LAUSR

This comprehensive Review focuses on the key challenges and recent progress regarding sodium-metal anodes employed in sodium-metal batteries (SMBs). The metal anode is the essential component of emerging energy storage systems such as sodium sulfur and sodium selenium, which are discussed as example full-cell applications. We begin with a description of the differences in the chemical and physical properties of Na metal versus the oft-studied Li metal, and a corresponding discussion regarding the number of ways in which Na does not follow Li-inherited paradigms in its electrochemical behavior. We detail the major challenges for Na-metal systems that at this time limit the feasibility of SMBs. The core Na anode problems are the following interrelated degradation mechanisms: An unstable solid electrolyte interphase with most organic electrolytes, "mossy" and "lath-like" metal dendrite growth for liquid systems, poor Coulombic efficiency, and gas evolution. Even solid-state Na batteries are not immune, with metal dendrites being reported. The solutions may be subdivided into the following interrelated taxonomy: Improved electrolytes and electrolyte additives tailored for Na-metal anodes, interfacial engineering between the metal and the liquid or solid electrolyte, electrode architectures that both reduce the current density during plating-stripping and serve as effective hosts that shield the Na metal from excessive reactions, and alloy design to tune the bulk properties of the metal per se. For instance, stable plating-stripping of Na is extremely difficult with conventional carbonate solvents but has been reported with ethers and glymes. Solid-state electrolytes (SSEs) such as beta-alumina solid electrolyte (BASE), sodium superionic conductor (NASICON), and sodium thiophosphate (75Na2S·25P2S5) present highly exciting opportunities for SMBs that avoid the dangers of flammable liquids. Even SSEs are not immune to dendrites, however, which grow through the defects in the bulk pellet, but may be controlled through interfacial energy modification. We conclude with a discussion of the key research areas that we feel are the most fruitful for further pursuit. In our opinion, greatly improved understanding and control of the SEI structure is the key to cycling stability. A holistic approach involving complementary post-mortem, in situ, and operando analyses to elucidate full battery cell level structure-performance relations is advocated.