Imaging the microstructure of lithium and sodium metal in anode-free solid-state batteries using electron backscatter diffraction

‘Anode-free’ or, more fittingly, metal reservoir-free cells could drastically improve current solid-state battery technology by achieving higher energy density, improving safety and simplifying manufacturing. Various strategies have been reported so far to control the morphology of electrodeposited alkali metal films to be homogeneous and dense, but until now, the microstructure of electrodeposited alkali metal is unknown, and a suitable characterization route is yet to be identified. Here we establish a reproducible protocol for characterizing the size and orientation of metal grains in differently processed lithium and sodium samples by a combination of focused ion beam and electron backscatter diffraction. Electrodeposited films at Cu|Li6.5Ta0.5La3Zr1.5O12, steel|Li6PS5Cl and Al|Na3.4Zr2Si2.4P0.6O12 interfaces were characterized. The analyses show large grain sizes (>100 µm) within these films and a preferential orientation of grain boundaries. Furthermore, metal growth and dissolution were investigated using in situ electron backscatter diffraction, showing a dynamic grain coarsening during electrodeposition and pore formation within grains during dissolution. Our methodology and results deepen the research field for the improvement of solid-state battery performance through a characterization of the alkali metal microstructure. The microstructure of alkali metals in anode-free cells is currently unknown. Here, using a combination of focused ion beam and electron backscatter diffraction, this morphology is investigated, with in situ scanning electron microscopy showing dynamic grain coarsening during electrodeposition.