固-固相变储热材料的研究进展

与固-液相变材料相比,固-固相变材料（SS-PCMs）受到的关注较少;鉴于SS-PCMs具有储能密度高、无毒且腐蚀性小、相变时无液体产生且体积变化较小、不易发生相分离以及过冷度小等优点,因而是一类具有发展潜力的相变材料。本文基于SS-PCMs的研究现状,对近年来几类重要SS-PCMs如多元醇SS-PCMs、高分子类SS-PCMs及无机盐类SS-PCMs的研究进展进行了综述。简要阐述了SS-PCMs的分类以及各类SS-PCMs的性能、相变储热机制和优缺点。同时介绍了选择固-固相变材料应用时的基本原则,并针对相变材料热导率低,过冷度大、稳定性差等问题的改性研究进行了综述,还简要综述了SS-PCMs的应用研究。最后指出,未来的研究应着眼于解决已合成SS-PCMs的缺陷,开发多功能的SS-PCMs,并在SS-PCMs的实际应用方面实现突破。     

中温相变蓄热材料研究进展

对中温相变蓄热材料(PCM)的定义范畴、应用领域、国内外发展现状进行了评述。中温PCM主要针对90~550℃的热动力环境,在太阳能热发电、有机朗肯循环、移动蓄热技术、分布式能源系统等方面有广阔的应用前景。指出进一步的研究方向是拓展中温PCM的应用场合,规范长期稳定性的表征与测试手段,重视与换热器开发以及应用领域的整合,并提出硝酸盐熔融盐混和物将是今后一段时期内中温PCM研发和培育的重点产品对象。     

Graphite foams infiltrated with phase change materials as alternative materials for space and terrestrial thermal energy storage applications

In this work, a numerical study is proposed to investigate and predict the thermal performance of graphite foams infiltrated with phase change materials, PCMs, for space and terrestrial energy storage systems. The numerical model is based on a volume averaging technique while a finite volume method has been used to discretize the heat diffusion equation. A line-by-line solver based on tri-diagonal matrix algorithm has been used to iteratively solve the algebraic discretization equations. Because of the high thermal conductivity of graphite foams, the PCM-foam system thermal performance has been improved significantly. For space applications, the average value of the output power of the new energy storage system has been increased by more than eight times. While for terrestrial applications, the average output power using carbon foam of porosity 97% is about five times greater than that for using pure PCM.     

Polyethylene glycol‐sugar composites as shape stabilized phase change materials for thermal energy storage

Polyethylene glycol (PEG)‐sugar composites have been investigated as cost effective shape‐stabilized phase change materials for thermal energy storage. PEGs form internal hydrogen bonds stabilizing their chains at solid state. However low molecular weight PEGs are liquid due to short chains as high molecular weight PEGs have too little concentration of hydroxyl groups. Therefore, glucose, fructose, and lactose are used as hydrogen bond source in this study. Consequently it is found that sugars stabilized PEGs up to 90% PEG constitution in solid state except for 90%PEG10,000/10% fructose blend. Fourier transform‐infrared (FT‐IR) analysis revealed considerable interactions between PEGs. The maximum changes in the spectra were observed in the OH stretching region as band broadening due to increasing hydrogen bonding interactions. Differential scanning calorimetry (DSC) analysis are used to determine phase change temperatures and enthalpy of the shape‐stabilized composites that are slightly lower than those of PEG precursors due to the interference effect of sugar in crystallization process. The enthalpies of the blends are 89%, 95%, and 94% of expected from 90%PEG/10% glucose blends, 93%, 94%, and 93% of expected from 90% PEG/10% fructose blends, and 99%, 96%, and 96% of expected from 90% PEG/10% lactose blends respectively when PEGs with 1,000; 6,000; and 10,000 g/mol average molecular weights are used respectively. The diameter of the spherulitic crystals of PEGs decreases with the addition of any of sugar derivatives and spherulites of the composites turns to semi‐amorphous solid structures at temperatures above melting point of PEG precursor. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

