Harald Mehling

Review on thermal energy storage with phase change: materials, heat transfer analysis and applications

Abstract Thermal energy storage in general, and phase change materials (PCMs) in particular, have been a main topic in research for the last 20 years, but although the information is quantitatively enormous, it is also spread widely in the literature, and difficult to find. In this work, a review has been carried out of the history of thermal energy storage with solid–liquid phase change. Three aspects have been the focus of this review: materials, heat transfer and applications. The paper contains listed over 150 materials used in research as PCMs, and about 45 commercially available PCMs. The paper lists over 230 references.

Heat transfer enhancement in water when used as PCM in thermal energy storage

Efficient and reliable storage systems for thermal energy are an important requirement in many applications where heat demand and supply or availability do not coincide. Heat and cold stores can basically be divided in two groups. In sensible heat stores the temperature of the storage material is increased significantly. Latent heat stores, on the contrary, use a storage material that undergoes a phase change (PCM) and a small temperature rise is sufficient to store heat or cold. The major advantages of the phase change stores are their large heat storage capacity and their isothermal behavior during the charging and discharging process. However, while unloading a latent heat storage, the solid–liquid interface moves away from the heat transfer surface and the heat flux decreases due to the increasing thermal resistance of the growing layer of the molten/solidified medium. This effect can be reduced using techniques to increase heat transfer. In this paper, three methods to enhance the heat transfer in a cold storage working with water/ice as PCM are compared: addition of stainless steel pieces, copper pieces (both have been proposed before) and a new PCM-graphite composite material. The PCM-graphite composite material showed an increase in heat flux bigger than with any of the other techniques.

PCM-module to improve hot water heat stores with stratification

Hot water heat stores with stratification are a common technology used in solar energy systems and reuse of waste heat. Adding a PCM module at the top of the water tank would give the system higher storage density, and compensate heat loss in the top layer. The work presented here includes experimental results and numerical simulation of the system using an explicit finite-difference method. Experiments and simulations were carried out using different cylindrical PCM modules. With only 1/16 of the volume of the store being PCM, 3/16 of water at the top of the store was held warm for 50% to 200% longer and the average energy density was increased by 20% to 45%. Furthermore, these 3/16 of water were reheated by the heat from the module after being cooled down in only 20 min.

Determination of enthalpy-temperature curves of phase change materials with the temperature-history method: improvement to temperature dependent properties

The temperature-history method, proposed by Yinping et al, is a simple and economic way to determine the main thermophysical properties of materials used in thermal energy storage based on solid–liquid phase change. It is based on comparing the temperature history of a phase-change material sample and a sample of a well known material upon cooling down. In this paper we describe a further developed evaluation procedure to determine cp and h as temperature dependent values which was not the case in Yinpings method, based on the same experimental procedure. Given the suitability of these properties to calculate thermal energy storage using these materials, the method is proposed to present the results obtained in the form of enthalpy–temperature curves. A discussion about the errors produced by this method and an experimental improvement are proposed too.

Verification of a T-history installation to measure enthalpy versus temperature curves of phase change materials

Phase change materials (PCM) are able to store thermal energy in small temperature intervals very efficiently due to their high latent heat. Accurate knowledge of the enthalpy as a function of temperature, or the storage capacity at each temperature, is the key to design any application. Conventional methods for thermal analysis however often lack sufficient accuracy or sample size to be applied to PCM. The T-history method is a simple method to determine the storage capacity of PCM and allows the use of large sample sizes. The experimental setup and methods of data analysis have been significantly improved in recent years. In this paper, a proper methodology to verify the correct setup and data analysis method of a T-history installation using standard materials with known properties is described and tested. The implementation of the T-history method has been done at the ZAE-Bayern. Three standard materials, gallium, water and hexadecane, were measured, as well as two commercial PCM, RT27 and sodium acetate trihydrate graphite compound (SAT+G). The obtained results confirm that the T-history installation can be used to analyse different PCM.

Thermal performance of sodium acetate trihydrate thickened with different materials as phase change energy storage material

The use of phase change materials (PCMs) in energy storage has the advantage of high energy density and isothermal operation. Although the use of only non-segregating PCMs is a good commercial approach, some desirable PCM melting points do not seem attainable with non-segregating salt hydrates at a reasonable price. The addition of gellants and thickeners can avoid segregation of these materials. In this paper, sodium acetate trihydrate is successfully thickened with bentonite and starch. Cellulose gives an even better thickened PCM, but temperatures higher than 65 °C give phase separation. The mixtures would show a similar thermal behavior as the salt hydrate, with the same melting point and an enthalpy decrease between 20% and 35%, depending on the type and amount of thickening material used.

Modeling of subcooling and solidification of phase change materials

Phase change materials (PCM) are able to store thermal energy in small temperature intervals very efficiently due to their high latent heat. Particularly high storage capacity is found in salt hydrates. Salt hydrates however often show subcooling, thus inhibiting the release of the stored heat. In the state of the art simulations of PCM, the effect of subcooling is almost always neglected. This is a practicable approach for small subcooling, but it is problematic for subcooling in the order of the driving temperature gradient on unloading the storage. In this paper, we first present a new algorithm to simulate subcooling in a physically proper way. Then, we present a parametric study to demonstrate the main features of the algorithm and a comparison of computed and experimentally obtained data. The new algorithm should be particularly useful in simulating applications with low cooling rates, for example building applications.

PHASE CHANGE MATERIALS AND THEIR BASIC PROPERTIES

This section is an introduction into materials that can be used as Phase Change Materials (PCM) for heat and cold storage and their basic properties. At the beginning, the basic thermodynamics of the use of PCM and general physical and technical requirements on perspective materials are presented. Following that, the most important classes of materials that have been investigated and typical examples of materials to be used as PCM are discussed. These materials usually do not fulfill all requirements. Therefore, solution strategies and ways to improve certain material properties have been developed. The section closes with an up to date market review of commercial PCM, PCM composites and encapsulation methods.

Melting and nucleation temperatures of three salt hydrate phase change materials under static pressures up to 800 MPa

Phase change materials (PCMs) are used for efficient thermal energy storage. When a PCM melts and solidifies, it absorbs and releases a large amount of heat within a small temperature interval. Salt hydrates are interesting PCMs with high storage density, but their solidification is often problematic due to large subcooling. From thermodynamic theory, it should be possible to cause nucleation by applying high pressure to the subcooled melt, and thereby reduce subcooling. However, for the design of a pressure based triggering system there are still many unknown factors. In this context, we investigated the pressure dependence of the melting and nucleation temperatures. We present experimental data of three inorganic PCMs under static pressures up to 800 MPa. For NaOAc 3H2O we observed a shifting of the nucleation temperature from −20°C at ambient pressure to +40°C at 800 MPa. This confirms that within this pressure range, the nucleation temperature of NaOAc 3H2O is shifted above room temperature. For CaCl2 6H2O, a good agreement with reported melting temperature data was observed, and the range of experimental data was extended. For KF 4H2O, the shift of the melting temperature was found to differ considerably from theoretic predictions.

PHASE CHANGE MATERIALS: APPLICATION FUNDAMENTALS

This chapter covers fundamentals for the application of PCM for different systems and products. The chapter starts with an introduction into heat transfer mechanisms by analytical and numerical models. Then different designs for storages are discussed including their advantages and disadvantages with respect to liquids and gases as heat transfer medium. The chapter ends with a presentation of the different PCM measurement technologies. These technologies are DSC for small samples, and T -history method for bigger samples. In situ measurement will also be commented.