生物炭/二十烷复合定型相变材料制备及其光热、电热转换和储存性能

禹兴海; 李艳安; 唐海慰; 韩玉琦; 王永生

doi:10.13801/j.cnki.fhclxb.20220223.002

生物炭/二十烷复合定型相变材料制备及其光热、电热转换和储存性能

doi: 10.13801/j.cnki.fhclxb.20220223.002

禹兴海^{1, 2, ,},
李艳安²,
唐海慰²,
韩玉琦^{2, 3},
王永生^{2, 3}

1.
河西学院　柔性复合材料应用基础研究所，张掖 734000
2.
河西学院　化学化工学院，张掖 734000
3.
甘肃省河西走廊特色资源利用省级重点实验室，张掖 734000

基金项目: 国家自然科学基金(21865008)；甘肃省自然科学基金(20JR5RA198)

详细信息

通讯作者:
禹兴海，博士，教授，硕士生导师，研究方向为高分子复合材料　E-mail：yuxinghai455@163.com

中图分类号: TK02
计量
- 文章访问数: 1123
- HTML全文浏览量: 597
- PDF下载量: 51
- 被引次数: 0
出版历程
- 收稿日期: 2021-11-09
- 修回日期: 2022-01-03
- 录用日期: 2022-01-22
- 网络出版日期: 2022-02-25
- 刊出日期: 2023-01-15

Form-stabilized phase change composites based on biochar and n-Eicosane for photo- and electro-thermal conversion and heat storage

YU Xinghai^{1, 2
, ,},
LI Yan’an²,
TANG Haiwei²,
HAN Yuqi^{2, 3},
WANG Yongsheng^{2, 3}

1.
Institute of Flexible Composite Materials, Hexi University, Zhangye 734000, China
2.
College of Chemistry and Chemical Engineering, Hexi University, Zhangye 734000, China
3.
Key Laboratory of Hexi Corridor Resources and Utilization of Gansu, Hexi University, Zhangye 734000, China

Funds: National Natural Science Foundation of China (21865008); Natural Science Foundation of Gansu Province (20JR5RA198)

