(准)共晶系相变储能材料的研究进展

节能技术的发展是当今非常现实的问题,这些技术的发展方向之一是各行业的热能储存。相变储能材料由于其较大的潜热和恒温性,被广泛应用于潜热储能系统和热管理系统中。然而,单一相变材料的相变温度和潜热比较固定,难以同时满足多种储能应用对各种潜热、相变温度等性质的要求。因此,人们开展了关于二元或多元共晶相变体系的研究。本文介绍了近年来国内外（准）共晶相变储能材料及其复合材料的研究进展,探讨了（准）共晶相变储能材料的理论设计机理,指出了（准）共晶相变储能材料存在的不同问题并提出建议,最后指出了（准）共晶系相变储能材料在实际应用领域的局限,提出未来在寻找新型相变储能材料,建立传热理论模型,对（准）共晶系复合相变储能材料的力学性能、耐老化性能、储能密度低和高温条件下的耐久性差等方面需要进一步探索。     

A novel UV‐cured interpenetrating organic–inorganic hybrid polymer network based phase change materials (IPN‐PCM)

The purpose of this paper is to introduce a novel UV‐cured interpenetrating polymer networked phase change materials (IPN‐PCMs), on which no article has been found in the so far published research. Maleated castor oil (MCO) was synthesized via maleinization reaction of castor oil with maleic anhydride. Organic–inorganic hybrid interpenetrating polymer networked (IPN) materials containing both cationic and radical sections and IPN‐PCMs containing tetradecanol, hexadecanol, and octadecanol were prepared. The chemical structure of MCO and organic–inorganic hybrid IPN‐PCMs were determined by using Fourier Transform Infrared Spectroscopy (FT‐IR). Differential scanning calorimetry (DSC) was used for examining the phase‐change behaviors of the materials. Thermal stability was investigated by thermogravimetric analysis (TGA). Moreover, the surface formation of the specimen was investigated by scanning electron microscopy (SEM). In conclusion, our study proved that because of their high latent heat storage scope and high thermal stability, the obtained organic–inorganic hybrid IPN‐PCMs could be used as thermal energy storage materials. POLYM. ENG. SCI., 58:870–875, 2018. © 2017 Society of Plastics Engineers     

Vergleich dreier Latentwärmespeicherkonzepte zur effizienten Nutzung von Niedertemperaturwärme

In order to store thermal energy at a low temperature, three types of latent heat storage systems are presented and compared. The storage systems are a direct contact latent heat storage system, a latent heat system with an encapsulated phase change material (PCM) and a water reservoir with a PCM jacket. These heat systems are utilized for an efficient use of renewable energies and low‐temperature waste heat. The storage medium is a salt hydrate with a melting point of 27 °C. This work presents the three concepts including corresponding applications and a discussion of the experimental results.     

金属有机骨架基复合相变储热材料研究进展

固-液相变材料的品种多且潜热大,是潜热储热技术的重要工作介质。因其存在的液相泄漏问题,现阶段常将此类相变材料与多孔载体复合以提升相变材料的应用性能及使用寿命。金属有机骨架（MOFs）是一种新型多孔材料,具有高比表面积、高孔隙率以及孔径和表面性质可调控等优势,将其用作相变材料的载体具有潜在的发展前景。本文对MOF基复合相变材料的研究进行了全面综述,详细介绍了以MOFs为载体、以MOFs衍生多孔碳为载体和以MOFs原位生长于高导热基体所得复合材料为载体而制得的多种复合相变材料。MOFs的微孔结构所产生的强毛细管力对固-液相变材料有很强的固定作用;制备较大孔径的MOFs或者对MOFs进行修饰以调节MOF与相变材料间的相互作用,都有利于提高相变材料的负载率,从而提升复合相变材料的潜热;对MOFs进行高温碳化处理得到MOFs衍生多孔碳能有效解决MOFs孔径过小的问题,并能通过对其进行氮掺杂或磷掺杂来增强载体与相变材料间的氢键作用,从而获得具有高负载率和相变潜热的复合相变材料;为了增强MOF基复合相变材料的导热性能,先将MOFs原位合成在高导热基体上以利用高导热基体提供连续的传热网络,可以有效提升复合相变材料的导热系数。将原位生长在高导热基体上的MOFs进行高温碳化处理可以得到MOFs衍生多孔碳与高导热基体的复合材料,将其作为载体可以进一步增强复合相变材料的导热性能。文中最后指出,今后对于MOF基复合相变储热材料所用MOFs和相变材料的种类、MOFs与相变材料间相互作用对储热性能的影响、MOFs与相变材料复合后的稳定性等方面还需进一步探索,将MOFs的催化、检测等功能与相变材料的储热控温功能相结合制备多功能材料也是未来的发展方向之一。     

