Preparation and thermal stability of ternary sulfate molten salt

以硫酸钠、硫酸钾和硫酸镁为原料,采用在硫酸钠-硫酸钾二元共晶盐中加入硫酸镁的方法制备三元硫酸熔盐。应用TG-DSC联用分析仪、热常数分析仪、X射线衍射仪以及热循环法对复合熔盐的熔点、相变潜热、热导率、比热容、分解点以及热稳定性进行表征。结果表明：所制备的三元硫酸熔盐熔点分布在667.5～669.7 ℃之间,较二元熔盐熔点降低了160 ℃左右,硫酸镁含量为30%（质量分数）的三元硫酸熔盐相变潜热值最大为94.3 J/g,比热容最大为1.13 J/(g·K)（720℃≤T≤800℃）,导热系数为0.41 W/(m·K),分解温度为1070 ℃,经50次热循环后,相变潜热值降低约4.34%,熔点和物相保持基本恒定,具有良好的热稳定性。该研究为硫酸盐作为高温传热蓄热介质提供了依据。     

Thermal properties of a low-melting-point nitrate molten salt system

利用硝酸盐熔盐熔点低、比热容高、热分解温度高的特性,制备一种新型硝酸盐熔盐[在Ca（NO₃）₂：KNO₃为0.47：0.53的熔盐体系中添加0.1%~15%的新型添加剂],并对该熔盐的热力学特性及使用成本进行了测试分析。结果表明,新型熔盐的熔点为120.1℃,熔化潜热为76.37 J/g,分解温度为588℃,平均比热容为1.598 J/（g·K）,相比较于传统的Solar salt和Hitec熔盐热力学性能具有较大提升。采用测量范围内比热容的积分平均值来代替整个温度范围内熔盐的比热容,通过计算得出该体系熔盐的显热蓄热成本为108元/（kW·h）。此外,对新型熔盐的热扩散系数以及导热系数进行的测试分析,进一步证明了该熔盐在太阳能光热发电中作为蓄热传热介质具有巨大的潜在应用价值。     

辛酸/月桂酸作为相变蓄冷材料的热性能研究

利用差示扫描量热法和低温显微技术研究辛酸、月桂酸及其二元系统的热性能,建立辛酸/月桂酸二元系统相图。实验结果表明:辛酸/月桂酸二元系统的相图较复杂,辛酸质量分数较低时发生转熔,转熔温度约为14℃,转熔点相应的辛酸质量分数为60%;辛酸质量分数较高时发生共晶,共晶熔融温度为7.44℃,相变潜热为136.43J/g,共晶点相应的辛酸质量分数为80%,该共晶熔融温度适合于空调蓄冷。辛酸/月桂酸共晶混合物经过60次、120次冻熔循环后,其共晶熔融温度、熔融热、比热未发生明显变化,具有较好的热稳定性,可用作相变蓄冷材料。     

石墨泡沫/共晶盐复合相变材料制备

选择KNO3/NaNO3二元体系按照质量比4∶6制备共晶盐,对共晶盐进行了熔点及熔化潜热的测量;将石墨泡沫这一新型材料作为强化基体,共晶盐作为相变材料（PCM）,采用熔融浸渗法制备了适用于太阳能热发电系统储能装置的石墨泡沫/共晶盐复合相变材料。采用扫描电镜对复合相变材料表面的微观结构进行了表征,并对其熔点、潜热、等效导热系数等热物性参数进行了测试。结果表明：共晶盐与石墨泡沫复合效果比较理想;复合前后共晶盐的熔点和潜热几乎没有发生变化;复合相变材料的等效导热系数得到了显著提升,石墨泡沫对相变材料起到了导热强化作用,满足高温蓄热的要求。     

