木基生物质碳化骨架负载聚乙二醇相变材料及表面修饰对蓄传热性能的强化

朱祥宁; 冯黛丽; 冯妍卉; 林林; 张欣欣

doi:10.7498/aps.72.20222466

摘要

以相变芯材为核心的复合相变材料的潜热储存技术, 对解决可再生能源间歇性问题有着关键作用. 本研究以天然竹木为原材料, 使用高温碳化方法得到碳化竹木, 并使其分别吸附氧化石墨烯和还原氧化石墨烯, 最终与聚乙二醇(PEG2000)复合形成稳定的复合相变材料. 实验结果表明, 还原氧化石墨烯可以达到很好的包封率、热导率和光热转换效率提升效果. 碳化竹木/还原氧化石墨烯/聚乙二醇三元复合相变材料包封率高达81.11%, 熔化潜热为115.62 J/g, 凝固潜热为104.39 J/g, 热导率大幅提升至1.09 W/(m·K)(纯PEG2000的3.7倍), 光热转换效率大幅提高至88.35% (纯PEG2000的3.1倍).

关键词:

Abstract

Thermal energy storage technology can shift the peak and fill the valley of heat, which lays the foundation for realizing the goal of “emission peak and carbon neutrality”. Among various thermal energy storage techniques, the latent heat storage technology based on composite phase change materials can provide large storage capacity with a small temperature variation, and shows great potential in solving the intermittency issue of renewable energy. As a sustainable and renewable material, natural wood has the advantages of a unique anisotropic three-dimensional structure, perfect natural channel, low price, and rich resources. Therefore, the carbonized wood obtained from high-temperature carbonization of natural wood is an excellent choice as a supporting skeleton of composite phase change materials. On the other hand, polyethylene glycol is widely used in energy storage because of its suitable phase transition temperature (46–65℃), high latent heat (145–175 J/g), and stable performance. In this study, carbonized bamboo is prepared at high temperatures. To improve heat storage, thermal conductivity, and photo-thermal conversion properties, the carbonized bamboo is functionalized by graphene oxide and reduced graphene oxide, respectively. Finally, polyethylene glycol is implanted into modified carbonized bamboo to form shape-stabilized phase change materials. Their microstructures, morphologies, and thermophysical properties are characterized. The experimental results show that graphene oxide and reduced graphene oxide can change the surface polarity of carbonized bamboo, thus reducing the interfacial thermal resistance between the carbonized bamboo skeleton and polyethylene glycol, and improving the encapsulation ratio, thermal conductivity, and photo-thermal conversion efficiency without affecting the crystallization behavior of polyethylene glycol. The encapsulation ratio of carbonized bamboo/reduced graphene oxide/polyethylene glycol ternary phase change material is as high as 81.11% (only 4.67% lower than the theoretical value), its latent heat of melting and solidification are 115.62 J/g and 104.39 J/g, its thermal conductivity is greatly increased to 1.09 W/(m·K) (3.7 times that of pure polyethylene glycol), accompanied by substantial growth in its photo-thermal conversion efficiency, reaching 88.35% (3.1 times that of pure polyethylene glycol). This research develops a biomass-derived porous composite phase change material with high heat storage density, high heat transfer rate, and high photo-thermal conversion ability.

Keywords:

作者及机构信息

北京科技大学能源与环境工程学院, 北京　100083

通信作者: 冯黛丽, dlfeng@ustb.edu.cn ; 冯妍卉, yhfeng@me.ustb.edu.cn ;

基金项目: 国家自然科学基金 (批准号: 52176054, 52236006)资助的课题.

Authors and contacts

School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China

Corresponding author: Feng Dai-Li, dlfeng@ustb.edu.cn ; Feng Yan-Hui, yhfeng@me.ustb.edu.cn ;

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 52176054, 52236006).

文章全文

参考文献

[1]	Shen F, Luo W, Dai J, Yao Y, Zhu M, Hitz E, Tang Y, ChenY, Sprenkle V L, Li X 2016 Adv. Mater. 28 1600377
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施引文献

图 1 　(a) 天然竹木的碳化过程; (b) 碳化竹木吸附氧化石墨烯和还原氧化石墨烯的过程; (c) 碳化骨架和PEG2000复合过程

Fig. 1. (a) The carbonization process of natural bamboo wood; (b) the adsorption process of GO and RGO by carbonized wood; (c) the composite process of carbon skeleton and PEG2000.

下载: 全尺寸图片幻灯片

图 2 几种材料的横截面SEM图像

Fig. 2. SEM images of cross-section.

下载: 全尺寸图片幻灯片

图 3 (a) NBW和CBW的孔径分布; (b) CBW的拉曼图谱

Fig. 3. (a) Pore size distribution of NBW and CBW; (b) Raman spectra of CBW.

