Article(id=1319969657029767634, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319969627665445134, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20230424, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1687190400000, receivedDateStr=2023-06-20, revisedDate=1688659200000, revisedDateStr=2023-07-07, acceptedDate=null, acceptedDateStr=null, onlineDate=1792634890086, onlineDateStr=2026-10-22, pubDate=1705680000000, pubDateStr=2024-01-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792634890086, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792634890086, creator=13701087609, updateTime=1792634890086, updator=13701087609, issue=Issue{id=1319969627665445134, tenantId=1146029695717560320, journalId=1263187385517883426, year='2024', volume='52', issue='1', pageStart='1', pageEnd='370', issueExtLink='null', onlineDate='null', pubDate='1705680000000', pubDateStr='2024-01-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792634883085, creator='13701087609', updateTime=1792641944622, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1319999245965443838, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319969627665445134, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1319999245965443839, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319969627665445134, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=218, endPage=228, ext={EN=ArticleExt(id=1319969657222705619, articleId=1319969657029767634, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Enhanced Performance of Ag2Se-Based Flexible Thermoelectric Films Based on Functional Units Ordering Strategy, columnId=1263922772401635899, journalTitle=Journal of the Chinese Ceramic Society, columnName=Review, runingTitle=null, highlight=null, articleAbstract=

Thermoelectric (TE) materials as one of clean energy materials can realize the direct conversion between heat and electricity. Flexible TE films have attracted recent attention because they can be used to fabricate flexible TE generators (f-TEGs) to replace batteries that need to be charged or replaced frequently to power rapidly developing wearable electronic devices. Bi2Te3-based films exhibit the optimum TE performance at room temperature (RT), but Bi2Te3-based films are easy to oxidize, and Te is expensive, rare, and toxic, so suitable alternatives need to be explored. Silver selenide (Ag2Se) is a narrow bandgap semiconductor and has a superior TE performance at RT. Furthermore, compared with element Te, element Se is less toxic and more abundant. However, the TE properties of Ag2Se are still lower than that of Bi2Te3. This review summarized the mechanism of improving the TE properties and flexibility of Ag2Se by functional unit order strategy, and provided a route to enhance the TE properties and flexibility of Ag2Se.

Typical strategies for improving the zT values of Ag2Se-based films include the introduction of secondary phase, defect engineering, stoichiometry manipulation, etc.. However, charge carrier and phonon transport in TE material are strongly coupled with each other, seriously restricting the improvement of TE performance. The functional unit order is an effective strategy to optimize the performance of materials. Functional units with different roles constructed orderly in materials can enhance a synergistic effect between functional units and thus improve the performance. For Ag2Se-based flexible TE films, the effect of functional unit ordering and the synergetic effect between functional units on the electronic, phonon transport, and flexibility were discussed. The S-doped Ag2Se film shows a power factor ~954 μW·m-1·K-2 at 300 K and superior flexibility (94.4% of the original electrical conductivity was preserved after bending for 2 000 times around a rod with a radius of 4 mm). The S-doped Ag2Se film consists of a special "core-shell" microstructure, namely, the "core" is an S-doped Ag2Se phase and the "shell" (thickness of 15 nm) is Se-doped Ag2S and amorphous S mixed phase. The formation of the "core-shell" microstructure is mainly due to the different affinities between Ag and Se and Ag and S. The "core" acts as TE functional units because of the well-preserved conductive paths formed by well-crystallized S-doped Ag2Se grains, thus maintaining a high electrical conductivity of the film. The "shell" acts as a flexible functional unit to enhance the flexibility of the film mainly due to the inherently flexible amorphous S phase and the ductile Se-doped Ag2S. Moreover, the thermal conductivity of the film is low because of the strengthened phonon scattering resulting from the hetero-interfaces and the intrinsically low thermal conductivity of the amorphous S phase and the Se-doped Ag2S nanograins.