纳米Fe2O3/硬脂酸/十八醇纳米复合相变蓄热材料的性能研究

针对有机相变材料热导率低的问题,将高热导率的纳米Fe₂O₃添加到硬脂酸/十八醇二元有机复合蓄热相变材料中,制备纳米复合蓄热相变材料。从分散剂的种类、分散剂与纳米材料的添加量以及超声时间4个方面研究其对纳米复合相变蓄热材料的稳定性及热物性的影响。结果表明,阴离子表面活性剂的分散效果优于阳离子和非离子表面活性剂。复合相变材料中添加质量分数为0.8%,十二烷基苯磺酸钠(SDBS)和质量分数为0.4%Fe₂O₃的体系,超声时间为80 min时,纳米Fe₂O₃在相变材料中的分散效果最好。添加纳米Fe₂O₃后复合蓄热相变材料的相变潜热及相变温度有所下降,热导率提高34.9%。300次热循环复合相变材料的相变温度波动区间不超过0.41℃,相变潜热波动区间不超过4.0%,热稳定性良好。     

Synthesis and lithium storage property of high-performance N-doped reduced graphene oxide

石墨烯是一种具有高比表面积、高导电性和良好化学稳定性的新型二维碳材料,在电化学储能领域具有广阔的应用前景。氮原子掺杂可以制造结构缺陷并改变电荷分布,有利于增强其电化学储能性能。本工作以尿素为氮源,与氧化石墨烯混合冻干,经过高温热还原制备出氮掺杂石墨烯材料,研究了热还原温度对其化学组成、形貌结构以及电化学储锂性能的影响。研究结果表明,随着热还原温度的升高,材料的氮含量下降,石墨化程度升高,电导率提高。将其作为负极材料组装成锂离子半电池进行测试,样品N-rGO-800在0.05 A/g的电流密度下表现出高达876 mA·h/g的稳定比容量,优于目前文献报道的比容量。在1 A/g的大电流密度下,其依然具有584 mA·h/g的比容量,经过850圈的长循环,容量保持稳定,显示出该材料优异的循环和倍率性能。     

癸酸-棕榈酸二元复合相变材料的相变特性研究

通过熔融共混法制备一系列二元脂肪酸复合相变材料,并利用步冷曲线法确定癸酸-棕榈酸(CA-PA)二元复合相变材料的最佳质量配比为86∶14,其共晶温度为22.1℃。采用傅里叶红外光谱仪(FT-IR)、冷热加速循环实验和瞬态平面热源法(TPS)等研究CA-PA复合相变材料的结构与性能,发现CA-PA的FT-IR曲线上同时存在CA和PA的特征吸收峰,表明CA与PA是通过分子力作用在一起的。然后对CA-PA进行400次5~80℃冷热加速循环后,发现其相变温度变化不大于0.5℃,可见CA-PA热稳定性良好,且导热系数为0.151 W/(m·K)。同时,根据差示扫描量热仪(DSC)分析得到CA-PA的相变温度和相变潜热分别为21.78℃和154.7 J/g,这与通过步冷曲线得到的共晶温度十分符合,因此该CA-PA复合相变材料适用于建筑节能和热回收领域。     

Phase change and heat transfer characteristics of a eutectic mixture of palmitic and stearic acids as PCM in a latent heat storage system

The phase change and heat transfer characteristics of a eutectic mixture of palmitic and stearic acids as phase change material (PCM) during the melting and solidification processes were determined experimentally in a vertical two concentric pipes energy storage system. This study deals with three important subjects. First is determination of the eutectic composition ratio of the palmitic acid (PA) and stearic acid (SA) binary system and measurement of its thermophysical properties by differential scanning calorimetry (DSC). Second is establishment of the phase transition characteristics of the mixture, such as the total melting and solidification temperatures and times, the heat transfer modes in the melted and solidified PCM and the effect of Reynolds and Stefan numbers as initial heat transfer fluid (HTF) conditions on the phase transition behaviors. Third is calculation of the heat transfer coefficients between the outside wall of the HTF pipe and the PCM, the heat recovery rates and heat fractions during the phase change processes of the mixture and also discussion of the effect of the inlet HTF parameters on these characteristics. The DSC results showed that the PA–SA binary system in the mixture ratio of 64.2:35.8 wt% forms a eutectic, which melts at 52.3 °C and has a latent heat of 181.7 J g⁻¹, and thus, these properties make it a suitable PCM for passive solar space heating and domestic water heating applications with respect to climate conditions. The experimental results also indicated that the eutectic mixture of PA–SA encapsulated in the annulus of concentric double pipes has good phase change and heat transfer characteristics during the melting and solidification processes, and it is an attractive candidate as a potential PCM for heat storage in latent heat thermal energy storage systems.     