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     

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。     

Photocrosslinked biobased phase change material for thermal energy storage

A series of novel photocrosslinked biobased shape‐stabilized phase change materials (PCMs) based on octadecanol, eicosanol and docosanol have been prepared by UV technique for the purpose of thermal energy storage applications. Epoxidized soybean oil was reacted with acrylic acid to form acrylated soybean oil (ASO). The structure and composition, cross‐section morphology, thermal stability performances and phase change behaviors of ASO and UV‐cured PCMs were examined by using Attenuated total reflection fourier transform infrared spectroscopy, thermogravimetric analysis system (TGA), scanning electron microscopy, and differential scanning calorimetry. The results indicate that the UV‐cured biobased PCMs possess perfect phase change properties and a suitable working temperature range. The heating process phase change enthalpy is measured between 30 and 68 J/g, and the freezing process phase change enthalpy is found between 18 and 70 J/g. The decomposition of UV‐cured PCMs started at 260 °C and reached a maximum of 430 °C. All the biobased UV‐cured PCMs improved latent heat storage capacity in comparison with the pristine ASO sample. With the obtained results we conclude that, these materials promise a great potential in thermal energy storage applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43757.     

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。     

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。     

用于储能的复合定形相变材料的制备与性能研究

以泡沫聚合法制得的超多孔水凝胶(SPH)为基材,季铵盐类离子液体(ILPCM)为相变材料,氧化石墨烯(GO)为添加剂,制备了一种新型的复合定形相变材料(GO-ILPCM/SPH),且对其性能进行了表征。研究结果表明:SPH是一种潜在的复合定形相变材料的基材,可负载较多的ILPCM,质量分数最高可达约85%。GO-ILPCM/SPH是一种优良的储能相变材料,具有适合冷藏产品的相变温度4℃及较高的相变潜热(约150J/g)。制备的复合定形相变材料具有较快的储热和放热速率,适当地添加GO一类导热性高的物质,可提高其相变储热和放热速率,进而在应用中提高热能利用效率。     

The overall crystallization behavior of polyethylene/wax blends as phase change materials for thermal energy storage: A mini review

This review paper deals with the overall crystallization behavior of polyethylene/wax blends as phase change materials (PCMs) for thermal energy storage with the determination of their thermal properties. The addition of molten wax to the polyethylenes decreases the crystallization and melting temperatures of the blends. However, incorporating fillers to the polyethylene/wax blends can either decrease or increase the crystallization and melting temperatures of the composites depending on the filler type. The normalized enthalpy values of linear low-density polyethylene showed no significant change when increasing the wax content. On the contrary, the normalized enthalpy values of the wax in the blends were lesser than that of pure wax and increased with increasing wax content. Since the wax in the blend had a lower crystallinity compared to pure wax, this influences its effectiveness as a PCM for thermal energy storage. The effect of different polyethylenes on the wax morphology gave rise to enhance phase separation when wax was blended to high-density polyethylene as compared to the other polyethylenes. On the contrary, the effect of various waxes on the morphology of polyethylene resulted in different morphologies due to the molecular weight of the wax used and the structure of the polyethylene chain. The addition of fillers to the polyethylene (PE)/wax samples resulted in enhanced phase separation. The overall isothermal crystallization rate and the equilibrium melting temperature of PEs in the PEs/wax blends were depressed by wax addition due to the wax dilution effect.     

纳米材料/十四酸混合相变蓄热材料的制备与特性

选用纳米金属Cu和碳素材料石墨烯纳米片（GnPs）为改性剂分别添加至十四酸（MA）中,制备出Cu质量分数为1%、2%、3%和4%的Cu/MA混合相变蓄热材料及GnPs质量分数为1%、2%和3%的GnPs/MA混合相变蓄热材料,并对混合相变材料性能进行表征。结果表明：Cu/MA固态和液态热导率随Cu质量分数增加呈线性提高,1%（质量）GnPs/MA固态热导率较纯MA显著提高101.51%,随GnPs质量分数增加,热导率增幅减缓;FT-IR谱图表明Cu与MA及GnPs与MA间的混合均为物理作用;DSC结果显示添加Cu或GnPs可降低MA的过冷度和相变潜热,且随质量分数增加,相变潜热逐渐降低;4%（质量）Cu/MA和3%（质量）GnPs/MA放热时间相比于纯MA分别减少了23.4%和38.7%;4%（质量）Cu/MA和3%（质量）GnPs/MA在经历300次快速热循环试验后,晶体结构和相变温度基本保持不变,相变潜热分别降至168 J·g^-1和181 J·g^-1左右,仍满足蓄放热要求,两种材料均具有良好的热循环稳定性。     

