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Formation and impact of nanoscopic oriented phase domains in electrochemical crystalline electrodes

Nature Materials volume 22, pages 92–99 (2023)Cite this article

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Abstract

Electrochemical phase transformation in ion-insertion crystalline electrodes is accompanied by compositional and structural changes, including the microstructural development of oriented phase domains. Previous studies have identified prevailingly transformation heterogeneities associated with diffusion- or reaction-limited mechanisms. In comparison, transformation-induced domains and their microstructure resulting from the loss of symmetry elements remain unexplored, despite their general importance in alloys and ceramics. Here, we map the formation of oriented phase domains and the development of strain gradient quantitatively during the electrochemical ion-insertion process. A collocated four-dimensional scanning transmission electron microscopy and electron energy loss spectroscopy approach, coupled with data mining, enables the study. Results show that in our model system of cubic spinel MnO2 nanoparticles their phase transformation upon Mg2+ insertion leads to the formation of domains of similar chemical identity but different orientations at nanometre length scale, following the nucleation, growth and coalescence process. Electrolytes have a substantial impact on the transformation microstructure (‘island’ versus ‘archipelago’). Further, large strain gradients build up from the development of phase domains across their boundaries with high impact on the chemical diffusion coefficient by a factor of ten or more. Our findings thus provide critical insights into the microstructure formation mechanism and its impact on the ion-insertion process, suggesting new rules of transformation structure control for energy storage materials.

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Fig. 1: Oriented phase domains in compositionally uniform cathode NPs.
Fig. 2: The oriented phase domain morphologies in discharged NPs and the origin from the symmetry change.
Fig. 3: Nucleation, growth and coalescence of oriented phase domains within cathode NPs across the entire discharge process.
Fig. 4: Oriented phase domains in different electrolyte conditions and their impacts on strain gradients and ion diffusion.

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Data availability

The 4D-STEM and EELS data associated with this paper can be found at https://doi.org/10.13012/B2IDB-4717991_V1. Additional data are available on request from the corresponding authors.

Code availability

The codes used for the 4D-STEM strain mapping, oriented phase domain analysis, EELS analysis, radial distribution function and pair correlation function calculations can be accessed at https://github.com/chenlabUIUC/OrientedPhaseDomain. Additional codes are available on request from the corresponding authors.

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Acknowledgements

This work was primarily (sample preparation, majority of the 4D-STEM, EELS, XRD characterizations, electrochemical testing and data analysis) supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under award DE-SC0022035 (W.C., Z.T. and Q.C.). Some of the 4D-STEM experiments and the atomic-scale imaging were supported by Intel Corporation through an SRC project, award 54071821 (R.Y. and J.-M.Z.) and the Energy & Biosciences Institute through the EBI-Shell programme (W.C., S.P., C.Z., H.Y., J.-M.Z. and Q.C.). The DFT calculation and GITT and EIS measurements were supported in part by the US Army Construction Engineering Research Laboratory, Temperature Insensitive High-Density Lithium-Ion Batteries, award W9132T-21-2-0008 (A.X.B.Y., H.J., E.E., A.P. and P.V.B.). The preparation of dry solvents in the glovebox was supported in part by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the US Department of Energy, Office of Science, Basic Energy Sciences (K.T. and A.A.G.). The analysis of XRD data by Rietveld refinement was supported by a DIGI-MAT fellowship from the NSF DGE programme, award 1922758 (Z.W.R. and D.P.S.) using instrumentation partially supported by NSF through the University of Illinois Materials Research Science and Engineering Center DMR-172063. We thank Z. Ou and J. W. Smith at the University of Illinois for discussions on radial distribution function. We thank C. Qian and L. Yao at the University of Illinois for assistance with MATLAB coding in the analysis of the radial distribution functions and strain gradients. We thank N. Admal at the University of Illinois for discussions on domain morphology and phase separation. We thank Y. Yang at Columbia University for discussions on electrochemical tests.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA

    Wenxiang Chen, Xun Zhan, Renliang Yuan, Saran Pidaparthy, Adrian Xiao Bin Yong, Hyosung An, Zhichu Tang, Kaijun Yin, Arghya Patra, Zachary W. Riedel, Daniel P. Shoemaker, Paul V. Braun, Jian-Min Zuo & Qian Chen

  2. Materials Research Laboratory, University of Illinois, Urbana, IL, USA

    Wenxiang Chen, Xun Zhan, Adrian Xiao Bin Yong, Hyosung An, Arghya Patra, Zachary W. Riedel, Daniel P. Shoemaker, Hong Yang, Andrew A. Gewirth, Paul V. Braun, Elif Ertekin, Jian-Min Zuo & Qian Chen

  3. Department of Mechanical Science and Engineering, University of Illinois, Urbana, IL, USA

    Heonjae Jeong, Paul V. Braun & Elif Ertekin

  4. Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana, IL, USA

    Cheng Zhang, Hong Yang, Paul V. Braun & Qian Chen

  5. Department of Chemistry, University of Illinois, Urbana, IL, USA

    Kim Ta, Hong Yang, Andrew A. Gewirth, Paul V. Braun & Qian Chen

  6. Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, IL, USA

    Kim Ta & Andrew A. Gewirth

  7. Shell International Exploration and Production Inc., Houston, TX, USA

    Ryan M. Stephens

  8. Beckman Institute for Advanced Science and Technology, University of Illinois, Urbana, IL, USA

    Paul V. Braun & Qian Chen

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  1. Wenxiang Chen
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Contributions

W.C., J.-M.Z. and Q.C. planned the research and led the project. W.C. performed material processing and conducted electrochemical measurements. X.Z., R.Y., W.C., S.P. and K.Y. conducted the 4D-STEM and STEM imaging. S.P., W.C., X.Z. and K.Y. conducted EELS mapping. W.C., X.Z., R.Y., J.-M.Z. and Q.C. analysed and interpreted the electron microscopy data. W.C., with assistance from H.A. and A.P., analysed and interpreted the electrochemical results. Z.W.R. and D.P.S. performed the analysis of XRD data by Rietveld refinement. A.X.B.Y., H.J. and E.E. performed the DFT calculations. Z.T., C.Z., K.T. and H.Y. assisted in sample preparation. A.P., H.A., P.V.B. and A.A.G. assisted with GITT and EIS measurements. H.A. assisted with preparation of schematics. W.C., J.-M. Z. and Q.C. wrote the manuscript. R.M.S., J.-M.Z. and Q.C. supervised the research. All authors contributed to the discussion of the results.

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Correspondence to Jian-Min Zuo or Qian Chen.

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Nature Materials thanks Matthew McDowell and Colin Ophus for their contribution to the peer review of this work.

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Supplementary Notes 1‒7, Tables 1‒3, Figs. 1‒30 and refs.

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Chen, W., Zhan, X., Yuan, R. et al. Formation and impact of nanoscopic oriented phase domains in electrochemical crystalline electrodes. Nat. Mater. 22, 92–99 (2023). https://doi.org/10.1038/s41563-022-01381-4

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