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摘要: 相變儲能技術的發展對于促進新能源開發和提高能源利用效率具有非常重要的意義。相變材料由于具有高儲能密度和小體積變化等優勢引起了人們的廣泛關注。然而，相變材料在固–液相轉變過程中易發生液體泄漏而限制了其應用。因此，人們選擇用多孔支撐材料來解決相變材料的泄露問題。介孔二氧化硅材料由于具有良好的物理化學穩定性、生物相容性、阻燃性能、低毒性、耐腐蝕性、尺寸可控、表面形貌可調和高比表面積等優點，其作為載體材料能綜合提高相變復合物的各方面性能并拓寬相變儲能材料的應用空間。對近年來國內外關于介孔二氧化硅載體的孔尺寸、孔結構和孔表面性質對相變材料結晶行為的影響等方面進行了綜合分析，并對今后提高介孔二氧化硅相變材料儲能效率的研究方法的前景做了展望。Abstract: Increasing concerns surrounding the rising global energy demand has forced humans to look for alternative energy sources such as the development and utilization of natural gas and nuclear energy, or to increase the efficiency of energy use, thereby optimizing the use of energy. Improving energy efficiency is an effective method that can quickly and efficiently reduce the energy demand and supply gap. Furthermore, developing new technologies for energy storage and energy saving is an effective way to solve the energy crisis, which is of great significance for the sustainable development of energy. Latent heat storage has become a popular research topic owing to its large energy storage density and small temperature changes during energy storage and its excellent thermal stability and high safety. Currently, phase-change materials have been widely used in solar heating systems, air conditioning systems, thermally regulated textiles, energy-efficient building construction, temperature-controlled greenhouses and other fields. The development of phase-change energy storage technology is significant for promoting the development of alternative energy sources and improving energy efficiency. However, phase change materials are prone to liquid leakage during the solid-liquid phase transition, which limits their application. To solve this problem, researchers have started introducing porous support materials to phase-change materials. Porous support materials have attracted extensive research attention in recent years owing to their outstanding properties such as high specific surface area, large pore volume, and low density. Porous support materials can absorb phase-change materials in their pores through the physical adsorption phenomena such as capillary action and interfacial tension, and thereby gradually develop into important substrates for phase-change material encapsulation. Inorganic materials are used as carriers for phase change energy storage materials. Compared with organic carrier materials, inorganic carrier materials have higher mechanical strength, flame retardancy and thermal conductivity, which can reduce the production cost of phase-change energy storage materials, and have a high research value. Mesoporous silica materials have good physical and chemical stability, biocompatibility, flame retardancy, low toxicity, corrosion resistance, controllable size, adjustable surface morphology and high specific surface area. They can comprehensively improve the performance of various aspects of phase change composites and broaden the application space of phase change energy storage materials. In this review, the effects of pore size, pore structure, and pore surface properties on the crystallization behavior of phase change materials in mesoporous silica carriers developed in recent years were comprehensively analyzed, and prospects of research methods for heat storage efficiency were explored.
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圖 1 正二十烷@二氧化硅復合物的制備示意圖。（a）起始物料；（b）納米二氧化硅孔中的正二十烷分子（右側圖為孔隙內壁可能的結構圖）；（c）孔隙中含有正二十烷的硅顆粒的結構（顆粒直徑約為100 nm）；（d）正二十烷@二氧化硅顆粒自組裝成微米大小的空心球體[24]
Figure 1. Schematic diagram of the preparation of n-eicosane@silica composite: (a) starting materials; (b) n-eicosane molecules in the pores of nano-silica (the figure on the right is a possible structural diagram of the inner wall of the pore); (c) structure of silicon particles containing n-eicosane in the pores (approximately 100 nm); (d) self-assembly of n-eicosane@silica particles into micrometer-sized hollow spheres[24]
