Phase Change Materials For Storage Research Articles

Hydrophobic composite phase change coating: Preparation, performance and application

The utilization of composite phase change materials in energy storage and solar thermal applications is significantly restrained by their inherent non-hydrophobic surfaces and susceptibility to contamination. This study presents a novel synthesis of modified paraffin (Pa) @ silica (SiO2) nanocapsules through an efficient in situ hydrolysis and polycondensation reaction utilizing tetraethyl orthosilicate (TEOS) as the silicon source, paraffin as the phase change material, and hexamethyldisilazane (HMDS) as the surface modifier. These nanocapsules were then employed to formulate a composite phase change coating (PSC-1) by spraying onto a substrate of lithium silicate (Li2SiO3), a green inorganic binder. This coating combines self-cleaning and energy storage functionalities. The thermal characterization of PSC-1 revealed an enthalpy of phase transition of 92.95 J/g at a core-shell ratio of 1.5:1 and an HMDS to TEOS volume ratio of 1:1. Additionally, the thermal conductivity of PSC-1 was measured at 0.505 W/m∙K, which is approximately 53 % higher than that of pure paraffin. PSC-1 also demonstrated superior hydrophobicity, with a static water contact angle of 132.6°. Enhancing its practicality, the coating was subsequently dyed black and assessed for photothermal conversion efficiency, which was determined to be around 68 %. The integration of robust self-cleaning properties and high-efficiency thermal characteristics renders PSC-1 a highly promising material for broad applications in solar energy conversion and storage.

A shape-stable phase change material for high-temperature thermal energy storage based on coal fly ash and Na2SO4-K2SO4

Using coal fly ash (CFA) as the skeleton material and binary sulfates of Na2SO4-K2SO4 as the phase change material (PCM), high-temperature coal fly ash based phase change thermal storage materials (CPCM) were successfully synthesized. The influences of CFA fractions and types on the morphology, physicochemical properties, and thermal characteristics of the composites were intensively investigated. Results show that the heat storage density and thermal conductivity of CPCMs increase with the PCM content. Particularly, the CPCM60-A composite, comprising 60 wt% Na2SO4-K2SO4 eutectic and 40 wt% CFA-A, exhibits excellent chemical compatibility and stable shape retention after sintering. Furthermore, CPCM60-A demonstrates the highest phase change latent heat of 60.43 J/g and thermal conductivity of 0.61 W/(m·K). The influence of CFA types reveals that CFA-A with a higher ratio of SiO2 and Al2O3, lower carbon content, and a rich porous structure is more suitable to fabricate molten salt heat storage materials. This work demonstrates that CFA, a byproduct of coal-fired industry, is a promising skeleton material for the fabrication of high-temperature CPCM composites, offering a novel approach for enhancing the efficiency and cost-competitiveness of solar power and waste heat recovery systems.

A novel approach for solidification enhancement of phase change materials through direct contact with a boiling fluid: An experimental investigation and visualization

Due to their remarkable properties, such as high latent heat and stable temperatures during phase transitions, phase change materials (PCMs) are widely used in thermal energy storage (TES) and thermal management systems (TMSs). However, their low thermal conductivity has limited their broader application across various industries. This study experimentally explores, for the first time, the effects of injecting boiling fluid (BF) into the PCM container as a new method to enhance heat transfer during the solidification process of PCM. To this end, Paraffin wax and acetone with saturation temperature lower than paraffin’s freezing point are selected as PCM and BF, and the influence of four various parameters, namely the initial PCM temperature (75, 85, and 95 °C), the height of the PCM inside the container (15 cm, 25 cm, and 35 cm), the flow rate of the BF (0.32, 0.46, and 0.57 L/min), and the nozzle diameter (2 mm, 3 mm, and 4 mm), on the solidification behavior of PCM, temperature distribution inside the container, and heat transfer enhancement (released energy and Nusselt number) is thoroughly scrutinized. In order to visualize and further evaluate the two simultaneous phase transitions (vaporization of the BF and solidification of the PCM), a Hele-Shaw cell with a height, width, and thickness of 50, 20, and 1 cm is considered as the PCM storage system. The findings indicate that when the BF is injected into the paraffin storage, the high heat transfer coefficient of boiling superbly improves the thermal behavior of PCM, and the solidification process occurs in a much shorter time. Also, boiling of the acetone inside the container and its direct contact with paraffin leads to a significant mixing inside the container and the creation of vortices and turbulent flow in the system, which further improves the freezing phenomenon. Furthermore, it was observed that regardless of other parameters, the flow rate of BF is the most crucial parameter, and after that, the height of the paraffin and the initial temperature have the greatest impact. By employing the highest flow rate, the proposed technique is capable of freezing 0.7, 0.5, and 0.3 L of paraffin in 48, 33, and 18 s, respectively, indicating multiple times of improvement in the full solidification time compared to previous studies.

