Thermal conductivity enhancement of porous shape-stabilized composite phase change materials for thermal energy storage applications: a review
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摘要: 先進的相變儲能材料是推動儲能技術發展的核心和關鍵，在促進新能源開發和提高能源利用率中起著至關重要的作用。因在相變過程中具有高儲能密度和小體積變化等優勢，相變材料中應用最多的是固?液相變材料。然而在其相變過程中會發生固態向液態的轉變，為了避免其在液相狀態下的泄露，需要加以定形才能使用。多孔基復合相變材料在有效防止固液相變發生泄露的同時，還需兼顧定形復合相變材料傳熱性能的提升。本文針對這個問題進行了大量的調研，對近年來國內外在提高多孔基定形復合相變材料傳熱性能方面的研究進行了綜合分析，介紹了三種強化傳熱的方法，分別是使用高導熱多孔材料做載體材料、摻雜高導熱納米材料做添加劑以及構筑高導熱多級結構多孔材料，并對提升復合相變材料傳熱性能研究方法的前景作了展望。Abstract: How to realize the efficient use of the renewable energy sources is a present-day challenge to the technologists and has become an important issue in their large scale applications. Energy storage not only reduces the mismatch between supply and demand but also improves the performance and reliability of energy systems and plays an important role in conserving the energy. Current energy storage techniques mainly include sensible heat storage, latent heat storage and chemical reaction heat storage. The researchers place emphasis on the latent heat storage due to its advantages of high heat storage density, little temperature fluctuation and easily controllable utility system. In principle, phase change materials (PCMs) are used for the latent heat storage to absorb and release large amounts of latent heat during their phase change process. Therefore, PCMs are the key factor for the development of latent energy storage technology and play the crucial role in exploring new energy and improving energy utilization. The solid-liquid transition is more efficient compared with the other transformations due to its high latent heat density and small volume change. However, the leakage of solid-liquid PCMs above the melting point from the thermal storage system still hinders their practical applications. Considerable efforts have been devoted to introducing the porous support and development of shape-stabilized composite PCMs to address this technical issue. During the melting or solidifying processes, the PCMs store or release latent heat, while the support materials confine the melted phase from leaking and keep the whole system in the solid state. Moreover, low thermal conductivity of PCMs may degrade the performance for energy storage and thermal regulation during the melting and freezing cycles and restrict their final applications. Therefore, the necessity to enhance thermal conductivity of porous shape-stabilized composite PCMs is evident. In this paper, the recent researches on the enhancement of conductivity of porous shape-stabilized composite PCMs were reviewed. We studied the thermal conductivity enhancement techniques, which included impregnation of PCMs into porous materials with high thermal conductivity, introducing of high conductivity nano-materials and porous support materials into PCMs, construction of hybrid composite for shape stabilized phase change materials. The evaluation of each thermal conductivity enhancement technique was discussed. Finally, we had provided a brief outlook and future challenges in enhancing thermal conductivity of porous shape-stabilized composite PCMs.
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圖 1 不同孔徑泡沫金屬及石蠟/泡沫金屬基復合相變材料的照片. （a） 泡沫鎳；（b） 石蠟/泡沫金屬鎳復合相變材料；（c） 泡沫銅；（d） 石蠟/泡沫金屬銅復合相變材料 (I：5PPI，II：10PPI，III：25PPI)[13]
Figure 1. Images of metal foam and paraffin/metal foam composite PCMs with different pore sizes: (a) nickel foams; (b) paraffin/nickel foam composite PCMs; (c) copper foams; (d) paraffin/copper foam composite PCMs (I: 5PPI, II: 10PPI, III: 25PPI)[13]
圖 3 載體及石墨烯/Al2O3復合材料的結構和熱性能圖. （a） 大孔氧化鋁，石墨烯包覆的多孔氧化鋁，十八酸填充的多孔氧化鋁和十八酸填充的石墨烯包覆的多孔氧化鋁的照片；（b） 石墨烯包覆的多孔氧化鋁的掃描電鏡圖；（c） 十八酸和十八酸填充的石墨烯包覆的多孔氧化鋁的差示掃描量熱曲線圖；（d~f） 十八酸填充的多孔氧化鋁和十八酸填充的石墨烯包覆的多孔氧化鋁的熱傳輸演化圖[49]
Figure 3. Structural and thermal properties of the carrier and graphene/Al2O3 composites: (a) photographs of PAO, G?PAO, SA?PAO, and SA?G?PAO;(b) SEM image of G?PAO; (c) DSC curves of SA and SA?G?PAO composite; (d–f) thermal transport evolution of SA?PAO and SA?G?PAO[49]
表 1 使用高導熱多孔材料做載體材料強化復合相變材料的傳熱性能
Table 1. Enhanced thermal property by impregnation of PCMs into porous materials with high thermal conductivity
復合相變材料體系 復合相變材料
熱導率/(W?m?1?K?1)熱導率提升幅度/%
（與純相變材料相比）參考文獻 載體材料 相變材料 N摻雜的多孔碳 聚乙二醇2000 0.41 51.9 [3] 泡沫金屬鎳 碳酸鉀 17.59 — [11] 泡沫金屬鎳 碳酸鈉 20.38 — [11] 泡沫金屬鎳 氫氧化鈉 13.21 — [11] 泡沫金屬鎳 氫氧化鋰 14.57 — [11] 泡沫金屬鎳 碳酸鋰 24.7 — [11] 泡沫金屬鎳 石蠟 1.20 293 [13] 泡沫金屬銅 石蠟 4.90 1507 [13] 膨脹石墨 石蠟 0.82 272.7 [15] 膨脹石墨 豆蔻酸?棕櫚酸?硬脂酸 2.51 900 [18] 氧化石墨烯 石蠟 0.985 223 [20] 還原氧化石墨烯 脂肪酸 — 150 [21] 碳納米管 癸酸?月桂酸?棕櫚酸 0.67 — [27] 碳納米管海綿 石蠟 1.20 500 [28] 活性碳 十八烷 0.26 40.1 [30] 納米多孔碳 聚乙二醇4000 0.42 50 [32] 氮摻雜多孔碳 聚乙二醇2000 0.41 52 [33] 碳量子點 聚乙二醇8000 0.94 236 [34] 介孔碳 石蠟 0.35 125 [36] 多孔碳 十六醇 0.41 120 [35] 碳微管/石墨烯 十八酸 — 330 [37] 氧化石墨烯?石墨烯納米片氣凝膠 聚乙二醇1000 1.43 361 [40] 還原氧化石墨烯@多孔碳 十八酸 0.60 27.7 [41] 泡沫金剛石 石蠟 6.70 2580 [42] 
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表 2 摻雜高導熱納米材料做添加劑強化復合相變材料的傳熱性能
Table 2. Enhanced thermal property by introducing of high conductivity nano-materials and porous support materials into PCMs
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