二维纳米片基复合相变储热材料研究进展

相变材料（PCMs）作为潜热储存和释放的介质,能够解决热能供需矛盾,从而缓解能源危机。纯相变材料具有能量密度高、温度范围广、能量输出稳定性强等优点,但其热导率低和在相变过程发生渗漏的缺点阻碍了其广泛的应用和发展。通过将PCMs与二维纳米片复合,PCMs热导率低和渗漏问题被有效解决。通过在导热机理方面进行详细阐述的基础上,综述了近几年来有关碳基二维纳米片、六方氮化硼（h-BN）纳米片、二硫化钼等复合储热材料的研究进展,为高性能二维纳米片基复合PCMs的设计提供一定的研究思路。     

脂肪酸相变材料的研究进展及应用

中长链脂肪酸及其混合物具有良好的热物性、热稳定性和化学稳定性,是非常廉价易得的一类有机相变材料.综述了脂肪酸固-液相变材料在潜热蓄热领域的发展现状,主要介绍了常用脂肪酸相变材料及其低共熔混合物的热物性和热稳定性特点,指出了其强化传热方式,总结了国内外脂肪酸复合相变材料的制备方法.     

The use of lipids as phase change materials for thermal energy storage

Phase change materials (PCMs) are substances capable of absorbing and releasing large amounts of thermal energy (heat or cold) as latent heat at constant temperature as they undergo a change in state of matter (phase transition), commonly, between solid and liquid phases. Since the late 1940s, researchers have recognized the potential for phase change materials to play an essential part in energy storage systems and the search for suitable substances has received increasing interest. Currently, the global PCM market is estimated to grow from $ 460 million in 2013 to approximately $ 1.15 billion by 2018. Fats, oils, and their derivatives are diverse in their structures and among the few renewable feedstocks available that have melting and enthalpy profiles among other properties comparable to those of commercial paraffin waxes currently used in PCM applications. This has led to the investigation of triglycerides, fatty acids, esters, alcohols, and other lipid‐based derivatives as potential PCMs and much research examining lipid‐based materials as PCMs has been published. This article gives a brief overview of phase change materials, highlights the various types of lipid substances examined for PCM applications, and suggests potential future areas of study.     

相变热界面材料导热增强及定形改善的研究进展

将相变时伴随潜热的相变材料（phase change material, PCM）特别是潜热值较大的固-液PCM引入热界面材料（TIM）领域,有望获得兼具储热和导热双功能的新型热界面材料——相变热界面材料（phase change thermal interface material, PCTIM）。然而,鉴于固-液相变材料的热导率普遍较低且存在液相流动泄漏问题,使得增强热传导并同时提升固-液相变材料的定形性成为研制高性能相变热界面材料（PCTIM）的关键。本文系统评述了国内外研究者在提升相变热界面材料热导率以及改善其定形性方面的策略及其研究进展。文中指出,目前强化PCTIM导热的手段主要有添加高导热填料、促使填料有序结构化以及使用低熔点金属等。在改善定形性方面,已运用的策略主要包括使用柔性载体负载固-液PCM以在保证一定柔性的基础上克服其液相泄漏问题,使用固-固PCM来取代固-液PCM来彻底避免液相泄漏问题的出现,以及将固-液PCM封装在微米级或纳米级胶囊内,旨在牺牲借助液相PCM增加柔性的功能,而且通过提高PCTIM的潜热值来提升其抗热流冲击性能。文章指出,当前已研制的PCTIM热...     

