All-solid-state lithium ion batteries (ASSLBs) are considered next-generation devices for energy storage due to their advantages in safety and potentially high energy density. As the key component in ASSLBs, solid-state electrolytes (SSEs) with non-flammability and good adaptability to lithium metal anodes have attracted extensive attention in recent years. Among the current SSEs, composite solid-state electrolytes (CSSEs) with multiple phases have greater flexibility to customize and combine the advantages of single-phase electrolytes, which have been widely investigated recently and regarded as promising candidates for commercial ASSLBs. Based on existing investigations, herein, we present a comprehensive overview of the recent developments in CSSEs. Initially, we introduce the historical development from solid-state ionic conductors to CSSEs, and then summarize the fundamentals including mechanisms of lithium ion transport, key evaluation parameters, design principles, and key materials. Four main types of advanced structures for CSSEs are classified and highlighted according to the recent progress. Moreover, advanced characterization and computational simulation techniques including machine learning are reviewed for the first time, and the main challenges and perspectives of CSSEs are also provided for their future development.

A review of composite solid-state electrolytes for lithium batteries: fundamentals, key materials and advanced structures.

Freeze casting, also known as ice templating, is a particularly versatile technique that has been applied extensively for the fabrication of well-controlled biomimetic porous materials based on ceramics, metals, polymers, biomacromolecules, and carbon nanomaterials, endowing them with novel properties and broadening their applicability. The principles of different directional freeze-casting processes are described and the relationships between processing and structure are examined. Recent progress in freeze-casting assisted assembly of low dimensional building blocks, including graphene and carbon nanotubes, into tailored micro- and macrostructures is then summarized. Emerging trends relating to novel materials as building blocks and novel freeze-cast geometries-beads, fibers, films, complex macrostructures, and nacre-mimetic composites-are presented. Thereafter, the means by which aligned porous structures and nacre mimetic materials obtainable through recently developed freeze-casting techniques and low-dimensional building blocks can facilitate material functionality across multiple fields of application, including energy storage and conversion, environmental remediation, thermal management, and smart materials, are discussed.

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Freeze Casting: From Low-Dimensional Building Blocks to Aligned Porous Structures-A Review of Novel Materials, Methods, and Applications.

Summary Li metal has been attracting increasing attention as an anode in all-solid-state batteries because of its lowest electrochemical potential and high capacity, although the problems caused by dendritic growth impedes its further application. For a long time, all-solid-state Li metal batteries (ASLBs) are regarded to revive Li metal due to high mechanical strength. However, numerous works revealed that the dendrite issue widely exists in ASLBs, and the mechanism is complex. This review provides a systematic and in-depth understanding of the thermodynamic, kinetic, electrochemical, chemomechnical, structural stability, and characterizations of Li dendrite in ASLBs. First, the mechanisms for dendrite formation and propagation in polymer, ceramic and glass electrolyte were discussed. Subsequently, based on these mechanisms of dendrite growth, we reviewed various strategies for dendrite suppression. Furthermore, advanced characterization techniques were reviewed for better understanding of dendrite in solid-state batteries.

Lithium Dendrite in All-Solid-State Batteries: Growth Mechanisms, Suppression Strategies, and Characterizations

With the increasing diversification of portable electronics and large-scale energy storage systems, conventional lithium-ion batteries (LIBs) with graphite anodes are now approaching their theoretical limits. Lithium metal, as the "Holy Grail" electrode for next-generation rechargeable batteries, is being revisited to meet the booming demand for high energy density electrodes due to its ultrahigh theoretical specific capacity and negative redox potential. Nevertheless, typical issues like notorious dendrite growth still hamper the bulk application of Li metal anodes. Dendrite growth renders increased surface area of the lithium metal, causing persistent depletion of the electrolyte and active materials, facilitating catastrophic failure of the battery, and even inducing fatal safety hazards. The consequences become more serious during operation at high current densities and over long cycling life. Therefore, it is urgent to suppress and even eliminate dendrite formation during the Li plating/stripping process. This Account highlights several innovative strategies for dendrite suppression, dendrite regulation, and dendrite elimination from the perspective of interface energy and bulk stresses. First, we review the fundamental mechanism of dendrite formation and growth in Li metal anodes. We show that the dendrite morphology could be substantially ameliorated, in theory, by homogenizing the electric field distribution, lowering the Li ion concentration gradient, and facilitating mechanical blocking. Next, we address the problem of dendrite suppression by applying two-dimensional (2D) materials to Li metal systems and preventing dendrite penetration through stress release and mechanical blocking. Graphene with a high specific area and vermiculite sheets (VSs) with a large physical rigidity were demonstrated to be efficacious in reinforcing Li anodes and polymer electrolytes separately. However, Li dendrite growth is a continuous process and remains inevitable with increasing current density and cycling life. Instead of suppressing dendrite growth, we focus on how to regulate homogeneous Li dendrite formation and growth. Dendrite regulation means to allow dendrite growth but take steps to transform it into Li with a smooth morphology. We introduce two main strategies to regulate Li growth: (i) guiding Li nucleation and (ii) controlling the Li growth pathways and directions. These processes greatly rely on the interface energy between the substrate and Li atoms. Elimination of the dendrites, which is the most formidable challenge for dendrite control, can also be achieved by dynamically engineering the force, such as deflecting the electric field by Lorentz force in a magnetic field, enhancing the integrated yield stress by the design of bulk nanostructured materials, and reducing the lateral Li diffusion barrier by a biomimetic co-deposition process. Solutions to the challenges of dendrite control in Li metal anodes can provide safe next-generation rechargeable lithium metal batteries that have a long cycling life. We also hope that our strategies presented in this Account can offer promise for other metal batteries.