The Ag2Se/PVP composite film has a high power factor of ~1 910 μW·m-1·K-2 and a superior flexibility at 300 K. Most Ag2Se grains with coherent interfaces in the Ag2Se/PVP composite film indicate that the Ag2Se TE functional unit is constructed, leading to a high electrical conductivity. The formation of the unique microstructure is related to the special sintering mechanism and the effect of PVP. The superior flexibility (i.e., 98% of the original electrical conductivity is preserved after bending for 1 000 times around a rod with a radius of 4 mm) is due to the good adhesion and viscosity of PVP acting as a flexible functional unit. The composite film has a pretty low thermal conductivity because of PVP with an extremely low intrinsic thermal conductivity and it contains numerous nano-sized- to micron-sized-pores and Ag2Se/PVP hetero-interfaces.

The Ag2Se/Se/PPy composite film has an exceptionally high power factor of ~2 240 μW·m-1·K-2 and excellent flexibility at 300 K. The Ag2Se/Se/PPy composite film has a superior crystallinity of Ag2Se grains and continuous grain boundaries without defects, indicating that the Ag2Se TE functional unit is constructed, leading to a high electrical conductivity. There exist energy-filtering effects at the heterointerfaces of Ag2Se/Se and Ag2Se/PPy in the film, leading to a high Seebeck coefficient. The formation of the unique microstructure is related to the special sintering mechanism. The superior flexibility (i.e., 92.5% of the original electrical conductivity is preserved after bending for 1 500 times around a rod with a radius of 4 mm) is due to the good adhesion and viscosity of PPy acting as a flexible functional unit. Moreover, the nano-sized to submicron-sized pores, and the Ag2Se/PPy and Ag2Se/Se heterointerfaces in the composite film can scatter short- to long-wavelength phonons because PPy has an intrinsic low thermal conductivity, the composite film has a low thermal conductivity.

Summary and prospects

The functional unit order is an effective strategy to optimize the performance of materials. For Ag2Se-based TE films, the TE functional units ordering (such as coherent adjacent Ag2Se grains, good crystalline qualities, continuous grain boundaries, and core-shell nanostructure) and flexible functional units were constructed in Ag2Se-based films. The effective regulation of electron and phonon transport and flexibility was realized due to the synergistic effect between different functional units, thus increasing the electrical conductivity, reducing the thermal conductivity, and improving the flexibility. The more work are needed to verify whether the relevant strategies are universal.

, authors=Zixing WANG, Jiajia LI, Ying LIU, Kefeng CAI, authorsList=Zixing WANG, Jiajia LI, Ying LIU, Kefeng CAI, authorCompany=null, correspAuthors=Kefeng CAI, authorNote=

WANG Zixing (1991-), male, Doctoral candidate. E-mail:

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CAI Kefeng (1964-), male, Ph.D., Professor. E-mail:
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热电材料是一种能够实现热能和电能相互转换的清洁能源材料。近年来,随着可穿戴电子设备的蓬勃发展,柔性热电材料成为研究热点。热电材料中载流子和声子传输表现出强耦合特性,严重制约热电性能的提升。功能基元序构是一种优化材料性能的有效策略。在材料中构筑不同作用机制的功能基元,并将功能基元进行序构,同时增强功能基元间的协同效应,可以有效地提升材料的性能。本工作主要以硒化银基柔性热电薄膜为例,介绍功能基元序构和功能基元间协同效应对电、声输运性能和柔性的作用机制。

, authors=王子兴, 李佳佳, 刘莹, 蔡克峰, authorsList=王子兴, 李佳佳, 刘莹, 蔡克峰, authorCompany=null, correspAuthors=蔡克峰, authorNote=