Preparation and properties of novel ceramic composites based on microencapsulated phase change materials (MEPCMs) with high thermal stability

Ceramic composites are widely used in medium/high temperature thermal energy storage (TES) and catalysis. Due to the high latent heat of phase change materials (PCMs), it is an effective method to improve the TES capacity by combining PCMs with ceramic materials. However, PCMs are easy to leak after being heated, so they need to be microencapsulated. Furthermore, for porous ceramic catalytic composites, the leakage of PCMs will block the pores, which seriously hinders their application. In this paper, a novel microencapsulated phase change material (MEPCM) with thermal expansion void was prepared using “double-layer coating, sacrificing inner layer” method. Based on that, two kinds of ceramic composites have been prepared. One is a TES material which composed of alumina, glass frit (GF) and MEPCMs. Thermal analysis results showed that the composite can still maintain stable heat storage performance after 200 melting-solidification cycles with little latent heat loss. Another is a multifunctional porous composite phase change material (CPCM) by loading Ce and Mn as catalyst via solution combustion synthesis (SCS) method, which can be used in low temperature SCR catalysis and other catalytic fields (100–300 °C). Based on MEPCMs with thermal expansion void, the two ceramic composites show great potential in energy storage and catalysis.     

Particle Technology in the Formulation and Fabrication of Thermal Energy Storage Materials

This article reviews the state of the art of the formulation and fabrication of sensible, latent, and thermochemical thermal energy storage (TES) materials with special focus on the role of particle technology in enhancing the performance of these materials. Molten salt-based sensible TES materials have been intensively studied, particularly the use of doped nanoparticles for enhancing specific heat capacity and thermal conductivity. For latent TES, the inclusion of property enhancers is among the most effective approaches to address the low thermal conductivity and supercooling issues of phase change materials (PCMs), whereas the encapsulation of PCMs and structurally stabilized composite PCMs are the favorable methods to address leakage and chemical incompatibility challenges. Thermochemical TES materials are often incorporated with an inert or an active host matrix for structural stabilization.     

有机-无机复合相变材料的研究进展

有机相变材料具有过冷度小、无相分离、蓄热强等优势,在相变储热领域一直受到广泛的关注。然而,较低的热导率、液相泄漏和较差的热稳定性成为限制其应用的瓶颈缺陷。近几年,有机-无机复合相变材料的研究成为新的热点,极大地促进了有机相变材料的应用和发展。本文综述了常见的提高有机相变材料导热性能的高导热性纳米材料,以及制备有机-无机定形复合相变材料常选用的多孔支撑材料,并从制备方法、作用方式和热物性等方面介绍了有机-无机复合相变材料,复合相变材料相比于单一纯相变材料具有诸多优越的性能。预测有关结构优化、封装工艺并与高效储能系统结合的研究会成为有机-无机复合相变材料未来的发展趋势。     

无机水合盐相变材料过冷度抑制方法的研究进展

无机水合盐相变材料具有较高的相变潜热、原料易得、安全性高等优点,在未来中低温储能领域有巨大的应用潜力,但其在相变过程中易出现“过冷”与“相分离”等现象,严重影响了其热稳定性能,相关问题可通过添加成核剂、增稠剂进行解决。但无机水合盐在液态下会发生泄漏,需要将其限制在一定区域内。通过多孔材料吸附、微胶囊化等方法可以对无机水合盐相变材料进行封装,多孔材料如膨胀石墨、膨润土、泡沫金属等可以吸附无机水合盐,防止其相变过程发生泄漏。微胶囊包覆则是通过将相变材料微胶囊化封装在壳材内,常用壳材包括聚甲基丙烯酸甲酯、三聚氰胺?甲醛树脂或聚脲树脂等,此外,无机SiO2壁材也是常用的材料。通过吸附封装或者微胶囊化,可以将无机水合盐相变材料限制在一定区域内,提高无机水合盐相变材料的分散性能,降低其过冷度、改善相分离现象,进一步提高无机水合盐相变循环的热稳定性,是解决无机水合盐相变材料在相变过程中渗漏问题的有效方法。本工作综述了无机水合盐相变材料过冷、相分离问题的研究现状,总结了采用多孔材料吸附和微胶囊化抑制或解决无机水合盐过冷度的研究进展,并对今后无机水合盐储能应用研究提出了建议与展望。     

