不同维度Ag2Se构筑柔性热电薄膜的性能优化与器件集成研究

doi:10.15541/jim20240129

无机材料学报 ›› 2024, Vol. 39 ›› Issue (11): 1221-1227.DOI: 10.15541/jim20240129 CSTR: 32189.14.10.15541/jim20240129

所属专题：【能源环境】热电材料(202409)

不同维度Ag₂Se构筑柔性热电薄膜的性能优化与器件集成研究

张哲¹(), 孙婷婷¹, 王连军¹^,²(), 江莞¹^,²^,³

1.材料科学与工程学院, 纤维材料改性国家重点实验室东华大学上海 201620
2.先进玻璃制造技术教育部工程研究中心东华大学上海 201620
3.功能材料研究中心, 东华大学上海 201620

收稿日期:2024-03-18 修回日期:2024-05-12 出版日期:2024-11-20 网络出版日期:2024-06-24
通讯作者: 王连军, 教授. E-mail: wanglj@dhu.edu.cn
作者简介:张哲(1999-), 女, 硕士研究生. E-mail: 239156115@qq.com
基金资助:
国家自然科学基金(U23A20685);上海市教委科研创新项目(2021-01-07-00-03-E00110)

Flexible Thermoelectric Films with Different Ag₂Se Dimensions: Performance Optimization and Device Integration

ZHANG Zhe¹(), SUN Tingting¹, WANG Lianjun¹^,²(), JIANG Wan¹^,²^,³

1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
2. Engineering Research Center of Advanced Glass Manufacturing Technology, Ministry of Education, Donghua University, Shanghai 201620, China
3. Institute of Functional Materials, Donghua University, Shanghai 201620, China

Received:2024-03-18 Revised:2024-05-12 Published:2024-11-20 Online:2024-06-24
Contact: WANG Lianjun, professor. E-mail: wanglj@dhu.edu.cn
About author:ZHANG Zhe (1999-), female, Master candidate. E-mail: 239156115@qq.com
Supported by:
National Natural Science Foundation of China(U23A20685);Innovation Program of Shanghai Municipal Education Commission(2021-01-07-00-03-E00110)

摘要/Abstract

摘要：

Ag₂Se热电薄膜及器件因其窄带隙半导体特性在室温下显示出良好的热电性能, 成为近年来可穿戴热电能源转换领域的研究热点。常见的Ag₂Se薄膜多由纳米颗粒堆积构筑而成, 纳米材料维度对堆积网络的热电传输特性具有重要影响。本研究采用溶剂热法和模板法分别制备了不同维度的Ag₂Se纳米材料, 通过喷涂工艺结合高温热处理, 在聚酰亚胺基底上构筑了柔性Ag₂Se热电薄膜, 系统研究了Ag₂Se纳米材料维度对薄膜微观结构和热电性能的影响。与一维纳米线结构相比, 零维Ag₂Se纳米颗粒构筑的热电薄膜具有更优的导电网络和热电性能, 薄膜的室温功率因子可达199.6 μW·m^-1·K^-2, 而在375 K时功率因子为257.9 μW·m^-1·K^-2, 表现出良好的热电性能。基于性能优异的Ag₂Se薄膜, 进一步设计集成了具有四条热电臂的柔性热电器件。该器件具有良好的机械柔性和输出性能, 以20 mm为弯曲半径, 在弯曲循环1000次后, 内阻仅增加了8.2%; 在30 K的温差下, 器件开路电压可达9.1 mV, 最大输出功率达43.7 nW。本研究为制备柔性Ag₂Se热电薄膜材料与器件提供了新的思路和方向。

关键词: Ag₂Se热电材料, 材料维度, 柔性热电薄膜, 热电器件

Abstract:

