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Grain boundary zirconia-modified garnet solid-state electrolyte

Nature Materials (2025)Cite this article

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Abstract

We report a method for promoting electrochemical stability in garnet Li6.4La3Zr1.4Ta0.6O12 solid-state electrolyte based on a composite two-phase oxide–oxide microstructure. Grain boundary precipitation of the controlled distribution of amorphous zirconium oxide microparticles is achieved through the addition of reactive tantalum carbide. During ambient-atmosphere sintering, the carbide decomposes through an in situ reaction, the ‘extra’ Ta substituting for Zr within the Li6.4La3Zr1.4Ta0.6O12 lattice. Density functional theory (DFT) calculations identify a thermodynamically favourable reaction path and show how substituting Ta5+ at Zr4+ sites affects the crystal structure as well as bulk ionic and electronic conductivities. Quantitative stereology highlights that zirconia also acts as a sintering aid, reducing compact porosity. Cryogenic focused-ion-beam scanning electron microscopy and fractography analysis of cycled solid-state electrolytes illustrates that near-universally observed intergranular Li-metal dendrite propagation is suppressed by the two-phase microstructure, favouring transgranular dendrites instead. Importantly, DFT demonstrates that compared with the Li6.4La3Zr1.4Ta0.6O12 surface, the zirconium oxide surface per se is less electronically conductive and does not trap excess electrons to reduce Li ions. This is a key reason for the substantial improvement in the electrochemical properties over the single-phase baseline.

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Fig. 1: Synthesis and multiscale characterization of ZrO2-LLZTO and baseline LLZTO SSEs.
Fig. 2: Three-dimensional compositional mapping of ZrO2-LLZTO and baseline LLZTO particles.
Fig. 3: Electrochemical characterization of symmetric Li metal cells using ZrO2-LLZTO and baseline LLZTO SSEs.
Fig. 4: Post-mortem SEM analysis of dendrite growth behaviour.
Fig. 5: DFT analysis of bulk and surface electronic structure in ZrO2 and LLZTO.

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The data supporting the findings of this study are available within the article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

Y.W., H.F., P.J., M.F. and Y.Q. were supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy (DOE) through the Advanced Battery Materials Research Program (Battery500 Consortium, contract number 674882). V.R., K.G.N., B.S.V., P.P.M. and D.M. were supported by the Mechano-Chemical Understanding of Solid Ion Conductors, an Energy Frontier Research Center funded by the US DOE, Office of Science, Office of Basic Energy Science, contract number DE-SC0023438. S.K.’s research at Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the US DOE under contract number DE-AC05-00OR22725, was supported by the US DOE’s Office of Energy Efficiency and Renewable Energy for the Vehicle Technologies Office’s Advanced Battery Materials Research Program. H.F. acknowledges the Office of Advanced Research Computing (OARC) at Rutgers, The State University of New Jersey for providing access to the Amarel cluster and associated research computing resources that have contributed to the results reported here. H.F. and P.J. acknowledge resources from the National Renewable Energy Laboratory High-Performance Computing Facilities (with Kestrel and Swift computing systems). The acquisition of the VersaProbe-IV XPS was supported by the National Science Foundation Major Research Instrumentation program (grant number 2117623). This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated by the US DOE’s Office of Science. Los Alamos National Laboratory, an affirmative action equal opportunity employer, is managed by Triad National Security, LLC, for the US DOE’s National Nuclear Security Administration (NNSA), under contract number 89233218CNA000001. This research used the hard X-ray nanoprobe beamline at 3-ID of the National Synchrotron Light Source II, US DOE, Office of Science User Facility, operated for the DOE’s Office of Science by Brookhaven National Laboratory under contract number DESC0012704. This work was supported by The Welch Foundation (F-2206). Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC (NTESS), a wholly owned subsidiary of Honeywell International Inc., for DOE/NNSA under contract number DE-NA0003525. This written work is authored by an employee of NTESS. The employee, not NTESS, owns the right, title and interest in and to the written work and is responsible for its contents. Any subjective views or opinions that might be expressed in the written work do not necessarily represent the views of the US government. The publisher acknowledges that the US government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this written work or allow others to do so, for US government purposes. The DOE will provide public access to results of federally sponsored research in accordance with the DOE Public Access Plan.