Capric-lauric & capric-palmitic/modified bentonite composite as phase change materials for thermal energy storage

This paper proposes a new double layer structure shape-stabilized thermal energy storage wallboard (TESW), by employing microwave radiation modified bentonite (Bm) to stabilize capric acid-lauric acid (CA-LA) and capric acid-palmitic acid (CA-PA) as major components of internal and external wallboard. Leakage test showed that CA-LA/Bm and CA-PA/Bm had good morphological stability. The chemical compatibility, phase change behaviors, and microstructure of CA-LA/Bm and CA-PA/Bm were analyzed. The maximal loading capacities of CA-LA/Bm and CA-PA/Bm can be reached 45 % and 50 %, respectively. In addition, the mechanical and thermal performance of CA-LA/Bm and CA-PA/Bm-based thermal energy storage concrete (CL&CP/Bm-TESC) was systematically studied. The Digital Image Correlation (DIC) technology was used to collect and analyze the speckle images of CL&CP/Bm-TESC20 before and after 100 cycles of phase change, determining the evolution of principal strains during the deformation and failure processes. It is worth noting that the numerical simulation results of the designed double layer structure shape-stabilized CA-LA&CA-PA/Bm-based thermal energy storage wallboard (CL&CP/Bm-TESW) show better temperature adjusting performance. These results demonstrate that the prepared composite of CA-LA/Bm and CA-PA/Bm has potential application in the field of thermal energy storage.

Thermal conductivity enhancement of polyethylene glycol/NF composite as stabilized phase change materials for thermal energy storage

Polyethylene glycol (PEG) has the advantages of large latent heat of phase transition, a wide range of phase transition, and cheap price, but the application of PEG in the latent thermal energy storage (TES) systems is hindered due to its lower heat transfer rate and leakage. Porous metal foam has excellent thermal conductivity and high strength, which can effectively improve the problems of PEG. In this study, PEG/nickel foam (NF) composite phase change materials (PCM) were prepared by vacuum molten impregnation method using NF as substrate. It was found that PEG had good compatibility with NF, and the highest impregnation rate of PEG6000/NF reached 85.73 %. The thermal conductivity of PEG2000/NF can be increased to 1.58 1.58 W·m−1 K−1, nearly 4 times larger than that of pure PEG. The phase change temperature range of the composite PCM is 51–63 °C, and the phase change enthalpy is 67.8–126.3 J·g−1. Furthermore, the PEG/NF composite demonstrated outstanding photothermal conversion properties and high thermal stability, which can be widely used in the field of building temperature control and device heat dissipation.

Dynamic simulation of a combined solar system including phase change material storage and its experimental validation

Thermal energy storage is a key issue in efficient energy system applications, especially in renewable energies. In this respect, phase change materials (PCM) have attracted interest as an active solution for efficient energy management, particularly in the building sector. This paper presents a modelling of a PCM thermal battery in solar system assisted by heat pump. The storage stores the heat produced by unglazed solar panels (Batisol®) and releases it into a heat pump. Then this heat is sent to two other PCM storages. In this way, the low-temperature heating and domestic hot water needs of a commercial building in winter are met. The storage consists of a block of PCM contained between two plates of heat transfer fluid. It acts as a plate heat exchanger that can be charged and discharged simultaneously. The objective of the study is to dynamically simulate the thermal behaviour of this storage for different hot inlet temperature profiles. A rectangular profile is used to validate the model using experimental results. Then, a solar system assisted by heat pump and three PCM storages is dynamically simulated. This 2D model would be useful to validate a simpler model for optimising the operational parameters of the system.

