冻融循环对膨胀石墨-硼掺杂碳纳米管/水泥复合材料热电性能的影响

王涛涛; 魏剑; 惠嘉伟; 郭宇鹏; 张思卿; 张妍彬; 乔薪余

doi:10.13801/j.cnki.fhclxb.20230616.001

冻融循环对膨胀石墨-硼掺杂碳纳米管/水泥复合材料热电性能的影响

doi: 10.13801/j.cnki.fhclxb.20230616.001

西安建筑科技大学　材料科学与工程学院，西安 710055

基金项目: 国家自然科学基金面上项目(51578448；52272089)；陕西省杰出青年科学基金(2021JC-43)；陕西省自然科学基础研究计划-重大基础研究项目(2017ZDJC-18)；陕西省教育厅协同创新项目(20JY042)

详细信息

通讯作者:
魏剑，博士，教授，博士生导师，研究方向为热电水泥基复合材料　E-mail: weijian@xauat.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2023-04-24
- 修回日期: 2023-06-05
- 录用日期: 2023-06-07
- 网络出版日期: 2023-06-16
- 刊出日期: 2024-02-01

Effect of freeze-thaw cycles on thermoelectric properties of expanded graphite-boron-doped carbon nanotubes/cement composites

College of Materials Science and Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, China

Funds: National Natural Science Foundation of China (51578448; 52272089); Shaanxi Provincial Outstanding Youth Science Foundation (2021JC-43); Shaanxi Provincial Natural Science Basic Research Program-Major Basic Research Project (2017ZDJC-18); Shaanxi Provincial Department of Education Collaborative Innovation Project (20JY042)

摘要

摘要: 利用温差发电的热电水泥基复合材料可以实现热能与电能的相互转换来降低城市环境温度和资源消耗，但热电转换效率过低及易受环境影响等问题制约了它的大规模应用。针对这个问题，本文提出了在高Seebeck系数的硼掺杂碳纳米管(Boron-doped carbon nanotubes，B-CNTs)基础上，添加高导电的膨胀石墨(Expanded graphite，EG)，通过B-CNTs和EG多尺度混杂协同作用，整体提高水泥基复合材料的功率因数，相比于未添加膨胀石墨的水泥基复合材料功率因数提升了10倍，为1.49 μW·m⁻¹·℃⁻²。冻融循环后的EG-B-CNTs/水泥复合材料导致孔隙率增加和水分的存在，引入了固-固、液-固等高密度缺陷界面，使载流子散射强度增加，出现水泥基复合材料冻融循环Seebeck系数强化现象。当冻融循环15次时，10.0wt%EG-5.0wt%B-CNTs/水泥复合材料功率因数为1.54 μW·m⁻¹·℃⁻²。本文研究为改善热电水泥基复合材料性能及环境条件对于未来可行性应用提供了理论基础。
- 硼掺杂碳纳米管 /
- 膨胀石墨 /
- 冻融循环 /
- 水泥基复合材料 /
- 热电性能
Abstract: Thermoelectric cementitious composites using temperature difference power generation can realize the mutual conversion of thermal and electrical energy to reduce urban environmental temperature and resource consumption, but the low efficiency of thermoelectric conversion and vulnerability to environmental impact have restricted its large-scale application. To address this issue, this study proposes the addition of highly conductive expanded graphite (EG) to boron-doped carbon nanotubes (B-CNTs) with high Seebeck coefficients to improve the overall power factor of cementitious composites by the synergistic effect of multi-scale hybridization of B-CNTs and EG. The power factor of the cementitious composites was improved by 10 times to 1.49 μW·m⁻¹·℃⁻² compared with that of the cementitious composites without the addition of expanded graphite. The EG-B-CNTs/cement composites after freeze-thaw cycling result in increased porosity and the presence of moisture, which introduce high-density defect interfaces such as solid-solid and liquid-solid, resulting in an increase in carrier scattering intensity and an enhanced Seebeck coefficient for freeze-thaw cycling of cement matrix composites. The power factor of 10.0wt%EG-5.0wt%B-CNTs/cement composite is 1.54 μW·m⁻¹·℃⁻² when freeze-thaw cycles are performed 15 times. The research in this paper provides a theoretical basis for improving the performance and environmental conditions of thermoelectric cement matrix composites for future viable applications.
- boron-doped carbon nanotubes /
- expanded graphite /
- freeze-thaw cycles /
- cement-based composites /
- thermoelectric properties

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图 1 水泥基复合材料制备工艺示意图

Figure 1. Schematic diagram of the preparation process of cement-based composites

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图 2 冻融循环过程示意图

Figure 2. Freeze-thaw cycle experiment process diagram

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图 3 水泥基复合材料热电测试装置示意图^[20]

V—Potential at both ends of the cement sample

Figure 3. Schematic diagram of thermoelectric testing device for cement-based composite materials^[20]

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图 4 不同EG含量的EG-5.0wt%B-CNTs/水泥复合材料的SEM图像：(a) 0.0wt%；(b) 5.0wt%；(c) 7.0wt%；(d) 10.0wt%

Figure 4. SEM images of EG-5.0wt%B-CNTs/cement composites with different EG contents: (a) 0.0wt%; (b) 5.0wt%; (c) 7.0wt%; (d) 10.0wt%

