基于多孔支撑体的形状稳定复合相变储能材料的研究进展

固-液相变材料（PCMs）是热能储存（TES）技术发展的关键因素,然而一些固有的问题如泄漏和热导率低等严重制约了相变材料的性能。因此,选择合适的方法构建形状稳定的复合相变材料（FSCPCMs）,并有效地提高其热导率是实现相变材料实用化的重要前提。多孔载体封装相变材料为构建具有高储能密度和优异热传输性能的定形复合相变材料提供了一条有效的途径。本文对不同FSCPCMs的制备、结构热学性能、应用等方面进行了综述,详细总结和讨论了孔径和几何形状、表面改性、作用力、组成等因素对FSCPCMs相变行为的影响。重点介绍了具有高热导率、高负载率和高潜热的新型多孔复合相变材料的设计和应用。最后,基于理论、数值和实验方法,展望了FSCPCMs在约束结构中的相变和多尺度传热方面未来的研究方向及其在能源转换方面的商业化应用。     

石墨纳米片尺寸对复合相变材料储热特性的影响

为了探究二维纳米材料的尺寸对复合相变材料储热特性的影响, 将膨胀石墨分别超声振荡10、30和90 min, 得到3种不同尺寸的石墨纳米片:GNS-10、GNS-30、GNS-90, 添加到十六醇中制备出纳米复合相变材料。利用SEM、XRD和Hot Disk等方法对其微观结构和性能进行表征和测试的同时, 对比研究了Maxwell、Bruggeman及Nielsen模型对热导率的计算结果。结果显示, 石墨纳米片尺寸越大, 对复合相变材料热导率的提升幅度越大。当GNS-10添加量为10%(质量分数)时, 热导率提升了约517%。Nielsen模型在形状因子A取100~180时可以较好地预测实验值。与大幅增长的热导率相比, 复合相变材料相变温度、相变焓的变化可忽略不计。此外, 石墨纳米片的加入明显缩短了储热材料的凝固速率, 有效热导率的提高是产生这种效果的主要原因。     

有机相变储能材料导热增强方法研究进展

有机相变储能材料是相变储能材料的重要分支,其主要缺点之一是热导率较低,极大地限制了其应用.目前提高有机相变储能材料热导率常用的方法是利用复合手段增强整个体系的导热性能,如添加纳米粒子、微胶囊化和多孔基质吸附等.本工作对当前有机相变储能材料增强导热的方法、工艺、原料、导热增强机理及存在的问题等作了综述,并对下一步的研究与发展方向作了展望.     

生物质碳化衍生物强化相变材料各向热导率的研究进展

相变材料由于具有较高的潜热值和良好的温度控制性能,已经被广泛应用于建筑节能、余热废热回收、电池热管理、太阳能热能储存等领域。然而,相变材料在固-液相变过程中的泄漏和导热性能差等缺点限制了它们的进一步发展。生物质碳化衍生物具有的多孔微观结构和良好的导热性克服了相变材料相变时的液漏和自身导热能力差等问题,成为相变材料良好的载体选择。由于生物质碳化衍生物多孔碳材料具有各向同性和各向异性的结构,因此,生物质碳化衍生物多孔碳材料强化相变材料的热导率分为各向同性热导率强化和各向异性热导率强化。     

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。     

赤藓糖醇相变储热材料研究进展

赤藓糖醇具有较高的相变焓、无毒以及优异的热稳定性，作为综合性能较好的中温相变储能材料被广泛研究。但是，赤藓糖醇在相变过程中存在易泄漏、过冷度大以及导热性能较差的缺点，导致其热能的利用效率不高，极大地限制了其作为储热材料的应用。本文综述了近年来在解决赤藓糖醇相变储热材料易泄漏、过冷度高和热导率低等问题的研究进展。赤藓糖醇定型复合相变储热材料的制备方法主要有共混压制法、静电纺丝法、微胶囊法及多孔材料吸附法等，可根据不同制备方法采取相应复合策略以达到对其封装定型、降低过冷度和提高热导率的目的。最后认为未来对赤藓糖醇复合相变储热材料的研究除了解决其本身存在的热性能问题，还需对其进行功能化，以拓展其应用前景。     