Ag₂Se-based thermoelectric films and devices have become a popular research topic in the field of wearable thermoelectric energy conversion due to their narrow bandgap semiconductor properties, which exhibit good thermoelectric properties at room temperature. These films are typically constructed by stacking nanoparticles, and the dimensions of nanomaterials significantly impact the thermoelectric transport properties of the network. In this study, Ag₂Se nanomaterials with different dimensions were prepared by solvothermal and template methods, and flexible Ag₂Se thermoelectric films were constructed on polyimide substrates using Ag₂Se nanomaterials with different dimensions by spraying process combined with high-temperature post processing. The effects of the dimensionality of Ag₂Se nanomaterials on the microstructures and thermoelectric properties of the films were then systematically investigated. Zero dimensional Ag₂Se nanoparticles exhibited superior conductive networks and thermoelectric properties in comparison to one dimensional nanowire structures. Furthermore, the room temperature power factor of the films reached 199.6 μW·m^-1·K^-2, and the power factor was 257.9 μW·m^-1·K^-2 at the temperature of 375 K, which indicated the good thermoelectric properties of the films. Additionally a device was designed and integrated based on the Ag₂Se films, with four thermoelectric arms and excellent performance. The device exhibited good mechanical flexibility and output performance with internal resistance increased by only 8.2% after 1000 bending cycles (bending radius: 20 mm), and the device displayed an open-circuit voltage of 9.1 mV and a max output power of 43.7 nW at a temperature difference of 30 K. This study presents a novel approach for the preparation of flexible Ag₂Se-based thermoelectric thin-film materials and devices.

Key words: Ag₂Se thermoelectric material, nanomaterial dimension, flexible thermoelectric film, thermoelectric device

中图分类号:

TQ174

张哲, 孙婷婷, 王连军, 江莞. 不同维度Ag₂Se构筑柔性热电薄膜的性能优化与器件集成研究[J]. 无机材料学报, 2024, 39(11): 1221-1227.

ZHANG Zhe, SUN Tingting, WANG Lianjun, JIANG Wan. Flexible Thermoelectric Films with Different Ag₂Se Dimensions: Performance Optimization and Device Integration[J]. Journal of Inorganic Materials, 2024, 39(11): 1221-1227.

图/表 9

图1 不同维度Ag2Se纳米粉体的XRD谱图

Fig. 1 XRD patterns of Ag2Se nanopowders with different dimensions

图2 不同维度Ag2Se纳米粉体的SEM照片

Fig. 2 SEM images of Ag2Se nanopowders with different dimensions (a) Ag2Se NWs; (b) Ag2Se NPs

图3 不同维度Ag2Se纳米粉体在乙醇溶剂中的分散性和稳定性

Fig. 3 Dispersion and stability of Ag2Se nanopowders with different dimensions in ethanol (a) Photograph of the dispersion after mixing; (b) Photograph of the dispersion after resting for 12 h

图4 不同维度纳米材料构筑Ag2Se薄膜退火(a, c)前(b, d)后的SEM照片

Fig. 4 SEM images of Ag2Se thin films made from nanomaterials with different dimensions (a, c) before and (b, d) after annealing (a, b) Ag2Se NWs-films; (c, d) Ag2Se NPs-films

图5 不同维度纳米材料构筑薄膜的XRD谱图

Fig. 5 XRD patterns of Ag2Se thin films made from nanomaterials with different dimensions

表1 不同维度纳米材料构筑Ag2Se薄膜的室温热电性能

Table 1 Room temperature thermoelectric properties of Ag2Se films made from nanomaterials with different dimensions

Sample	S/(μV·K⁻¹)	σ/(S·cm^-1)	PF/(μW·m⁻¹·K⁻²)	n/cm⁻³	μ/(cm²·V⁻¹·s⁻²)
Ag₂Se NPs-films	-77.9	329.0	199.6	4.8×10¹⁸	117.5
Ag₂Se NWs-films	-76.8	139.5	82.3	4.7×10¹⁸	81.5

