(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。     

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.     

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。     

硬脂酸/活化凹凸棒石复合相变储热材料的制备与表征

以热活化的甘肃临泽凹凸棒石为基体,采用热熔法和浸渍法制备了硬脂酸/活化凹凸棒石复合相变储热材料。利用红外光谱仪(FTIR)、X射线衍射仪(XRD)和扫描电子显微镜(SEM)等方法表征了复合材料的结构,采用示差量热扫描仪(DSC)和储放热实验考察了复合材料的储/放性能和稳定性。结果表明采用热熔法和溶液浸渍法制备的材料具有相同的结构,硬脂酸按38.5%的负载率以物理作用吸附于活化凹凸棒石表面,其相应的相变焓分别为68.44 J/g和69.06 J/g。稳定性实验表明2种材料均具有良好的化学稳定性,但热稳定性存在差异,热熔法制备的复合材料的热稳定性优于浸渍法制备的复合材料。     

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.     

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。     

CaCl2·6H2O/多孔Al2O3复合相变材料的制备与热性能

将CaCl2·6H2O作为相变材料,3%的硼砂作为成核剂,以多孔Al2O3作为基体,通过真空浸渍法和多孔Al2O3的毛细吸附作用,制得不同比例的CaCl2·6H2O/多孔Al2O3复合相变材料,并进一步对其微观结构和热性能进行了分析。N2吸附脱附等温线分析证明,多孔Al2O3具有较大的比表面积。SEM照片和FTIR光谱说明CaCl2·6H2O被成功吸附入Al2O3的多孔结构中。DSC曲线显示,复合相变材料的熔融潜热可达99.81 J/g,说明其具有良好的相变储热性能。     

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     

组合相变材料强化固液相变传热可视化实验

采用高清相机和红外热像技术，对组合相变材料融化-凝固循环过程与传热特性开展了可视化实验研究。以填充三种石蜡的相变蓄热腔体为研究对象，追踪了腔体内固液相界面的动态演化过程和温度分布的变化规律。在此基础上，考察了相变材料布置顺序对蓄热腔体热性能的影响，分析了组合相变材料蓄热腔体的相变行为及强化传热特性。结果表明，相变温度较高的相变材料应靠近加热壁面布置；组合相变材料蓄热腔体存在多个固液相界面现象，不同相变材料可同时融化/凝固；与单一相变材料相比，组合相变材料的应用改善了蓄热腔体各单元相变速率的均匀性，提高了平均相变速率；组合相变材料虽然降低了蓄热腔体的显热蓄热量，但减小了温度变化速率，增强了系统的稳定性，并显著增加了潜热蓄热量，有效提高了相变蓄热腔体的总蓄热量。     

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。     

电驱动PEG/EG复合相变材料的制备与性能

以聚乙二醇（PEG）为相变组分，膨胀石墨（EG）为支撑材料，采用真空浸渍的方法制备了PEG/EG电热转换相变储能材料。改变复合相变材料中EG的质量分数，探究其在电热转换与热能存储效率、定形效果、相变焓值、储放热速率等方面的作用。结果表明，EG不仅能够提高复合相变材料的导热性能，还赋予其导电性能。当EG质量分数为5%时，PEG/EG复合相变材料具有良好的电热转换性能，在外加电压为7 V时，其电热转换与热能存储效率达到80.6%。同时，复合相变材料表现出良好的定形效果、较高的相变焓值（152.2 J/g）和优异的导热性能，与纯PEG相比，其储热所用时间减少了73%，储放热速率大幅提高。因此，PEG/EG复合相变材料在电驱动热能存储系统和能量转换与存储等领域具有广阔的应用前景。     

