水泥基复合材料热电效应综述：机制、材料、影响因素及应用

崔一纬; 魏亚

doi:10.13801/j.cnki.fhclxb.20200423.002

水泥基复合材料热电效应综述：机制、材料、影响因素及应用

doi: 10.13801/j.cnki.fhclxb.20200423.002

崔一纬,
魏亚^,

清华大学　土木工程系　土木工程安全与耐久教育部重点实验室，北京 100084

基金项目: 国家重点研发计划(2018YFB1600200)

详细信息

通讯作者:
魏亚，博士，副教授，博士生导师，研究方向为水泥基材料变形力学性能多尺度模拟表征、长寿命道路材料与结构、结构新材料研发　E-mail：yawei@tsinghua.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2020-03-23
- 录用日期: 2020-04-19
- 网络出版日期: 2020-04-24
- 刊出日期: 2020-09-15

A review of thermoelectric effect of cement-based composites: Mechanism, material, factor and application

CUI Yiwei,
WEI Ya^,

Key Laboratory of Civil Engineering Safety and Durability of China Education Ministry, Department of Civil Engineering, Tsinghua University, Beijing 100084, China

摘要

摘要: 在水泥基复合材料中掺入功能填料会使其获得将热能转化为电能的热电效应，可用于环境热量转换收集、混凝土结构健康检测传感器和智慧交通系统等方面。本文总结了热电水泥基复合材料(TECC)的热电效应机制、常用的功能填料、制备过程及主要工程应用，重点分析了不同功能填料对TECC热电效应的增强效果和机制，及材料分散程度、水分、疲劳荷载、温度循环等因素对TECC热电效应的影响机制。本综述指明了TECC在理论和应用方面的研究新方向，对今后水泥基复合材料热电效应的实验设计和性能提升具有指导作用。
- 热电效应 /
- 水泥基复合材料 /
- 热电性能 /
- 功能填料 /
- Seebeck系数
Abstract: Incorporating functional fillers into the cement-based material can enable them to obtain the thermoelectric effect of converting thermal energy into electrical energy, which can be used in energy harvesting, concrete structure health monitoring and intelligent transportation system. This paper summarizes the thermoelectric effect mechanism, functional fillers, fabrication process and engineering application of thermoelectric cement-based composites (TECC). Particularly, this paper mainly focuses on the enhancement effect and mechanism of different functional fillers on the thermoelectric effect of TECC, as well as the effect of dispersion degree of functional filler, moisture, fatigue load, temperature cycle and other factors on the thermoelectric effect of TECC. This review points out the new research direction of TECC in theory and application, which will guide the experimental design and performance improvement of the thermoelectric effect of cement-based composites.
- thermoelectric effect /
- cement-based composite /
- thermoelectric properties /
- functional filler /
- Seebeck coefficient

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图 1 热电水泥基复合材料(TECC)电阻率随功能填料含量变化示意图

Figure 1. Scheme of resistivity variation of thermoelectric cement-based composites (TECC) with content of functional filler

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图 2 温差作用下热端到冷端的载流子流动示意图

Figure 2. Schematic representation of carrier flow from hot side to cold side under temperature difference((a) Electrons flow from hot side to cold side; (b) Holes flow from hot side to cold side)

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图 3 热电优值Z_T与载流子浓度的关系^[14-15]

Figure 3. Relationship between thermoelectric figure of merit Z_T and carrier concentration^[14-15]

S—Seebeck coefficient; P_F—Power factor; k—Thermal conductivity; σ—Electrical conductivity

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图 4 TECC的发展历史

Figure 4. History of TECC

CF—Carbon fiber; CNTs—Carbon nanotubes; CFRC—Carbon fiber reinforced cement-based composite

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图 5 掺入不同长度碳纤维的水泥砂浆在加热和冷却过程中电压随温差的变化^[20]

Figure 5. Variation of Seebeck voltage vs temperature difference during heating and cooling of cement mortars containing carbon fiber with different lengths^[20]

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图 6 碳纤维含量与TECC的电导率及Seebeck系数的关系^[16]

Figure 6. Relationship between content of carbon fiber vs. conductivity and Seebeck coefficient of TECC^[16]

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图 7 单层石墨烯(a)、单壁碳纳米管(b)和多壁碳纳米管(c)的结构^[46]