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。     

纳米复合相变蓄热材料的制备与特性

相变蓄热材料（phase change materials,PCMs）是相变蓄热技术研究的基础。针对普通相变蓄热材料热导率低的缺点,采用纳米技术改善石蜡的相变传热性能,从而提高其热导率及热扩散系数。通过纳米颗粒-石蜡复合材料熔化过程测试和纳米颗粒沉降过程观察,确定铜纳米颗粒和Hitenol BC-10分别作为实验用纳米颗粒和分散剂,在制备稳定的纳米铜颗粒-石蜡复合相变材料的基础上,对其热物性进行了实验研究。结果表明纳米铜颗粒的添加使得石蜡热导率增幅最大,实验测得固态纳米铜-石蜡热导率提高7.9%,液态提高3.8%,而固、液态热扩散系数则分别提高了20.6%和16%。     

复合相变储能砂浆性能实验研究

通过将复合相变储能材料应用在建筑墙体材料中,达到调节室内热舒适度、降低建筑能耗目的.研究了普通砂浆和复合相变储能材料不同龄期的抗折强度和抗压强度,热循环对不同龄期复合相变储能砂浆抗折强度和抗压强度的影响,以及石蜡相变储能砂浆的控温性能.结果表明:复合相变储能砂浆可以满足普通砂浆的基本力学性能要求;热循环后对复合相变控温砂浆力学性能影响很小;相变储能砂浆模拟房内的温度波动小于普通砂浆,可改善居住舒适度.     

硬脂醇改性的氧化石墨烯/正十八烷复合相变材料的热物性研究

向正十八烷中加入高导热填充物形成复合相变材料（PCM）,可以很好地提升其导热性能,同时,为了保证符合相变材料的高热导率、分散性和再循环可靠性,利用硬脂醇修饰氧化石墨烯（GO）,形成改性石墨烯（MG）与正十八烷的复合相变材料。分别制备了改性石墨烯质量分数为0、1%、2%、3%、4%（质量）的改性石墨烯/正十八烷复合相变材料,并经过扫描电镜测试、红外光谱分析、差示扫描量热实验及导热分析等测试对其形貌结构及热物性进行表征和研究。实验表明制备的改性石墨烯/正十八烷复合相变材料具有很好的分散性;当纳米石墨烯片的质量分数达到4%时,复合相变材料的热导率相对于纯正十八烷高出了131.9%。     

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。     

新型建筑用二元复合定型相变材料的制备及性能评价

针对建筑节能领域,提出了一种由十二醇（LA,C₁₂H₂₆O）和硬脂酸（SA,C₁₈H₃₆O₂）组成的具有适宜相变温区且相变潜热较高的二元相变材料LA-SA,并以膨胀珍珠岩和陶粒为多孔吸附材料制备出复合定型相变材料,探究了不同吸附材料对于定型相变材料热物性的影响。二元相变材料LA-SA的最优配比为质量分数82%十二醇+18%硬脂酸,其熔融相变温度为21.3℃,相变潜热为205.9 kJ/kg,且热稳定性能良好。以膨胀珍珠岩和陶粒为吸附材料,通过真空吸附法制备出了两种建筑用定型相变材料,并对其进行了SEM、FTIR、TG及DSC性能表征,结果表明：LA-SA与两种吸附材料的复合过程仅为物理吸附且复合良好,吸附后的定型相变材料的相变潜热有一定的降低;相比于陶粒,膨胀珍珠岩对相变材料的吸附率较高,且对相变材料热性能影响较小;LA-SA/膨胀珍珠岩熔融相变温度为22.7℃,相变潜热为165.3 kJ/kg,可应用于建筑节能材料的制备。     

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     

脂肪酸相变储能材料热性能研究进展

在以往所研究的相变材料中,脂肪酸由于展现出优越的性能,得到了研究者更多的关注,但同样存在相变温度不适宜和导热性能差等热性能问题。本工作通过现有文献对脂肪酸相变储能材料的热性能进行系统分析,提出了脂肪酸与脂肪酸、脂肪醇及石蜡复合3种有效解决相变温度不适宜的方法;针对导热性能差提出了多孔材料吸附、添加碳材料或金属粒子和微胶囊化3种高效易行的强化传热方式,进而说明这一领域目前研究重点。同时,对脂肪酸储能材料的相变性能、导热增强方法及导热增强剂进行了比较,分析了各自的优缺点。最后,对脂肪酸相变储能材料热性能研究的不足之处进行了探究,并指出了制备出更多能应用于建筑节能和纺织等领域的脂肪酸相变储能材料和着重研究脂肪酸与石蜡的复合等进一步研究方向。     