硬脂醇/膨胀石墨复合相变材料的制备及储热性能

相变储热技术是解决热量在时空上分配不平衡问题的有效手段之一,研制高性能的复合相变材料（phase change material, PCM）成为当前研究者关注的重点。硬脂醇（stearyl alcohol, SAL）等有机PCM目前主要存在热导率偏低以及循环稳定性较差等问题而限制了实际应用。以SAL作为PCM,膨胀石墨（expanded graphite, EG）为高导热多孔基质,采用吸附定形工艺制备了16种SAL/EG复合PCMs[EG含量为7%、14%、21%、28%（质量）;样品密度为700kg/m³、800kg/m³、900kg/m³、1000kg/m³]。对复合PCMs样品的微观结构、储热能力、导热性能、循环稳定性及充放热性能进行研究与分析。结果表明：SAL完全填充于EG的多孔网络。当样品密度为900kg/m³,EG质量分数为28%的水平热导率最高,其值为28.58W/(m ? K),相比于纯SAL[0.38W/(m ? K)]提高了74倍,该值大约是相对应垂直热导率[5.99W/(m ? K)]的4.8倍。另外在构建的充放热性能试验台上研究了样品中心位置的储/放热性能,结果显示样品密度为900kg/m³,EG质量分数为28%的样品充放热速率最大,固-液潜热吸热和放热阶段所经历的时间分别为53min和20min。与此同时验证了样品的导热性能和熔化-凝固特性,说明SAL/EG复合PCMs具有稳定可靠的储/放热性能。     

Feasibility study for thermal protection by microencapsulated phase change micro/nanoparticles during cryosurgery

Although considerable progresses have been made in cryosurgery to treat tumor, thermal injury to collateral structures is still a known complication of cryosurgery. In this study, a new method was proposed to prevent the healthy tissue around the cancerous tissue from thermal injury by microencapsulated phase change micro/nanoparticles, in which the phase change materials (PCMs) with large latent heat and low thermal conductivity are microencapsulated by liposome and delivered to the healthy tissue by mainline, arterial injection, hypodermic injection or direct injection. The three-dimensional transient temperature field in human body containing one tumor and embedded PCMs in the surrounding healthy tissue was numerically studied. The effects of the PCMs concentration, the phase change temperature, the temperature range near the phase change point, the latent heat and the PCMs distribution (especially the number of sides that PCMs cover, and the distance between the PCMs domain and the cancerous domain) were further discussed. The computational analysis showed that embedding PCMs in the healthy tissue around the cancerous tissue can significantly reduce the cryoinjury to the surrounding healthy tissue. The result also suggested that not embedding the PCMs directly adjacent to the cancerous tissue will help to improve the protection efficacy.     

无机芯微胶囊相变材料的研究进展

综合了近几年对无机芯相变微胶囊的报道,针对微胶囊相变材料（MCPCM）做了总结与概括,从其制备方法和应用领域进行了系统研究,并探讨了现存的问题以及需改进的方面。得到以下结论：微胶囊相变材料（MCPCM）是采用微胶囊封装技术对固-液型相变材料包覆封装的具有核壳结构的复合材料,可广泛地应用在太阳能光热储存、工业余热回收和传热流体领域。无机相变材料具有高储热密度、相变温度恒定、低成本等优点,因此无机芯微胶囊相变材料具有更好的应用空间。但目前采用的微胶囊相变材料也有其自身的缺点,如聚合物导热系数低,相变温度范围小等,有待于进一步研究。     

改善石蜡相变材料导热性能的研究进展

近年来石蜡作为一种相变储能材料受到越来越多的关注,由于石蜡PCM本身的导热系数偏低,导致储能系统在吸热或放热过程中的有效热率极低,热量无法快速有效地进行存储和释放。因此,提高石蜡PCM的导热系数成为了近年来的研究重点。主要从翅片结构、组合相变材料、复合相变材料、相变材料微胶囊化这几个方面总结了在改善石蜡PCM导热性能方面的国内外研究状况。     

Preparation and characterization of paraffin microcapsules for energy-saving applications