Figure 7. Structures of single-layer graphene(a), single wall carbon nanotubes(b) and multiwall carbon nanotubes(c)^[46]

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图 8 加入不同含量碳纳米管的碳纤维增强水泥基复合材料(CFRC)的Seebeck系数和电阻率^[36]

Figure 8. Seebeck coefficient and resistivity of carbon fiber reinforced cement-based composites(CFRC) with variable carbon nanotubes contents^[36]

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图 9 不同碳纳米管掺量的碳纳米管增强水泥基复合材料的Seebeck系数、电导率(插图是掺量为15.0wt%碳纳米管的复合材料放大图)、热导率及热电优值^[37]

Figure 9. Seebeck coefficient, electrical conductivity (Insert is a magnified image of the composite with 15.0wt% carbon nanotubes), thermal conductivity and thermoelectric figure of merit of carbon nanotubes reinforced cement-based composites with variable carbon nanotubes addition^[37]

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图 10 不同钢纤维体积分数的水泥基复合材料的绝对热电动势率^[13]

Figure 10. Absolute thermoelectric power of cement-based composites with various volume fractions of steel fiber^[13]

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图 11 TECC的制造工艺

Figure 11. Fabrication process of TECC

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图 12 p型碳纳米管增强水泥基和n型碳纳米管增强水泥基复合材料在干燥前后的电导率和Seebeck系数^[1]

Figure 12. Electrical conductivity and Seebeck coefficient of p-type carbon nanotubes reinforced cement-based and n-type carbon nanotubes reinforced cement-based composites measured before and after drying^[1]

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图 13 疲劳载荷为1.5 kN时不同疲劳次数下膨胀石墨-碳纤维增强水泥基复合材料电导率和Seebeck系数随温度的变化曲线^[67]

Figure 13. Variation of conductivity and Seebeck coefficient of expanded graphite-carbon fiber reinforced cement-based composite with temperature under different fatigue times at fatigue load of 1.5 kN^[67]

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图 14 建筑物隔墙内砂浆电压和温度梯度的变化^[8]

Figure 14. Change of voltage of mortar and temperature gradient in building partition^[8]

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图 15 p型与n型TECC组成的热电发电机结构模型及多个p/n型TECC组成的热电模型

Figure 15. Cement-based thermoelectric generator module consisting of a p-type and n-type TECC and thermoelectric module containing many p/n-type TECCs

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表 1 TECC中功能填料总结

Table 1. Summary of functional fillers for TECC

Classification		Typical conductive phase material
Criteria	Category	Typical conductive phase material
Material component	Carbonaceous material	CF, CNTs, graphene, graphite, EG
	Metal or metal oxide	SF, ZnO, Fe₂O₃, Bi₂Te₃, Ca₃Co₄O₈, Bi₂O₃, MnO₂
	Others	SS, MSFA
Filler scale	Macroscale	SS, MSFA, SF
	Microscale	CF, graphite, Fe₂O₃, Ca₃Co₄O₈, Bi₂O₃
	Nanoscale	CNT, graphene, nano MnO₂, nano ZnO, nano Fe₂O₃, EG
Dimension	2D	Graphene
	1D	CNT
	0D	Nano MnO₂, nano ZnO, nano Fe₂O₃
p/n type	p-type	CF, CNTs, graphene, ZnO, Fe₂O₃, Bi₂Te₃, Ca₃Co₄O₈, Bi₂O₃, SS, MSFA
p/n type	n-type	SF, Graphite, EG, MnO₂
Notes: MSFA—Magnetically separated fly ash; SF—Steel fiber; SS—Steel slag; EG—Expanded graphite.

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表 2 已有文献中水泥基复合材料热电性能总结

Table 2. Summary of thermoelectric properties of cement-based composites in the existing literatures

