柔性可穿戴碲化铋基热电器件的研究进展

张彤; 李杰; 叶施莹; 吴凯; 任松; 方剑

doi:10.13801/j.cnki.fhclxb.20240008.006

柔性可穿戴碲化铋基热电器件的研究进展

doi: 10.13801/j.cnki.fhclxb.20240008.006

张彤¹,
李杰¹,
叶施莹^{2, 3},
吴凯⁴,
任松^{2, 3},
方剑^{2, 3, ,}

1.
江苏省纺织产品质量监督检验研究院，南京 210007
2.
苏州大学　纺织与服装工程学院，苏州 215021
3.
苏州大学　现代丝绸国家工程实验室，苏州 215023
4.
苏州大学　材料与化学化工学部，苏州 215123

基金项目: 江苏省市场监督管理局科技计划项目(KJ2023023)；国家自然科学基金面上项目(52173059)；江苏省高校自然科学研究项目重大项目(21KJA540002)

详细信息

通讯作者:
方剑，博士，教授，博士生导师，研究方向为电活性纤维材料和柔性智能可穿戴纺织品　E-mail: jian.fang@suda.edu.cn

中图分类号: TB332
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- 文章访问数: 404
- HTML全文浏览量: 239
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- 被引次数: 0
出版历程
- 收稿日期: 2023-10-30
- 修回日期: 2023-12-05
- 录用日期: 2024-01-02
- 网络出版日期: 2024-01-09
- 刊出日期: 2024-07-01

Advances in flexible wearable bismuth telluride-based materials thermoelectric devices

ZHANG Tong¹,
LI Jie¹,
YE Shiying^{2, 3},
WU Kai⁴,
REN Song^{2, 3},
FANG Jian^{2, 3
, ,}

1.
Jiangsu Textile Product Quality Supervision and Inspection Institute, Nanjing 210007, China
2.
College of Textile and Clothing Engineering, Soochow University, Suzhou 215021, China
3.
National Engineering Laboratory for Modern Silk, Soochow University, Suzhou 215023, China
4.
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China

Funds: Science and Technology Program of Jiangsu Administration for Market Regulation (KJ2023023); National Natural Science Foundation of China (52173059); Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions (21KJA540002)

摘要

摘要: 随着全球能源的消耗加剧，热电器件的开发应用成为解决能源消耗问题的有效途径之一，其中，碲化铋(Bi₂Te₃)基柔性热电器件因在可穿戴领域逐步实现应用，得到了学界和业界的广泛关注。然而，受其材料成本较高、刚性结构等多方面因素的限制，Bi₂Te₃基柔性热电器件难以在保持高效热电性能的同时，实现柔性可穿戴化应用。本文系统地阐述了当前Bi₂Te₃基柔性热电器件在材料复合与柔性结构设计上的研究进展，特别是在柔性结构设计上，涵盖了块状、膜类及纱线型3种结构。最后，总结分析了Bi₂Te₃柔性热电器件未来可能面临的挑战与发展趋势，以期促进热电器件在可穿戴领域实现广泛应用。
- 碲化铋 /
- 热电材料 /
- 热电器件 /
- 热电薄膜 /
- 热电织物 /
- 可穿戴热电
Abstract: As the global energy consumption increasing rapidly, development and application of thermoelectric devices have become one of the effective ways to solve the problem. Among them, bismuth telluride (Bi₂Te₃)-based flexible devices attract widespread attention because they have been applied in the wearable sector gradually. However, due to the limitations of high material cost, rigid structure, and other factors, it is difficult for Bi₂Te₃-based flexible thermoelectric devices to achieve flexible wearable applications while maintaining efficient thermoelectric properties. This paper systematically reviews the current research progress of Bi₂Te₃-based flexible thermoelectric devices in terms of material composites and flexible structure design, especially in terms of flexible structure design, which covers three types of structures: Ingot-, film- and yarn- shaped. Finally, it summarizes and analyzes the possible future challenges and development trends of Bi₂Te₃-based flexible thermoelectric devices, to facilitate the realization of a wide range of applications for thermoelectric devices in the wearable field.
- bismuth telluride (Bi₂Te₃) /
- thermoelectric material /
- thermoelectric devices /
- thermoelectric thin film /
- thermoelectric fabrics /
- wearable thermoelectric