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Authors and Affiliations

  1. Materials Science and Engineering Program & Texas Materials Institute (TMI), The University of Texas at Austin, Austin, TX, USA

    Vikalp Raj, Yixian Wang, Shimao Deng, Andrew Scott Manning, Yijin Liu & David Mitlin

  2. School of Engineering, Brown University, Providence, RI, USA

    Min Feng & Yue Qi

  3. School of Mechanical Engineering, Purdue University, West Lafayette, IN, USA

    Kaustubh G. Naik, Bairav S. Vishnugopi & Partha P. Mukherjee

  4. Center for Integrated Nanotechnologies, Sandia National Laboratories, Albuquerque, NM, USA

    Manish Jain & Brad L. Boyce

  5. Power Sources Technology Group, Sandia National Laboratories, Albuquerque, NM, USA

    Noah B. Schorr, Martin Salazar, Alexander M. Heusser & Josefine D. McBrayer

  6. National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA

    Xiaojing Huang

  7. Computational Sciences and Engineering Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Sergiy Kalnaus

  8. Center for Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, NM, USA

    John Watt

  9. Department of Physics, Rutgers University, Camden, NJ, USA

    Hong Fang

  10. Center for Computational and Integrative Biology, Rutgers University, Camden, NJ, USA

    Hong Fang

  11. Virginia Commonwealth University, Richmond, VA, USA

    Puru Jena

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  1. Vikalp Raj
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Contributions

V.R., Y.W. and D.M. conceived the idea and designed the experiments. V.R., Y.W. and A.S.M. performed the synthesis, materials characterization and electrochemical measurements. S.D., X.H. and Y.L. carried out the synchrotron experiments and related data analysis. M.F., K.G.N., B.S.V., H.F., P.J., P.P.M. and Y.Q. carried out the computational simulations. N.B.S., M.S., A.M.H. and J.D.M. helped with the electrochemical measurements. M.J. and B.L.B. performed the mechanical property measurements. S.K. and J.W. participated in the discussion of data analysis. V.R., Y.W. and D.M. wrote the first draft of the paper. All authors discussed the results and revised the paper.

Corresponding authors

Correspondence to Vikalp Raj, Yixian Wang or David Mitlin.

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Competing interests

V.R. and D.M. are inventors on US patent applications (PCT/US2024/029976) related to reactive synthesis methods. The other authors declare no competing interests.

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Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–33, Tables 1–9, and Notes 1 and 2.

Supplementary Video 1

SEM video displaying lithium nucleation on LLZTO upon electron exposure.

Supplementary Data 1

A text file containing the computational codes and data.

Supplementary Data 2

DFT calculation for the optimized structures.

Supplementary Data 3

DFT calculation for the optimized structures.

Supplementary Data 4

DFT calculation for the optimized structures.

Supplementary Data 5

DFT calculation for the optimized structures.

Supplementary Data 6

DFT calculation for the optimized structures.

Supplementary Data 7

DFT calculation for the optimized structures.

Supplementary Data 8

DFT calculation for the optimized structures.

Supplementary Data 9

DFT calculation for the optimized structures.

Supplementary Data 10

DFT calculation for the optimized structures.

Supplementary Data 11

DFT calculation for the optimized structures.

Supplementary Data 12

DFT calculation for the optimized structures.

Supplementary Data 13

DFT calculation for the optimized structures.

Source data

Source Data Fig. 1

DFT and XPS data used to plot Fig. 1e–h.

Source Data Fig. 2

Pearson coefficient data used to plot Fig. 2b,c,e,f.

Source Data Fig. 3

Electrochemical data used to plot Fig. 3a–d.

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Raj, V., Wang, Y., Feng, M. et al. Grain boundary zirconia-modified garnet solid-state electrolyte. Nat. Mater. (2025). https://doi.org/10.1038/s41563-025-02374-9

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