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Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes

Nature Materials volume 19, pages 428–435 (2020)Cite this article

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Abstract

All-solid-state Li-ion batteries promise safer electrochemical energy storage with larger volumetric and gravimetric energy densities. A major concern is the limited electrochemical stability of solid electrolytes and related detrimental electrochemical reactions, especially because of our restricted understanding. Here we demonstrate for the argyrodite-, garnet- and NASICON-type solid electrolytes that the favourable decomposition pathway is indirect rather than direct, via (de)lithiated states of the solid electrolyte, into the thermodynamically stable decomposition products. The consequence is that the electrochemical stability window of the solid electrolyte is notably larger than predicted for direct decomposition, rationalizing the observed stability window. The observed argyrodite metastable (de)lithiated solid electrolyte phases contribute to the (ir)reversible cycling capacity of all-solid-state batteries, in addition to the contribution of the decomposition products, comprehensively explaining solid electrolyte redox activity. The fundamental nature of the proposed mechanism suggests this is a key aspect for solid electrolytes in general, guiding interface and material design for all-solid-state batteries.

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Fig. 1: Voltage profiles and differential capacity curve of the LPSC-C electrode.
Fig. 2: Formation energies of Li-vacancy configurations of argyrodite LixPS5Cl and comparison of experimental and calculated voltage profiles.
Fig. 3: XRD patterns and fits of the LPSC-C electrodes before and after cycling.
Fig. 4: Solid-state 31P NMR spectra of pristine, oxidized and reduced LPSC-C.
Fig. 5: Schematic of the electrochemical activity of argyrodite LPSC on oxidation (delithiation) and reduction (lithiation).
Fig. 6: Formation energies of Li-vacancy configurations of garnet LLZO and NASICON LAGP solid electrolytes, and comparison of experimental and calculated oxidation potentials.

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The datasets generated during and/or analysed during the current study are available from the corresponding authors on reasonable request.

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Acknowledgements

The authors thank K. Goubitz, M. Steenvoorden and F. Ooms for their assistance with experiments and C. Robledo for her assistance with the schematic graphic. Financial support is acknowledged from the Netherlands Organization for Scientific Research (NWO) under the VICI grant no. 16122, from the eScience Centre and NWO under the joint CSER and eScience programme for Energy Research grant no. 680.91.087 and from the Advanced Dutch Energy Materials (ADEM) programme of the Dutch Ministry of Economic Affairs, Agriculture and Innovation.

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  1. These authors contributed equally: Tammo K. Schwietert, Violetta A. Arszelewska.

Authors and Affiliations

  1. Storage of Electrochemical Energy, Faculty of Radiation Science and Technology, Delft University of Technology, Delft, the Netherlands

    Tammo K. Schwietert, Violetta A. Arszelewska, Chao Wang, Chuang Yu, Alexandros Vasileiadis, Niek J. J. de Klerk, Jart Hageman, Yaolin Xu, Eveline van der Maas, Erik M. Kelder, Swapna Ganapathy & Marnix Wagemaker

  2. Robert Bosch GmbH, Corporate Sector Research and Advance Engineering, Renningen, Germany

    Thomas Hupfer & Ingo Kerkamm

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Contributions

T.S., A.V. and N.J.J.d.K. carried out the DFT simulations and T.S. and A.V. analysed the data. C.Y. and C.W. synthesized the solid electrolytes. T.S., C.W., V.A. carried out the electrochemical measurements and T.S. and V.A. analysed the data. T.S., V.A. and C.W. carried out the XRD measurements and V.A., T.S. and S.G. analysed the data. V.A. measured and analysed the NMR data. C.Y., E.v.d.M., Y.X. and J.H. carried out preliminary measurements. T.H., I.K. and E.M.K. contributed to the discussion of results. M.W. supervised the project. S.G. and M.W. designed the research. T.S., V.A., S.G. and M.W. wrote the manuscript.

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Correspondence to Swapna Ganapathy or Marnix Wagemaker.

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Extended data

Extended Data Fig. 1 Molecular dynamics simulations of Li4PS5Cl, Li6PS5Cl and Li11PS5Cl.

a, Radial distribution function (RDF) of the S-S bonds in (de)lithiated LixPS5Cl for x = 4, 6, and 11 during a 400 K DFT-MD simulation. During delithiation an increase in S-S bonds is seen around 2.1 Å, indicating that the formation of S-S bonds originates from the oxidation of S in the argyrodite. On top of the peaks, bonds at corresponding radii are displayed. It is important to realize that the timescale at which these structural transformations can be evaluated is very limited and therefore sluggish transformations fall outside the scope of this evaluation. b, Radial distribution function (RDF) of the P-S bonds of (de)lithiated LixPS5Cl for x = 4, 6 and 11 during a 400 K DFT-MD simulation, For the lithiated phase, Li11PS5Cl, a drop in intensity is observed at r = 2.1 Ả, consistent with breaking P-S bonds in the PS4 groups. This is expected because the P atoms can compensate for the change in valence as a consequence of the lithiation. The MD simulations indicate that the Li4PS5Cl and Li11PS5Cl compositions are extremely unstable, having very low activation barriers towards decomposition. Their instability suggests that these compositions will only occur locally in the material, rapidly initiating local decomposition, which will nevertheless require the associated oxidation or reduction potential predicted by the convex hull shown in Fig. 2b. c, Relaxed structures of LixPS5Cl for x = 4, 6 and 11 after a 400 K DFT-MD simulation. The violet, orange, yellow and green spheres indicate lithium, phosphorous, sulfur, and chlorine respectively.

Extended Data Fig. 2 6Li MAS NMR spectra of the cathodic mixtures and anodic mixtures.

6Li MAS NMR spectra of the cathodic mixtures (a-d) and anodic mixtures (e–g) of Li6PS5Cl in the In|LPSC|LPSC-C and Li-In|LPSC|LPSC-C solid-state batteries respectively. After first charge of the In|LPSC|LPSC-C solid-state cell, formation of LiCl is observed (b). First discharge shows formation at a new resonance frequency corresponding to Li3PS4 (c, d). The solid state cell, which starts from lithiation process (f), results in formation of Li2S, confirmed with the spectrum of the reference Li2S (g).

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Schwietert, T.K., Arszelewska, V.A., Wang, C. et al. Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes. Nat. Mater. 19, 428–435 (2020). https://doi.org/10.1038/s41563-019-0576-0

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