Regulation Mechanism on A Bilayer Li₂O‐Rich Interface between Lithium Metal and Garnet‐Type Solid Electrolytes

Abstract

The practical implementation of garnet‐type solid electrolytes, such as Li6.4La3Zr1.4Ta0.6O12 (LLZTO), faces the significant challenge of Li dendrites. Though artificial interfacial strategies are effective in dendrite suppression, further investigation is needed to understand the mechanism of homogeneous Li deposition and its practicability under real‐world conditions. Herein, a bilayer interface is constructed to address these issues. Such a bilayer interface consists of one conformal Li2O‐rich layer, generated by rubbing LLZTO pellets inside molten Li with low‐dose In2O3, and another Li2O layer deposited through atomic layer deposition (ALD). The regulatory effect of the initial Li2O‐rich layer on achieving uniform Li deposition is explored, and the critical current density is enhanced to 2.4 mA cm−2. However, simple interfacial strategy is insufficient to prevent anodic degradation for cycling at room temperature without stack pressure, leading to increased current leakage and directly reducing Li+ within the electrolyte. After insulating it with a second ALD‐Li2O layer that minimally hampers ionic conduction, the Li/Li symmetric cells achieve long cycling life exceeding 1000 h at 0.5 mA cm−2 and maintain stable operation even at 2 mA cm−2. This work provides valuable insights for interfacial strategies towards practical solid‐state batteries.

Interfacial engineering for high‐performance garnet‐based solid‐state lithium batteries

“…Furthermore, the alloyed negative electrode or interface resulting from lithium alloying undergoes significant volumetric changes during continuous alloying/dealloying processes, consequently resulting in an increase in interfacial impedance. 97 In addition to single-element layers, in order to further enhance the multifunctionality of interfaces, some metal oxides or multi-element compounds such as Al 2 O 3 , 98 ZnO, 99 fluorinated graphite (CF x ), 100 titanium oxide nanoclusters, 101 In 2 O 3 , and SnO 2 , 102,103 Co 3 O 4 , 104 Li 2 O, 105 and AgSn 0.6 Bi 0.4 O x 106 have also been used as interfacemodifying layer materials. For example, Jiang et al 105 proposed a dual-layer strategy, where the inner layer is composed of dense ALD-Li 2 O with good electronic insulation and high ionic conductivity, and the outer layer is made up of the chemical reaction byproduct Li 2 O.…”

“…97 In addition to single-element layers, in order to further enhance the multifunctionality of interfaces, some metal oxides or multi-element compounds such as Al 2 O 3 , 98 ZnO, 99 fluorinated graphite (CF x ), 100 titanium oxide nanoclusters, 101 In 2 O 3 , and SnO 2 , 102,103 Co 3 O 4 , 104 Li 2 O, 105 and AgSn 0.6 Bi 0.4 O x 106 have also been used as interfacemodifying layer materials. For example, Jiang et al 105 proposed a dual-layer strategy, where the inner layer is composed of dense ALD-Li 2 O with good electronic insulation and high ionic conductivity, and the outer layer is made up of the chemical reaction byproduct Li 2 O. By combining these two layers effectively, the generation of dynamic voids are moved away from the Li/LLZTO surface, ensuring a smooth transfer of Li + at the interface.…”