Li/Garnet Interface Stabilization by Thermal-Decomposition Vapor Deposition of an Amorphous Carbon Layer

Applying interlayers is the main strategy to address the large area specific resistance (ASR) of Li/garnet interface. However, studies on eliminating the Li₂CO₃ and LiOH interfacial lithiophobic contaminants are still insufficient. Here, thermal-decomposition vapor deposition (TVD) of a carbon modification layer on Li_6.75La₃Zr_1.75Ta_0.25O₁₂ (LLZTO) provides a contaminant-free surface. Owing to the protection of the carbon layer, the air stability of LLZTO is also improved. Moreover, owing to the amorphous structure of the low graphitized carbon (LGC), instant lithiation is achieved, and the ASR of the Li/LLZTO interface is reduced to 9 Ω cm². Lithium volatilization and Zr⁴⁺ reduction are also controllable during TVD. Compared with its high graphitized carbon counterpart (HGC), the LGC-modified Li/LLZTO interface displays a higher critical current density of 1.2 mA cm⁻², as well as moderate Li plating and stripping, which provides enhanced polarization voltage stability.     

Regulating Nonclassical Pathways of Silicalite‐1 Crystallization through Controlled Evolution of Amorphous Precursors

Differentiating mechanisms of zeolite crystallization is challenging owing to the vast number of species in growth solutions. The presence of amorphous colloidal particles is ubiquitous in many zeolite syntheses, and has led to extensive efforts to understand the driving force(s) for their self‐assembly and putative roles in processes of nucleation and growth. In this study, we use a combination of in situ scanning probe microscopy, particle dissolution measurements, and colloidal stability assays to elucidate the degree to which silica nanoparticles evolve in their structure during the early stages of silicalite‐1 synthesis. We show how changes in precursor structure are mediated by the presence of organics, and demonstrate how these changes lead to significant differences in precursor–crystal interactions that alter preferred modes of crystal growth. Our findings provide guidelines for selectively controlling silicalite‐1 growth by particle attachment or monomer addition, thus allowing for the manipulation of anisotropic rates of crystallization. In doing so, we also address a longstanding question regarding what factors are at our disposal to switch from a nonclassical to classical mechanism.