HTML全文

图 1 3种不同形态的Bi₂Te₃基柔性热电器件

Figure 1. Three different forms of Bi₂Te₃-based flexible thermoelectric devices

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图 2 (a) 热电发电机(TEG)结构图及其设备应用^[30]；(b) 完成的TEG器件结构图^[6]

Figure 2. (a) Structure of thermoelectric generator (TEG) and its applications^[30]; (b) Structure of the TEG^[6]

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图 3 (a) 柔性热电发电机(f-TEG)的制造工艺^[20]；(b) TEG实样图^[46]；(c) 热电器件结构图^[44]；(d) 中空结构器件结构图^[45]；(e) 中空结构器件在手指表面的弯曲图^[45]

Figure 3. (a) Manufacturing process of f-TEG^[20]; (b) TEG sample drawing^[46]; (c) Structure of the TEG^[44]; (d) Structure of the hollow structure device^[45]; (e) Bending diagram of a hollow structure device on the surface of a finger^[45]

R_L—; WTEG—

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图 4 (a) 带有太阳能吸收器的热电器件示意图^[56]；(b) 可拉伸器件的设计图^[57]

Figure 4. (a) Schematic diagram of a thermoelectric device with solar absorber^[56]; (b) Design drawings of stretchable devices^[57]

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图 5 (a) 锯齿形针迹；(b) 袜型针迹；(c) 平纹针迹^[58]；(d) 弯曲状态下的纱线型热电器件^[59]；(e) 1 m×15.5 cm的织物^[60]

Figure 5. (a) Serrated stitch; (b) Sock needle; (c) Plain stitch^[58]; (d) Yarn TEG in bent conditions^[59]; (e) 1 m×15.5 cm fabric^[60]

TET—

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表 1 Bi₂Te₃基热电器件应用总结

Table 1. Summary of Bi₂Te₃-based thermoelectric device applications

Device type	Thermoelectric materials	Substance*	Input voltage/mV	Power factor/ (μW·m⁻¹·K⁻²)	Power density/ (µW·cm⁻²)	Seebeck coefficient/ (μV·K⁻¹)	Ref.
Flexible ingot- shaped thermoelectric devices	SWCNT Bi₂Te₃	—	23 (135 K)	891.6 (340 K)	—	—	[16]
	Bi_0.5Te_1.5Te₃ (P-type) Bi₂Te_2.8Se_0.2 (N-type)	PIF	2800-3300 (Body temperature)	—	3.5	—	[20]
	Bi_0.5Sb_1.5Te₃ (P-type) Bi₂Se_0.3Te_2.7 (N-type)	FPCB	63	—	8.68	—	[44]
	Bi_0.5Sb_1.5Te₃ (P-type) Bi₂Se_0.5Te_2.5 (N-type)	FPCB	5.35	—	4.75	—	[45]
	CNTs P, N Bi₂Te₃	PDMS	920	—	570	—	[46]
Flexible film- shaped thermoelectric devices	Bi₂Te₃ PVDF	PET	2.3 (Natural exhalation)	133 (P) 124 (N)	—	—	[6]
	N bismuth telluride (Graphene) P bismuth telluride (SWCNT)	Polyimide (PI)	23 (135 K)	55 (P) 108 (N)	—	—	[30]
	Bi₂Te₃ PEDOT:PSS DMSO	—	—	—	—	45±2.1	[40]
	Bi₂Te₃	AIN	—	1130	—	—	[48]
	Bi₂Te₃	MASnI₃	—	—	—	—	[49]
	Bi₂Te₃	PIF	155.1 (46℃)	—	2530	—	[55]
	Bi_0.4Sb_1.6Te₃ (P-type) Bi₂Se_0.3Te₂ (N-type)	PIF	55.15 (AM 1.5 G)	—	—	166.37 (P) −116.38 (N)	[56]
	Bi₂Te₃	Ecoflex	—	—	150	—	[57]
Flexible yarn- shaped thermoelectric devices	Bi₂Te₃ PVP	—	—	—	—	3062	[32]
	Bi₂Te₃- Sb₂Te₃-PAN	—	15.8, 14.8, 11.9	—	62, 11, 9	—	[58]
	Bi_0.4Sb_1.3Te₃ (P-type) Bi₂Te_3.3Se_0.2 (N-type)	Polyimide filament PDMS	—	—	58	—	[59]
	Bi₂Te₃	Extreme filaments PEDOT	—	—	613 (25 K)	—	[60]
Notes: Input voltage is the voltage produced by a device at a certain temperature; Power factor is the ratio of the power dissipated to the product of the input volts times amps; Power density is the power generated per square centimeter of the TEG; Seebeck coefficient is defined as follows: S=−ΔV/ΔT with S being the Seebeck coefficient, ΔT the temperature difference between the ends of the material, and ΔV the potential difference; PEDOT—Poly(3, 4-ethylenedioxythiophene; PVP—Polyvinyl pyrrolidone; DMSO—Dimethyl sulfoxide; SWCNT—Single-walledcarbon nanotubes; PDMS—Polydimethylsiloxane; PIF—Polyimide film; PVDF—Polyvinylidene fluoride; PET—Polyethyleneterephthalate; FPCB—Flexible printedcircuit board; CNTs—Carbon nanotubes; PAN—; PSS—; MASnI₃—.

