搜索

x

留言板

尊敬的读者、作者、审稿人, 关于本刊的投稿、审稿、编辑和出版的任何问题, 您可以本页添加留言。我们将尽快给您答复。谢谢您的支持!

姓名
邮箱
手机号码
标题
留言内容
验证码

Cu1.8–x Sbx S热电材料的相结构与电热输运性能

赵英浩 张瑞 张波萍 尹阳 王明军 梁豆豆

引用本文:
Citation:

Cu1.8–x Sbx S热电材料的相结构与电热输运性能

赵英浩, 张瑞, 张波萍, 尹阳, 王明军, 梁豆豆

Phase structure and thermoelectric properties of Cu1.8–x Sbx S thermoelectric material

Zhao Ying-Hao, Zhang Rui, Zhang Bo-Ping, Yin Yang, Wang Ming-Jun, Liang Dou-Dou
PDF
HTML
导出引用
  • Cu1.8S基热电材料因其丰富的原料储备、低毒性及优良的电学和热学性能而成为具有应用潜力的热电材料. 本文采用机械合金化(mechanical alloying, MA)结合放电等离子烧结(spark plasma sintering, SPS)工艺制备了一系列Cu1.8–x Sbx S (x = 0, 0.005, 0.02, 0.03, 0.04)块体材料, 研究了不同Sb掺杂量对Cu1.8–x Sbx S相结构、微观形貌及热电性能的影响. 结果表明, 随着Sb含量的增加, Cu1.8–x Sbx S材料相结构由单相Cu1.8S转变为多相共存, 其块体均呈p型导电特征. 样品Cu1.77Sb0.03S在723 K时取得最高ZT值约为0.37, 比未掺杂Cu1.8S(0.33)提高了12%.
    Cu1.8S-based materials have become potential thermoelectric materials due to their rich raw material reserves, low toxicity, and excellent electrical and thermal properties. In this study, a series of Cu1.8–x Sbx S (x = 0, 0.005, 0.02, 0.03, 0.04) bulk materials is synthesized by using mechanical alloying combined with spark plasma sintering process. This preparation method can shorten the preparation cycle of materials, and effectively improve the research and development efficiency of thermoelectric (TE) materials due to its simple process. The effects of different Sb doping amounts on the structure, micromorphology, and thermoelectric transport properties of Cu1.8–x Sbx S phase are investigated. The results show that when 0 ≤ x < 0.02, the bulk samples are single-phase Cu1.8S. With the further increase of Sb doping to 0.02 ≤ x ≤ 0.04, the second phase CuSbS2 is formed when Sb content exceeds the solid solubility limit of x = 0.02 in Cu1.8S, all Cu1.8–x Sbx S bulk samples exhibit p-type conductivity characteristics. Benefitting from the synergistic phonon scattering effect by multiscale defects, such as point defects (${\rm{Sb}}_{{\rm{Cu}}}^{ \bullet\bullet }$, $ {\rm{V}}_{\rm{S}}^{ \bullet \bullet } $), nanopores, secondary phases (CuSbS2), and dislocations, the thermal conductivity κ declines significantly from 1.76 W·m–1·K–1 (x = 0) to 0.99 W·m–1·K–1 at 723 K for the Cu1.76Sb0.04S sample. Finally, the peak dimensionless TE figure of merit (ZT ) value of 0.37 is achieved at 723 K for Cu1.77Sb0.03S resulting from a low thermal conductivity of 1.11 W·m–1·K–1 combining an appropriate power factor of 563 μW·m–1·K–2, which is 12% higher than that (0.33) of pristine Cu1.8S. Although the Sb doped Cu1.8S-based samples have lower thermal conductivity κ, the reduced power factor cannot be offset by reducing the thermal conductivity κ, so the TE figure of merit (ZT ) value is not significantly improved. Therefore, there is still much room for improving the performance of Sb doped Cu1.8S-based thermoelectric material, and its thermoelectric performance can be further optimized through nano-second phase recombination, energy band engineering, and introducing multi-scale defects, etc. Our results suggest that the introduction of Sb into thermoelectric materials is an effective and convenient strategy to improve ZT value by reducing thermal conductivity κ.
      通信作者: 张波萍, bpzhang@ustb.edu.cn
    • 基金项目: 国家重点研发计划(批准号: 2018YFB0703600)和国家自然科学基金(批准号: 11474176)资助的课题
      Corresponding author: Zhang Bo-Ping, bpzhang@ustb.edu.cn
    • Funds: Project supported by the National Key Research and Development Program of China (Grant No. 2018YFB0703600) and the National Natural Science Foundation of China (Grant No. 11474176)
    [1]

