Solid electrolytes (SEs) are widely considered as an ‘enabler’ of lithium anodes for high-energy batteries. However, recent reports demonstrate that the Li dendrite formation in Li7La3Zr2O12 (LLZO) and Li2S–P2S5 is actually much easier than that in liquid electrolytes of lithium batteries, by mechanisms that remain elusive. Here we illustrate the origin of the dendrite formation by monitoring the dynamic evolution of Li concentration profiles in three popular but representative SEs (LiPON, LLZO and amorphous Li3PS4) during lithium plating using time-resolved operando neutron depth profiling. Although no apparent changes in the lithium concentration in LiPON can be observed, we visualize the direct deposition of Li inside the bulk LLZO and Li3PS4. Our findings suggest the high electronic conductivity of LLZO and Li3PS4 is mostly responsible for dendrite formation in these SEs. Lowering the electronic conductivity, rather than further increasing the ionic conductivity of SEs, is therefore critical for the success of all-solid-state Li batteries.
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C.W. and F.H. gratefully acknowledge support by the Army Research Office (Award No. W911NF1510187) and the National Science Foundation (Award No. 1805159). A.S.W. and N.J.D. acknowledge support from the US Department of Energy, Advanced Research Projects Agency for Energy (ARPA-E), IONICS Program (Award No. DE-AR0000775). H.W. acknowledges the support of NIST Award 70NANB12H238, and the use of the cold neutron facility at the NIST Center for Neutron Research. The SEM test was supported by Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DESC0001160. The FIB–SEM was performed at the Center for Nanophase Materials Sciences at Oak Ridge National Lab, which is a DOE-BES supported user facility. C.W. and F.H. also acknowledge the support of the Maryland Nanocenter and its AIMLab and FabLab. We also thank B. Dunn for valuable discussions and R. G. Downing, H. Chen-Mayer and J. L. Weaver for the help on the NDP measurement.
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