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.     

聚乙二醇相变储能材料研究进展

聚乙二醇相变材料是一类相变焓较高、热滞后效应低的储能材料。本文综述了聚乙二醇相变储能材料的研究进展,重点论述了其制备方法、应用及展望。     

PEG/APS-SiO2/O-CNTs导热增强相变材料的制备及性能

以聚乙二醇(PEG)为相变材料,以3-氨丙基三乙氧基硅烷（APS）改性的二氧化硅(SiO2)为支撑材料,以氧化壁碳纳米管(O-CNTs)为导热增强材料,采用溶胶-凝胶法成功制备了PEG/APS-SiO2/O-CNTs导热增强型复合相变材料。通过FTIR、XRD、SEM、DSC等对材料的结构和热性能进行了表征。当PEG含量为82.0%时,复合相变材料仍然具有良好定型效果,熔化焓和结晶焓达到134.2 J/g、126.6 J/g,而且材料具有很好的储热稳定性,300次热循环后,其储热焓值仅下降3.3%。相比于纯PEG,添加了0.6%的O-CNTs的复合相变材料的导热增强率为28.1%, 达到0.41W/(m?K)。红外热成像结果表明,复合相变材料的储能效率明显提高。     

聚双甲基丙烯酸聚乙二醇酯固-固相变储能材料的制备

制备了以聚甲基丙烯酸为骨架、聚乙二醇(PEG)为工作物质的新型高分子固-固相变储能材料。对PEG和几种不同的相变材料分别进行DSC测试,对PEG分子量为4000的相变材料进行非等温DSC测试。结果表明,与纯PEG相比,相变材料的相转变温度降低12.3℃,相变焓降低45 J/g。随着聚乙二醇分子量由2000依次增加为4000,6000,10000,相变材料的相转变温度分别为44.8,52.9,63.8和74.3℃,相变焓分别为142.9,203.2,190.1,231.4 J/g,均有增加的趋势。随着升温速率增加,PEG分子量为4000的PCM的相变温度依次升高,分别为47.4,50.0和53.1℃。     

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。     

新型相变蓄热材料的热物性测试

为了寻找新型相变蓄热材料,对不同配比下NaCl/KCl/MgCl2三元体系的熔点进行了测量,提出了一种新型三元相变蓄热材料质量分数之比为20%NaCl/20%KCl/60%MgCl2;搭建了准稳态法测试试验台,并利用试验台对新型三元相变蓄热材料的主要热物性参数,包括比热、导热系数和熔解热进行了测试。测定温度范围61.21—573.65℃;利用多项式函数对导热系数和比热试验数据进行了拟合,拟合平均相对偏差小于1.5%。试验结果表明,新型相变蓄热材料潜热大、蓄热密度高、且具有较高的导热系数,具有广阔的工程应用前景。     

膨胀石墨基相变储能材料的研究

利用膨胀石墨孔隙结构的吸附性能,制备了石蜡/膨胀石墨、聚乙二醇/膨胀石墨、十四醇/膨胀石墨相变储能复合材料,用差示扫描热量法研究了材料的热性能.结果表明,复合材料的相变潜热随着石蜡、聚乙二醇、十四醇含量的增加而增加.复合材料的导热性能随着石蜡、聚乙二醇、十四醇含量的增加而小.膨胀石墨的多孔结构对石蜡、聚乙二醇、十四醇有很好的吸附性能,石蜡、聚乙二醇、十四醇在固一液相变时,未见有液态石蜡、聚乙二醇、十四醇的渗出.     

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.     

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。     

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。     

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。     

复合纺丝法制备PEG/PVA相变储能初生纤维

采用不同相对分子质量的聚乙二醇(PEG)与聚乙烯醇(PVA)进行湿法复合纺丝制备PEG/PVA相变储能初生纤维,对PEG与PVA溶液的相容性、PEG的凝固性能、PEG/PVA纤维的相变潜热及纤维形貌进行了研究。结果表明:PEG 2000与PVA复合纺丝得到的相变储能初生纤维具有较高的相变潜热,PEG 2000与PVA的质量比小于3:10时,PEG 2000在纺丝过程中流失量较小,纤维截面随着PEG 2000含量的增加而由肾形向圆形变化。     

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。     

Properties of crosslinked blends of pellethene and multiblock polyurethane containing poly(ethylene oxide) for biomaterials