下载: 全尺寸图片幻灯片

图 4 CBW, GOCBW, RGOCBW, PEG-CBW, PEG-GOCBW, PEG-RGOCBW 和 PEG2000的FT-IR光谱(a)和XRD图谱(b)

Fig. 4. (a) FT-IR spectroscopy and (b) XRD patterns of CBW, GOCBW, RGOCBW, PEG-CBW, PEG-GOCBW, PEG-RGOCBW, and PEG2000.

下载: 全尺寸图片幻灯片

图 5 CBW, GOCBW, RGOCBW, PEG-CBW, PEG-GOCBW, PEG-RGOCBW和PEG2000的TG曲线(a)和DSC曲线(b)

Fig. 5. TG curves (a) and DSC curves (b) of CBW, GOCBW, RGOCBW, PEG-CBW, PEG-GOCBW, PEG-RGOCBW.

下载: 全尺寸图片幻灯片

图 6 (a) NBW, CBW, GOCBW, RGOCBW, PEG-CBW, PEG-GOCBW, PEG-RGOCBW和PEG2000的热导率; (b) 生物质复合相变材料的包封率和热导率比较

Fig. 6. (a) Thermal conductivities of NBW, CBW, GOCBW, RGOCBW, PEG-CBW, PEG-GOCBW, PEG-RGOCBW, and PEG2000; (b) comparison of encapsulation ratio and thermal conductivity of biomass composite phase change materials.

下载: 全尺寸图片幻灯片

图 7 CBW, GOCBW, RGOCBW, PEG-CBW, PEG-GOCBW和PEG-RGOCBW的应力-应变曲线

Fig. 7. Stress-strain curves of CBW, GOCBW, RGOCBW, PEG-CBW, PEG-GOCBW, and PEG-RGOCBW.

下载: 全尺寸图片幻灯片

图 8 PEG-CBW, PEG-GOCBW, PEG-RGOCBW和PEG2000的温升曲线(a), 光转换效率(b)和红外热成像图片(c)

Fig. 8. Temperature rise curve (a), photothermal conversion efficiency (b), and infrared thermal images (c) of PEG-CBW, PEG-GOCBW, PEG-RGOCBW, and PEG2000.

下载: 全尺寸图片幻灯片

表 1 NBW和CBW的孔隙参数

Table 1. Pore parameters of NBW and CBW.

样品孔隙率/% 平均孔径/nm 总孔容/
(cm³·g^–1) 总孔面积/
(m²·g^–1)

NBW 39.24 22.17 0.49 88.91
CBW 79.95 46.95 5.34 454.59

下载: 导出CSV

表 2 PEG-CBW, PEG-GOCBW, PEG-RGOCBW的相变参数

Table 2. Phase change parameters of PEG-CBW, PEG-GOCBW, PEG-RGOCBW.

样品 T_m/T_f ΔH_m/ΔH_f $ \gamma $/%

PEG2000 52.47/30.86 193.00/176.60 —
PEG-CBW 46.86/36.76 44.56/37.13 52.66
PEG-GOCBW 50.14/35.00 79.49/67.64 71.53
PEG-RGOCBW 50.06/37.15 115.62/104.39 81.11