组合式相变材料最佳相变温度的热力学分析

采用组合式相变材料的蓄热系统较单一相变材料具有更为优越的传热和热力学性能,而相变温度对于蓄热系统性能具有重要的影响。为了使结果更具普适性,以热力学有效能分析为基础并忽略具体换热器形式和传热过程,推导了使用不同相变材料数时每种相变材料最佳相变温度的理论公式,并根据最佳相变温度计算了有效能利用率随着相变材料数的变化,结果表明当PCMs数增加到4种时,理论最大有效能利用率已达80%以上,比使用单一相变材料的理论最大有效能利用率高50%左右。以573.15 K热能蓄能为例,计算了使用1~4种相变材料时相应的最佳相变温度与最大有效能利用率,并以此为依据给出了实际最佳相变材料组合。     

Development of thermal energy storage concrete

In this paper, a two-step procedure to produce thermal energy storage concrete (TESC) is described. At the first step, thermal energy storage aggregates (TESAs) were made from porous aggregates absorbing phase changing materials (PCMs). At the second step, TESC was produced with a normal mixing method and using TESAs. An adequate amount of PCM can be incorporated into concrete by the two-step procedure. It can be seen experimentally that the energy storage capacity of the TESC was comparable with that of a commercially available PCM. The experimental results showed that the geometrical features of the porous structure of the aggregates had significant effect on their absorbing ability of the PCM. Aggregates with large pore connectivity factor and transport tunnel in boundary part can absorb more PCM. It was also found that the phase changing behavior was affected by the volume fraction of PCM in concrete.     

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.     

Phase change material with flexible crosslinking for thermal energy storage

The utilization of renewable energy through phase change materials (PCMs) is particularly attractive for the realization of sustainable society. Herein, a flexible but reliable solid–solid PCM was successfully synthesized by the integration of quadruple H-bonding crosslinks with polyethylene glycol (PEG)-based polyurethanes. The strong quadruple H-bonding from the dimerization of 2-ureido-4 [1H]-pyrimidinone (UPy) units could act as dynamic cross-links to maintain shape stability. PEG chains in flexible polymer network serve as phase change ingredients, affording thermal energy storage capacity. The physical crosslink density and phase change enthalpy can be adjusted. In contrast to chemical crosslinks, the physical crosslinks of UPy provide reprocessability of the prepared PCMs and show little hindrance on the crystallization of PEG chains. The chemical structure, phase transformation, crystallization, and thermal properties of prepared PCMs were characterized by fourier transform infrared spectroscopy, differential scanning calorimetry (DSC), X-ray diffraction, polarizing microscope, and thermogravimetric analysis. DSC analysis shows that the prepared PCM can store 101.9 J g⁻¹ when PCMs undergo phase change process. Moreover, the accelerated thermal cycling test and leakage test are also conducted to illustrate the thermal reliability and shape-stable properties. These PCMs that possess high phase change enthalpy and outstanding reprocessability are alternative for solar energy collection and waste heat recovery. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48497.     

正十八烷/OBC/EG复合定型相变材料制备及热物性

针对正十八烷相变易泄漏的问题,采用烯烃嵌段共聚物（olefin block copolymer,OBC）作为封装结构,制备复合定型相变材料。并通过添加膨胀石墨（expanded graphite,EG）,改善其热导率低的问题。研究结果表明,当OBC的质量分数为20%时,复合相变材料未发现明显泄漏,定型效果较好,此时复合相变材料的相变焓为166.87 J/g,相较纯十八烷（227.40 J/g）下降26.62%。针对添加有不同质量分数EG的复合相变材料,其热导率随EG含量的增加而增大。其中当EG质量分数为5%时,复合相变材料热导率为4.179 W/(m?K),较纯相变材料热导率[0.24 W/(m?K)提高了约16倍,即EG能够有效提高复合相变材料的导热性能。此外,5%含量下的复合相变材料相变焓约为149.54 J/g,且在经历50次循环后,相变温度和相变焓均未有明显变化,即制备的复合相变材料具有较好的热稳定性。因此,该复合相变材料在建筑节能方面具有应用潜力。