Double-network aerogel-based eutectic composite phase change materials for efficient solar energy storage and building thermal management

Phase change materials (PCMs) have shown great promise in solar energy storage and thermal management of buildings. Nevertheless, the solid-liquid PCMs currently used in these applications face multiple challenges that need to be addressed, such as inadequate solar absorption capacity, leakage issues, and low phase change enthalpy. In this research, urea and sodium acetate trihydrate (SAT) were employed as the main PCMs, while disodium hydrogen phosphate dodecahydrate (DHPD) served as the nucleating agent. Additionally, we used polyvinyl alcohol/silica (PVA/SiO2) aerogel as a porous support structure. Carbon nanotubes (CNTs) were also introduced as photothermal conversion materials to fabricate a photothermal conversion-type double-network aerogel-based eutectic composite PCM (ECPCM). The prepared ECPCM exhibited excellent shape stability, high mechanical strength, and outstanding photothermal conversion performance. Moreover, the ECPCM demonstrated good flame retardancy, low supercooling, and the absence of phase separation issues. Furthermore, the ECPCM demonstrated efficient solar energy storage capacity and outstanding performance in building thermal management. This study offers a new perspective on the advancement of ECPCMs in solar energy storage and thermal management of buildings.

Dynamic evaluation of a vapor compression refrigeration cycle combined with a PCM storage tank for improving condenser performance

In this study, a vapor compression refrigeration cycle integrated with a phase change material (PCM) storage tank has been dynamically simulated over a 24-h period. The primary objective of this system is to reduce electric energy consumption during on-peak hours (12:00–19:00) and shift it to off-peak hours (1:00–10:00). During off-peak hours, the vapor compression refrigeration system stores cooling energy in the PCM storage tank. The stored cooling energy is then reused during on-peak hours to pre-cool the condenser inlet refrigerant, enhancing the cooling system's performance and reducing electric consumption during on-peak hours. Oleic acid, eutectic mixtures of 45 % capric acid and 55 % lauric acid by weight (CL), a commercial blend of salt hydrate and paraffin wax (SP224A), and CaCl2.6H2O have been selected as the PCM mediums. The effects of weather conditions and PCM storage tank parameters on the system's performance have been investigated. The results indicate that SP224A performs the best in most weather conditions. The maximum electric peak load shaving occurred under Ramsar city weather conditions, achieving 98.85 %. Additionally, the compressor's electric energy consumption is reduced by about 23.38 %. Moreover, increasing the length of PCM storage pipes leads to a reduction in compressor energy consumption during on-peak hours, as well as electric peak load shaving, with an improvement of up to 156 %.

Solid–Liquid Phase Equilibrium of the n-Nonane + n-Undecane System for Low-Temperature Thermal Energy Storage

The current article presents an exploration of the solid–liquid phase diagram for a binary system comprising n-alkanes with an odd number of carbon atoms, specifically n-nonane (n-C9) and n-undecane (n-C11). This binary system exhibits promising characteristics for application as a phase change material (PCM) in low-temperature thermal energy storage (TES), due to the fusion temperatures of the individual components, thereby motivating an in-depth investigation of the solid–liquid phase diagram of their mixtures. The n-nonane (n-C9) + n-undecane (n-C11) solid–liquid phase equilibrium study herein reported includes the construction of the phase diagram using Differential Scanning Calorimetry (DSC) data, complemented with Hot–Stage Microscopy (HSM) and low-temperature Raman Spectroscopy results. From the DSC analysis, both the temperature and the enthalpy of solid–solid and solid–liquid transitions were obtained. The binary system n-C9 + n-C11 has evidenced a congruent melting solid solution at low temperatures. In particular, the blend with a molar composition xundecane = 0.10 shows to be a congruent melting solid solution with a melting point at 215.84 K and an enthalpy of fusion of 13.6 kJ·mol–1. For this reason, this system has confirmed the initial signs to be a candidate with good potential to be applied as a PCM in low-temperature TES applications. This work aims not only to contribute to gather information on the solid–liquid phase equilibrium on the system n-C9 + n-C11, which presently are not available in the literature, but especially to obtain essential and practical information on the possibility to use this system as PCM at low temperatures. The solid–liquid phase diagram of the system n-C9 + n-C11 is being published for the first time, as far as the authors are aware.

