A critical current density on stripping (CCS) is identified that results in dendrite formation on plating and cell failure. When the stripping current density removes lithium from the interface faster than it can be replenished, voids form in the lithium at the interface and accumulate on cycling increasing the local current density at the interface and ultimately leading to dendrite formation on plating, short-circuit and cell death. This occurs even when the overall current density is significantly below the threshold for dendrite formation on plating. For the Li / Li6PS5Cl / Li cell, this is 0.2 and 1 mA•cm -2 at 3 and 7 MPa pressure respectively, compared with a critical current for plating of 2 mA•cm -2 at both 3 and 7 MPa. The pressure dependence on stripping indicates creep rather than Li diffusion is the dominant mechanism transporting Li to the interface. The critical stripping current is a major factor limiting the power density of lithium anode solid state cells. Significant pressure may be required to achieve even modest power densities in solid state cells.

A novel templating method to create 3D bicontinuous structured hybrid electrolytes with improved mechanical properties for all-solid-state lithium batteries.

All-solid-state batteries potentially offer safe, high-energy-density electrochemical energy storage, yet are plagued with issues surrounding Li microstructural growth and subsequent cell death. We use 7Li NMR chemical shift imaging and electron microscopy to track Li microstructural growth in the garnet-type solid electrolyte, Li6.5La3Zr1.5Ta0.5O12. Here, we follow the early stages of Li microstructural growth during galvanostatic cycling, from the formation of Li on the electrode surface to dendritic Li connecting both electrodes in symmetrical cells, and correlate these changes with alterations observed in the voltage profiles during cycling and impedance measurements. During these experiments, we observe transformations at both the stripping and plating interfaces, indicating heterogeneities in both Li removal and deposition. At low current densities, 7Li magnetic resonance imaging detects the formation of Li microstructures in cells before short-circuits are observed and allows changes in the electrochemical profiles to be rationalized.