    葛振华, 张波萍, 于昭新, 刘勇, 李敬锋 2012 物理学报 61 048401Google Scholar

    Ge Z H, Zhang B P, Yu Z X, Liu Y, Li J F 2012 Acta Phys. Sin. 61 048401Google Scholar

    [2]

    赵立东, 张波萍, 李敬锋, 刘玮书, 周敏 2007 稀有金属材料与工程 36 408Google Scholar

    Zhao L D, Zhang B P, Li J F, Liu W S, Zhou M 2007 Rare Metal Mat. Eng. 36 408Google Scholar

    [3]

    张贺, 骆军, 朱航天, 刘泉林, 梁敬魁, 饶光辉 2012 物理学报 61 086101Google Scholar

    Zhang H, Luo J, Zhu H T, Liu Q Lin, Liang J K, Rao G H 2012 Acta Phys. Sin. 61 086101Google Scholar

    [4]

    王作成, 李涵, 苏贤礼, 唐新峰 2011 物理学报 60 027202Google Scholar

    Wang Z C, Li H, Su X L, Tang X F 2011 Acta Phys. Sin. 60 027202Google Scholar

    [5]

    Snyder G J, E S Toberer 2008 Nat. Mater. 7 105Google Scholar

    [6]

    Francis J D 1999 Science 285 703Google Scholar

    [7]

    He J, Tritt T M 2017 Science 357 k9997Google Scholar

    [8]

    Tan G, Zhao L, Kanatzidis M G 2016 Chem. Rev. 116 12123Google Scholar

    [9]

    Zhu T, Liu Y, Fu C, Heremans J P, Snyder J G, Zhao X 2017 Adv. Mater. 29 1605884Google Scholar

    [10]

    Liu Z, Mao J, Liu T, Chen G, Ren Z 2018 MRS. Bull. 43 181Google Scholar

    [11]

    Liu Z, Sun J, Mao J, Zhu H, Ren W, Zhou J, Wang Z, Singh D J, Sui J, Chu C, Ren Z 2018 Proc. Natl. Acad. Sci. U. S. A. 115 5332Google Scholar

    [12]

    Wang L, Li J, Zhang C, Ding T, Xie Y, Li Y, Liu F, Ao W, Zhang C 2020 J. Mater. Chem. A 8 1660Google Scholar

    [13]

    Qiu P F, Zhu Y Q, Qin Y T, Shi X, Chen L D 2016 APL Mater. 4 104805Google Scholar

    [14]

    Zhao L, Wang X, Fei F Y, Wang J, Cheng Z, Dou S, Wang J, Snyder G J 2015 J. Mater. Chem. A 3 9432Google Scholar

    [15]

    Ge Z, Zhang B, Chen Y, Yu Z, Liu Y, Li J 2011 Chem. Commun. 47 12697Google Scholar

    [16]

    Dennler G, Chmielowski R, Jacob S, Capet F, Roussel P, Zastrow S, Nielsch K, Opahle I, Madsen G K H 2014 Adv. Energy Mater. 4 1301581Google Scholar

    [17]

    Qin P, Qian X, Ge Z H, Zheng L, Feng J, Zhao L D 2017 Inog. Chem. Front. 4 1192Google Scholar

    [18]

    Ge Z, Liu X, Feng D, Lin J, He J 2016 Adv. Energy Mater. 6 1600607Google Scholar

    [19]

    Ge Z H, Chong X, Feng D, Zhang Y X, Qiu Y, Xie L, Guan P W, Feng J, He J 2019 Mater. Today Phys. 8 71Google Scholar

    [20]

    Zou L, Zhang B, Ge Z, Gao C, Zhang D, Liu Y 2013 Phys. Status Solidi A. 210 2550Google Scholar

    [21]

    Qin P, Ge Z, Feng J 2017 J. Alloys Compd. 696 782Google Scholar

    [22]

    Yao Y, Zhang B, Pei J, Han Y, Zhou M 2016 Ceram. Int. 42 17518Google Scholar

    [23]