A series of microencapsulated phase-change materials (PCMs) with styrene–divinyl benzene shells composed of an n-octadecane (OD or C₁₈)–n-hexadecane (HD or C₁₆) mixture as the core were synthesized by an emulsion polymerization method. The effects of the core/shell ratio (C/S) and surfactant concentration (C_surf) on the thermal properties and encapsulation ratios of the PCMs were investigated. The chemical structures and morphological properties of the microcapsules were characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy analysis, respectively. The characteristic peaks of the paraffin mixtures and shell material located in the FTIR spectrum of the microencapsulated PCMs proved that the encapsulation of the PCM mixture was performed successfully. The thermal properties of the paraffin microcapsules were determined by differential scanning calorimetry (DSC) and thermogravimetric analysis. DSC analysis demonstrated that the microcapsules containing the maximum amount of paraffin mixture (C/S = 2:1) and the minimum C_surf (45 mmol/L) had the highest latent heat value of 88 kJ/kg and a latent heat of temperature of 21.06°C. Moreover, the maximum encapsulation ratio of the paraffin mixture was found to be 56.77%. With respect to the analysis results, the encapsulated binary mixture, which consisted of OD–HD with a poly(styrene-co-divinyl benzene) shell, is a promising material for thermal energy storage applications operating at low temperatures, such as in the thermal control of indoor temperatures and air-conditioning applications in buildings for desirable thermal comfort and energy conservation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47874.     

Experimental Investigation of Performances of Microcapsule Phase Change Material for Thermal Energy Storage

Performances of microcapsule phase change material (MPCM) for thermal energy storage are investigated. The MPCM for thermal energy storage is prepared by a complex coacervation method with gelatin and acacia as wall materials and paraffin as core material in an emulsion system. A scanning electron microscope (SEM) was used to study the microstructure of the MPCM. In thermal analysis, a differential scanning calorimeter (DSC) was employed to determine the melting temperature, melting latent heat, solidification temperature, and solidification latent heat of the MPCM for thermal energy storage. The SEM micrograph indicates that the MPCM has been successfully synthesized and that the particle size of the MPCM is about 81 μm. The DSC output results show that the melting temperature of the MPCM is 52.05 °C, the melting latent heat is 141.03 kJ/kg, the solidification temperature is 59.68 °C, and the solidification latent heat is 121.59 kJ/kg. The results prove that the MPCM for thermal energy storage has a larger phase change latent heat and suitable phase change temperature, so it can be considered as an efficient thermal energy storage material for heat utilizing systems.     

石蜡的聚烯烃定形包覆研究

低熔点石蜡为芯材,聚苯乙烯、聚丙烯和聚乙烯3种高分子材料作支撑材料,以加热熔融的方法制备了3种定形复合相变材料,确定了3种高分子材料对潜热为222.01 kJ/kg的17℃石蜡的最大包裹量分别为w(石蜡)=46%、51%、73%。用差示扫描量热仪对3种定形复合相变材料进行了测定,分析了所制备的定形复合相变材料的相变温度、相变潜热、热稳定性等性能。结果表明,石蜡经过高分子材料包覆之后,其相变温度有所降低,相变焓值有所提高,而且该定形相变材料可以加工成粉体材料,进一步拓展了产品的应用领域。     

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。     

碳酸盐复合蓄热材料的制备及热物性研究

以二元碳酸盐（Li₂CO₃-K₂CO₃,BC,62：38,摩尔比）和三元碳酸盐（K₂CO₃-Li₂CO₃-Na₂CO₃,TC,1：2：1,摩尔比）为相变材料,以氧化镁为基体材料,通过混合烧结法制备陶瓷基复合蓄热材料。二元碳酸盐复合材料（BCC）和三元碳酸盐复合材料（TCC）的熔点与相应混合碳酸盐的熔点相近,分别为465.1℃和386.4℃,并在其最高使用温度（800℃）范围内维持较高的比热容;且复合材料的潜热值均大于150.0 J/g。基于XRD和SEM的表征分析,两种复合蓄热材料具有较好的化学稳定性,且基体材料能很好地混合支撑相变材料。两种复合材料分别进行50次热循环,其热物性参数没有发生明显变化,具有较好的热循环稳定性。