摘要

摘要: 为解决单一有机相变材料二十烷(n-Eicosane)导热性差及在相变过程中易发生泄漏的问题，本实验选取玉米秸秆作为生物质原料，通过700℃高温热解、KOH刻蚀改性制备了具有多级孔道结构的生物炭(KBC)材料，再通过乙醇熔融、真空浸渍的方法将二十烷封装到生物炭内部孔道，得到了一种生物炭/二十烷(KBC/n-Eicosane)复合定型相变材料。通过SEM、XRD、FTIR等表征手段研究了复合材料的微观结构和形貌，同时利用TG及DSC测试了复合相变材料的热稳定性和储热性能，并探讨了复合相变材料中二十烷不同用量与焓值的关系。结果表明，复合相变材料的焓值与二十烷的用量成正比，当复合相变材料中生物炭与二十烷的质量比为 1∶2 时，复合相变材料未明显泄漏，定型效果良好，此时对应的熔融焓和凝固焓值分别为121.3 J·g⁻¹ 和117.6 J·g⁻¹，经过100次循环储热和放热性能测试后，未产生渗漏现象，相变焓值亦无明显变化，表明该复合相变材料的储热能力和稳定性较好。此外，还通过模拟太阳光辐射和接入直流电源的方式测试了复合相变材料的光热转换和电热转换能力，结果表明，复合相变材料能高效的将太阳光热和电能转换为热能并加以储存和释放，因此，本实验所制备的复合相变材料不仅是一种性能优异的相变储热材料，而且可以实现对不同形式能源的高效转化和利用，在清洁能源的转换和利用方面具有一定的应用潜力。
- 生物炭 /
- 二十烷 /
- 复合定型相变材料 /
- 光热转换 /
- 电热转换 /
- 储热性能
Abstract: To overcome the obstacles of poor thermal conductivity of pure n-Eicosane, a typical single-phase change material, and prevent the melt from leaking during the phase change process, a biochar/n-Eicosane based composite phase change material that possesses high form stabilization, photo- and electric-thermal converting, and enhanced phase change heat transfer was prepared. Firstly, corn straw was selected as the raw material of biomass, and pyrolyzed at higher temperature. Following a KOH etching procedure at 700℃, a biochar support with large surface area and hierarchically interconnected pores were obtained. Then, KBC/n-Eicosane composite phase change materials were prepared by injecting n-Eicosane into biochar skeletons via ethanol melting and vacuum impregnation. The as-prepared composite materials were characterized by SEM, XRD, FTIR and other characterization methods. The thermal stability and heat storage capacity were also tested by TG and DSC. The effect of mass content of n-Eicosane to melting enthalpy and crystallization enthalpy were calculated, and the results reveal that the optimized mass content is m_KBC∶m_n-Eicosane=1∶2 associated with the melting enthalpy and crystallization enthalpy of 121.3 J·g⁻¹ and 117.6 J·g⁻¹, respectively. Notably, after 100 thermal cycles, the melting enthalpy and crystallization enthalpy have negligible changes, and no clear liquid leaking is observed through all thermal cycles, indicating significant thermal storage ability and cycling stability. In addition, the ability of photo- and electro-thermal conversion and storage of the composite phase charge materials were tested by simulated sunlight irradiating and DC power supply powering. The results display that the KBC/n-Eicosane composite phase materials are capable of converting solar energy or electric energy into thermal energy and storing as latent heat with excellent performance. Thus, the as-prepared KBC/n-Eicosane are not merely a phase charge materials with remarkable properties, but can realize varied energy transformation and storage, showing great potential for use in green and renewable energy conversion and storage.
- biochar /
- n-Eicosane /
- composite phase change material /
- solar-thermal conversion /
- electro-thermal conversion /
- thermal energy storage

HTML全文

图 1 生物炭(BC)在不同改性条件下的N₂吸附-脱附曲线 ((a)、(b)) 和孔径分布曲线 ((c)、(d))

Figure 1. N₂ adsorption-desorption curves ((a), (b)) and pore distributions curves ((c), (d)) of biochar (BC) under different treatments

V—Volum; w—Mass; KBC—KOH etched biochar

下载: 全尺寸图片幻灯片

图 2 试样KBC ((a)、(b)) 和KBC/二十烷(n-Eicosane) ((c)、(d))的SEM图像

Figure 2. SEM images of KBC ((a), (b)) and KBC/n-Eicosane ((c), (d))

下载: 全尺寸图片幻灯片

图 3 KBC、n-Eicosane及KBC/n-Eicosane复合相变材料的FTIR图谱

Figure 3. FTIR spectra of KBC, n-Eicosane and KBC/n-Eicosane composite phase change materials

下载: 全尺寸图片幻灯片

图 4 KBC、n-Eicosane、KBC/n-Eicosane (a) 及不同质量比KBC/n-Eicosane (b) 复合相变材料的XRD图谱

Figure 4. XRD patterns of KBC, n-Eicosane and KBC/n-Eicosane (a), and KBC/n-Eicosane with different mass contents (b) phase change materials

下载: 全尺寸图片幻灯片

图 5 KBC、n-Eicosane及KBC/n-Eicosane复合相变材料的TG曲线

Figure 5. TG curves of KBC, n-Eicosane and KBC/n-Eicosane composite phase change materials

下载: 全尺寸图片幻灯片

图 6 KBC/n-Eicosane复合相变材料的防泄漏性能照片

Figure 6. Pictures of leakproof performance of KBC/n-Eicosane composite phase change materials