    Liang D, Ge Z, Li H, Zhang B, Li F 2017 J. Alloys Compd. 708 169Google Scholar

    [24]

    Ge Z, Zhang Y, Song D, Chong X, Qin P, Zheng F, Feng J, Zhao L 2018 J. Mater. Chem. A 6 14440Google Scholar

    [25]

    Tang H, Zhuang H, Cai B, Asfandiyar A, Dong J, Sun F, Li J 2019 J. Mater. Chem. C 7 4026Google Scholar

    [26]

    Bayikadi K S, Wu C T, Chen L, Chen K, Chou F, Sankar R 2020 J. Mater. Chem A 8 5332Google Scholar

    [27]

    Chen T, Zhang K, Wang H, Su W, Mehmood F, Wang T, Zhai J, Wang X, Huo T, Wang C 2020 J. Mater. Chem. C 8 1679Google Scholar

    [28]

    Zhao K, Qiu P, Song Q, Blichfeld A B, Eikeland E, Ren D, Ge B, Iversen B B, Shi X, Chen L 2017 Mater. Today Phys. 1 14Google Scholar

    [29]

    Poudel B, Hao Q, Ma Y, Lan Y, Minnich A, Yu B, Yan X, Wang D, Muto A, Vashaee D, Chen X, Liu J, Dresselhaus M S, Chen G, Ren Z 2008 Science 320 634Google Scholar

    [30]

    Li J, Zhang X, Chen Z, Lin S, Li W, Shen J, Witting I T, Faghaninia A, Chen Y, Jain A, Chen L, Snyder G J, Pei Y 2018 Joule 2 976Google Scholar

    [31]

    Zhao L D, Wu H J, Hao S Q, Wu C I, Zhou X Y, Biswas K, He J Q, Hogan T P, Uher C, Wolverton C, Dravid V P, Kanatzidis M G 2013 Energy Environ. Sci. 6 3346Google Scholar

    [32]

    Xu Q, Huang B, Zhao Y F, Yan Y F, Noufi R, Wei S H 2012 Appl. Phys. Lett. 100 061906Google Scholar

    [33]

    Chakrabarti D J, Laughlin D E 1983 Bull. Alloy Phase Diagrams 4 254Google Scholar

    [34]

    Tang C, Liang D, Li H, Luo K, Zhang B 2019 J. Adv. Ceram. 8 209Google Scholar

    [35]

    Zhou Y, Ge Z, Gan G, Song P, Feng J 2019 Solid State Sci. 95 105953Google Scholar

    [36]

    Zhang Y, Ma Z, Ge Z, Qin P, Zheng F, Feng J 2018 J. Alloys Compd. 764 738Google Scholar

    [37]

    Qin P, Ge Z, Feng J 2017 J. Mater. Res. 32 3029Google Scholar

  • 图 1  Cu1.8–x Sbx S (x = 0, 0.005, 0.02, 0.03, 0.04)粉体样品的室温 XRD图谱(2θ = 20º−60º) (a)和(0 1 20)晶面放大峰(b)

    Fig. 1.  XRD patterns of the Cu1.8–x Sbx S powder samples (x = 0, 0.005, 0.02, 0.03, 0.04) at 2θ range of 20°−60° (a) and the enlarged (0 1 20) peaks (b).

    图 2  Cu1.8–x Sbx S (x = 0, 0.005, 0.02, 0.03, 0.04)块体样品的XRD图谱 (a) 2θ = 20º−60º; (b) 2θ = 31º−33º

    Fig. 2.  XRD patterns of the Cu1.8–x Sbx S bulk samples (x = 0.00, 0.005, 0.02, 0.03, 0.04) at 2θ range of 20º−60º (a) and 31º−33º (b).

    图 3  Cu1.8–x Sbx S块体样品的晶粒尺寸分布及断口FESEM照, 其中x取值分别为(a) x = 0, (b) x = 0.005, (c) x = 0.02, (d) x = 0.03, (e) x = 0.04; (f) 密度和相对密度随x变化图

    Fig. 3.  Grain size distributions of Cu1.8–x Sbx S bulks with FESEM images of the fractured surfaces in the inset at (a) x = 0.00, (b) x = 0.005, (c) x = 0.02, (d) x = 0.03, (e) x = 0.04; (f) density and relative density.