Preparation and thermal energy storage properties of poly(n‐butyl methacrylate)/fatty acids composites as form‐stable phase change materials

This work is focused on the preparation, characterization, and determination of thermal energy storage properties of poly(n‐butyl methacrylate) (PnBMA)/fatty acid composites as form‐stable phase change material (PCM). In the composite materials, the fatty acids act as latent heat storage material whereas PnBMA serves as supporting material, which prevents the leakage of the melted fatty acids. The maximum encapsulation ratio for all fatty acids was found to be 40 wt%. The composites that do not allow PCM leakage in melted state were identified as form‐stable PCMs. The compatibility of fatty acids with PnBMA is investigated by optical microscopy (OM) and Fourier Transform Infrared (FT‐IR) spectroscopy. Thermal properties and thermal reliability of the form‐stable composite PCMs were determined using differential scanning calorimetry (DSC). DSC analysis revealed that the form‐stable composite PCMs had melting temperatures between 29.62°C and 53.73°C and latent heat values between 67.23 J/g and 87.34 J/g. Thermal stability of the composite PCMs was studied by thermal gravimetric (TG) analysis and the results indicated that the form‐stable PCMs had good thermal stability. In addition, thermal cycling test showed that the composite PCMs had good thermal reliability with respect to the changes in their thermal properties after accelerated 5,000 thermal cycling. On the basis of all results, it was also concluded that the prepared form‐stable composite PCMs had important potential for many thermal energy storage applications such as solar space heating of buildings by using wallboard, plasterboard or floors integrated with PCM. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

移动蓄热技术的研究进展

移动蓄热技术是缓解能量供求双方在时间、强度及地点上不匹配的有效方式,是合理利用能源及减轻环境污染的有效途径。本文概述了移动蓄热技术的在工业余热回收利用中的研究进展,分析了我国分散式热用户市场,讨论了化学能储热、显热储热、相变潜热储热技术在移动蓄热车应用中的优缺点,其中潜热储热具有储能密度高、体积小、能量供应稳定等特点,在移动蓄热车中有着广阔的应用前景。在此基础上,归纳了应用于不同热源温度的相变材料,并针对其低导热系数问题,总结了几种强化换热技术。指出了移动蓄热技术的发展方向,展望了移动蓄热技术的市场化应用前景。     

Preparation and thermal characterization of expanded graphite/paraffin composite phase change material

Expanded graphite (EG)/paraffin composite phase change materials (PCMs), with mass fraction of EG varying from 0 to 10 wt.%, were prepared and characterized. Polarizing optical microscope investigation showed that compact EG networks formed gradually with increase in the mass fraction of EG. These networks provided thermal conduction paths which enhanced the thermal conductivity of the composite PCMs, e.g., an addition of 10 wt.% EG resulting in a more than 10-fold increase in the thermal conductivity compared to that of pure paraffin. Thermal characterization of the composite PCMs with a differential scanning calorimeter (DSC) revealed the effect of the porous EG on the phase change behavior of paraffin. The shifts in the phase change temperatures were observed. The maximum deviation of the melting/freezing points of the composite PCMs from that of pure paraffin was 1.2 °C whereas that of the peak melting/freezing temperature was 5.6 °C. The DSC investigation also showed an anomaly in the latent heat of the paraffin in the composite PCMs in that it first increased and then decreased with increase in the EG fraction. Heat storage/retrieval tests of the composite PCMs in a latent thermal energy storage system showed that the heat storage/retrieval durations for EG(10)/paraffin(90) composite were reduced by 48.9% and 66.5%, respectively, compared to pure paraffin, which indicated a great improvement in the heat storage/retrieval rates of the system.     