圖 2 C17H36/MCM–41復合材料的影響因素對比。（a）MCM–41的SEM圖；（b）優化的C17H36晶體結構（黃色代表碳，綠色代表氫）；（c）不同填充率的C17H36/MCM–41復合材料的潛熱隨孔徑或孔隙率的變化（Φ為填充率）；（d）C17H36/MCM–41復合材料的潛熱和熔點隨填充率的變化（r為孔直徑）[41]
Figure 2. Comparison of influencing factors of C17H36/MCM-41 composite: (a) SEM image of MCM–41; (b) optimized C17H36 crystal structure (yellow represents carbon, green represents hydrogen); (c) latent heat of C17H36/MCM–41 composites with different filling rates varies with pore size or porosity (Φ is filling rate); (d) latent heat and melting point of C17H36/MCM–41 composite materials change with filling rates (r is pore diameter)[41]
圖 4 C16被吸附于SBA–15（7.8和17.2 nm），CPG（8.1和300 nm），C–SBA–15（15.6 nm）和KIT–6（8.6 nm）的示意圖（C—冷卻；H—加熱；D—維度；T16—分子在載體中的排列）[52]
Figure 4. Schematic diagram of C16 being adsorbed on SBA–15 (7.8 and 17.2 nm), CPG (8.1 and 300 nm), C–SBA–15 (15.6 nm) and KIT–6 (8.6 nm) (C: cooling; H: heating; D: dimension; T16: the molecular arrangements in the bulk)[52]
圖 5 PEG/RMS復合物的制備及性能示意圖。（a1）RMS合成過程示意圖；（a2）真空浸漬法制備相變復合物；（a3）PEG/RMS復合物形成機理示意圖；（b）DSC曲線；（c）理論焓值和實際焓值的對比圖[55]
Figure 5. Schematic diagram of preparation and performance of PEG/RMS complexes: (a1) schematic diagram of the synthesis process of RMS: (a2) vacuum impregnation method to prepare the phase change composites; (a3) schematic diagram of the formation mechanism of the PEG/RMS composites; (b) DSC curve; (c) comparison of theoretical and actual enthalpies[55]
圖 6 PEG/NFMS復合物的制備及性能示意圖。（a）NFMS的SEM圖；（b）NFMS的TEM圖；（c）PEG/NFMS的SEM圖；（d）80% PEG/NFMS和純PEG的TG圖；（e）復合物的焓值和熱損失率的對比圖[56]
Figure 6. Schematic diagram of the preparation and performance of PEG/NFMS complexes: (a) SEM images of NFMS; (b) TEM images of NFMS; (c) SEM images of PEG/NFMS; (d) TG image of 80% PEG/NFMS and pure PEG; (e) comparison of the enthalpy and heat loss rate of PEG/NFMS[56]
圖 7 SA/SiO2復合材料的制備及性能示意圖。（a）SA/SiO2復合物的制備示意圖；（b）SiO2微球BET圖；（c）SBA–15的BET圖；（d）MCM–41的BET圖；（e）復合物的DSC圖；（f）復合PCMs的實際熔融焓與理論熔融焓對比[67]
Figure 7. Schematic diagram of preparation and performance of SA/SiO2 composites: (a) schematic diagram of preparation of SA/SiO2 composites; (b) BET of SiO2 microspheres; (c) BET of SBA–15; (d) BET of MCM–41; (e) DSC of composites; (f) comparison of actual melting enthalpy and theoretical melting enthalpy of composite PCMs[67]
圖 8 SA/TAMSNs相變復合材料形貌及性能。（a）TAMSNs的SEM圖；（b）TAMSNs的TEM圖；（c1，d1和e1）泄漏測試前的SA和復合物；（c2，d2和e2）泄漏測試后的SA和復合物；（f和g）不同負載量的復合物DSC圖[71]
Figure 8. Morphology and properties of SA/TAMSNs phase change composites: (a) SEM image of TAMSNs; (b) TEM image of TAMSNs; (c1, d1 and e1) SA and compound before leakage test; (c2, d2 and e2) SA and compound after leakage test; (f and g) DSC of the compounds with different loadings[71]
圖 10 十八烷/HPS復合物的形貌及負載機理。（a）HPS和（b）十八烷/HPS復合物的照片；（c）HPS和（d）十八烷/HPS復合物的TEM圖；（e）表面修飾前后的HPS載體與十八烷分子的示意圖[80]
Figure 10. Morphology and loading mechanism of octadecane/HPS composites: the optical image of the HPS (a) and composited with octadecane (b); the SEM images of HPS (c) and composited with octadecane (d); (e) the hypothetical image of the arrangement of octadecane molecules on the composite PCM surfaces[80]
圖 11 氣凝膠基相變復合材料。（a）表面修飾前后氣凝膠中浸漬PCM的對比示意圖；（b）親水性至疏水性的表面改性和碳化過程示意圖；（c）M–SiO2，（d）M–SiO2–PA，（e）C–SiO2和（f）C–SiO2–OD復合材料的顯微結構的SEM圖像；（g）光熱轉換的機理和（h）不同樣品的光熱轉換曲線[81]
Figure 11. Aerogel-based composite PCMs: (a) schematic comparison of the PCM penetration in the untreated and treated aerogels; (b) illustration of the hydrophilic-to-hydrophobic surface modification and carbonization process; the SEM images of the microstructures (c) M–SiO2, (d) M–SiO2–PA, (e) C–SiO2 and (f) C–SiO2–OD composites; (g) the mechanism of light-to-heat conversion and (h) the curves of light-to-heat conversion by the different samples[81]
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