下载: 导出CSV

map

[1]	Shen F, Luo W, Dai J, Yao Y, Zhu M, Hitz E, Tang Y, ChenY, Sprenkle V L, Li X 2016 Adv. Mater. 28 1600377
[2]	Qian T T, Li J 2018 Energy 142 234 Google Scholar
[3]	Zhang S, Wu W, Wang S 2017 Energy 130 228 Google Scholar
[4]	Wang C, Feng L, Li W, Zheng J, Tian W, Li X 2012 Sol. Energy Mater. Sol. Cells 105 21 Google Scholar
[5]	Yang H, Wang Y, Yu Q, Cao G, Yang R, Ke J, Di X, Liu, F, Zhang W, Wang C 2018 Appl. Energy 212 455 Google Scholar
[6]	Huang X, Alva G, Liu L, Fang G 2017 Appl. Energy 200 19 Google Scholar
[7]	Min X, Fang M H, Huang Z H, Liu Y G, Huang Y T, Wen R L, Qian T T, Wu X W 2015 Sci. Rep. 5 12964 Google Scholar
[8]	Feng L L, Zheng J, Yang H Z, Yan L 2011 Sol. Energy Mater. Sol. Cells 95 644 Google Scholar
[9]	Qian T T, Li J, Deng Y 2016 Sci. Rep. 6 32392 Google Scholar
[10]	Karaman S, Karaipekli A, Sar A, Bier A 2011 Sol. Energy Mater. Sol. Cells 95 1647 Google Scholar
[11]	Qi G Q, Liang C L, Bao R Y, Liu Z Y, Yang W, Xie B H, Yang M B 2014 Sol. Energy Mater. Sol. Cells 123 171 Google Scholar
[12]	Qian T T, Li J, Min X, Deng Y, Guan W, Ma H 2015 Energy 82 333 Google Scholar
[13]	Seki, Y, Ince, Seyma, Ezan M A, Turgut A, Erek A 2015 Sol. Energy Mater. Sol. Cells 140 457 Google Scholar
[14]	Zhang N, Yuan Y P, Wang X, Cao X L, Yang X J, Hu S C 2013 Chem. Eng. J. 231 214 Google Scholar
[15]	Li B, Liu T, Hu L, Wang Y, Nie S 2013 Chem. Eng. J. 215 819
[16]	Zhao Y J, Min X, Huang Z H, Liu Y G, Wu X W, Fang M H 2018 Energy Build. 158 1049 Google Scholar
[17]	Zhang X G, Huang Z H, Yin Z Y, Zhang W Y, Huang Y T, Liu Y G, Fang M H, Wu X W, Min X 2017 Energy Build. 154 46 Google Scholar
[18]	Li Y Q, Samad Y A, Polychronopoulou K, Alhassan S M, Liao K 2014 J. Mater. Chem. A 2 7759 Google Scholar
[19]	Zhang Y, Song J W, Kierzewski, Iain, Li Y J, Gong Y H 2017 Energy Environ. Sci. 10 538 Google Scholar
[20]	Zhang Z T, Cao B Y 2022 Sci. China. Phys. Mech. 65 117003 Google Scholar
[21]	Qiang S, Jing O, Yi Z, Yang H 2017 Appl. Clay Sci. 146 14 Google Scholar
[22]	Zhang Y, Liu J, Su Z, Lu M, Liu S, Jiang T 2020 Constr. Build. Mater. 238 117717 Google Scholar
[23]	Zou T, Fu W W, Liang X L, Wang S F, Gao X N, Zhang Z G, Fang Y T, Henrik L, Mark J K 2020 Energy 190 116473 Google Scholar
[24]	Xie N, Li Z, Gao X, Fang Y, Zhang Z 2020 Int. J. Refrig. 110 178 Google Scholar
[25]	Yang J, Jia Y L, Bing N C, Wang L L, Xie H Q, Yu W 2019 Appl. Therm. Eng. 163 114412 Google Scholar
[26]	Zhang H, Wang L, Xi S, Xie H, Yu W 2021 Renew. Energy 175 307 Google Scholar
[27]	Liu Y, Yang Y, Li S 2016 J. Mater. Chem. A 10 1039
[28]	Li Z, Yang W, Jiang Z, He F, Wu J 2017 Appl. Energy 197 354 Google Scholar
[29]	Ma X C, Liu Y J, Liu H, Zhang L, Xu B, Xiao F 2018 Sol. Energy Mater. Sol. Cells 188 73 Google Scholar
[30]	Feng D L, Zang Y Y, Li P, Feng Y H, Yan Y Y, Zhang X X 2021 Compos. Sci. Technol. 210 108832 Google Scholar
[31]	Yu Z P, Feng D L, Feng Y H, Zhang X X 2022 Compos. Part A: Appl. Sci. Manufact. 152 106703 Google Scholar
[32]	Yuan P, Zhang P, Liang T, Zhai S P 2019 Appl. Surf. Sci. 485 402 Google Scholar
[33]	Xie B, Li C, Zhang B, Yang L, Chen J 2020 Energy Built Environ. 1 187
[34]	Hekimolu G, Sar A, Kar T, Kele S, Saleh T A 2021 J. Energy Storage 35 102288 Google Scholar
[35]	Wu S, Chen Y, Chen Z, Wang J, Cai M, Gao J 2021 Sci. Rep. 11 822 Google Scholar
[36]	Zhao Y J, Sun B, Du P P, Min X, Huang Z H, Liu Y G, Wu X W, Fang M H 2019 Mater. Res. Express 6 115515 Google Scholar
[37]	Chen Y, Cui Z, Ding H, Wan Y, Tang Z, Gao J 2018 Int. J. Mol. Sci. 19 3055 Google Scholar
[38]	Wan Y C, Chen Y, Cui Z X, Ding H, Gao S F, Han Z, Gao J K 2019 Sci. Rep. 9 11535 Google Scholar
[39]	Das D, Bordoloi U, Muigai H H, Kalita P 2020 J. Energy Storage 30 101403 Google Scholar
[40]	Yang H Y, Wang Y, Yu Q, Li G, Sun X, Yang R, Zhang Q, Liu F, Di X, Li J 2018 Energy 159 929 Google Scholar
[41]	Li C, Xie B, He Z, Chen J, Long Y 2019 Renew. Energy 140 862 Google Scholar
[42]	Zhang W, Zhang X, Zhang X, Yin Z, Liu Y, Fang M, Wu X, Min X, Huang Z 2019 Thermochim. Acta 674 21 Google Scholar
[43]	Atinafu D G, Dong W, Wang C, Wang G 2018 J. Mater. Chem. A 6 8969 Google Scholar
[44]	Wen R, Zhang W, Lv Z, Huang Z, Gao W 2018 Mater. Lett. 215 42 Google Scholar
[45]	Yang Z, Deng Y, Li J 2019 Appl. Therm. Eng. 150 967 Google Scholar

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木基生物质碳化骨架负载聚乙二醇相变材料及表面修饰对蓄传热性能的强化