王子兴(1991—),男,博士研究生。

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蔡克峰(1964—),男,博士,教授。
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基于功能基元序构策略提升Ag2Se基柔性热电薄膜的性能
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王子兴 , 李佳佳 , 刘莹 , 蔡克峰
硅酸盐学报 | 综合评述 2024,52(1): 218-228
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硅酸盐学报 |综合评述 2024 , 52 (1) : 218 -228
基于功能基元序构策略提升Ag2Se基柔性热电薄膜的性能
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王子兴 , 李佳佳, 刘莹, 蔡克峰
作者信息
  • 同济大学材料科学与工程学院,上海 201804
通讯作者:
蔡克峰(1964—),男,博士,教授。
作者简介:

王子兴(1991—),男,博士研究生。

Enhanced Performance of Ag2Se-Based Flexible Thermoelectric Films Based on Functional Units Ordering Strategy
Zixing WANG , Jiajia LI, Ying LIU, Kefeng CAI
Affiliations
  • School of Materials Science and Engineering, Tongji University, Shanghai 201804, China
  • Corresponding Author:
    CAI Kefeng (1964-), male, Ph.D., Professor. E-mail:

    WANG Zixing (1991-), male, Doctoral candidate. E-mail:

出版时间: 2024-01-20 doi: 10.14062/j.issn.0454-5648.20230424
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热电材料是一种能够实现热能和电能相互转换的清洁能源材料。近年来,随着可穿戴电子设备的蓬勃发展,柔性热电材料成为研究热点。热电材料中载流子和声子传输表现出强耦合特性,严重制约热电性能的提升。功能基元序构是一种优化材料性能的有效策略。在材料中构筑不同作用机制的功能基元,并将功能基元进行序构,同时增强功能基元间的协同效应,可以有效地提升材料的性能。本工作主要以硒化银基柔性热电薄膜为例,介绍功能基元序构和功能基元间协同效应对电、声输运性能和柔性的作用机制。

热电薄膜  /  硒化银  /  功能基元序构  /  柔性

Thermoelectric (TE) materials as one of clean energy materials can realize the direct conversion between heat and electricity. Flexible TE films have attracted recent attention because they can be used to fabricate flexible TE generators (f-TEGs) to replace batteries that need to be charged or replaced frequently to power rapidly developing wearable electronic devices. Bi2Te3-based films exhibit the optimum TE performance at room temperature (RT), but Bi2Te3-based films are easy to oxidize, and Te is expensive, rare, and toxic, so suitable alternatives need to be explored. Silver selenide (Ag2Se) is a narrow bandgap semiconductor and has a superior TE performance at RT. Furthermore, compared with element Te, element Se is less toxic and more abundant. However, the TE properties of Ag2Se are still lower than that of Bi2Te3. This review summarized the mechanism of improving the TE properties and flexibility of Ag2Se by functional unit order strategy, and provided a route to enhance the TE properties and flexibility of Ag2Se.

Typical strategies for improving the zT values of Ag2Se-based films include the introduction of secondary phase, defect engineering, stoichiometry manipulation, etc.. However, charge carrier and phonon transport in TE material are strongly coupled with each other, seriously restricting the improvement of TE performance. The functional unit order is an effective strategy to optimize the performance of materials. Functional units with different roles constructed orderly in materials can enhance a synergistic effect between functional units and thus improve the performance. For Ag2Se-based flexible TE films, the effect of functional unit ordering and the synergetic effect between functional units on the electronic, phonon transport, and flexibility were discussed. The S-doped Ag2Se film shows a power factor ~954 μW·m-1·K-2 at 300 K and superior flexibility (94.4% of the original electrical conductivity was preserved after bending for 2 000 times around a rod with a radius of 4 mm). The S-doped Ag2Se film consists of a special "core-shell" microstructure, namely, the "core" is an S-doped Ag2Se phase and the "shell" (thickness of 15 nm) is Se-doped Ag2S and amorphous S mixed phase. The formation of the "core-shell" microstructure is mainly due to the different affinities between Ag and Se and Ag and S. The "core" acts as TE functional units because of the well-preserved conductive paths formed by well-crystallized S-doped Ag2Se grains, thus maintaining a high electrical conductivity of the film. The "shell" acts as a flexible functional unit to enhance the flexibility of the film mainly due to the inherently flexible amorphous S phase and the ductile Se-doped Ag2S. Moreover, the thermal conductivity of the film is low because of the strengthened phonon scattering resulting from the hetero-interfaces and the intrinsically low thermal conductivity of the amorphous S phase and the Se-doped Ag2S nanograins.