Dendrites in Lithium Metal Anodes: Suppression, Regulation, and Elimination

Homogeneous and Fast Ion Conduction of PEO-Based Solid-State Electrolyte at Low Temperature

Lithium ion batteries are now the dominant power for electronics and will change the power supply for vehicles and help to smoothly integrate renewable energy sources such as solar and wind to grid. In lithium ion batteries with liquid electrolytes, the organic solvents are flammable and unstable at high voltage. Especially in lithium metal batteries (LMB) where lithium dendrites can grow, the solvents can be ignited once the dendrites shortcircuit with the cathodes. To meet the high energy density and safety requirement, it is desirable to develop solid state electrolytes with high stability and mechanical strength. The solid state electrolytes can be classified into two categories: inorganic electrolytes and solid polymer electrolytes (SPE). Inorganic electrolytes typically have ionic conductivity at room temperature (10−2–10−4 S cm−1) close to or even higher than liquid electrolyte. However, their stiffness and friability result in poor film processability and high interface resistance with electrodes.[1–7] SPE are composed of lithium salts dissociated in the polymer matrix in which Li+ is allowed to transport along with the segment motion of the polymer chains. As a result, SPE are stretchable and flexible, and thus compatible with the current film-based battery technology. However, the low ionic conductivity (<10−6 S cm−1) of SPE at ambient temperature and high-temperature instability restrict their wide utilization.[8–15] Great efforts have been devoted to improving the performance of SPE. Increasing the content of Li salts or decreasing the crystallinity of polymers with composite polymers or block copolymers were able to increase the ionic conductivity by orders of magnitude.[16–18] However, other properties of SPE such as the film forming property were decreased, leading to poor mechanical strength and thermal resistance. A successful strategy was rigid-flexible coupling that applied cellulose nonwoven to support the softened SPE.[11] Another widely employed approach is to add ceramic fillers which can interact with both the salt anions and the polymer segments to promote local amorphization and enhance Li+ transport.[19–24] Accordingly, the interaction can be tailored by screening fillers with Solid state electrolytes are the key components for high energy density lithium ion batteries and especially for lithium metal batteries where lithium dendrite growth is an inevitable obstacle in liquid electrolytes. Solid polymer electrolytes based on a complex of polymers and lithium salts are intrinsically advantageous over inorganic electrolytes in terms of processability and film-forming properties. But other properties such as ionic conductivity, thermal stability, mechanical modulus, and electrochemical stability need to be improved. Herein, for the first time, 2D additives using few-layer vermiculite clay sheets as an example to comprehensively upgrade poly(ethylene oxide)-based solid polymer electrolyte are introduced. With clay sheet additives, the polymer electrolyte exhibits improved thermal stability, mechanical modulus, ionic conductivity, and electrochemical stability along with reduced flammability and interface resistance. The composite polymer electrolyte can suppress the formation and growth of lithium dendrites in lithium metal batteries. It is anticipated that the clay sheets upgraded solid polymer electrolyte can be integrated to construct high performance solid state lithium ion and lithium metal batteries with higher energy and safety.

Simultaneously Enhancing the Thermal Stability, Mechanical Modulus, and Electrochemical Performance of Solid Polymer Electrolytes by Incorporating 2D Sheets

High-Performance Solid Polymer Electrolytes Filled with Vertically Aligned 2D Materials

MXene-Based Mesoporous Nanosheets Toward Superior Lithium Ion Conductors

Inorganic solid-state electrolyte (SSE) has offered a promising option for the safe rechargeable Li metal batteries. However, the solid-solid interfacial incompatibility greatly hampers the practical use. The interface becomes even worse during repeated Li plating/stripping, especially under high current density and long cycling operation. To promise an intimate contact and uniform Li deposition during cycling, we herein demonstrate a stress self-adapted Li/Garnet interface by integrating Li foil with a hyperelastic substrate. Consecutive and conformal physical contact was ensured at Li/Garnet interface during Li plating/stripping, therefore dissipating the localized stress, suppressing Li dendrite formation, and preventing Garnet cracks. Record long cycling life over 5000 cycles was achieved with the ultrasmall hysteresis of 55 mV at high current density of 0.2 mA cm-2. Our strategy provides a new way to stabilize Li/Garnet interface from the perspective of anode mechanical regulation and paves the way for the next generation solid-state Li metal batteries.

Long Cycling Life Solid-State Li Metal Batteries with Stress Self-Adapted Li/Garnet Interface.

\n In this paper, a data-driven approach for constructing elastoplastic constitutive law of microstructured materials is proposed by combining the insights from plasticity theory and the tools of artificial intelligence (i.e., constructing yielding function through ANN) to reduce the required amount of data for machine learning. Illustrative examples show that the constitutive laws constructed by the present approach can be used to solve the boundary value problems (BVPs) involving elastoplastic materials with microstructures under complex loading paths (e.g., cyclic/reverse loading) effectively. The limitation of the proposed approach is also discussed.

Qian Xiang

Papers

Simultaneously Enhancing the Thermal Stability, Mechanical Modulus, and Electrochemical Performance of Solid Polymer Electrolytes by Incorporating 2D Sheets

High-Performance Solid Polymer Electrolytes Filled with Vertically Aligned 2D Materials

MXene-Based Mesoporous Nanosheets Toward Superior Lithium Ion Conductors

Long Cycling Life Solid-State Li Metal Batteries with Stress Self-Adapted Li/Garnet Interface.

Exploring Elastoplastic Constitutive Law of Microstructured Materials Through Artificial Neural Network—A Mechanistic-Based Data-Driven Approach