(Invited) Functional Protective Coatings Based on Polysaccharides and Single-Ion Conducting Polymers for Li Metal Batteries
Authors: Vargas Ordaz Mariana , Gerbaldi Claudio , Gaberscek Miran , Dominko Robert 
Published: February 2024

Li metal batteries are regarded as a promising system to overcome the energy density limitations of the current graphite anode Li-ion batteries, by taking advantage of the low reduction potential of lithium metal (-3.04 V vs SHE) and extremely high theoretical capacity (3860 mAh g-1). However, its use is still plagued with challenges that must be solved in order to achieve a successful Li-metal battery operation, that primarily relies on the performance, stability, and reversibility of the anodic side. Those challenges are related to safety concerns, mainly caused by the uncontrolled growth of high surface area lithium (HSAL) and high volumetric expansion. In this sense, to enable the safe use of Li metal, the concept of protective coating has been proposed, enabling to tailor of adequate interphases that can thermodynamically stabilize the lithium metal surface, and therefore improve the lifespan and safety of the battery. The ideal coating should possess a balance between mechanical strength, flexibility, and ionic conductivity, at the time it enables a uniform and efficient transport of lithium ions. Additionally, it must be electronically insulating and possess high chemical and electrochemically stability. In this context, polymeric coatings can offer good flexibility and elasticity which makes them suitable to adapt to the volumetric changes during lithium stripping/deposition cycles. Moreover, they can form uniform films, creating an ideal contact with lithium metal surface. An attractive group of materials that can provide numerous advantages such as high chemical, mechanical and thermal stability, are polysaccharides, aside from being the highly abundant and renewable resource on the Earth, which can be obtained in different forms.

Several studies have shown that concentration polarization during battery operation is the main responsible for HSAL generation and limited cycle life, due to the coupled anion-cation movement in the electrolyte. To solve this problem the use of single-ion conducting polymers (SICPs) can result beneficial due to their immobilized anions to a polymeric backbone, which eases lithium ion transport, boosting lithium transference number (𝑡𝐿𝑖+). In addition, the selection of an appropriate polymeric backbone that can withstand volumetric changes, and allow a satisfactory ionic conductivity is essential. In this regard, the use of cellulose is preferred due to their film formation and mechanical properties, lightweight, high abundance, and biodegradability. Herein, a polymeric coating based on cellulose and P(LiMTFSI) single-ion conductor polymer is studied as a protective coating for metallic Li, in order to prevent HSAL initiation and propagation, as well as to enhance electrochemical stability in liquid and solid polymer electrolyte. The coating effectiveness is tested by casting the solution on activated lithium surface and performing lithium stripping/deposition in Li/Cu pouch cells. Additionally, the correlation with its electrochemical and physicochemical properties is performance based on microscopy and spectroscopy technics, to study the most relevant parameters influencing Coulombic Efficiency.