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参考文献(60)

[1]	CHEN X, LI C, GRÄTZEL M, et al. Nanomaterials for renewable energy production and storage[J]. Chemistry Society Reviews, 2012, 41(23): 7909-7937. doi: 10.1039/c2cs35230c
[2]	CONTI J, HOLTBERG P, DIEFENDERFER J, et al. International energy outlook 2016 with projections to 2040[R]. Washington: USDOE Energy Information Administration (EIA), 2016.
[3]	ARISTOV Y I. Adsorptive conversion of ultralow-temperature heat: Thermodynamic issues[J]. Energy, 2021, 236: 121892. doi: 10.1016/j.energy.2021.121892
[4]	UCHIDA K, TAKAHASHI S, HARII K, et al. Observation of the spin Seebeck effect[J]. Nature, 2008, 455(7214): 778-781. doi: 10.1038/nature07321
[5]	DREBUSHCHAK V. The peltier effect[J]. Journal of Thermal Analysis and Calorimetry, 2008, 91: 311-315. doi: 10.1007/s10973-007-8336-9
[6]	NA Y, KIM S, MALLEM S P R, et al. Energy harvesting from human body heat using highly flexible thermoelectric generator based on Bi₂Te₃ particles and polymer composite[J]. Journal of Alloys and Compounds, 2022, 924: 166575. doi: 10.1016/j.jallcom.2022.166575
[7]	HOU W, NIE X, ZHAO W, et al. Fabrication and excellent performances of Bi_0.5Sb_1.5Te₃/epoxy flexible thermoelectric cooling devices[J]. Nano Energy, 2018, 50: 766-776.
[8]	DAI X, WANG Y, LI K, et al. Joint-free single-piece flexible thermoelectric devices with ultrahigh resolution p-n patterns toward energy harvesting and solid-state cooling[J]. ACS Energy Letters, 2021, 6(12): 4355-4364. doi: 10.1021/acsenergylett.1c02005
[9]	GAO F L, MIN P, GAO X Z, et al. Integrated temperature and pressure dual-mode sensors based on elastic PDMS foams decorated with thermoelectric PEDOT:PSS and carbon nanotubes for human energy harvesting and electronic-skin[J]. Journal of Materials Chemistry A, 2022, 10(35): 18256-18266. doi: 10.1039/D2TA04862K
[10]	LIU Y, YIN L, ZHANG W, et al. A wearable real-time power supply with a Mg₃Bi₂-based thermoelectric module[J]. Cell Reports Physical Science, 2021, 2(6): 100445. doi: 10.1016/j.xcrp.2021.100445
[11]	KONG D, ZHU W, GUO Z, et al. High-performance flexible Bi₂Te₃ films based wearable thermoelectric generator for energy harvesting[J]. Energy, 2019, 175: 292-299. doi: 10.1016/j.energy.2019.03.060
[12]	KIM S J, LEE H E, CHOI H, et al. High-performance flexible thermoelectric power generator using laser multiscanning lift-off process[J]. ACS Nano, 2016, 10(12): 10851-10857. doi: 10.1021/acsnano.6b05004
[13]	LIU Z, TIAN B, LI Y, et al. Evolution of thermoelectric generators: From application to hybridization[J]. Nano Micro Small, 2023: 2304599.
[14]	HUANG L, LIN S, XU Z, et al. Fiber-based energy conversion devices for human-body energy harvesting[J]. Advanced in Materials, 2019, 32(5): 1902034.
[15]	李佳. 石墨烯/碲化铋/PEDOT:PSS纳米复合热电材料的制备与性能探究[D]. 上海: 上海应用技术大学, 2020. LI Jia. Preparation and thermoelectric properties of graphene/Bi₂Te₃/PEDOT:PSS nanocomposite thermoelectric materials[D]. Shanghai: Shanghai Institute of Technology, 2020(in Chinese).
