碳基定型复合相变材料的研究进展

doi:10.16085/j.issn.1000-6613.2024-0558

化工进展 ›› 2025, Vol. 44 ›› Issue (4): 2102-2118.DOI: 10.16085/j.issn.1000-6613.2024-0558

碳基定型复合相变材料的研究进展

安明泽¹^,²(), 张兵兵¹^,²^,³(), 王盛¹^,², 陈蔚洁¹^,²^,³, 刘世旺⁴, 薛斌¹^,², 徐国敏¹^,², 秦舒浩¹^,²^,⁴

^1.贵州省材料产业技术研究院，贵州贵阳 550022
^2.国家复合改性聚合物材料工程技术研究中心，贵州贵阳 550014
^3.贵州大学资源与环境工程学院，贵州贵阳 550025
^4.贵州大学材料与冶金学院，贵州贵阳 550025

收稿日期:2024-04-03 修回日期:2024-07-13 出版日期:2025-04-25 发布日期:2025-05-07
通讯作者: 张兵兵
作者简介:安明泽（1992—），男，硕士，助理研究员，研究方向为碳基复合相变储能材料。E-mail：amz921810@163.com。
基金资助:
贵州省基础研究（自然科学）项目（QKHJC-ZK[2023]YB158）;贵州省科技计划（黔科合支撑[2022]一般219,黔科合服企[2021]9）;贵州省黔东南州科技支撑计划(黔东南科合J字[2022]59)

Research progress on carbon-based stereotyped composite phase change materials

AN Mingze¹^,²(), ZHANG Bingbing¹^,²^,³(), WANG Sheng¹^,², CHEN Weijie¹^,²^,³, LIU Shiwang⁴, XUE Bin¹^,², XU Guomin¹^,², QIN Shuhao¹^,²^,⁴

^1.Guizhou Material Industrial Technology Institute, Guiyang 550022, Guizhou, China
^2.National Engineering Research Center for Compounding and Modification of Polymer Materials, Guiyang 550014, Guizhou, China
^3.College of Resources and Environmental Engineering Department, Guizhou University, Guiyang 550025, Guizhou, China
^4.College of Materials and Metallurgy, Guizhou University, Guiyang 550025, Guizhou, China

Received:2024-04-03 Revised:2024-07-13 Online:2025-04-25 Published:2025-05-07
Contact: ZHANG Bingbing

摘要/Abstract

摘要：

相变材料（PCMs）是指随温度变化而改变物质的物理性质并能提供潜热的材料，在太阳能热储存、电子设备、动力电池热管理、建筑温度控制等领域具有广泛的应用前景，在我国已经被列为国家级研发利用序列。然而，相变材料容易出现渗漏、热导率低、光吸收弱等问题，阻碍了其更广泛的应用和发展。为了克服这些固有问题，提高热物理性能，将碳基材料作为封装载体构建形状稳定的定型复合相变材料可以有效防止固-液相变渗漏，提高潜热性能。本文综述了碳纳米管、石墨烯、活性炭、生物炭等多孔碳支撑材料作为相变材料封装载体的主要研究进展，介绍了不同多孔碳材料作为封装载体对相变复合材料的热导率、潜热、相变温度、过冷度、形状稳定性和热循环稳定性等物理性能的影响，总结了不同多孔碳基复合相变材料在潜热性能方面的研究动态和各行业中的应用。最后，对多孔碳基材料在未来发展中的研究和面临的挑战进行了总结和展望。

关键词: 碳基, 载体, 相变, 复合材料, 热性能

Abstract:

Phase change materials (PCMs) refer to materials that change the physical properties of substances with temperature changes and can provide latent heat, which has a wide range of application prospects in the fields of solar thermal storage, electronic equipment, power battery thermal management and building temperature control, etc., and has been listed as a national R&D utilization sequence in China. However, problems such as leakage, low thermal conductivity and weak light absorption hinder the wider application and development of phase change materials. To overcome these inherent problems and improve their thermophysical properties, carbon-based materials used as encapsulation carrier to construct stable shape composite phase change materials can effectively prevent solid-liquid phase change leakage and improve the latent heat properties. In this paper, the main research progress of porous carbon supporting materials (such as carbon nanotubes, graphene, activated carbon, biochar, etc.) as PCMs encapsulation carriers was reviewed. The effects of different porous carbon materials as encapsulation carriers on the physical properties of PCM composites such as thermal conductivity, latent heat, phase transition temperature, subcooling, shape stability and thermal cycle stability were introduced. The research trends and applications of different porous carbon-based composite phase change materials in latent thermal properties were introduced. Finally, the future research and challenges of porous carbon-based materials were summarized and prospected.