图6 Ag2Se NPs薄膜的变温热电性能

Fig. 6 Thermoelectric properties of Ag2Se NPs-films at variable temperatures

图7 Ag2Se NPs薄膜器件的输出性能和弯曲性能

Fig. 7 Output performance and bending performance of devices with Ag2Se NPs-films (a) Open-circuit voltage of the device at different ΔT; (b) Output voltage and output power versus current of the device at different ΔT; (c) Variation of the internal resistance (R) of the device with bending cycles; Colorful figures are available on website

表2 本工作与文献中Ag2Se薄膜器件的输出性能对比

Table 2 Comparison of output performance for devices with Ag2Se-based thin films in this work and the literatures

TE legs	PF/(μW·m⁻¹·K⁻²)	N	P_max/nW	PD_max/(W·m^-2)	ΔT/K	Ref.
Ag₂Se/Nylon	987.4	4	460	2.3	30	[17]
Ag₂Se/PI	889.0	6	800	32.0	40	[28]
Ag₂Se/BC	291.0	10	280	0.05	20	[31]
Ag₂Se/PVDF	189.0	5	4.9	0.01	30	[32]
Ag₂Se/PI	199.6	4	43.7	0.54	30	This work

参考文献 13

[14]	WU H, SHI X, DUAN J, et al. Advances in Ag₂Se-based thermoelectrics from materials to applications. Energy & Environmental Science, 2023, 16(5): 1870.
[15]	WANG J, FAN W, YANG J, et al. Tetragonal-orthorhombic-cubic phase transitions in Ag₂Se nanocrystals. Chemistry of Materials, 2014, 26(19): 5647.
[16]	LIN S, GUO L, WANG X, et al. Revealing the promising near-room-temperature thermoelectric performance in Ag₂Se single crystals. Journal of Materiomics, 2023, 9(4): 754.
[17]	DING Y, QIU Y, CAI K, et al. High performance n-type Ag₂Se film on Nylon membrane for flexible thermoelectric power generator. Nature Communications, 2019, 10: 841.
[18]	LI X, LU Y, CAI K, et al. Exceptional power factor of flexible Ag/Ag₂Se thermoelectric composite films. Chemical Engineering Journal, 2022, 434: 134739.
[19]	YAN L, QI R, CHEN M, et al. Microstructurally tailored thin β-Ag₂Se films towards commercial flexible thermoelectrics. Advanced Materials, 2022, 34(7): 2104786.
[20]	WANG Z, LIU Y, LI J, et al. High-performance Ag₂Se film by a template method for flexible thermoelectric generator. Materials Today Physics, 2023, 36: 101147.
[21]	ZHANG K, ZHENG Q, WANG L, et al. Preparation and characterization of Ag₂Se-based ink used for inkjet printing. Journal of Inorganic Materials, 2022, 37(10): 1109. DOI
[22]	KOCZKUR K M, MOURDIKOUDIS S, POLAVARAPU L, et al. Polyvinylpyrrolidone (PVP) in nanoparticle synthesis. Dalton Transactions, 2015, 44(41): 17883.
[23]	JIANG C, WEI P, DING Y, et al. Ultrahigh performance polyvinylpyrrolidone/Ag₂Se composite thermoelectric film for flexible energy harvesting. Nano Energy, 2021, 80: 105488.
[24]	LIU Y, LU Y, WANG Z, et al. High performance Ag₂Se films by a one-pot method for a flexible thermoelectric generator. Journal of Materials Chemistry A, 2022, 10(48): 25644.
[25]	HOU S, LIU Y, YIN L, et al. High performance wearable thermoelectric generators using Ag₂Se films with large carrier mobility. Nano Energy, 2021, 87: 106223.
[26]	LIU Y, LI J, WANG Z, et al. High thermoelectric performance of flexible Ag/Ag₂Se composite film on nylon for low-grade energy harvesting. Journal of Materials Science & Technology, 2024, 179: 79.
[27]	ZANG J, MA Y, ZHAO Y, et al. Effect of post-annealing treatment on the thermoelectric properties of Ag₂Se flexible thin film prepared by magnetron sputtering method. Results in Physics, 2023, 45: 106222.