1—n-Eicosane; 2-5—m_KBC∶m_n-Eicosane=1∶3, 1∶2.5, 1∶2, 1∶1

下载: 全尺寸图片幻灯片

图 7 KBC、n-Eicosane及KBC/n-Eicosane复合相变材料的DSC 曲线

Figure 7. DSC curves of KBC, n-Eicosane and KBC/n-Eicosane composite phase change materials

下载: 全尺寸图片幻灯片

图 8 KBC/n-Eicosane复合相变材料的DSC循环图

Figure 8. DSC cycle diagram of KBC/n-Eicosane composite phase change materials

下载: 全尺寸图片幻灯片

图 9 KBC/n-Eicosane复合相变材料的导电性能(a)和U-I曲线(b)

Figure 9. Electrical conductivity test diagram (a) and U-I curve (b) of KBC/n-Eicosane composite phase change materials

下载: 全尺寸图片幻灯片

图 10 光照条件下不同温度n-Eicosane和KBC/n-Eicosane复合相变材料快照

Figure 10. Snapshots of n-Eicosane and KBC/n-Eicosane composite phase change materials at different temperatures under light conditions

下载: 全尺寸图片幻灯片

图 11 光照条件下n-Eicosane和 KBC/n-Eicosane复合相变材料吸放热温度曲线

Figure 11. Heat absorption and exothermic temperature curves of n-Eicosane and KBC/n-Eicosane composite phase change materials under light condition

下载: 全尺寸图片幻灯片

图 12 通电条件下不同温度KBC/n-Eicosane复合相变材料的快照

Figure 12. Snapshots of KBC/n-Eicosane composite phase change materials at different temperatures under current condition

下载: 全尺寸图片幻灯片

图 13 通电条件下KBC/n-Eicosane复合相变材料的吸放热温度曲线

Figure 13. Heat absorption and exothermic temperature curve of KBC/n-Eicosane composite phase change materials under current condition

下载: 全尺寸图片幻灯片

表 1 不同活化条件下制备的生物炭表面积及孔结构比较

Table 1. Specific surface area and porosity parameters of biochar at different activated conditions

	BC	KBC (1∶3)	KBC (1∶4)	KBC (1∶5)
Brunauer-Emmett-Teller surface /(m²·g⁻¹)	3.64	1532.40	1663.33	2354.55
Total volume in pores/ (cm³·g⁻¹)	0.004	0.83	0.85	1.22
Density function theory pore size /nm	2.12	29.61	32.43	38.73

下载: 导出CSV

表 2 n-Eicosane和KBC/n-Eicosane复合相变材料的DSC数据

Table 2. DSC data of n-Eicosane and KBC/n-Eicosane composite phase change materials

Mass ratio	Melting point/℃	Melting enthalpy/(J·g ⁻¹ )	Crystallization point/℃	Crystallization enthalpy/(J·g⁻¹ )
Pure n-Eicosane	40.0	256.1	31.2	−251.5
1∶0.5	38.2	84.5	33.6	−68.5
1∶1	39.1	90.15	33.2	−86.79
1∶1.5	38.8	99.87	33.7	−96.86
1∶2	39.1	121.3	30.6	−117.6

下载: 导出CSV

参考文献(32)

