With the ever-growing energy storage notably due to the electric vehicle market expansion and stationary applications, one of the challenges of lithium batteries lies in the cost and environmental impacts of their manufacture. The main process employed is the solvent-casting method, based on a slurry casted onto a current collector. The disadvantages of this technique include the use of toxic and costly solvents as well as significant quantity of energy required for solvent evaporation and recycling. A solvent-free manufacturing method would represent significant progress in the development of cost-effective and environmentally friendly lithium-ion and lithium metal batteries. This review provides an overview of solvent-free processes used to make solid polymer electrolytes and composite electrodes. Two methods can be described: heat-based (hot-pressing, melt processing, dissolution into melted polymer, the incorporation of melted polymer into particles) and spray-based (electrospray deposition or high-pressure deposition). Heat-based processes are used for solid electrolyte and electrode manufacturing, while spray-based processes are only used for electrode processing. Amongst these techniques, hot-pressing and melt processing were revealed to be the most used alternatives for both polymer-based electrolytes and electrodes. These two techniques are versatile and can be used in the processing of fillers with a wide range of morphologies and loadings.

All-solid-state lithium batteries (ASSLB) are very promising for the future development of next generation lithium battery systems due to their increased energy density and improved safety. ASSLB employing Solid Polymer Electrolytes (SPE) and Solid Composite Electrolytes (SCE) in particular have attracted significant attention. Among the several expected requirements for a battery system (high ionic conductivity, safety, mechanical stability), increasing the energy density and the cycle life relies on the electrochemical stability window of the SPE or SCE. Most published works target the importance of ionic conductivity (undoubtedly a crucial parameter) and often identify the Electrochemical Stability Window (ESW) of the electrolyte as a secondary parameter. In this review, we first present a summary of recent publications on SPE and SCE with a particular focus on the analysis of their electrochemical stability. The goal of the second part is to propose a review of optimized and improved electrochemical methods, leading to a better understanding and a better evaluation of the ESW of the SPE and the SCE which is, once again, a critical parameter for high stability and high performance ASSLB applications.

The effects of solvent absorption on the electrochemical and mechanical properties of polymer electrolytes for use in solid-state batteries have been measured by researchers since the 1980s. These studies have shown that small amounts of absorbed solvent may increase ion mobility and decrease crystallinity in these materials. Even though many polymers and lithium salts are hygroscopic, the solvent content of these materials is rarely reported. As ppm-level solvent content may have important consequences for the lithium conductivity and crystallinity of these electrolytes, more widespread reporting is recommended. Here we illustrate that ppm-level solvent content can significantly increase ion mobility, and therefore the reported performance, in solid polymer electrolytes. Additionally, the impact of absorbed solvents on other battery components has not been widely investigated in all-solid-state battery systems. Therefore, comparisons will be made with systems that use liquid electrolytes to better understand the consequences of absorbed solvents on electrode performance.

All-Solid-State Lithium Batteries (ASSLBs) are promising since they may enable the use of high potential materials as positive electrode and lithium metal as negative electrode. This is only possible through solid electrolytes (SEs) stated large electrochemical stability window (ESW). Nevertheless, reported values for these ESWs are very divergent in the literature. Establishing a robust procedure to accurately determine SEs’ ESWs has therefore become crucial. Our work focuses on bringing together theoretical results and an original experimental set up to assess the electrochemical stability window of the two NASICON-type SEs Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) and Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP). Using first principles, we computed thermodynamic ESWs for LATP and LAGP and their decomposition products upon redox potentials. The experimental set-up consists of a sintered stack of a thin SE layer and a SE-Au composite electrode to allow a large contact surface between SE and conductive gold particles, which maximizes the redox currents. Using Potentiostatic Intermittent Titration Technique (PITT) measurements, we were able to accurately determine the ESW of LATP and LAGP solid electrolytes. They are found to be [2.65–4.6 V] and [1.85–4.9 V] for LATP and LAGP respectively. Finally, we attempted to characterize the decomposition products of both materials upon oxidation. The use of an O₂ sensor coupled to the electrochemical setup enabled us to observe operando the production of O₂ upon LAGP and LATP oxidations, in agreement with first-principles calculations. Transmission Electron Microscopy (TEM) allowed to observe the presence of an amorphous phase at the interface between the gold particles and LAGP after oxidation. Electrochemical Impedance Spectroscopy (EIS) measurements confirmed that the resulting phase increased the total resistance of LAGP. This work aims at providing a method for an accurate determination of ESWs, considered a key parameter to a successful material selection for ASSLBs.