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Interface Instability in LiFePO4–Li3+xP1–xSixO4 All-Solid-State Batteries

Cite this: Chem. Mater. 2018, 30, 17, 5886–5895
Publication Date (Web):July 25, 2018
https://doi.org/10.1021/acs.chemmater.8b01746
Copyright © 2018 American Chemical Society

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    Abstract

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    All-solid-state batteries (ASSBs) based on noncombustible solid electrolytes are promising candidates for safe and high energy storage systems, but it remains a challenge to prepare systems with stable interfaces between the various solid components that survive both the synthesis conditions and electrochemical cycling. We have investigated cathode mixtures based on a carbon-coated LiFePO4 active material and Li3+xP1–xSixO4 solid electrolyte for potential use in all-solid-state batteries. Half-cells were constructed by combining both compounds into pellets by spark plasma sintering (SPS). We report the fast and quantitative formation of two solid solutions (LiFePO4–Fe2SiO4 and Li3PO4–Li2FeSiO4) for different compositions and ratios of the pristine compounds, as tracked by powder X-ray diffraction and solid-state nuclear magnetic resonance; X-ray absorption near-edge spectroscopy confirms the formation of iron silicates similar to Fe2SiO4. Scanning electron microscopy and energy dispersive X-ray spectroscopy reveal diffusion of iron cations up to 40 μm into the solid electrolyte even in the short processing times accessible by SPS. Electrochemical cycling of the SPS-treated cathode mixtures demonstrates a substantial decrease in capacity following the formation of the solid solutions during sintering. Consequently, all-solid-state batteries based on LiFePO4 and Li3+xP1–xSixO4 would necessitate iron ion blocking layers. More generally, this study highlights the importance of systematic studies on the fundamental reactions at the active material–solid electrolyte interfaces to enable the introduction of protective layers for commercially successful ASSBs.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.8b01746.

    • Table of refined lattice parameters; Rietveld refinements of X-ray diffractograms of starting materials and reference samples; comparisons of X-ray diffractograms and 31P MAS NMR measurements; visualization of the local environment of the phosphorus atoms in P-doped Li2FeSiO4 (Pmnb) and in LiFePO4; galvanostatic profiles (PDF)

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