[28]	LIU Y, ZHANG Q, HUANG A, et al. Fully inkjet-printed Ag₂Se flexible thermoelectric devices for sustainable power generation. Nature Communications, 2024, 15: 2141.
[29]	LI Y, LOU Q, YANG J, et al. Exceptionally high power factor Ag₂Se/Se/polypyrrole composite films for flexible thermoelectric generators. Advanced Functional Materials, 2022, 32(7): 2106902.
[30]	ZHU J, LI F, ZHAO L, et al. Study on the structure and thermoelectric performance of SnSe cubic phase stabilized by AgBiSe₂ alloying. Journal of Liaocheng University (Natural Science Edition), 2023, 36(4): 59.
[31]	PALAPORN D, MONGKOLTHANARUK W, TANUSILP S, et al. A simple method for fabricating flexible thermoelectric nanocomposites based on bacterial cellulose nanofiber and Ag₂Se. Applied Physics Letters, 2022, 120(7): 3901.
[32]	ZHOU H, ZHANG Z, SUN C, et al. Biomimetic approach to facilitate the high filler content in free-standing and flexible thermoelectric polymer composite films based on PVDF and Ag₂Se nanowires. ACS Applied Materials & Interfaces, 2020, 12(46): 51506.
[1]	SUN T, WANG L, JIANG W. Pushing thermoelectric generators toward energy harvesting from the human body: challenges and strategies. Materials Today, 2022, 57: 121.
[2]	ZHANG Z, SUN T, WANG L, et al. Research progress on n-type carbon nanotube-based thermoelectric materials. Journal of Liaocheng University (Natural Science Edition), 2023, 36(3): 29.
[3]	WANG Y, YANG L, SHI X L, et al. Flexible thermoelectric materials and generators: challenges and innovations. Advanced Materials, 2019, 31(29): 1807916.
[4]	WANG S, JIANG M, WANG L, et al. n-Type Pb-free AgBiSe₂ based thermoelectric materials with stable cubic phase structure. Journal of Inorganic Materials, 2023, 38(7): 807.
[5]	HU Z, FU Y, JIANG M, et al. Thermal stability of Nb/Mg₃SbBi interface. Journal of Inorganic Materials, 2023, 38(8): 931.
[6]	SHI X L, ZOU J, CHEN Z G. Advanced thermoelectric design: from materials and structures to devices. Chemical Reviews, 2020, 120(15): 7399.
[7]	PETSAGKOURAKIS I, TYBRANDT K, CRISPIN X, et al. Thermoelectric materials and applications for energy harvesting power generation. Science and Technology of Advanced Materials, 2018, 19(1): 836. DOI PMID
[8]	BLACKBURN J L, FERGUSON A J, CHO C, et al. Carbon- nanotube-based thermoelectric materials and devices. Advanced Materials, 2018, 30(11): 1704386.
[9]	WANG C, XIA K, WANG H, et al. Advanced carbon for flexible and wearable electronics. Advanced Materials, 2019, 31(9): 1801072.
[10]	YANG J, PU Y, YU H, et al. A cross-plane design for wearable thermoelectric generators with high stretchability and output performance. Small, 2023, 19(45): 2304529.
[11]	SUN T, ZHOU B, ZHENG Q, et al. Stretchable fabric generates electric power from woven thermoelectric fibers. Nature Communications, 2020, 11: 572. DOI PMID
[12]	YANG S, LI Y, DENG L, et al. Flexible thermoelectric generator and energy management electronics powered by body heat. Microsystems & Nanoengineering, 2023, 9(1): 106.
[13]	LIU Y, LI Y, WU M, et al. Nanoengineering approach toward high power factor Ag₂Se/Se composite films for flexible thermoelectric generators. ACS Applied Materials & Interfaces, 2023, 15(30): 36587.

不同维度Ag₂Se构筑柔性热电薄膜的性能优化与器件集成研究

Flexible Thermoelectric Films with Different Ag₂Se Dimensions: Performance Optimization and Device Integration

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