Key words: carbon-based, carrier, phase change, composites, thermal properties

中图分类号:

TK02

安明泽, 张兵兵, 王盛, 陈蔚洁, 刘世旺, 薛斌, 徐国敏, 秦舒浩. 碳基定型复合相变材料的研究进展[J]. 化工进展, 2025, 44(4): 2102-2118.

AN Mingze, ZHANG Bingbing, WANG Sheng, CHEN Weijie, LIU Shiwang, XUE Bin, XU Guomin, QIN Shuhao. Research progress on carbon-based stereotyped composite phase change materials[J]. Chemical Industry and Engineering Progress, 2025, 44(4): 2102-2118.

图/表 14

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CNTs载体	相变材料	制备方法	相变温度T_m/℃	过冷度 ΔT/℃	相变潜热 ΔH_m/J·g^-1	热导率K/W·(m·K)^-1	参考文献
S-MWCNTs：φ=815nm，L=0.52µm	石蜡	溶液吸附	57.7	7.1	178.2	0.324	[23]
L-MWCNTs：φ=3050nm，L=515µm			58.2	6.9	177.4	0.309	[23]
SWCNTs：φ=1.5nm，L＞5µm			56.8	6.3	146.1	0.550	[24]
SWCNTs：φ=1~2nm，L=0.5~2μm	丙烯酸十六酯	表面接枝	36.7	13.0	52.0	0.468	[25]
MWCNTs：φ=8nm，L=0.5~2μm	丙烯酸十六酯	表面接枝	38.0	11.2	40.0	0.877	[25]
氨基-SWCNTs：φ<2nm，L=1~3μm	PEG6000	溶液吸附	53.9	27.7	125.1	0.421	[26]
MWCNTs：φ=10~30nm，L=10~30μm, S_BET＞60m²/g	蜂蜡	真空注入	60.6	3.6	126.0	0.410	[27]
三维CNTs海绵	癸二酸	溶液吸附	121.1	0.4	131.8	7.270	[28]
三维CNTs海绵	PEG	水热还原	43.5	—	120.0	0.310	[29]
CNTs/MOF（金属有机骨架）：φ=30~50nm，L=10~20μm	PEG2000	真空注入	52.4	23	96.2	0.464	[30]
SWCNTs/聚苯乙烯泡沫（PS）：φ=2nm，L=30μm	石蜡		38.0~47.0	1.0~2.0	124.9	0.400	[31]
MWCNTs：φ_内=30~50nm，φ_外=50~60nm，L=5~30μm，S_BET=120m²/g	硬脂酸		59.3	11.4	91.94	7.159	[32]
CNTs-Cu/Cu₂O：φ=20~30nm	石蜡	水热还原结合原位沉积	61.2	—	81.3141	0.632	[33]

CNTs载体	相变材料	制备方法	相变温度T_m/℃	过冷度 ΔT/℃	相变潜热 ΔH_m/J·g^-1	热导率K/W·(m·K)^-1	参考文献
S-MWCNTs：φ=815nm，L=0.52µm	石蜡	溶液吸附	57.7	7.1	178.2	0.324	[23]
L-MWCNTs：φ=3050nm，L=515µm			58.2	6.9	177.4	0.309	[23]
SWCNTs：φ=1.5nm，L＞5µm			56.8	6.3	146.1	0.550	[24]
SWCNTs：φ=1~2nm，L=0.5~2μm	丙烯酸十六酯	表面接枝	36.7	13.0	52.0	0.468	[25]
MWCNTs：φ=8nm，L=0.5~2μm	丙烯酸十六酯	表面接枝	38.0	11.2	40.0	0.877	[25]
氨基-SWCNTs：φ<2nm，L=1~3μm	PEG6000	溶液吸附	53.9	27.7	125.1	0.421	[26]
MWCNTs：φ=10~30nm，L=10~30μm, S_BET＞60m²/g	蜂蜡	真空注入	60.6	3.6	126.0	0.410	[27]
三维CNTs海绵	癸二酸	溶液吸附	121.1	0.4	131.8	7.270	[28]
三维CNTs海绵	PEG	水热还原	43.5	—	120.0	0.310	[29]
CNTs/MOF（金属有机骨架）：φ=30~50nm，L=10~20μm	PEG2000	真空注入	52.4	23	96.2	0.464	[30]
SWCNTs/聚苯乙烯泡沫（PS）：φ=2nm，L=30μm	石蜡		38.0~47.0	1.0~2.0	124.9	0.400	[31]
MWCNTs：φ_内=30~50nm，φ_外=50~60nm，L=5~30μm，S_BET=120m²/g	硬脂酸		59.3	11.4	91.94	7.159	[32]
CNTs-Cu/Cu₂O：φ=20~30nm	石蜡	水热还原结合原位沉积	61.2	—	81.3141	0.632	[33]

