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

Abstract

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 providingmore »« less

Authors:

Chen, Xiao ^[1];

^[2];

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

^[5];

^[6];

^[2];

^[3];

^[2]

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)

Publication Date:: 2018-05-23

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

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

OSTI Identifier:: 1473685

Alternate Identifier(s):: OSTI ID: 1843219

Report Number(s):: PNNL-SA-132780
Journal ID: ISSN 2574-0962; 143605

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

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.  doi:10.1021/acsaem.8b00270.

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                    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

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                    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.

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@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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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 »

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

Abstract

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