New hybrid nano- and bio-based phase change material containing graphene-copper particles hosting beeswax-coconut oil for solar thermal energy storage: Predictive modeling and evaluation using machine learning

Although utilizing phase change materials (PCMs) for thermal energy storage and management has remarkably grown, the reliance on petroleum-based PCMs has raised concerns about their sustainability. Hence, in this study, the mixture of beeswax (BW) and coconut oil (CO) as a new biological-based PCM (bio-PCM) was developed. Also, the effect of 0.5, 1, and 2 wt% of graphene-copper (Gr-Cu) hybrid nanoparticles on the bio-PCM's ability in thermal energy storage (TES) was scrutinized. Thermal, chemical, physical, and stability specifications of BW-CO/Gr-Cu nano- and bio-based PCMs (bio-nPCMs) were examined by Differential Scanning Calorimeter (DSC), Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). Also, the thermal conductivity of bio-PCM and bio-nPCMs were explored in a range of temperatures from 25 to 60 °C. FTIR indicated no chemical reactions or new synthesis materials in the final composite. Also, all the used materials were recognized by XRD. DSC analysis showed that melting and solidification of bio-PCM start at 51 and 56 °C while adding 2 wt% Gr-Cu nanoparticles reduced the temperatures to 49.9 °C and 53.8 °C, respectively. In addition, bio-PCM had latent heats of 172.3 kJ/kg and 173.11 kJ/kg for melting and solidification, whereas 2 wt% Gr-Cu nanoparticles shifted them to 160.75 kJ/kg and 167.45 kJ/kg, in respect. On the other hand, the higher the concentration of Gr-Cu in the base PCM, the higher the thermal conductivity of bio-nPCMs maximally about 604 % higher than that of the base bio-PCM at T = 25 °C. Furthermore, a new model was proposed for the thermal conductivity that had an average error of 5 %. Machine learning was employed to estimate the thermal conductivity and latent heat. The former with R-squared, mean error (MSE), and average absolute relative deviation (%AARD) of 0.9996, 1.1253 × 10−4, 1.871, and the latter with 1, 4.7 × 10−10, and 0.01, respectively. The outcomes of this study present a procedure to develop future bio-PCMs and hybrid nanoparticles to pave the way to reaching net-zero carbon.

The Impact of Boron Nitride Additive on Thermal and Thermochromic Properties of Organic Thermochromic Phase Change Materials.

Thermochromic phase change materials (TPCMs) are gaining increasing interest among scientists. These multifunctional materials can store thermal energy but also, at the same time, during the phase transition, they can change colour. Thermal conductivity is also extremely important for this type of material, which is why various additives are used for this purpose. This work aimed to study the properties of thermochromic phase change materials with an inorganic modifier. Stearic acid, behenyl alcohol, and bromocresol purple were used as thermochromic system components, while boron nitride particles were used as an additive. The key tests for such systems are thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), which allow determining the thermal stability of the materials (at around 170 °C) and phase transition parameters (thermal energy storage of 300 J/g in the range of 40-75 °C). The thermochromic properties were tested, and satisfactory results were obtained. In the end, laser flash analysis (LFA) tests indicated that boron nitride improves the thermal conductivity of the organic thermochromic phase change material by almost 30%. The results showed that the tested materials have great potential as thermochromic phase change materials for thermal energy storage.

Experimental study of electricity generation from solar energy using organic phase change materials and thermoelectric generator

The study investigates using edible oils (ostrich, mutton, beef, coconut) as natural phase change materials for solar energy absorption and storage. Exposed to 900 W/m2 direct radiation by a solar simulator, these materials harness captured energy at a specific depth to generate electricity through a thermoelectric device. The experimental results showed that coconut oil exhibits the highest thermal energy storage efficiency among others, measuring at 39 %, while mutton tallow shows the lowest performance at 16.59 %. Additionally, the performance of a system employing coconut oil as the best material, in combination with iron oxide nanoparticles and carbonized sawdust (CS) was experimentally evaluated at different mass fractions (0.3 %, 0.6 %, and 0.9 %) to enhance thermal conductivity and sunlight absorption. The carbonized sawdust and its nanoparticles increased the thermal energy storage efficiency of the system by 62 % and 53 %, respectively. Moreover, the stored exergy by the phase change materials indicates that coconut oil and beef tallow had the highest and lowest exergy efficiencies of 6.3 % and 3.3 %, respectively. The combination of coconut oil with iron oxide nanoparticles and carbonized sawdust leads to 10 % and 7.9 % increased exergy efficiencies respectively.