[16]	LIU Y, DU Y, MENG Q, et al. Effects of preparation methods on the thermoelectric performance of SWCNT/Bi₂Te₃ bulk composites[J]. Materials, 2020, 13(11): 2636. doi: 10.3390/ma13112636
[17]	KIM J, BAE E J, KANG Y H, et al. Elastic thermoelectric sponge for pressure-induced enhancement of power generation[J]. Nano Energy, 2020, 74: 104824. doi: 10.1016/j.nanoen.2020.104824
[18]	JUNG K K, JUNG Y, CHOI C J, et al. Flexible thermoelectric generator with polydimethyl siloxane in thermoelectric material and substrate[J]. Current Applied Physics, 2016, 16(10): 1442-1448. doi: 10.1016/j.cap.2016.08.010
[19]	ZHANG Z, WANG B, QIU J, et al. Roll-to-roll printing of spatial wearable thermoelectrics[J]. Manufacturing Letters, 2019, 21: 28-34. doi: 10.1016/j.mfglet.2019.07.002
[20]	YUAN J, ZHU R. A fully self-powered wearable monitoring system with systematically optimized flexible thermoelectric generator[J]. Applied Energy, 2020, 271: 115250. doi: 10.1016/j.apenergy.2020.115250
[21]	BUBNOVA O, KHAN Z U, MALTI A, et al. Optimization of the thermoelectric figure of merit in the conducting polymer poly(3, 4-ethylenedioxythiophene)[J]. Nature Materials, 2011, 10(6): 429-433. doi: 10.1038/nmat3012
[22]	张洪银, 莫政宇. 热电材料ZT值的测量研究[J]. 内燃机与配件, 2023(4): 94-96. doi: 10.3969/j.issn.1674-957X.2023.04.030 ZHANG Hongyin, MO Zhengyu. Measurement of ZT values of thermoelectric materials[J]. Internal Combustion Engine & Parts, 2023(4): 94-96(in Chinese). doi: 10.3969/j.issn.1674-957X.2023.04.030
[23]	SINGH D, KUTBEE A T, GHONEIM M T, et al. Strain-induced rolled thin films for lightweight tubular thermoelectric generators[J]. Advanced Materials Technologies, 2018, 3(1): 1700192. doi: 10.1002/admt.201700192
[24]	PEI J, CAI B, ZHUANG H L, et al. Bi₂Te₃-based applied thermoelectric materials: Research advances and new challenges[J]. National Science Review, 2020, 7(12): 1856-1858. doi: 10.1093/nsr/nwaa259
[25]	TANG X, LI Z, LIU W, et al. A comprehensive review on Bi₂Te₃-based thin films: Thermoelectrics and beyond[J]. Interdisciplinary Materials, 2022, 1(1): 88-115. doi: 10.1002/idm2.12009
[26]	CHEN Y, HOU X, MA C, et al. Review of development status of Bi₂Te₃-based semiconductor thermoelectric power generation[J]. Advances in Materials Science and Engineering, 2018, 2018: 1-9.
[27]	HONG S, GU Y, SEO J K, et al. Wearable thermoelectrics for personalized thermoregulation[J]. Science Advances, 2019, 5(5): 0536.
[28]	WU B, GUO Y, HOU C, et al. From carbon nanotubes to highly adaptive and flexible high-performance thermoelectric generators[J]. Nano Energy, 2021, 89: 106487. doi: 10.1016/j.nanoen.2021.106487
[29]	GUO Z, YU Y, ZHU W, et al. Kirigami-based stretchable, deformable, ultralight thin-film thermoelectric generator for BodyNET application[J]. Advanced Energy Materials, 2022, 12(5): 2102993. doi: 10.1002/aenm.202102993
[30]	WU B, GUO Y, HOU C, et al. High-performance flexible thermoelectric devices based on all-inorganic hybrid films for harvesting low-grade heat[J]. Advanced Functional Materials, 2019, 29(25): 1900304. doi: 10.1002/adfm.201900304
