Recent advances in phase change materials for thermal energy storage.

Efficient storage of thermal energy can be greatly enhanced by the use of phase change materials (PCMs). The selection or development of a useful PCM requires careful consideration of many physical and chemical properties. In this review of our recent studies of PCMs, we show that linking the molecular structures of organic molecules to their physical properties can be used to focus attention on the most useful PCMs, including eutectic mixtures. Two of the major limitations concerning broader use of phase change materials are low thermal conductivity, especially for organic phase change materials, and suitable containment. We have addressed both issues in our recent investigations of novel form-stable composite PCMs with a freeze-cast matrix. The use of thorough experimental investigations, including cycling of materials hundreds or thousands of times through the melt-freeze processes, promotes our goals of advancing the use of PCMs for increased energy efficiency and sustainability.

Organic Phase Change Materials for Thermal Energy Storage: Influence of Molecular Structure on Properties.

Materials that change phase (e.g., via melting) can store thermal energy with energy densities comparable to batteries. Phase change materials will play an increasing role in reduction of greenhouse gas emissions, by scavenging thermal energy for later use. Therefore, it is useful to have summaries of phase change properties over a wide range of materials. In the present work, we review the relationship between molecular structure and trends in relevant phase change properties (melting temperature, and gravimetric enthalpy of fusion) for about 200 organic compounds from several chemical families, namely alkanes (paraffins), fatty acids, fatty alcohols, esters, diamines, dinitriles, diols, dioic acids, and diamides. We also review availability and cost, chemical compatibility, and thermal and chemical stabilities, to provide practical information for PCM selection. Compounds with even chain alkyl lengths generally give higher melting temperatures, store more thermal energy per unit mass due to more efficient packing, and are of lower cost than the comparable compounds with odd alkyl chains.

The Relative Thermodynamic Stability of Diamond and Graphite.

Recent density-functional theory (DFT) calculations raised the possibility that diamond could be degenerate with graphite at very low temperatures. Through high-accuracy calorimetric experiments closing gaps in available data, we reinvestigate the relative thermodynamic stability of diamond and graphite. For T<400 K, graphite is always more stable than diamond at ambient pressure. At low temperatures, the stability is enthalpically driven, and entropy terms add to the stability at higher temperatures. We also carried out DFT calculations: B86bPBE-25X-XDM//B86bPBE-XDM and PBE0-XDM//PBE-XDM results overlap with the experimental -TΔS results and bracket the experimental values of ΔH and ΔG, displaced by only about 2× the experimental uncertainty. Revised values of the standard thermodynamic functions for diamond are Δf Ho =-2150±150 J mol-1 , Δf So =3.44±0.03 J K-1 mol-1 and Δf Go =-3170±150 J mol-1 .

Data supporting the prediction of the properties of eutectic organic phase change materials.

The data presented in this article include the molar masses, melting temperatures, latent heats of fusion and temperature-dependent heat capacities of fifteen fatty acid phase change materials (PCMs). The data are used in conjunction with the thermodynamic models discussed in Kahwaji and White (2018) [1] to develop a computational tool that calculates the eutectic compositions and thermal properties of eutectic mixtures of PCMs. The computational tool is part of this article and consists of a Microsoft Excel® file available in Mendeley Data repository [2]. A description of the computational tool along with the properties of nearly 100 binary mixtures of fatty acid PCMs calculated using this tool are also included in the present article. The Excel® file is designed such that it can be easily modified or expanded by users to calculate the properties of eutectic mixtures of other classes of PCMs.