Study on the influence of thermal characteristics of hyperbranched polyurethane phase change materials for energy storage

A series of hyperbranched polyurethane (HB‐PU) phase change induced energy storage materials were prepared by polyethylene glycol (PEG), methylene diphenyl 4,4′‐diisocyanate (MDI), and hyperbranched polyester polyalcohol via a two‐step process. The influence of thermal characteristics of HB‐PU was investigated using differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD). It has been found that the thermal characteristics of HB‐PU are affected by some factors. Such as the molecular weight and content of soft segment, once the M_n of PEG soft segments is larger than the critical M_n (2000 g/mol), both the phase change enthalpy and temperature increase as M_n of PEG soft segment and soft segment content (SSC) increase. The influence of the microstructure of hard segment originates from diisocyanate and hyperbranched polyester polyalcohol, HB‐PUs with regular microstructure and lower generation of hyperbranched polyester polyalcohol have high energy storage capability. Furthermore, the conditions of measurement affect the thermal characteristics of materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polyester-based phase change materials with flexible poly(ethylene glycol) chains for thermal energy storage

Phase change materials are capable of storing renewable energy in an economical, feasible, and green way. Here, novel polyester-based solid–solid phase change materials (PPCMs) are synthesized through solvent-free crosslinking polymerization. Poly(ethylene glycol) (PEG) is used as the phase change ingredient, while crosslinked polyester acts as the supporting material. One chain end of PEG reliably bonds with the rigid skeleton, while another chain end is movable. The combination of reliable crosslinked structures with flexible PEG chains endows the PPCMs with good thermal storage capacity and outstanding thermal reliability simultaneously. Fourier transform infrared spectroscopy is adopted to confirm the chemical structures of PPCMs. Their excellent crystalline properties are confirmed by wide-angle X-ray diffraction and polarizing optical microscopy (POM). Phase change properties are investigated using differential scanning calorimetry (DSC) and POM images. It is obvious in the DSC results that PPCMs have good thermal storage capacity in the range 18–63 °C with phase change enthalpy reaching 139.0 J/g. POM images vividly reveal the crystallization process of PPCMs. Additionally, thermal stability is studied using thermogravimetric analysis, and the results show that PPCMs are thermally stable up to 300 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47108.     

空气能蓄冷用相变材料研制及热物性表征

针对自然冷源在建筑空气调节中的应用,以癸酸-月桂酸（CA-LA）低共熔混酸为相变材料,纳米Fe₂O₃为添加剂,膨胀石墨（EG）为基质材料,采用化学分散、超声振荡和物理吸附的方法制备CA-LAFe₂O₃/EG复合相变材料,并对材料进行性能表征。结果表明纳米Fe₂O₃质量分数为0.8%时与CA-LA混合均匀性较好,具有成核作用,消除了CA-LA的过冷度;EG质量分数为5.88%时,对CA-LAFe₂O₃（质量分数0.8%）具有较好的包覆效果,傅里叶变换红外光谱（FTIR）显示复合材料内部未发生化学反应,各物质之间属于物理吸附;纳米Fe₂O₃粒子和EG可加快材料相变过程,较CA-LA、CA-LA Fe₂O₃（质量分数0.8%）的冷却与结晶过程总时间缩短了39.4%,CA-LA Fe₂O₃（质量分数0.8%）/EG（质量分数5.88%）对应时间缩短78.2%,有利于空气能蓄冷过程的顺利进行;CA-LA Fe₂O₃（质量分数0.8%）/EG（质量分数5.88%）的相变焓为124.70kJ/kg,融化初始温度为18.66℃,结晶起始温度为19.87℃,较CA-LA的焓降低3.4%,融化与结晶过程温度区间均增大,材料的导热性能增强。定型复合相变材料热响应与受压方向有关,受压面切向方向温度响应速度远大于受压面法向方向,相变储能换热器设计时应考虑材料导热的各向异性特点。     