Preparation and characterization of innovative cement mortar incorporating fatty acid/expanded graphite composite phase change material for thermal energy storage

To explore the application of phase change energy storage materials in building energy conservation, in this study, an innovative composite thermal energy storage cement mortar (CTESCM) was developed using lauric acid–palmitic acid/expanded graphite (LA-PA/EG) as the composite phase change material (CPCM). Seven different CTESCM test blocks with different CPCM mass contents were prepared. The thermal characterization of the CTESCMs was achieved using a differential scanning calorimeter (DSC), a thermogravimetric analysis (TGA), thermal conductivity tests, and heat storage/release tests. The physical behavior was assessed using density, mechanical performance was assessed using compressive strength, and the microstructure was observed using a scanning electron microscope (SEM). The results indicate that the phase transition temperature of the CTESCMs was lower than that of the LA-PA/EG CPCM, and the latent heat consistently decreased with the decrease of the CPCM mass content. With the addition of the CPCM, which had a low-density porous structure, the thermal conductivity, density, and compressive strength of the CTESCMs decreased. CTESCM with a mass fraction of 20%C (20% cement) CPCM can be used for building energy conservation such as floor radiation heating systems.

Preparation and performance study of porous biochar-based shape-stabilized phase change materials for thermal energy storage

Preparation and performance study of porous biochar-based shape-stabilized phase change materials for thermal energy storage

Phase Change Materials for Thermal Energy Storage: A Concise Review

Thermal energy and its storage systems play an extensive role in day-to-day life. They store renewable energy and are capable of recovering generated heat from different systems. Storage of thermal energy can be classified into three types: sensible, latent and sorption heat storages. Thermal heat storages use different types of materials based on their capacity of heat storage, stability of duration and thermal conductivity. Various phase change materials (PCMs) that are suitable for thermal storage are reported. Low conversion ability limits their effectiveness. We reviewed some of the traditional materials synthesized recently that are used for thermal energy storage (TES). Recently developed TES materials exhibit high thermal conductivity, reduced super cooling and multiple phase change temperatures. Nano-enhanced PCMs produced an increase in thermal conductivity up to 32% with a reduction in latent heat by 32%. At this juncture, MXenes with high performance and extraordinary properties (thermal, mechanical, etc.) are of special significance. MXenes displayed an increased thermal conductivity up to 16% and 94% efficiency. In view of their structure and adaptability to be used in thermal storage systems, an attempt was made to review their role also in thermal storage applications. It is observed that MXenes highly impact storage and efficiency. Apart from MXenes, various types of PCMs along with their thermal characteristics are presented.

Innovative dodecane-hexadecane/expanded graphite composite phase change material for sub-zero cold storage applications

Utilization of phase change materials (PCMs) for cold energy storage has garnered increasing attention. This study focuses on the development of a composite PCM by integrating a novel eutectic dodecane-hexadecane (DD-HD) PCM into expanded graphite (EG), to cater to the demands of sub-zero cold energy storage applications, such as cold chain logistics. The study identified the optimal mass ratio of DD-HD as 80:20. A series of DD-HD/EG composites were fabricated through a combination of high-speed emulsification and physical adsorption methods. The adsorption capacity of EG for the eutectic PCM mixture was evaluated by examining the impact of EG fraction on the leakage of the composite PCM, revealing that the optimum EG fraction is 10 wt%. The composite PCM displayed a sub-zero phase change temperature of -12.09 ℃, a high melting enthalpy of 178.75 kJ/kg, and a high thermal conductivity of 5.18 W/(m•K). The thermal conductivity of the composite was enhanced by 22.52 times compared to the base PCM. Thermogravimetric analysis indicated that the decomposition temperature of DD-HD/EG was significantly higher than that of the base PCM. The composite demonstrated outstanding thermal reliability, as evidenced by thermal cycle tests. With its impressive thermal characteristics, this composite shows great potential for various cold energy storage applications.

