The utilization of intermittent renewable energy sources needs low-cost, reliable energy storage systems in the future. Among various electrochemical energy storage systems, redox flow batteries (RFBs) are promising with merits of independent energy storage and power generation capability, localization flexibility, high efficiency, low scaling-up cost, and excellent long charge/discharge cycle life. RFBs typically use metal ions as reacting species. The most exploited types are all-vanadium RFBs (VRFBs). Here, we discuss the core components for the VRFBs, including the development and application of different types of membranes, electrode materials, and stack system. In addition, we introduce the recent progress in the discovery of novel electrolytes, such as redox-active organic compounds, polymers, and organic/inorganic suspensions. Versatile structures, tunable properties, and abundant resources of organic-based electrolytes make them suitable for cost-effective stationary applications. With the active species in solid form, suspension electrolytes are expected to provide enhanced volumetric energy densities.

Ceramic solid state-electrolytes attract significant attention due to their intrinsic safety and, in the case of the garnet type Li_6.45Al_0.05La₃Zr_1.6Ta_0.4O₁₂ (LLZO), the possibility to use Li-metal anodes to provide high energy densities on a cell and battery level. However, one of the major obstacles hindering their wide-spread application is the translation and optimization of production processes from laboratory to industrial scale. Even though the plausibility of manufacturing components and cells via wet processing routes like tape casting and screen printing has been shown, the impact of the sensitivity of LLZO to air and protic solvents due to Li⁺/H⁺-exchange is not fully understood yet. An uncontrolled alteration of the powder surface results in poorly reproducible processing characteristics and electrochemical performance of the final battery components and full cells. This knowledge gap is the cause of the large performance variations reported across different research labs worldwide and is unacceptable for up-scaling to industrial level. To close this gap, the influence of the Li⁺/H⁺-exchange taking place at various steps in the manufacturing process was systematically investigated in this study. For the first time, this allowed a mechanistic understanding of its impact on the processability itself and on the resulting electrochemical performance of a free-standing LLZO separator. The importance of a close control of the pre-treatment and storage conditions of LLZO, as well as contact time with the solvent could be extracted for each step of the manufacturing process. As a result, we were able to optimize the processing of thin, dense, free standing LLZO separators and significantly improve the total Li-ion conductivity to 3.90 × 10⁻⁴ S cm⁻¹ and the critical current density to over 300 μA cm⁻² without making structural changes to separator or the starting material. These findings do not only enable a deeper understanding and control over the manufacturing process, but also show potential for further improvement of cell concepts already existing in literature.

Garnet‐based Li‐ion conductors are one of the most promising oxide‐ceramic solid electrolytes for next‐generation Li batteries. However, they undergo a Li⁺/H⁺ exchange (LHX) reaction with most protic solvents used in component manufacturing routes and even with moisture in ambient air. These protonated garnets show a lower Li‐ionic conductivity, and even if only the surface is protonated, this degraded layer hinders the Li‐ion exchange with, for example, a metallic Li anode. Furthermore, the resulting unstable surface properties during the processing in air lead to challenges with respect to reproducibility of the final component performance, limiting their commercial applicability. However, in recent years, the knowledge about the underlying chemical mechanisms has led to the development of mitigation strategies and enabled a push of this promising material class towards sustainable and scalable fabrication routes. This Minireview covers the following four aspects, which are relevant for a comprehensive understanding of these developments: (1) reports of LHX phenomenon in garnets exposed to air and solvents; (2) recent understandings of the fundamentals and properties of LHX; (3) strategies to prevent LHX and to recover garnets; and (4) sustainable application of LHX for material processing and energy‐related devices.