Enabling ultra-high energy density rechargeable Li batteries would have widespread impact on society. However the critical challenges of Li metal anodes (most notably cycle life and safety) remain unsolved. This is attributed to the evolution of Li metal morphology during cycling, which leads to dendrite growth and surface pitting. Herein, we present a comprehensive understanding of the voltage variations observed during Li metal cycling, which is directly correlated to morphology evolution through the use of operando video microscopy. A custom-designed visualization cell was developed to enable operando synchronized observation of Li metal electrode morphology and electrochemical behavior during cycling. A mechanistic understanding of the complex behavior of these electrodes is gained through correlation with continuum-scale modeling, which provides insight into the dominant surface kinetics. This work provides a detailed explanation of (1) when dendrite nucleation occurs, (2) how those dendrites evolve as a function of time, (3) when surface pitting occurs during Li electrodissolution, (4) kinetic parameters that dictate overpotential as the electrode morphology evolves, and (5) how this understanding can be applied to evaluate electrode performance in a variety of electrolytes. The results provide detailed insight into the interplay between morphology and the dominant electrochemical processes occurring on the Li electrode surface through an improved understanding of changes in cell voltage, which represents a powerful new platform for analysis.

A mechanistic analysis of voltage shape changes in lithium metal anodes explains how dead lithium causes capacity fade and failure.

Lithium solid electrolytes are a promising platform for achieving high energy density, long-lasting, and safe rechargeable batteries, which could have widespread societal impact. In particular, the ceramic oxide garnet Li 7 La 3 Zr 2 O 12 (LLZO) has been shown to be a promising electrolyte due to its stability and high ionic conductivity. Two major challenges for commercialization are the manufacture of thin layers and the creation of stable, low-impedance interfaces with both anode and cathode materials. Atomic layer deposition (ALD) has recently been shown to be a powerful method for depositing both solid electrolytes and interfacial layers to improve the stability and performance at electrode− electrolyte interfaces in battery systems. Herein, we present a thermal ALD process for LLZO, demonstrating the ability to tune composition within the amorphous as-deposited film, which is studied using in situ quartz crystal microbalance measurements. Postannealing using a variety of substrates and gas environments was performed, and the formation of the cubic phase was observed at temperatures as low as 555 °C, significantly lower than what is required for bulk processing. Additionally, challenges associated with achieving a dense garnet phase due to substrate reactivity, morphology changes, and Li loss under the necessary high-temperature annealing are quantified via in situ synchrotron X-ray diffraction.

We report a unique growth and migration behavior of Ge nanocrystallites mediated by the presence of Si interstitials under thermal annealing at 900°C within an H2O ambient. The Ge nanocrystallites were previously generated by the selective oxidation of SiGe nanopillars and appeared to be very sensitive to the presence of Si interstitials that come either from adjacent Si3N4 layers or from within the oxidized nanopillars. A cooperative mechanism is proposed, wherein the Si interstitials aid in both the migration and coarsening of these Ge nanocrystallites through Ostwald ripening, while the Ge nanocrystallites, in turn, appear to enhance the generation of Si interstitials through catalytic decomposition of the Si-bearing layers.

A new phenomenon of highly localized, nanoscale oxidation of silicon-containing layers has been observed. The localized oxidation enhancement observed in both Si and Si(3)N(4) layers appears to be catalyzed by the migration of Ge quantum dots (QDs). The sizes, morphology, and distribution of the Ge QDs are influenced by the oxidation of the Si-bearing layers. A two-step mechanism of dissolution of Si within the Ge QDs prior to oxidation is proposed.