Double metal MOF-based composite structure and performance as supercapacitor electrode

超级电容器作为一种新型储能原件,具有功率密度高和可快速充放电等优点。本文通过溶剂热法制备了铁锰双金属有机框架材料（FeMn-MOF）,并将其作为前驱体,经过高温热处理后,得到碳和金属氧化物的复合结构材料（C-MOF）。采用傅里叶变换红外光谱仪、X射线衍射仪和场发射扫描电子显微镜对制备得到的材料进行了结构表征,将高温处理后的材料作为电极材料应用于超级电容器,并对其进行了一系列的化学测试。当电流密度为0.5 A/g时,C-MOF基超级电容器的比容量最高可达388.9 F/g,C-MOF基超级电容器的比容量最高可达388.9 F/g。在2 A/g的电流密度下循环5000次后,比容量为初始值的201.5%,说明在循环的过程中C-MOF电极不仅具有良好的循环稳定性,还存在一个活化过程使其比容量增加。这将极大地提高MOF基复合结构材料作为超级电容器电极材料的应用价值,同时也为双金属MOF材料的研究与应用提供了新的思路。     

高温相变材料Al-Si合金选择及其与金属容器相容性实验研究

对高温相变材料铝硅合金的相变温度和潜热进行了分析测定,研究了其热稳定性,并对此类相变材料与金属容器的相容性进行了实验研究。实验结果表明,相变材料AlSi12相变温度适中而潜热大,可作为蓄热介质来储存太阳能；温度对AlSi12与不锈钢材料之间的扩散渗透影响显著。     

应用于日光温室墙体的相变材料热物性优化研究

建立日光温室计算传热模型,以室内空气温度和墙体内表面温度为指标,通过实验方法验证了所建立的传热模型准确性,最后分析相变材料相变温度、相变焓、导热系数、密度等热物性对室内最低温度和相变蓄热率的影响规律,确定被动式相变蓄热墙体和主-被动式相变蓄热墙体的最佳相变材料热物性,阐明了实际应用时相变材料选择原则。研究结果表明,所建立的日光温室传热模型具有较高准确性,可用于日光温室墙体相变材料热物性优化;主-被动式相变蓄热墙体最佳相变材料的相变温度为27 ℃,相变焓为200 kJ/kg,导热系数为0.35 W/（m·K）,密度为440 kg/m³,被动式相变蓄热墙体最佳相变材料的相变温度为26 ℃,相变焓为200 kJ/kg,导热系数为0.35 W/（m·K）,密度为792 kg/m³;最佳相变材料热物性应用时,2种墙体室内最低温度均可达到15.0 ℃,但是被动式相变蓄热墙体的相变蓄热率较主-被动式相变蓄热墙体减小29.5%。本研究可为相变材料在日光温室的高效利用提供参考。     

Thermal stability of Li2CO3-Na2CO3 based high-temperature phase change materials

利用静态熔融法制备了Li₂CO₃-Na₂CO₃(4∶6,质量比)二元熔盐.采用自制"自动热循环测试系统"测试了400~600 ℃内此二元熔盐1010次热循环,分析了其相变参数动态变化特性,利用DSC测试了其热稳定性,利用XRD分析了其化学组分.结果表明:"自动热循环测试系统"可以替代DSC定性测试相变材料的热循环稳定性;Li₂CO₃-Na₂CO₃二元熔盐熔化/凝固过程中主要以LiNaCO₃形式存在,其峰值温度为499.1 ℃,其相变潜热为365.5J/g;热循环过程中,此二元熔盐的熔化和凝固温度变化不大,相变潜热最大降低了45.3J/g;通过XRD物相分析,可知整个循环过程中此二元熔盐的物相没有明显的变化.总之,Li₂CO₃-Na₂CO₃二元熔盐能够满足太阳能高温热发电和其它高温储热需求.     