石墨烯载体	相变材料	制备方法	相变温度T_m/℃	过冷度 ΔT/℃	相变潜热 ΔH_m/J·g^-1	热导率K/W·(m·K)^-1	文献
GNPs：S_BET=300/500/750m²/g	棕榈酸	真空注入	61.16	1.35	188.98	2.11	[34]
				1.01
				0.96
GNPs：H＜6μm，S_BET=300m²/g	蜂蜡	溶液吸附	62.42	10.37	186.74	2.8	[35]
C₁₈-rGO	石蜡	溶液吸附	55.7	2.8	167.4	—	[36]
E₂C₁₆-g-GO	二甘醇十六烷基醚	化学接枝	43.3	23.9	70	—	[37]
PDA-rGO	环氧化甲氧基聚乙二醇	化学接枝	60.3	20.7	168.2	—	[38]
GA	月桂酸	真空注入	43.27	9	179.1	0.15	[39]
GA	月桂酸	真空注入	43.31	13.9	205.2	1.207	[40]
CNTs与GNPs共混：H_GNPs=4~7nm，L_CNTs=10μm，φ_CNTs=11nm	月桂酸	溶液吸附	40.8	9	198	0.87	[41]
CNTs-GA	石蜡	真空注入	46.56	2.74	245.5	0.836	[42]
GO-MEPCM			41.08	8.84	202.8	—	[43]
GO-MEPCM	正十二醇		26	—	170	0.279	[44]

石墨烯载体	相变材料	制备方法	相变温度T_m/℃	过冷度 ΔT/℃	相变潜热 ΔH_m/J·g^-1	热导率K/W·(m·K)^-1	文献
GNPs：S_BET=300/500/750m²/g	棕榈酸	真空注入	61.16	1.35	188.98	2.11	[34]
				1.01
				0.96
GNPs：H＜6μm，S_BET=300m²/g	蜂蜡	溶液吸附	62.42	10.37	186.74	2.8	[35]
C₁₈-rGO	石蜡	溶液吸附	55.7	2.8	167.4	—	[36]
E₂C₁₆-g-GO	二甘醇十六烷基醚	化学接枝	43.3	23.9	70	—	[37]
PDA-rGO	环氧化甲氧基聚乙二醇	化学接枝	60.3	20.7	168.2	—	[38]
GA	月桂酸	真空注入	43.27	9	179.1	0.15	[39]
GA	月桂酸	真空注入	43.31	13.9	205.2	1.207	[40]
CNTs与GNPs共混：H_GNPs=4~7nm，L_CNTs=10μm，φ_CNTs=11nm	月桂酸	溶液吸附	40.8	9	198	0.87	[41]
CNTs-GA	石蜡	真空注入	46.56	2.74	245.5	0.836	[42]
GO-MEPCM			41.08	8.84	202.8	—	[43]
GO-MEPCM	正十二醇		26	—	170	0.279	[44]

活性炭基体	相变材料	制备方法	相变温度T_m/℃	过冷度 ΔT/℃	相变潜热 ΔH_m/J·g^-1	热导率K/W·(m·K)^-1	参考文献
椰子壳AC：S_BET=1197.67m²/g，R=26.4Å	聚乙二醇	浸渍吸附法	62	20.5	90.2	—	[50]
大麻纤维AC	油酸-癸酸		7.53	2.57	52.7	0.312	[51]
大麻纤维AC	月桂酸-肉豆蔻酸		38.16	5.62	61.67	—	[52]
木质AC：φ=0.075mm	十六醇-肉豆蔻酸		42.38	4.06	76.24	—	[53]
泥炭土AC：S_BET=893m²/g，R=22Å	正十八烷		30.9	6.8	95.4	0.165	[54]
棕榈仁壳AC：S_BET=1169m²/g			—	—	57.56	—	[55]
棕榈仁壳AC：S_BET=183~1169m²/g			28.8	—	87.42	—	[56]
木质AC：S_BET=1468m²/g，R=5.8Å			—	—	101.8	0.168	[57]
棕榈仁壳AC	石蜡		29.2	2.4	57.3	1.17	[58]
木质AC/膨胀石墨/剥离石墨	正十八烷		30.65	8.09	72.45	—	[59]
木质AC：φ＞0.075mm	月桂醇-辛酸	真空注入	0.21	2.44	28.08	—	[60]