[1]	TAN B, HUANG Z H, YIN Z Y, et al. Preparation and thermal properties of shape stabilized composite phase change materials based on polyethylene glycol and porous carbon prepared from potato[J]. RSC Advances,2016,6(19):15821-15830. doi: 10.1039/C5RA25685B
[2]	NIU L B, BAI G Y, SONG J. 1,3∶2,4-di-(3,4-dimethyl)benzylidene sorbitol organogels used as phase change materials: Solvent effects on structure, leakage and thermal performance[J]. RSC Advances,2015,5(28):21733-21739. doi: 10.1039/C4RA15420G
[3]	郭静, 张渤, 牟思阳, 等. 二元脂肪酸/生物基SiO₂ 复合相变材料的制备与性能测试[J]. 复合材料学报, 2016, 33(11):2674-2681. GUO Jing, ZHANG Bo, MU Siyang, et al. Preparation and properties of binary fatty acids/bio-based SiO₂ phase change composites[J]. Acta Material Compositae Sinica,2016,33(11):2674-2681(in Chinese).
[4]	赵亮, 邢玉明, 芮州峰, 等. 空气浴条件下三水醋酸钠相变材料的储热性能实验[J]. 复合材料学报, 2018, 35(8):2208-2215. ZHAO Liang, XING Yuming, RUI Zhoufeng, et al. Experimental study on the thermal energy storage characteristic of sodium acetate trihydrate as phase change material under the air bath condition[J]. Acta Materiae Compositae Sinica,2018,35(8):2208-2215(in Chinese).
[5]	苑坤杰, 张正国, 方晓明, 等. 水合无机盐及其复合相变储热材料的研究进展[J]. 化工进展, 2016, 35(6):1820-1826. YUAN Kunjie, ZHANG Zhengguo, FANG Xiaoming, et al. Research progress of inorganic hydrated salts and their phase change heat storage composites[J]. Chemical Industry and Engineering Progress,2016,35(6):1820-1826(in Chinese).
[6]	汪翔, 陈海生, 徐玉杰, 等. 储热技术研究进展与趋势[J]. 科学通报, 2017, 62(15):1602-1610. doi: 10.1360/N972016-00663 WANG Xiang, CHEN Haisheng, XU Yujie, et al. Advances and prospects in thermal energy storage[J]. Chinese Science Bulletin,2017,62(15):1602-1610(in Chinese). doi: 10.1360/N972016-00663
[7]	桑国臣, 曹艳洲, 樊敏, 等. 硫铝酸盐水泥基复合相变储能砂浆的制备及其性能[J]. 复合材料学报, 2018, 35(8):2124-2131. SANG Guochen, CAO Yanzhou, FAN Min, et al. Preparation and properties of sulphoaluminate cement-based composite phase change storage mortar[J]. Acta Materiae Compositae Sinica,2018,35(8):2124-2131(in Chinese).
[8]	SARI A. Fabrication and thermal characterization of kaolin-based composite phase change materials for latent heat storage in buildings[J]. Energy and Buildings,2015,96:193-200. doi: 10.1016/j.enbuild.2015.03.022
[9]	孟多, 赵康, 王东旭. 二元脂肪酸/硅藻土助滤剂定形相变复合材料的制备及性能[J]. 复合材料学报, 2018, 35(9):2558-2565. MENG Duo, ZHAO Kang, WANG Dongxu. Preparation and properties of binary fatty acid mixture/diatomite filter aid form-stable phase change composite[J]. Acta Materiae Compositae Sinica,2018,35(9):2558-2565(in Chinese).
[10]	ATINAFU D G, DONG W J, WANG J J, et al. Synthesis and characterization of paraffin/metal organic gel derived porous carbon/boron nitride composite phase change materials for thermal energy storage[J]. European Journal of Inorganic Chemistry,2018,2018(48):5167-5175. doi: 10.1002/ejic.201800811