Structure and regional optimization of a phase change material Trombe wall system

Trombe walls (TW) have been an effective passive solar technology for enhancing building energy efficiency. Considering the thermal storage and regulation capabilities of phase change materials (PCM) in solar energy utilization, TW with PCM (PCMTW) were designed and optimized to further improve building energy performance. This study investigated the combined effects of PCM phase change temperature, PCM location and ventilation strategies on a single-layer PCMTW. Moreover, a novel double-layer PCMTW was proposed and evaluated across various climate regions of China in consideration of the effect of PCM phase change temperature combinations. Results show that the single-layer PCMTW with PCM22 placed next to inner surface and ventilation achieved the lowest annual energy consumption. The selection of PCM phase change temperature was crucial for various climatic conditions. Compared to the traditional building, the highest heating energy-saving was 118.16 kWh/m2 achieved in Changchun with PCM22 + 28, and the highest cooling energy-saving was 45.71 kWh/m2 achieved in Haikou with PCM25 + 28. Additionally, the double-layer PCMTW was recommended for climate regions where the daily average temperature and the daily average solar emissivity were 20–25 °C and below 4 kWh/m2 in summer, and below 10 °C and 2–6 kWh/m2 in winter.

Unlocking the power of LiOH: Key to next-generation ultra-compact thermal energy storage systems

This study explores the potential of untapped lithium hydroxide (LiOH) as a phase change material for thermal energy storage. By overcoming the challenges associated with the liquid LiOH leakage, we successfully thermal-cycled LiOH in a laboratory scale experimentation, and observed its stability (>500 thermal cycles), without chemical decomposition. This step has never been performed to date. Its solid-to-liquid reversible transitions temperatures and related solidification/melting enthalpies values have been verified. Then, the first experimental characterization of LiOH's thermal properties shows unexpected values for its heat capacity, thermal conductivity and diffusivity, in contradiction with the few ones available in literature. This opens avenues for LiOH's applications for the storage of sensible and latent heat, as shown through the increased cycle efficiency potential of a thermal energy storage system if based on its energy storage capacity; up to six times more volumetric energy density compared to traditional Solar Salt-based systems used in the solar tower plant (4.5 GJ/m3 vs. 0.76 GJ/m3 over 1000 thermal cycles). Additionally, we observed a softening phenomenon that occurs inconsistently during heating, but which may account for its excellent melting properties and the interplay with other raw chemicals. This new insight contributes certainly to the underlying mechanisms in the synthesis of another promising heat storage material in development: the peritectic compound Li4Br(OH)3. This pioneering work suggests LiOH as a promising ultra-compact thermal energy storage material for filling the intermediary gap from current to next-generation solar power plants, although its large-scale application requires further investigation to achieve economic viability.

Editor's Note for article entitled “Phase change materials for thermal management and energy storage: A review”

Editor's Note for article entitled “Phase change materials for thermal management and energy storage: A review”

Bis(dialkylammonium)-based hybrid organic–inorganic ionic materials as solid–solid phase change materials

The application of phase change materials (PCMs) in thermal energy storage (TES) systems is often restricted by challenges such as volume expansion, phase segregation, stability issues and potential leakage, particularly prominent in conventional solid–liquid PCMs. In response to these limitations, solid–solid PCMs have emerged as a promising alternative, garnering increasing attention. While both organic and inorganic solid–solid PCMs have been extensively studied, hybrid organic/inorganic materials represent a distinct class of solid–solid PCMs that have recently garnered significant interest due to their inherent properties such as high thermal stability, non-flammability or long cycle life. Organic-inorganic layered perovskites are emerging as potential good solid–solid PCMs as they present energetic solid–solid transitions and high thermal stability. In this work we propose the synthesis and thorough thermal characterization and cyclability of a series of new hybrid organic–inorganic ionic materials based on n-dialkylamines of different lengths (C8, C10, C12 and C18) with general formula of the type 2[(CnH2n+1)2NH2][MX4], using three different tetrachlorometalates anions ([FeCl4]2-, [MnCl4]2- and [CuCl4]2-). Among the new ionic materials prepared six of them have shown solid–solid transition enthalpies higher than 100 J/g. In particular, the 3 bearing the secondary n-dioctadecylamines as cations have shown unprecedent solid–solid transitions enthalpies ca. 90 °C, for this kind of ionic materials of 167.5 J/g, 157.7 J/g and 146.9 J/g for [DODA]2[MnCl4], [DODA]2[CuCl4] and [DODA]2[FeCl4] respectively. In addition, the latter ionic materials have undergone reliability tests showing excellent performance up to 500 heating/cooling cycles.