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图 5 不同EG含量的EG-5.0wt%B-CNTs/水泥复合材料的抗压强度(a)和孔隙率(b)

Figure 5. Compressive strength (a) and porosity (b) of EG-5.0wt%B-CNTs/cement composites as a function of different EG content

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图 6 不同EG含量的EG-5.0wt%B-CNTs/水泥复合材料的Seebeck系数随温度变化关系

Figure 6. Variation of Seebeck coefficient with temperature for EG-5.0wt%B-CNTs/cement composites with different EG contents

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图 7 不同EG含量的EG-5.0wt%B-CNTs/水泥复合材料电导率随温度变化关系

Figure 7. Temperature dependence of electrical conductivity of EG-5.0wt%B-CNTs/cement composites with different EG contents

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图 8 不同EG含量的EG-5.0wt%B-CNTs/水泥复合材料的功率因数随温度变化关系

Figure 8. Relationship between power factor and temperature of EG-5.0wt%B-CNTs/cement composites with different EG contents

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图 9 不同冻融循环次数的10.0wt%EG-5.0wt%B-CNTs/水泥复合材料的SEM图像：(a) 0次；(b) 5次；(c) 15次；(d) 25次；(e) 35次

Figure 9. SEM images of 10.0wt%EG-5.0wt%B-CNTs/cement composites with different numbers of freeze-thaw cycle: (a) 0 times; (b) 5 times; (c) 15 times; (d) 25 times; (e) 35 times

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图 10 不同冻融循环次数的10.0wt%EG-5.0wt%B-CNTs/水泥复合材料进行抗压强度测试的破碎形态：(a) 0次；(b) 5次；(c) 15次；(d) 25次；(e) 35次

Figure 10. Crushing morphology of 10.0wt%EG-5.0wt%B-CNTs/cement composites with different numbers of freeze-thaw cycles for compressive strength testing: (a) 0 times; (b) 5 times; (c) 15 times; (d) 25 times; (e) 35 times

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图 11 10.0wt%EG-5.0wt%B-CNTs/水泥复合材料的抗压强度(a)和孔隙率(b)与冻融循环次数的关系

Figure 11. Relationship between the compressive strength (a) and porosity (b) of 10.0wt%EG-5.0wt%B-CNTs/cement composites with the number of freeze-thaw cycles

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图 12 水泥基复合材料冻融循环过程示意图

Figure 12. Schematic diagram of the freeze-thaw cycle process of cement matrix composites

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图 13 10.0wt%EG-5.0wt%B-CNTs/水泥复合材料的热电性能与冻融循环的关系：(a) Seebeck系数；(b) 电导率；(c) 功率因数；(d) 最佳优值(Z_T)

Figure 13. Relationship between thermoelectric properties of 10.0wt%EG-5.0wt%B-CNTs/cement composites and freeze-thaw cycles: (a) Seebeck coefficient; (b) Conductivity; (c) Power factor; (d) Optimum value (Z_T)

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图 14 冻融循环15次的10.0wt%EG-5.0wt%B-CNTs/水泥复合材料单位面积内的输出功率和热电转换效率与高温端温度的变化关系

Figure 14. Variation of output power and thermoelectric conversion efficiency per square meter versus high temperature end temperature for 10.0wt%EG-5.0wt%B-CNTs/cement composites with 15 freeze-thaw cycles

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图 15 10.0wt%EG-5.0wt%B-CNTs/水泥复合材料在冻融循环中的孔隙变形行为

Figure 15. Pore deformation behavior of 10.0wt%EG-5.0wt%B-CNTs/cement composites during freeze-thaw cycles

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表 1 膨胀石墨(EG)-硼掺杂碳纳米管(B-CNTs)/水泥复合材料的材料组成

Table 1. Material composition of expanded graphite (EG)-boron-doped carbon nanotube (B-CNTs)/cement composites

Sample	EG content/g	B-CNTs content/g	Cement content/g
5.0wt%B-CNTs/cement	0.0	1.0 (5.0wt%)	20.0
5.0wt%EG/cement	1.0 (5.0wt%)	0.0	20.0
5.0wt%EG-5.0wt%B-CNTs/cement	1.0 (5.0wt%)	1.0 (5.0wt%)	20.0
7.0wt%EG-5.0wt%B-CNTs/cement	1.4 (7.0wt%)	1.0 (5.0wt%)	20.0
10.0wt%EG-5.0wt%B-CNTs/cement	2.0 (10.0wt%)	1.0 (5.0wt%)	20.0

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表 2 水泥试样冻融循环前浸泡不同时间的质量变化

Table 2. Changes in mass of cement specimens immersed for different time before freeze-thaw cycles

Sample	Changes in mass of cement specimens/g
Sample	0 h	8 h	16 h	24 h	32 h	40 h	48 h
1	7.766	8.636	8.639	8.640	8.639	8.640	8.640
2	7.712	8.897	8.899	8.899	8.890	8.892	8.891
3	7.896	9.140	9.141	9.141	9.142	9.144	9.145
4	7.643	8.731	8.734	8.736	8.738	8.737	8.738
Note: Samples 1, 2, 3, 4 represent 5, 15, 25, 35 freeze-thaw cycles, respectively.

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