Alkali alkanoate ionic liquids for thermal energy storage at mid-to-high temperature: Synthesis and thermal–physical characterization

Abstract

Thermal energy storage is gaining much attention and experiencing a renascence in last years. In this sense, storing thermal energy in form of latent heat is of special interest due higher energy density, lower energy losses and higher energy efficiency. To store thermal energy as latent heat the presence of a phase change material (PCM) is needed and its performance the key for its implementation in a thermal energy storage (TES) system and the temperature at which the phase change takes place, low (<150 °C) or high (>150 °C) temperature, will condition the application of a given PCM. In this context, the development of PCM materials to store latent heat at mid-to-high temperature in between 150 °C and 350 °C is of special interest e.g., in the field of concentrated solar power or heat recovery. There are already some solid–liquid phase change materials working in this range of temperature e.g., sugar alcohols, aromatic organic compound, inorganic salts, or blend of inorganic salts but all of them present different drawbacks, such as vapor pressure, degradation, low thermal conductivity, corrosion, etc. In consequence, there is a need to explore new PCM materials in this range of temperature applications. In this context, ionic liquids could play a key role in the development of novel PCMs due to their intrinsic properties. Indeed, ILs are gaining increased attention in the field of thermal energy storage in the last years but mainly in the low temperature range (<150 °C) remaining their application in the mid-to-high temperature range in between 150 °C and 350 °C underestimated. In this work, we prepared six different alkali alkanoate ionic liquids, namely [Na][MeOC₂], [K][MeOC₂], [Na][MeOC₃], [K][MeOC₃], [Na][MeOC₄] and, [K][MeOC₄] by direct reaction between the desired methyl methoxycarboxylate ester with NaOH or KOH. The prepared ionic liquids were structurally characterized, and their thermal–physical properties evaluated. Five of them but [K][MeOC₃] showed good enthalpy values ranging from 119 J/g to 197 J/g and four of them [Na][MeOC₂], [K][MeOC₂], [Na][MeOC₄] and, [K][MeOC₄] have showed excellent thermal stability above 380 °C. In addition, these four ionic liquids have successfully passed the cyclability test showing no significant enthalpy losses (between 0 % minimum and 7 % maximum) after 50 heating/cooling cycles compiling with the cycling category F of the RAL-GZ 896 (Quality Association PCM). All in all, these prepared ionic liquids surpass sugar alcohols in terms of cyclability and thermal stability and are comparable with the inorganic salts e.g. NaNO₃ employed in the studied range of mid-to-high temperature (150–350 °C).