Capric acid and stearic acid mixture impregnated with gypsum wallboard for low‐temperature latent heat thermal energy storage

A novel form‐stable phase change wallboard (PCW) was prepared for low‐temperature latent heat thermal energy storage by incorporating eutectic mixture of capric acid and stearic acid and gypsum wallboard. Thermal properties of form‐stable PCW were measured by DSC analysis. The form‐stable PCW has good thermal reliability with respect to the changes in its thermal properties after accelerated thermal cycling. Thermal performance test indicated that the use of such a type of PCW can decrease indoor air temperature fluctuation due to absorption of heat by the eutectic phase change material. Copyright © 2007 John Wiley & Sons, Ltd.     

硬脂酸丁酯/多孔石墨定形相变材料的实验研究

本文利用多孔石墨的毛细管作用吸附硬脂酸丁酯制成了一种定形相变材料,利用DSC研究了硬脂酸丁酯质量含量不同的定形相变材料的相变温度、相变潜热和热稳定性,得出硬脂酸丁酯含量的临界值。研究结果表明:硬脂酸丁酯和纳米多孔石墨形成的定形相变材料相变温度合适、相变潜热较大、热稳定性好,是适合于在建筑墙体中使用的相变材料。     

Thermal performance of a eutectic mixture of lauric and stearic acids as PCM encapsulated in the annulus of two concentric pipes

Thermal performance characteristics of a eutectic mixture of lauric and stearic acids as phase change material (PCM) during the melting and solidification processes were determined experimentally in a vertical two concentric pipe-energy storage system. This study deals with three important subjects: The first one is to determine the eutectic composition ratio of the lauric acid (LA) and stearic acid (SA) binary system, and to measure its thermophysical properties by DSC. The second one is to establish the thermal characteristics of the mixture such as total melting and solidification times, the heat transfer modes in melted and solidified PCM, and the effect of Reynolds and Stefan numbers as inlet heat transfer fluid (HTF) conditions on the phase transition behaviors. The final one includes the calculations of the heat transfer coefficients between the outside wall of the HTF pipe and the PCM, and heat fractions during the melting and solidification processes of the mixture, and also the discussion of the effect of inlet HTF parameters on these characteristics. The LA–SA binary system in the mixture ratio of 75.5:24.5 wt % forms a eutectic, which melts at 37°C and has a latent heat of 182.7 J g⁻¹, and, thus, these properties make it an attractive phase change material used for passive solar space heating applications such as building and greenhouse heating with respect to the climate conditions. The experimental results indicated that the mixture encapsulated in the annulus of two concentric pipes has good thermal and heat transfer characteristics during the melting and solidification processes, and it has potential for heat storage in passive solar space heating systems.     

Na_2SO_4·10H_2O复合相变储能体系的热力学测试

制备了一种Na2SO4.10H2O共晶相变蓄冷材料,其相变温度在8℃左右,可作为空调蓄冷材料。本文主要研究了复合相变体系的热化学性质和材料的相变特性。本研究测定出材料的相变潜热为114.37kJ/kg,固体平均比热容为4.68kJ/(kg.K),液体平均比热容为16.18kJ/(kg.K)。材料的主要成分为Na2SO4.10H2O,NaCl,NH4Cl,羧甲基纤维素(CMC)等,其主要特点是原料来源丰富,潜热和显热蓄冷量较大。     

Experimental Study on Hybrid Organic Phase Change Materials Used for Solar Energy Storage

