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Revealing the role of the cathode–electrolyte interface on solid-state batteries



Interfaces have crucial, but still poorly understood, roles in the performance of secondary solid-state batteries. Here, using crystallographically oriented and highly faceted thick cathodes, we directly assess the impact of cathode crystallography and morphology on the long-term performance of solid-state batteries. The controlled interface crystallography, area and microstructure of these cathodes enables an understanding of interface instabilities unknown (hidden) in conventional thin-film and composite solid-state electrodes. A generic and direct correlation between cell performance and interface stability is revealed for a variety of both lithium- and sodium-based cathodes and solid electrolytes. Our findings highlight that minimizing interfacial area, rather than its expansion as is the case in conventional composite cathodes, is key to both understanding the nature of interface instabilities and improving cell performance. Our findings also point to the use of dense and thick cathodes as a way of increasing the energy density and stability of solid-state batteries.

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Fig. 1: Designed SE–cathode interfaces enhance understanding of the effect of interface on performance.
Fig. 2: LCO crystallographic orientations and top surface microstructures.
Fig. 3: Comparison of composite and dense cathodes and halide SE SSBs.
Fig. 4: Interfacial impedance of Li- and Na-ion systems during the first charge (0.1 C).
Fig. 5: Correlation between capacity fade and interfacial resistance.
Fig. 6: DFT calculated LCO–LYC interface structure.

Data availability

The authors declare that all data supporting the findings of this study are available within the paper and its Supplementary Information files. Additional data are available from the corresponding authors upon reasonable request.


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Work at the University of Illinois at Urbana–Champaign is supported by the US Army CERL W9132T-19–2–0008. Aspects of this work were carried out in the University of Illinois Materials Research Laboratory Central Facilities. We thank R. Haasch of the Materials Research Laboratory for the acquisition of XPS data and instructive discussions. We thank P. Sun and M. Caple of the Braun group for fruitful discussions.

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Authors and Affiliations



B.Z. and P.V.B. conceived the idea. C.K. and J.B.C. conducted the electroplating of dense LCO cathodes and collected liquid-cell electrochemical cycling data. B.Z. synthesized SEs, designed and performed SSB tests, conducted the impedance analysis and conducted structural characterization via electron microscopy. A.P. synthesized the dense NCO cathodes and carried out X-ray diffraction pole figure acquisition, refinement and data analysis. A.X.B.Y. and E.E. conducted DFT calculations. B.Z. and P.V.B. wrote the paper, with contributions from all co-authors.

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Correspondence to John B. Cook or Paul V. Braun.

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Peer review information Nature Materials thanks Matthew McDowell and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Discussion Sections 1–14, Figs. 1–39 and Tables 1 and 2.

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Zahiri, B., Patra, A., Kiggins, C. et al. Revealing the role of the cathode–electrolyte interface on solid-state batteries. Nat. Mater. 20, 1392–1400 (2021).

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