聚乙二醇/涤纶接枝共聚固-固相转变贮热材料

为了制备热稳定性好、蓄热性能优异的固-固相转变材料(PCM),研究采用化学法合成了聚乙二醇(PEG)/涤纶(PET)PCM。实验结果表明,PEG/PET PCM的热力学性能与PEG的分子量、PEG/PET质量配比以及不同交联体系有关。化学接枝法合成的PEG/PET PCM,最大相变焓可达112.02 J/g,热稳定性提高,热滞后性减小,PEG/PET PCM在众多领域具有广泛应用。     

添加碳素复(混)合相变储热材料的研究及应用进展

相变储热材料因具有储热密度大、相变温度变化小且过程易控制等优点而在许多领域具有重要应用。但传统的相变储热材料存在导热系数低及固-液相变过程中液态泄漏问题,阻碍了其实际应用。碳材料如石墨、碳纤维、碳泡沫和膨胀石墨,他们都具有高导热系数、低密度和良好的化学稳定性。将碳材料添加到相变储热材料中或与相变储热材料进行复合,从而构成碳素复(混)合相变储热材料,储热材料的导热系数及其性能可明显提高。本文综述了碳素复(混)合相变储热材料的研究进展。利用膨胀石墨的多孔特性吸附有机物制备膨胀石墨基复合相变储热材料,其储热密度大、导热系数高、性能稳定、成本低且在固-液相变过程中没有液态的流动性问题,是未来研究和应用最重要的碳素复合相变储热材料。     

Novel phase change materials based on fatty acid eutectics and triallyl isocyanurate composites for thermal energy storage

In this study, a series of dimension‐stabilized fatty acid eutectics and triallyl isocyanurate (TAIC) composite phase change materials were prepared via in situ reaction by blending the fatty acids and TAIC, in which the fatty acids were introduced as a phase change material (PCM), and TAIC performed as a supporting material by self‐crosslinking. Fourier transform infrared spectroscopy, X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy (SEM), and thermogravimetric analysis were applied to investigate the chemical structure, crystalline properties, phase transition behavior, microstructure, and thermal stability of the composites. The results indicated that the composite possessed excellent thermal reliability and heat storage durability even after 300 heating–cooling cycles. Moreover, the composites had applicable phase transition temperatures in the range of 26–40 °C and satisfying latent heat storage capacities of higher than 110 J/g. The SEM images showed that the particle size of the nanoparticles of the composites was about 200 nm after treatment. The dimensional measurement of the composites proved a high service temperature of 100 °C, indicating that the composites were promising for thermal energy storage materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44866.     

相变储能致密微胶囊的制备

分别采用界面聚合法、自由基聚合法首次制备了以聚脲为第一层壁材,以苯乙烯-二乙烯苯共聚物为第二层壁材,相变点16℃的石蜡为芯材的相变储热致密微胶囊.采用激光粒度分布仪、红外光谱分析仪.差示扫描量热分析仪、热重分析仪分析了制备的致密微胶囊的粒径分布、结构组成以及热性能.结果表明,相变储热致密微胶囊是复合相变材料,微胶囊的粒径均匀,热稳定性好,致密性优良不渗漏,其蓄热能力较好、可广泛应用于节能储能的目的.     

石膏基复合相变储能材料的研究进展

建筑能耗、工业能耗和交通能耗是能源消耗的主要方式。其中,建筑能耗约占能源消耗的40%左右,建筑能耗的持续上升会增加碳排放和加速化石能源的消耗,因此提升建筑材料的保温节能性能逐渐成为建筑材料领域的研究热点。储热技术不仅可以降低建筑能耗,还可以减少环境污染。相变储能材料具有优异的储放热能力,是实现热能储存以及温度控制的重要技术手段,在建筑节能领域有广阔的应用前景。该文主要综述了石膏基复合相变储能材料的研究进展,根据石膏基相变材料的不同,分析归纳了石膏基有机相变材料和石膏基复合相变材料,介绍了浸渍法、多孔材料吸附法、微胶囊法等制备石膏基复合相变储能材料的方法和机理,以及影响石膏基相变储能材料的因素。最后,展望了石膏基相变储能材料的研究方向。