The solar energy utilization in built environment has been limited due to its low heat flux, uneven distribution in time and space and temporal difference in day and night. The phase change materials have been used to collect the fluctuant solar energy to form a stable energy source for the terminal equipment of the buildings. In this study, the hybrid organic phase change materials was prepared for the capillary radiant heating system which formed a cascade utilization of solar energy. Firstly, lauric acid and stearic acid were selected as the basic organic phase change materials and the binary equilibrium phase diagram was completed based on the method of step cooling curve according to the experimental tests data. The results showed that the phase transition temperature of the mixed acid at the lowest eutectic point was 31.2℃ and the latent heat value was 264.3 kJ/kg when the mass mixing ratio was 70% for lauric acid and 30% for stearic acid. Secondly, the expanded graphite was used as an additive to enwrap the mixed acid and enhance the heat conductivity. The experimental results showed that when the mass proportion of expanded graphite in the mixed acid was 10%, the mixed acid could be completely enclosed by expanded graphite and the stability of melting and solidification was optimal. Additionally, the phase transition temperature of the hybrid phase change material was 31.5℃ and the latent heat value was 217.4 kJ/kg. The novel hybrid phase change material has a lower eutectic point and a higher latent heat of phase change, so it has a large application space and is quite suitable for the cascade utilization of solar energy with capillary network heating system.     

Compatibility between cordierite-mullite ceramics and PCMs

以煅烧铝矾土、滑石及石英为原料,采用挤出成型,制备堇青石-莫来石复相蜂窝陶瓷,用这种显热储热陶瓷（简称基体）封装PCM制备潜热/显热复合储热材料。设计F系列封装剂配方组成,选择PCM为AlSi₂₀、Na₂SO₄,制得PCM/蜂窝陶瓷复合储热材料,热震循环（200～900 ℃）30次,每次循环在900 ℃保温12 h。利用XRD、SEM、TG-DSC等分析相组成、微观结构、封装剂与基体结合性、基体与PCM相容性、复合储热材料的相变温度及相变焓。结果表明,经1440 ℃烧成的蜂窝陶瓷,Wa、Pa、D及a轴抗压强度分别为2.38%、6.32%、2.65 g/cm3,25.77 MPa;XRD显示相组成为堇青石、莫来石及少量镁铝尖晶石;30次热震后,Wa、Pa略有升高,D及σa略有降低。封装剂剪切强度测定结果表明,封装剂F2与基体结合强度最大,达2.53 MPa,SEM显示F2与基体结合良好。热震30次后,基体断面SEM图表明,PCM无渗漏。TG-DSC结果表明,经30次热循环后,AlSi20/蜂窝陶瓷复合储热材料的相变范围为571.7～583.5 ℃,峰值为578.3 ℃,峰值温度偏移不超过0.7%。复合储热材料具有优良的储热性能。     

Investigation of a eutectic mixture of sodium acetate trihydrate and urea as latent heat storage

In this paper, the pseudobinary system CH₃COONa·3H₂O---CO(NH₂)₂ is studied by means of differential scanning calorimetry (DSC). Its eutectic mixture is found to melt congruently at 30°C, its heat of fusion is 200.5 J/g, considering the temperature of phase change and its heat storage capacity. This eutectic mixture is an excellent material for latent heat storage of solar energy.     

NaCl-MgCl2-CaCl2相图计算方法研究

为满足规模化太阳能热发电中对传热蓄热的要求,针对储能材料开展探究。以熔融盐热物性及经济性作为筛选条件,选定来源广泛、价格低廉、工作温度范围宽、黏度低、相变潜热大的NaCl、MgCl₂和CaCl₂三元熔盐体系开展深入研究。应用修正的准化学溶液模型,在子二元系基础上推导计算三元混合熔盐NaCl-MgCl₂-CaCl₂相图。结果表明,该熔盐混合物共晶点温度为412.45 ℃,NaCl、MgCl₂和CaCl₂的摩尔分数分别为50.99%、22.78%和26.23%,与已有文献数据相比,误差在3%以内,验证了方法的准确性,为构建熔盐氯化物相图数据库奠定了部分基础。