[31]	AWASTHI R, MANCHANDA S, DAS P, et al. Poly(vinylpyrrolidone)[M]. Engineering of Biomaterials for Drug Delivery Systems. 2018: 255-272.
[32]	AKRAM R, KHAN J S, QAMAR Z, et al. Ultra-low thermal conductivity and thermoelectric properties of polymer-mixed Bi₂Te₃ nanofibers by electrospinning[J]. Journal of Materials Science, 2022: 1-13.
[33]	WANG X, MENG F, WANG T, et al. High performance of PEDOT:PSS/SiC-NWs hybrid thermoelectric thin film for energy harvesting[J]. Journal of Alloys and Compounds, 2018, 734: 121-129. doi: 10.1016/j.jallcom.2017.11.013
[34]	FAN X, NIE W, TSAI H, et al. PEDOT:PSS for flexible and stretchable electronics: Modifications, strategies, and applications[J]. Advanced Science, 2019, 6(19): 1900813. doi: 10.1002/advs.201900813
[35]	DU Y, SHEN S Z, CAI K, et al. Research progress on polymer-inorganic thermoelectric nanocomposite materials[J]. Progress in Polymer Science, 2012, 37(6): 820-841. doi: 10.1016/j.progpolymsci.2011.11.003
[36]	CHEN Y, ZHAO Y, LIANG Z. Solution processed organic thermoelectrics: towards flexible thermoelectric modules[J]. Physics Energy and Environmental Science, 2015, 8(2): 401-422. doi: 10.1039/C4EE03297G
[37]	FAN Z, LI P, DU D, et al. Significantly enhanced thermoelectric properties of PEDOT:PSS films through sequential post-treatments with common acids and bases[J]. Advanced Energy Materials, 2017, 7(8): 1602116. doi: 10.1002/aenm.201602116
[38]	KIM G H, SHAO L, ZHANG K, et al. Engineered doping of organic semiconductors for enhanced thermoelectric efficiency[J]. Nature Materials, 2013, 12(8): 719-723. doi: 10.1038/nmat3635
[39]	DU Y, CAI K, SHEN S Z, et al. Multifold enhancement of the output power of flexible thermoelectric generators made from cotton fabrics coated with conducting polymer[J]. RSC Advances, 2017, 7(69): 43737-43742. doi: 10.1039/C7RA08663F
[40]	KIM W S, ANOOP G, JEONG I S, et al. Feasible tuning of barrier energy in PEDOT:PSS/Bi₂Te₃ nanowires-based thermoelectric nanocomposite thin films through polar solvent vapor annealing[J]. Nano Energy, 2020, 67: 104207. doi: 10.1016/j.nanoen.2019.104207
[41]	ZHOU C, DUN C, GE B, et al. Highly robust and flexible n-type thermoelectric film based on Ag₂Te nanoshuttle/polyvinylidene fluoride hybrids[J]. Nanoscale, 2018, 10(31): 14830-14834.
[42]	DUN C, HEWITT C A, HUANG H, et al. Layered Bi₂Se₃ nanoplate/polyvinylidene fluoride composite based n-type thermoelectric fabrics[J]. ACS Applied Materials & Interfaces, 2015, 7(13): 7054-7059.
[43]	ZHAO Y, FU X, LIU B, et al. Ultra-stretchable hydrogel thermocouples for intelligent wearables[J]. Science China Materials, 2023: 1-7.
[44]	KIM J, KHAN S, WU P, et al. Self-charging wearables for continuous health monitoring[J]. Nano Energy, 2021, 79: 105419. doi: 10.1016/j.nanoen.2020.105419
[45]	SHI Y, WANG Y, MEI D, et al. Design and fabrication of wearable thermoelectric generator device for heat harvesting[J]. IEEE Robotics and Automation Letters, 2017, 3(1): 373-378.