Eudragit S (methyl methacrylate methacrylic acid copolymer)/fatty acid blends as form‐stable phase change material for latent heat thermal energy storage

By composing (Eudragit S) with fatty acids (stearic acid (SA), palmitic acid (PA), and myristic acid (MA)), form‐stable phase change materials (PCMs), which can retain the same shape in a solid state even when the temperature of the PCMs is over the melting points of the fatty acids, are prepared. The compatibility of fatty acids with the Eudragit S is proved by microscopic investigation and infrared (FTIR) spectroscopy. The melting and crystallization temperatures and the latent heats of melting and crystallization of the form‐stable PCMs are measured by Differential Scanning Calorimetry (DSC) method. The maximum mass percentage of all fatty acids in the form‐stable PCMs is found as 70%, and no leakage of fatty acid is observed at the temperature range of 50–70°C for several heating cycles. Thermal properties obtained from the DSC analysis indicate that the Eudragit S/fatty acid blends as form‐stable PCM have great potential for passive solar latent heat thermal energy storage (LHTES) applications in terms of their satisfactory thermal properties and utility advantage. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1402–1406, 2006     

Sustainable lignin-based polyols as promising thermal energy storage materials

Six lignin-based polyols (LBPs) have been prepared by cationic ring opening polymerization of an oxirane in the presence of an organosolv lignin in tetrahydrofuran (THF) as reaction media and co-monomer. The prepared LBPs have been characterized and tested for the first time as phase change materials (PCMs) for thermal energy storage (TES) at low temperature. It was found a strong influence of the LBPs composition on their performance to storage thermal energy. Thus, LBPs with higher THF wt% content and lower oxirane/THF mass ratio exhibit the highest latent heats. Furthermore, a clear inversely proportional trend between the oxirane/THF mass ratio and the melting temperatures of the prepared LBPs was noticed. Among the prepared LBPs, the highest obtained latent heat was 53.7 J/g demonstrating the potential application of lignin as feedstock for PCMs preparation. To the best of our knowledge, this is the first time that a biomass derived PCM based on lignin has been studied and considered for TES applications at low temperature. LBPs show energetic solid–liquid transitions that point out their promising potential as bio-PCMs. This work paves the way to introduce new bio-based PCMs from lignin in TES systems, for example, in a more sustainable construction sector.     

多孔介质在高温相变蓄热中的强化换热

采用实验方法,验证了金属泡沫、膨胀石墨在高温蓄热系统中强化换热的作用。实验结果表明,在250～290℃之间,金属泡沫多孔材料能够提高纯硝酸钠的换热率2.1倍。由于多孔材料严重抑制了自然对流,在液相加热阶段,硝酸钠与多孔材料混合物的换热率不高于纯硝酸钠的一半。通过比较底部加热和顶部加热两种加热方式下蓄热系统的换热性能,进一步揭示了多孔材料对自然对流的影响。     

Polymeric phase change composites for thermal energy storage

This article describes a group of thermal energy storage (TES) composites that combine TES and structural functionality. The composites are encapsulations of low melt temperature phase change materials (PCM) such as paraffin waxes in polymer matrices. Room temperature cured bisphenol‐A epoxy and styrene–ethylene–butylene–styrene (SEBS) polymers are chosen as matrix materials because of their excellent chemical and mechanical properties. The polymeric network structure in the composite encapsulates the PCMs, which transform from the solid to the liquid phase. The PCMs provide the energy storage function via the solid–liquid latent heat effect. The resulting composite exhibits dry‐phase transition in the sense that fluid motion of the PCM, when in the liquid phase, is inhibited by the structure of the polymer matrix. The polymer matrix is formulated to provide structural functionality. The latent heat, thermal conductivity and contact conductance, and structural moduli of composites having various PCM‐to‐matrix volume fractions are measured. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1240–1251, 2004     

Energetische Evaluierung von Kältespeichern und Abwärmenutzung für Kühl‐ und Gefrieranwendungen

A thermodynamic analysis of cold storage systems and waste heat usage for refrigeration and freezing applications is presented. The focus is set mainly on the energetic efficiency of the systems. The environment is considered as an infinite heat sink to which the heat from the refrigeration compartment can be transported directly. Five different concepts are presented and evaluated based on the annual electric energy and primary energy demand.