overlithiated LixMn2O4 Epitaxial Thin-Film Electrodes". United States. https://doi.org/10.1021/acsaem.8b00270. https://www.osti.gov/servlets/purl/1473685.
@article{osti_1473685,
title = {Strain-Driven Mn-Reorganization in Overlithiated LixMn2O4 Epitaxial Thin-Film Electrodes},
author = {Chen, Xiao and Vörös, Márton and Garcia, Juan C. and Fister, Tim T. and Buchholz, D. Bruce and Franklin, Joseph and Du, Yingge and Droubay, Timothy C. and Feng, Zhenxing and Iddir, Hakim and Curtiss, Larry A. and Bedzyk, Michael J. and Fenter, Paul},
abstractNote = {Here, lithium manganate LixMn2O4 (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.},
doi = {10.1021/acsaem.8b00270},
journal = {ACS Applied Energy Materials},
number = 6,
volume = 1,
place = {United States},
year = {2018},
month = {5}
}

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Figures / Tables:

Figure 1 Figure 1: Crystal structure (side view of close-packed oxygen arrays) for (a) tetragonal $λ$-Li2Mn2O4; (b)(c) monoclinic m-LiMnO2 with 2 different stacking orientations and (d) orthorhombic o-LiMnO2. Red, purple and green balls represent oxygen, manganese and lithium atoms, respectively. Projected electron density profiles along [111] direction for each structure are depictedmore » on the right.« less

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