碳基定型复合相变材料的研究进展

Research progress on carbon-based stereotyped composite phase change materials

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生物炭基体			PCMs	导热增强剂	制备方法	相变温度T_m/℃	过冷度 ΔT/℃	相变潜热 ΔH_m/J·g^-1	热导率K/W·(m·K)^-1	参考文献
生物质	S_BET/m²·g^-1	R/nm	PCMs	导热增强剂	制备方法	相变温度T_m/℃	过冷度 ΔT/℃	相变潜热 ΔH_m/J·g^-1	热导率K/W·(m·K)^-1	参考文献
松果	289.69	3.078	棕榈酸	—	真空注入	59.25	0.12	84.74	0.393	[65]
竹子	—		十六醇-硬脂酸	—	浸渍吸附	45.29	—	68.85	—	[66]
云杉木	454	3.1~6.4	十二烷、十四烷、十八烷	—	真空注入	31.1	—	91.5	—	[67]
冻干马铃薯	42.6	204.7	聚乙二醇4000	—	浸渍吸附	51.67	17.76	91.8	—	[68]
杏仁壳	291.21	2.33	聚乙二醇	—	真空注入	62.76	30.63	82.73	0.402	[69]
针叶木	7.3	36.6	正二十烷	—	真空注入	37	7.1	53.4	—	[70]
小麦秸秆	11.9	34.1	正二十烷	—	浸渍吸附	37	8.8	75	—	[70]
冻干马铃薯	—	—	PEG	—	浸渍吸附	56.5	18.6	158.8	4.489	[71]
冻干白萝卜	—	—	PEG	—	真空注入	56.5	18.6	159.7	1.746	[71]
蔗糖@MgO	869~1101	16~30	石蜡	—	浸渍吸附	—	—	182.0	—	[72]
芒草、油菜和污泥	7.4~77.6	—	正十二醇和正十二烷	—	超声浸渍吸附	8.2~24.7	—	73.7 90.5	—	[73]
梧桐木	—	10~20	月桂酸	—		41	2.1	177.9	—	[74]
枣核	412.1	3.816	PEG4000	—	真空注入	52.5	—	112.3	0.54	[75]
枣核	1132.7	3.398	PEG4000	铜微球	真空注入	52	—	108.2	0.63	[75]
水葫芦	14.001	11.92	石蜡	铝粉	浸渍吸附	57.67	—	179.4	0.349	[76]
竹子	485.6		正十二烷	MWCNTs	真空浸渍吸附	-7.7	—	127.4	—	[77]
杨木粉生物炭	—		PEG10000	Fe₃O₄/石墨烯纳米片	超声辅助浸渍吸附	55.21	18.66	98.12	0.225	[78]
松果、松木锯末、造纸厂污泥	53.83~86.43	17.16~11.27	椰子油	—		22.71~24.85	—	74.6	0.034	[79]
稻壳	8.586	2.35~4.75	椰子油	—	真空注入	22.95	19.92	70.08	0.2	[80]
			棕榈油	—		3.68	1.44	25.24	0.23
			棕榈蜡	—		52.23	1.39，22.13	92.13	0.11
			大豆蜡	—		16	19.52，34.1	89.91	0.16

复合相变材料	制备方法	形态稳定性说明	参考文献
脂肪酸/CNTs	将脂肪酸接枝到CNTs上，并与脂肪酸混合	纳米填料在复合材料结构内均匀分布	[81]
1-十八醇（OD）/MWCNT	①OD在65°C下加热并与MWCNT结合，然后在75°C下回流48h	OD接枝的MWCNT复合材料由于MWCNT和OD之间较强的胶体引力而具备良好的形态稳定性	[82]
1-十八醇（OD）/MWCNT	②将OD接枝的MWCNT与OD在振荡器中混合30min	纳米填料均匀分布在整个OD表面	[82]
石蜡/铜泡沫和石蜡/镍泡沫	采用真空浸渍法	无论使用何种类型的金属泡沫，石蜡都与金属泡沫完全相容	[83]
石蜡（n-壬烷）/剥落石墨纳米片（xGnP）	将混合石蜡与xGnP或石墨烯在热甲苯中制备复合材料，然后进行溶剂萃取和真空干燥	所研究的纳米石墨颗粒对PCMs的吸收能力有显著差异，石墨烯作为导电填料不能很好吸收大部分石蜡，然而，石蜡在石墨薄片间被有效吸收	[84]
赤藓糖醇/碳纤维	采用熔融分散法（MD）结合新型热压法（HP）进行研究	采用熔融分散法制备复合材料时，碳纤维分散均匀；在热压法下，碳纤维出现在相变材料的颗粒附近	[85]

复合相变材料	循环次数	相变温度T_m/℃	相变潜热 ΔH_m/J·g^-1	参考文献
CA-H/EG	0	25.04	177.8	[86]
CA-H/EG	1000	24.61	171.5	[86]
CA-PS/EG	0	27.04	144.4	[86]
CA-PS/EG	1000	27.14	130.6	[86]
OA-MA/EG	0	6.8	136.3	[87]
OA-MA/EG	100	6.9	136.8	[87]
MA-PA-SA/EG	0	41.61	153.5	[88]
	500	41.18	152.6
	1000	41.92	151.0

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