A series of multiblock polyurethanes, containing various poly(ethylene oxide) (PEO; number‐average molecular weight = 400–3400) contents (0–80 wt %) and prepared from hexamethylene diisocyanate/PEO/poly(dimethylsiloxane) diol/polybutadiene diol/1,4‐butanediol, were used as modifying additives (30 wt %) to improve the properties of biomedical‐grade Pellethene. Different molecular weights of PEO were used to keep poly(ethylene glycol) at a fixed molar content, if possible, although the PEO content, related to the PEO block length in the multiblock polyurethanes, was varied from 0 to 80 wt %. The hydrophilic PEO component was introduced through the addition of PEO‐containing polyurethanes and dicumyl peroxide as a crosslinking agent in a Pellethene matrix. As the PEO content (PEO block length) increased, the hydrogen‐bonding fraction of the crosslinked Pellethene/multiblock polyurethane blends increased, and this indicated an increase in the phase separation with an increase in the PEO content in the crosslinked Pellethene/multiblock polyurethane blends. According to electron spectroscopy for chemical analysis, the ratio of ether carbon to alkyl carbon in the crosslinked Pellethene/multiblock polyurethane blends increased remarkably with increasing PEO content. The water contact angle of the crosslinked Pellethene/multiblock polyurethane blend film surfaces decreased with increasing PEO content. The water absorption and mechanical properties (tensile modulus, strength, and elongation at break) of the crosslinked Pellethene/multiblock polyurethane blend films increased with increasing PEO content. The platelet adhesion on the crosslinked Pellethene/multiblock polyurethane blend film surfaces decreased significantly with increasing PEO content. These results suggest that crosslinked Pellethene/multiblock polyurethane blends containing the hydrophilic component PEO may have potential for biomaterials that come into direct contact with blood. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2348–2357, 2004     

聚乙二醇/SiO2定形相变材料在沥青中的相变储热性能

利用多孔二氧化硅的良好吸附性,将不同计量的聚乙二醇在硅溶胶胶凝过程中吸附于硅凝胶的孔隙结构中制备聚乙二醇/二氧化硅定形相变材料（PEG/SiO₂ SSPCM）;并将其与熔融沥青共混获得不同聚乙二醇含量的沥青-定形相变材料（Asphalt-SSPCM）。借助孔径分析仪和扫描电镜（SEM）表征了载体二氧化硅孔结构和PEG/SiO₂ SSPCM的表观形貌;通过X射线衍射仪（XRD）、综合热分析仪（DSC/TG）和傅里叶红外光谱仪（FTIR）考察了沥青中PEG/SiO₂ SSPCM的晶体结构、储热性能、热稳定性及化学兼容性;通过本文作者课题组研发的温度模拟试验箱测试了Asphalt-SSPCM的降温效果。结果表明,二氧化硅凝胶具有丰富的孔结构并能将聚乙二醇吸附于其介孔结构中;沥青中PEG/SiO₂ SSPCM仍含有聚乙二醇晶体,其储热能力随聚乙二醇含量的增加而增大,当聚乙二醇含量为76.1%时,相变焓高达117.5J/g,且不同聚乙二醇含量的沥青-定形相变材料均表现出良好的热稳定性;PEG/SiO₂ SSPCM与沥青的化学兼容性良好,二者之间仅是物理作用;Asphalt-SSPCM的降温效果显著,可有效改善沥青路面的高温性能;并基于相变理论,分析了沥青-定形相变材料的相变储热原理。     

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。     

壳管式潜热蓄能系统换热特性

针对目前石蜡潜热蓄能系统效率低下的特点,构建了石蜡/膨胀石墨混合相变材料的潜热蓄能系统,研究了其蓄/放热特性,并与纯石蜡相变材料系统进行了对比分析,讨论了不同换热流体流量下的蓄/放热过程的时间周期。用焓法处理相变区域,对该潜热蓄能系统的整体蓄热过程进行数值模拟。研究结果表明,对于石蜡／膨胀石墨复合相变材料,其导热性能较纯石蜡有很大提高,但由于添加了膨胀石墨而减弱了蓄热中石蜡的对流换热。流量提高对蓄/放热速率有明显的改善。焓法模型能全面反映蓄能系统的换热与流动特性,数值计算的结果与实验数据吻合较好。     

Discontinuous carbon fiber/polyamide composites with microencapsulated paraffin for thermal energy storage

This work focuses on the development of multifunctional thermoplastic composites with thermal energy storage capability. A polyamide 12 (PA12) matrix was filled with a phase change material (PCM), constituted by paraffin microcapsules (T_melt = 43 °C), and reinforced with carbon fibers (CFs) of two different lengths (chopped/CF “long”[CFL] and milled/CF “short” [CFS]). DSC tests showed that the melting/crystallization enthalpy values increase with the PCM weight fraction up to 60 J/g. The enthalpy was 41–94% of the expected value and decreased with an increase in the fiber content, because the capsules were damaged by the increasing viscosity and shear stresses during compounding. Long CFs increased the elastic modulus (+316%), tensile strength (+26%), and thermal conductivity (+54%) with respect to neat PA12. Thermal imaging tests evidenced a slower cooling for the samples containing PCM, and once again the CFS-containing samples outperformed those with CFL, due to the higher effective PCM content. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47408.     

用于储存自然冷能的相变材料制备及蓄冷特性

自然冷能作为新能源中的一种,清洁无污染且资源丰富,其开发利用的前景广阔。然而自然冷能的温差较小且很难直接利用,需要通过一个特殊的系统装置储存,而其核心部分是相变储能材料的制备。文中选取CaCl2.6H2O为主料,通过实验的方法研制了一种相变温度为29℃左右适合储存自然冷能的相变材料,得到20 g CaCl2.6H2O+质量分数2%SrCl2.6H2O+1 g羧甲基纤维素钠的蓄热体系比较稳定,其过冷度为1.8℃且无明显相分离现象。同时还采用了参比温度曲线法对该材料的相变潜热进行了测算,其相变潜热为144 kJ/kg。     

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。