[11]	方桂花, 刘殿贺, 张伟, 等. 复合类相变蓄热材料的研究进展[J]. 化工新型材料, 2021, 49(6):6-10. FANF Guihua, LIU Dianhe, ZHANG Wei, et al. Recent advance on composite phase change thermal storage material[J]. New Chemical Materials,2021,49(6):6-10(in Chinese).
[12]	吴丽梅, 刘庆欣, 王晓龙, 等. 相变储能材料研究进展[J]. 材料导报, 2021, 35(Z1):501-506. WU Limei, LIU Qingxin, WANG Xiaolong, et al. Review on phase change energy storage materials[J]. Materials Reports,2021,35(Z1):501-506(in Chinese).
[13]	周四丽, 张正国, 方晓明. 固-固相变储热材料的研究进展[J]. 化工进展, 2021, 40(3):1371-1383. ZHOU Sili, ZHANG Zhengguo, FANG Xiaoming. Research progress of solid-solid phase change materials for thermal energy storage[J]. Chemical Industry and Engineering Progress,2021,40(3):1371-1383(in Chinese).
[14]	张向倩. 相变储能材料的研究进展与应用[J]. 现代化工, 2019, 39(4): 67-70. ZHANG Xiangqian, Research progress and applications of phase change materials for energy storage[J]. Modern Chemical Industry, 2019, 39(4): 67-70(in Chinese).
[15]	王崇云, 王维, 冯利利, 等. 正二十烷与膨胀石墨共改性三水合醋酸钠相变材料储热性能[J]. 复合材料学报, 2014, 31(3):824-829. WANG Chongyun, WANG Wei, FENG Lili, et al. Phase change property of sodium acetate trihydrate modified with n-eicosane and expanded graphite[J]. Acta Materiae Compositae Sinica,2014,31(3):824-829(in Chinese).
[16]	李军, 陈人杰, 谢德龙, 等. 还原氧化石墨烯气凝胶/二十烷相变材料的制备及性能[J]. 精细化工, 2021, 38(5): 947-953. LI Jun, CHEN Renjie, XIE Delong, et al. Preparation and properties of reduced graphene oxide aerogel/eicosane phase change materials[J]. 2021, 38(5): 947-953(in Chinese).
[17]	FEI H, DU W Q, HE Q, et al. Study of phase-transition characteristics of new composite phase change materials of capric acid-palmitic acid/expanded graphite[J]. ACS Omega,2020,5(42):27522-27529. doi: 10.1021/acsomega.0c03665
[18]	TANG Y J, LIN Y X, JIA Y T, et al. Improved thermal properties of stearyl alcohol/high density polyethylene/expanded graphite composite phase change materials for building thermal energy storage[J]. Energy and Buildings,2017,153:41-49. doi: 10.1016/j.enbuild.2017.08.005
[19]	胡立鹃, 吴峰, 彭善枝, 等. 生物质活性炭的制备及应用进展[J]. 化学通报, 2016, 79(3): 205-212. HU Lijuan, WU Feng, PENG Shanzhi, et al. Progress in preparation and utilization of biomass-based activated carbons[J]. Chemistry, 2016, 79(3): 205-212(in Chinese).
[20]	GOLDFARB J L, DOU G, SALARI M, et al. Biomass-based fuels and activated carbon electrode materials: An integrated approach to green energy systems[J]. ACS Sustainable Chemistry & Engineering,2017,5(4):3046-3054. doi: 10.1021/acssuschemeng.6b02735
[21]	计海洋, 汪玉瑛, 刘玉学, 等. 生物炭及改性生物炭的制备与应用研究进展[J]. 核农学报, 2018, 32(11):2281-2287. doi: 10.11869/j.issn.100-8551.2018.11.2281 JI Haiyang, WANG Yuying, LIU Yuxue, et al. Advance in preparation and application of biochar and modified biochar[J]. Journal of Nuclear Agricultural Sciences,2018,32(11):2281-2287(in Chinese). doi: 10.11869/j.issn.100-8551.2018.11.2281
