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

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.