[46]	JUNG K K, JUNG Y, CHOI C J, et al. Flexible thermoelectric generator with polydimethyl siloxane in thermoelectric material and substrate[J]. Current Applied Physics, 2016, 16(10): 1442-1448. doi: 10.1016/j.cap.2016.08.010
[47]	YU Y, ZHU W, KONG X, et al. Recent development and application of thin-film thermoelectric cooler[J]. Frontiers of Chemical Science and Engineering, 2020, 14: 492-503.
[48]	AHMED A, HAN S J S R. Fabrication, micro-structure characteristics and transport properties of co-evaporated thin films of Bi₂Te₃ on AlN coated stainless steel foils[J]. Scientific Reports, 2021, 11(1): 4041. doi: 10.1038/s41598-021-83476-7
[49]	MORIMOTO M, KAWANO S, MIYAMOTO S, et al. Electronic structure and thermal conductance of the MASnI₃/Bi₂Te₃ interface: A first-principles study[J]. Scientific Reports, 2022, 12(1): 217. doi: 10.1038/s41598-021-04234-3
[50]	GHASEMI A, KEPAPTSOGLOU D, GALINDO P L, et al. Van der Waals epitaxy between the highly lattice mismatched Cu-doped FeSe and Bi₂Te₃[J]. NPG Asia Materials, 2017, 9(7): e402. doi: 10.1038/am.2017.111
[51]	HE Q L, LIU H, HE M, et al. Two-dimensional superconductivity at the interface of a Bi₂Te₃/FeTe heterostructure[J]. Nature Communications, 2014, 5(1): 4247. doi: 10.1038/ncomms5247
[52]	NI Y, SUN B, LI J, et al. Thermal transport in Bi₂Te₃-PbTe segmented thermoelectric nanofilms[J]. Chinese Journal of Physics, 2022, 75: 199-205. doi: 10.1016/j.cjph.2021.11.032
[53]	HUANG C, LIU J, ZHAO L, et al. Advances in atomic oxygen resistant polyimide composite films[J]. Composites Part A: Applied Science and Manufacturing, 2023: 107459.
[54]	CAO Z, KOUKHARENKO E, TUDOR M, et al. Flexible screen printed thermoelectric generator with enhanced processes and materials[J]. Sensors and Actuators A: Physical, 2016, 238: 196-206. doi: 10.1016/j.sna.2015.12.016
[55]	杨龙, 尤汉, 唐可琛, 等. Bi₂Te₃柔性热电器件的制备与发电性能研究[J]. 传感器与微系统, 2021, 40(10): 14-16, 20. YANG Long, YOU Han, TANG Kechen, et al. Research on preparation and power generation performance of Bi₂Te₃ flexible thermoelectric device[J]. Transducer and Microsystem Technologies, 2021, 40(10): 14-16, 20(in Chinese).
[56]	JUNG Y S, JEONG D H, KANG S B, et al. Wearable solar thermoelectric generator driven by unprecedentedly high temperature difference[J]. Nano Energy, 2017, 40: 663-672. doi: 10.1016/j.nanoen.2017.08.061
[57]	YANG Y, HU H, CHEN Z, et al. Stretchable nanolayered thermoelectric energy harvester on complex and dynamic surfaces[J]. Nano Letters, 2020, 20(6): 4445-4453. doi: 10.1021/acs.nanolett.0c01225
[58]	LEE J A, ALIEV A E, BYKOVA J S, et al. Woven-yarn thermoelectric textiles[J]. Advanced Materials, 2016, 28(25): 5038-5044. doi: 10.1002/adma.201600709
[59]	ZHENG Y, HAN X, YANG J, et al. Durable, stretchable and washable inorganic-based woven thermoelectric textiles for power generation and solid-state cooling[J]. Energy & Environmental Science, 2022, 15(6): 2374-2385.
[60]	JING Y, LUO J, HAN X, et al. Scalable manufacturing durable, tailorable and recyclable multifunctional woven thermoelectric textile system[J]. Energy & Environmental Science, 2023, 16(10): 4334-4344.