The Ag2Se/PVP composite film has a high power factor of ~1 910 μW·m-1·K-2 and a superior flexibility at 300 K. Most Ag2Se grains with coherent interfaces in the Ag2Se/PVP composite film indicate that the Ag2Se TE functional unit is constructed, leading to a high electrical conductivity. The formation of the unique microstructure is related to the special sintering mechanism and the effect of PVP. The superior flexibility (i.e., 98% of the original electrical conductivity is preserved after bending for 1 000 times around a rod with a radius of 4 mm) is due to the good adhesion and viscosity of PVP acting as a flexible functional unit. The composite film has a pretty low thermal conductivity because of PVP with an extremely low intrinsic thermal conductivity and it contains numerous nano-sized- to micron-sized-pores and Ag2Se/PVP hetero-interfaces.

The Ag2Se/Se/PPy composite film has an exceptionally high power factor of ~2 240 μW·m-1·K-2 and excellent flexibility at 300 K. The Ag2Se/Se/PPy composite film has a superior crystallinity of Ag2Se grains and continuous grain boundaries without defects, indicating that the Ag2Se TE functional unit is constructed, leading to a high electrical conductivity. There exist energy-filtering effects at the heterointerfaces of Ag2Se/Se and Ag2Se/PPy in the film, leading to a high Seebeck coefficient. The formation of the unique microstructure is related to the special sintering mechanism. The superior flexibility (i.e., 92.5% of the original electrical conductivity is preserved after bending for 1 500 times around a rod with a radius of 4 mm) is due to the good adhesion and viscosity of PPy acting as a flexible functional unit. Moreover, the nano-sized to submicron-sized pores, and the Ag2Se/PPy and Ag2Se/Se heterointerfaces in the composite film can scatter short- to long-wavelength phonons because PPy has an intrinsic low thermal conductivity, the composite film has a low thermal conductivity.

Summary and prospects

The functional unit order is an effective strategy to optimize the performance of materials. For Ag2Se-based TE films, the TE functional units ordering (such as coherent adjacent Ag2Se grains, good crystalline qualities, continuous grain boundaries, and core-shell nanostructure) and flexible functional units were constructed in Ag2Se-based films. The effective regulation of electron and phonon transport and flexibility was realized due to the synergistic effect between different functional units, thus increasing the electrical conductivity, reducing the thermal conductivity, and improving the flexibility. The more work are needed to verify whether the relevant strategies are universal.

thermoelectric film  /  silver selenide  /  functional units ordering  /  flexible
王子兴, 李佳佳, 刘莹, 蔡克峰. 基于功能基元序构策略提升Ag2Se基柔性热电薄膜的性能. 硅酸盐学报, 2024 , 52 (1) : 218 -228 . DOI: 10.14062/j.issn.0454-5648.20230424
Zixing WANG, Jiajia LI, Ying LIU, Kefeng CAI. Enhanced Performance of Ag2Se-Based Flexible Thermoelectric Films Based on Functional Units Ordering Strategy[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (1) : 218 -228 . DOI: 10.14062/j.issn.0454-5648.20230424
  • 国家自然科学基金(92163118; 51972234)
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doi: 10.14062/j.issn.0454-5648.20230424
  • 接收时间:2023-06-20
  • 首发时间:2026-10-22
  • 出版时间:2024-01-20
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  • 收稿日期:2023-06-20
  • 修回日期:2023-07-07
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国家自然科学基金(92163118; 51972234)
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    同济大学材料科学与工程学院,上海 201804

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蔡克峰(1964—),男,博士,教授。
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小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
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