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separationHigh nucleation rateAdequate crystallization rate Physical properties Subtle volume variation during phase transformationLow vapor pressure at the operating temperature Chemical properties Long‐term chemical stabilityNoncorrosive, nontoxic, nonpolluting, nonflammable, and nonexplosive to ensure safety and harmless to the surroundings Economics AbundanceEasy availabilityLow costGood recyclability Schematic illustration of classification of PCMs.

      Source: Based on [7, 12].

Solid–liquid PCMs Advantages Disadvantages
Inorganic PCMs High energy storage densitiesHigh thermal conductivitiesLow costs SupercoolingPhase separation
Organic PCMs High energy storage densitiesWide range of phase change temperature for convenient useIsothermal characteristicsNo phase separationLow or negligible supercoolingGood compatibilityNontoxicity and noncorrosionDesirable thermal and chemical stability for long‐term useAbundant natural resources Poor shape stability (leakage during phase transition)Low thermal conductivityWeak energy conversion ability

      Polymeric phase change composites, as TES units, can be roughly divided into two categories: phase change polymers presented in Figure 2.2 as working substance and common polymers as supporting component. In this chapter, we put our emphases on the innovations of shape‐stabilized and thermally conductive polymeric phase change composites, covering processing method, structural design, and materials selection. Also, energy conversion routes and potential applications associated with polymeric phase change composites are highlighted. Finally, a brief perspective on future opportunities and challenges for high‐performance and multifunctional polymeric phase change composites is proposed.

      Organic solid–liquid PCMs suffer from liquid phase leakage in the process of phase transition, resulting in decrease of energy storage density, pollution of related devices, and security risks. Shape‐stabilized PCMs are composed of working substance and supporting material, and the latter predominately includes polymers with good compatibility and thermal stability, nanomaterials with desirable structure, and porous scaffolds with excellent mechanical properties.[13] Micro/nanoencapsulated techniques, physical blending with supporting materials, incorporating porous scaffolds, and crosslinking‐solidity strategy have been adopted to improve the shape stability of PCMs, which are magnified in this chapter.

      To the best of our knowledge, the methods used to evaluate the shape stability of PCMs have not been unified and standardized. Thermal mechanical analyzer (TMA) and dynamic rheometer are usually used to quantitatively measure the size change of materials to evaluate their shape stability. With the increase of temperature, the size or dimension of samples will automatically adjust when subjected to constant normal force, and thus the shape stability can be determined by the change degree of the size or dimension. Generally speaking, the smaller the change of the sample size, the better the shape‐stabilizing effect of the material.[14] In addition to monitoring change of sample size in rheological test, dynamic temperature scanning can be used to compare the difference of storage modulus between pure sample and composites, further to judge the shape‐stabilizing effect.[15] Moreover, facile and qualitative leakage experiments are conducted to intuitively reflect the shape‐stabilizing effect in most cases. The samples are directly placed on a hot stage or in an oven and then heated to different temperatures for varying durations, followed by tracking real‐time photography with a digital camera to record the change of shape and size and leakage status of samples. It is more reasonable to calculate the mass change of samples before and after leakage test.[16, 17] Additionally, Shi et al.[18] measured the dropping point to determine the shape‐stabilizing effect of samples.

      2.2.1 Micro/Nanoencapsulated Method

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