[22]	孙建财, 周丹丹, 王薇, 等. 生物炭改性及其对污染物吸附与降解行为的研究进展[J]. 环境化学, 2021, 40(5):1503-1513. doi: 10.7524/j.issn.0254-6108.2020102106 SUN Jiancai, ZHOU Dandan, WANG Wei, et al. Research progress on modification of biochar and its adsorption and degradation behavior[J]. Environmental Chemistry,2021,40(5):1503-1513(in Chinese). doi: 10.7524/j.issn.0254-6108.2020102106
[23]	禹兴海, 罗齐良, 潘剑, 等. 一种生物炭基柔性固态超级电容器的制备及性能研究[J]. 化工学报, 2019, 70(9):3590-3600. YU Xinghai, LUO Qiliang, PAN Jian, et al. Preparation and properties of flexible supercapacitor based on biochar and solid gelelectrolyte[J]. CIESC Journal,2019,70(9):3590-3600(in Chinese).
[24]	XIANG Y Z, DENG Q, DUAN H L, et al. Effects of biochar application on root traits: A meta-analysis[J]. GCB Bioenergy,2017,9(10):1563-1572. doi: 10.1111/gcbb.12449
[25]	欧阳金波, 陈建, 刘峙嵘, 等. 生物质源多孔碳制备及其对废水中药物吸附研究进展[J]. 化工学报, 2020, 71(12):5420-5429. OUYANG Jinbo, CHEN Jian, LIU Zhirong, et al. Research progress on preparation of biomass-derived porous carbon and its adsorption of pharmaceuticals in wastewater[J]. CIESC Journal,2020,71(12):5420-5429(in Chinese).
[26]	张隐, 黄慧玲, 魏留洋, 等. 生物质炭/ZnO复合材料的制备及其吸附-光催化性能[J]. 复合材料学报, 2019, 36(9):2187-2195. ZHANG Yin, HUANG Huiling, WEI Liuyang, et al. Preparation and adsorption-photocatalysis properties of biochar/ZnO composites[J]. Acta Materiae Compositae Sinica,2019,36(9):2187-2195(in Chinese).
[27]	丛宏斌, 赵立欣, 姚宗路, 等. 中国农作物秸秆资源分布及其产业体系与利用路径[J]. 农业工程学报, 2019, 35(22): 132-140. CONG Hongbin, ZHAO Lixin, YAO Zonglu, et al. Distribution of crop straw resources and its industrial system and utilization path in China[J]. Transactions of the CSAE, 2019, 35(22): 132-140 (in Chinese).
[28]	魏忠平, 朱永乐, 赵楚峒, 等. 生物炭吸附重金属机理及其应用技术研究进展[J]. 土壤通报, 2020, 51(3):741-747. WEI Zhongping, ZHU Yongle, ZHAO Chutong, et al. Research advances on biochar adsorption mechanism for heavy metals and its application technology[J]. Chinese Journal of Soil Science,2020,51(3):741-747(in Chinese).
[29]	武爱莲, 丁玉川, 焦晓燕, 等. 玉米秸秆生物炭对褐土微生物功能多样性及细菌群落的影响[J]. 中国生态农业学报, 2016, 24(6):736-743. WU Ailian, DING Yuchuan, JIAO Xiaoyan, et al. Effect of corn-stalk biochar on soil microbial functional diversity and bacterial community in cinnamon soils[J]. Chinese Journal of Eco-Agriculture,2016,24(6):736-743(in Chinese).
[30]	毛俏婷, 胡俊豪, 姚丁丁, 等. 生物炭催化生物质热化学转化利用的研究进展[J]. 化工进展, 2020, 39(4):1302-1307. MAO Qiaoting, HU Junhao, YAO Dingding, et al. Biochar for thermo-chemical conversion of biomass: A review[J]. Chemical Industry and Engineering Progress,2020,39(4):1302-1307(in Chinese).
[31]	CHEN L J, ZOU R Q, XIA W, et al. Electro- and photodriven phase change composites based on wax-infiltrated carbon nanotube sponges[J]. ACS Nano,2012,6(12):10884-10892. doi: 10.1021/nn304310n
[32]	梁善庆, 李思程, 王慧翀, 等. 石墨导热膜对电热实木复合地板基材传热性能的影响[J]. 东北林业大学学报, 2019, 47(8):67-81. LIANG Shanqing, LI Sicheng, WANG Huichong, et al. Effect of thermal conductive graphite film on heat transfer performance of electrothermal parquet flooring substrate[J]. Journal of Northeast Forestry University,2019,47(8):67-81(in Chinese).