On the flash sintering behavior of Li:ZnO—Evidence of electrode asymmetry driven by electrochemical reactions

Abstract The synthesis, subsequent flash sintering (FS) characteristics and microstructures of pure and Li‐incorporated ZnO powders are reported. At low concentrations, Li is a substitutional occupant in ZnO but becomes an amphoteric dopant (substitutional and interstitial occupant) at higher concentrations inferred from a contraction reversal of the unit cell volume. Increasing Li reduces the average flash temperature of ZnO modestly by 15°C, and a doubling of the linear shrinkage. A discernible color smear (yellow–white–dark) stretching from the anode to cathode imputable to strong electromigration is also observed. Microanalyses of the electrode regions establish clear evidence of electrochemical (EC) lithiation into ZnO and the formation of Li–Zn compounds not observed in conventional sintering (CS). Interestingly, in contrast to CS, the addition of Li enhances coarsening during FS, suggestive of a dissolution–reprecipitation process concurrent with the EC lithiation process. Evidence for considerable (local) yet tangible temperature, chemical and microstructural asymmetry among electrodes driven by EC reactions is presented. Probable mechanisms, leading to these observations, are discussed.