Stabilization of garnet/Li interphase by diluting the electronic conductor

The high interfacial resistance and lithium (Li) dendrite growth are two major challenges for solid-state Li batteries (SSLBs). The lack of understanding on the correlations between electronic conductivity and Li dendrite formation limits the success of SSLBs. Here, by diluting the electronic conductor from the interphase to bulk Li during annealing of the aluminium nitride (AlN) interlayer, we changed the interphase from mixed ionic/electronic conductive to solely ionic conductive, and from lithiophilic to lithiophobic to fundamentally understand the correlation among electronic conductivity, Li dendrite, and interfacial resistance. During the conversion-alloy reaction between AlN and Li, the lithiophilic and electronic conductive LiAl diffused into Li, forming a compact lithiophobic and ionic conductive Li₃N, which achieved an ultrahigh critical current density of 2.6/14.0 mA/cm² in the time/capacity-constant mode, respectively. The fundamental understanding on the effect of interphase nature on interfacial resistance and Li dendrite suppression will provide guidelines for designing high-performance SSLBs.