Matrix	Functional filler	Thermoelectric property					Type	Year	Ref.
Matrix	Functional filler	σ/(S·m^–1)	S/(μV·℃^–1)	k/(W(m·K)^–1)	P_F/(μW·m^–1·K^–2)	Z_T	Type	Year	Ref.
Cement paste	—	—	–2	—	—	—	n	1999	[18]
Cement paste	0.5wt% CF	—	12	—	—	—	p	1999	[19]
Cement paste	1.0wt% CF	0.2	19.73	0.22	—	1.334×10^–7(27℃)	p	2014	[21]
Concrete	0.5wt% CF	—	125.1	—	—	—	p	2008	[22]
Cement paste	0.5wt% Bromine-intercalated CF	—	14.93	—	—	—	p	2000	[23]
Mortar	50vol% MSFA+0.4vol% CF	3.3	2 637.16	—	—	—	p	2017	[7]
Cement paste	200wt% SS+0.4wt% CF	0.17	12.4	—	—	—	p	2013	[24]
Concrete	300wt% SS	—	48	—	—	—	p	2008	[25]
Cement paste	0.2vol% SF	0.313×10^–2	–68	—	—	—	n	2004	[13]
Cement paste	0.3wt% Ca₃Co₄O₈+CF	—	58.6	—	—	—	p	2013	[26]
Cement paste	5.0wt% Fe₂O₃+CF	—	90.23	—	—	—	p	2014	[27]
	5.0wt% Bi₂O₃+ CF	—	97.94	—	—	—	p
Cement paste	1.0wt% Bi₂Te₃+0.4wt% CF	0.16	21.4	—	—	—	p	2014	[28]
Cement paste	5.0wt% Nano α-Fe₂O₃	1.7×10^–6	2 500	—	—	—	p	2016	[29]
	5.0wt% Nano ZnO	0.2×10^–6	3 300	—	—	—	p
Cement paste	5.0wt% Fe₂O₃+1.0wt% CF	~0.5×10^–4	2 750	0.22	2.08(55.5℃)	3.11×10^–3(55.5℃)	p	2016	[14]
Cement paste	5.0wt% Nano MnO₂	1.88×10^–4	–3 085	0.72	—	7.60×10^–7(34.5℃)	n	2018	[30]
Cement paste	3.56wt% Al doped ZnO	25×10^–3	0.187	—	—	—	p	2017	[31]
Cement paste	5.0wt% nano NiO	6.76×10^–3	4 050	—	—	—	P	2019	[32]
Cement paste	20wt% Graphite+1.2wt% CF	—	17.29	—	—	—	p	2011	[33]
	30wt% Graphite+0.6wt% CF	—	–52.23	—	—	—	n
Concrete	5.0wt% Graphite	—	2 270	—	—	—	p	2008	[34]
Cement paste	5.0wt% EG+1.2wt% CF	0.78	–11.59	—	7.85×10^–4(33℃)	—	n	2017	[35]
Cement paste	15wt% EG	24.8	~–51	3.213	6.38(79℃)	6.82×10^–4(75℃)	n	2018	[2]
Cement paste	1.0wt% CNTs+0.4wt% CF	0.0014	22.6	—	—	—	p	2013	[36]
Cement paste	15wt% CNTs	0.8	57.98	0.818	0.25(75℃)	9.33×10^–5(75℃)	p	2018	[37]
Cement paste	1.0wt% p-CNTs	0.69	20	—	2.2×10^–4	—	p	2019	[1]
	1.0wt% n-CNTs	2.19	–58	—	0.007	—	n
Cement paste	15.0wt% Graphene	1 620	34	1.327	—	0.44×10^–3(70℃)	p	2019	[38]

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水泥基复合材料热电效应综述：机制、材料、影响因素及应用

doi: 10.13801/j.cnki.fhclxb.20200423.002

通讯作者:
魏亚，博士，副教授，博士生导师，研究方向为水泥基材料变形力学性能多尺度模拟表征、长寿命道路材料与结构、结构新材料研发　E-mail：yawei@tsinghua.edu.cn

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A review of thermoelectric effect of cement-based composites: Mechanism, material, factor and application

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水泥基复合材料热电效应综述：机制、材料、影响因素及应用

doi: 10.13801/j.cnki.fhclxb.20200423.002

通讯作者: 魏亚，博士，副教授，博士生导师，研究方向为水泥基材料变形力学性能多尺度模拟表征、长寿命道路材料与结构、结构新材料研发 E-mail：yawei@tsinghua.edu.cn

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A review of thermoelectric effect of cement-based composites: Mechanism, material, factor and application

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通讯作者:
魏亚，博士，副教授，博士生导师，研究方向为水泥基材料变形力学性能多尺度模拟表征、长寿命道路材料与结构、结构新材料研发　E-mail：yawei@tsinghua.edu.cn