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1. Elasticity-oriented design of solid-state batteries: challenges and perspectives

   https://doi.org/10.1039/D1TA01545A  

   Ren, Yuxun; Hatzell, Kelsey Bridget (January 2021, Journal of Materials Chemistry A)

   null (Ed.)

   Engineering energy dense electrodes (e.g. lithium metal, conversion cathodes, etc.) with solid electrolytes is important for enhancing the practical energy density of solid-state batteries. However, large electrode volumetric strain can cause significant drive fracture, delamination, and accelerate degradation. This review discusses transport and chemo-mechanical challenges associated with energy dense solid state batteries. In particular, this review focuses on summarizing work which provides design strategies for implementation on energy dense anodes with rigid solid electrolytes. This review further assesses the properties which impact the elasticity of inorganic solid electrolytes and inorganic/organic hybrid electrolyte. Finally, this review discusses the advanced characterization approaches for analyzing the coupled electrochemistry/transport/mechanical phenomena that occur at buried solid-solid interfaces 

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2. Regulating Li‐Ion Transport through Ultrathin Molecular Membrane to Enable High‐Performance All‐Solid‐State–Battery

   https://doi.org/10.1002/smll.202303625  

   Rajendran, Sathish; George, Antony; Tang, Zian; Neumann, Christof; Turchanin, Andrey; Arava, Leela_Mohana_Reddy (June 2023, Small)

   Abstract Solid‐state lithium metal batteries with garnet‐type electrolyte provide several advantages over conventional lithium‐ion batteries, especially for safety and energy density. However, a few grand challenges such as the propagation of Li dendrites, poor interfacial contact between the solid electrolyte and the electrodes, and formation of lithium carbonate during ambient exposure over the solid‐state electrolyte prevent the viability of such batteries. Herein, an ultrathin sub‐nanometer porous carbon nanomembrane (CNM) is employed on the surface of solid‐state electrolyte (SSE) that increases the adhesion of SSE with electrodes, prevents lithium carbonate formation over the surface, regulates the flow of Li‐ions, and blocks any electronic leakage. The sub‐nanometer scale pores in CNM allow rapid permeation of Li‐ions across the electrode–electrolyte interface without the presence of any liquid medium. Additionally, CNM suppresses the propagation of Li dendrites by over sevenfold up to a current density of 0.7 mA cm⁻²and enables the cycling of all‐solid‐state batteries at low stack pressure of 2 MPa using LiFePO₄cathode and Li metal anode. The CNM provides chemical stability to the solid electrolyte for over 4 weeks of ambient exposure with less than a 4% increase in surface impurities. 

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3. Fundamental mechanistic insights into the catalytic reactions of Li─S redox by Co single-atom electrocatalysts via operando methods

   https://doi.org/10.1126/sciadv.adi5108  

   Xu, Weixuan; Lang, Shuangyan; Wang, Kaiyang; Zeng, Rui; Li, Huiqi; Feng, Xinran; Krumov, Mihail R; Bak, Seong-Min; Pollock, Christopher J; Yeo, Jingjie; et al (August 2023, Science Advances)

   Lithium-sulfur batteries represent an attractive option for energy storage applications. A deeper understanding of the multistep lithium-sulfur reactions and the electrocatalytic mechanisms are required to develop advanced, high-performance batteries. We have systematically investigated the lithium-sulfur redox processes catalyzed by a cobalt single-atom electrocatalyst (Co-SAs/NC) via operando confocal Raman microscopy and x-ray absorption spectroscopy (XAS). The real-time observations, based on potentiostatic measurements, indicate that Co-SAs/NC efficiently accelerates the lithium-sulfur reduction/oxidation reactions, which display zero-order kinetics. Under galvanostatic discharge conditions, the typical stepwise mechanism of long-chain and intermediate-chain polysulfides is transformed to a concurrent pathway under electrocatalysis. In addition, operando cobalt K-edge XAS studies elucidate the potential-dependent evolution of cobalt’s oxidation state and the formation of cobalt-sulfur bonds. Our work provides fundamental insights into the mechanisms of catalyzed lithium-sulfur reactions via operando methods, enabling a deeper understanding of electrocatalysis and interfacial dynamics in electrical energy storage systems. 

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4. Two-step crystallization and solid–solid transitions in binary colloidal mixtures

   https://doi.org/10.1073/pnas.2008561117  

   Fang, Huang; Hagan, Michael F.; Rogers, W. Benjamin (November 2020, Proceedings of the National Academy of Sciences)

   null (Ed.)

   Crystallization is fundamental to materials science and is central to a variety of applications, ranging from the fabrication of silicon wafers for microelectronics to the determination of protein structures. The basic picture is that a crystal nucleates from a homogeneous fluid by a spontaneous fluctuation that kicks the system over a single free-energy barrier. However, it is becoming apparent that nucleation is often more complicated than this simple picture and, instead, can proceed via multiple transformations of metastable structures along the pathway to the thermodynamic minimum. In this article, we observe, characterize, and model crystallization pathways using DNA-coated colloids. We use optical microscopy to investigate the crystallization of a binary colloidal mixture with single-particle resolution. We observe classical one-step pathways and nonclassical two-step pathways that proceed via a solid–solid transformation of a crystal intermediate. We also use enhanced sampling to compute the free-energy landscapes corresponding to our experiments and show that both one- and two-step pathways are driven by thermodynamics alone. Specifically, the two-step solid–solid transition is governed by a competition between two different crystal phases with free energies that depend on the crystal size. These results extend our understanding of available pathways to crystallization, by showing that size-dependent thermodynamic forces can produce pathways with multiple crystal phases that interconvert without free-energy barriers and could provide approaches to controlling the self-assembly of materials made from colloids. 

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5. Probing lithium mobility at a solid electrolyte surface

   https://doi.org/10.1038/s41563-023-01535-y  

   Woodahl, Clarisse; Jamnuch, Sasawat; Amado, Angelique; Uzundal, Can B.; Berger, Emma; Manset, Paul; Zhu, Yisi; Li, Yan; Fong, Dillon D.; Connell, Justin G.; et al (April 2023, Nature Materials)

   Abstract Solid-state electrolytes overcome many challenges of present-day lithium ion batteries, such as safety hazards and dendrite formation^1,2. However, detailed understanding of the involved lithium dynamics is missing due to a lack of in operando measurements with chemical and interfacial specificity. Here we investigate a prototypical solid-state electrolyte using linear and nonlinear extreme-ultraviolet spectroscopies. Leveraging the surface sensitivity of extreme-ultraviolet-second-harmonic-generation spectroscopy, we obtained a direct spectral signature of surface lithium ions, showing a distinct blueshift relative to bulk absorption spectra. First-principles simulations attributed the shift to transitions from the lithium 1 sstate to hybridized Li-s/Ti-dorbitals at the surface. Our calculations further suggest a reduction in lithium interfacial mobility due to suppressed low-frequency rattling modes, which is the fundamental origin of the large interfacial resistance in this material. Our findings pave the way for new optimization strategies to develop these electrochemical devices via interfacial engineering of lithium ions. 

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