Solid electrolytes are ion-conducting solids that replace the liquid salt solution in an electrochemical cell and act at the same time as the separator between the electrodes. Garnet-type oxide ceramics doped with aluminium, niobium or germanium reach conductivities of 10-4 to 10-3 S per centimetre at room temperature once they are sintered to high density [1], and substitution on the zirconium site has been reported to raise the value further [2]. Sulfide glasses and glass-ceramics conduct lithium faster, in some compositions above 10-3 S per centimetre, and being softer they can be densified by cold pressing, but they release hydrogen sulfide on contact with moisture [3]. Polymer and ceramic-polymer composite electrolytes trade conductivity for compliance and ease of processing [4]. In a cell the total resistance is rarely set by the bulk alone: grain boundaries, space-charge layers and the electrode-electrolyte interface add to it, and the contact area changes as the electrode expands and contracts during cycling, so interlayers and external pressure are used to keep the interface intact [5]. Lithium penetration along grain boundaries and pores limits the usable current density, and how to suppress it without raising the interfacial resistance is still debated [3].
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