    图 4  Cu1.8–x Sbx S (x = 0, 0.005, 0.02, 0.03, 0.04)块体样品的电输运性能 (a) 电导率; (b) Seebeck系数; (c) 功率因子

    Fig. 4.  Temperature dependence of electrical transport properties for Cu1.8–x Sbx S (x = 0, 0.005, 0.02, 0.03, 0.04) bulks: (a) Electrical conductivity σ; (b) Seebeck coefficient α; (c) power factor PF.

    图 5  Cu1.8–x Sbx S (x = 0, 0.005, 0.02, 0.03, 0.04)块体样品的热输运性能 (a) 总热导率κ; (b) 洛伦兹常数L; (c) 电子热导率与总热导率的比值κe /κ

    Fig. 5.  Temperature dependence of thermal transport properties for Cu1.8–x Sbx S (x = 0, 0.005, 0.02, 0.03, 0.04) bulks: (a) Total thermal conductivity κ; (b) Lorenz number L; (c) the ratios of electronic thermal conductivity to total thermal conductivity (κe /κ).

    图 6  (a) Cu1.8–x Sbx S (x = 0, 0.005, 0.02, 0.03, 0.04)块体的ZT值; (b) 723 K时不同Cu1.8S基材料的热电性能对比[18,21,34-37]

    Fig. 6.  (a) Temperature dependence of ZT for Cu1.8–x Sbx S (x = 0, 0.005, 0.02, 0.03, 0.04) bulks; (b) comparisons of thermoelectric properties of different Cu1.8S-based materials at 723 K[18,21,34-37].

  • [1]

    葛振华, 张波萍, 于昭新, 刘勇, 李敬锋 2012 物理学报 61 048401Google Scholar

    Ge Z H, Zhang B P, Yu Z X, Liu Y, Li J F 2012 Acta Phys. Sin. 61 048401Google Scholar

    [2]

    赵立东, 张波萍, 李敬锋, 刘玮书, 周敏 2007 稀有金属材料与工程 36 408Google Scholar

    Zhao L D, Zhang B P, Li J F, Liu W S, Zhou M 2007 Rare Metal Mat. Eng. 36 408Google Scholar

    [3]

    张贺, 骆军, 朱航天, 刘泉林, 梁敬魁, 饶光辉 2012 物理学报 61 086101Google Scholar

    Zhang H, Luo J, Zhu H T, Liu Q Lin, Liang J K, Rao G H 2012 Acta Phys. Sin. 61 086101Google Scholar

    [4]

    王作成, 李涵, 苏贤礼, 唐新峰 2011 物理学报 60 027202Google Scholar

    Wang Z C, Li H, Su X L, Tang X F 2011 Acta Phys. Sin. 60 027202Google Scholar

    [5]

    Snyder G J, E S Toberer 2008 Nat. Mater. 7 105Google Scholar

    [6]

    Francis J D 1999 Science 285 703Google Scholar

    [7]

    He J, Tritt T M 2017 Science 357 k9997Google Scholar

    [8]

    Tan G, Zhao L, Kanatzidis M G 2016 Chem. Rev. 116 12123Google Scholar

    [9]

    Zhu T, Liu Y, Fu C, Heremans J P, Snyder J G, Zhao X 2017 Adv. Mater. 29 1605884Google Scholar

    [10]

    Liu Z, Mao J, Liu T, Chen G, Ren Z 2018 MRS. Bull. 43 181Google Scholar

    [11]

    Liu Z, Sun J, Mao J, Zhu H, Ren W, Zhou J, Wang Z, Singh D J, Sui J, Chu C, Ren Z 2018 Proc. Natl. Acad. Sci. U. S. A. 115 5332Google Scholar

    [12]

    Wang L, Li J, Zhang C, Ding T, Xie Y, Li Y, Liu F, Ao W, Zhang C 2020 J. Mater. Chem. A 8 1660Google Scholar

    [13]

    Qiu P F, Zhu Y Q, Qin Y T, Shi X, Chen L D 2016 APL Mater. 4 104805Google Scholar

    [14]

    Zhao L, Wang X, Fei F Y, Wang J, Cheng Z, Dou S, Wang J, Snyder G J 2015 J. Mater. Chem. A 3 9432Google Scholar

    [15]

    Ge Z, Zhang B, Chen Y, Yu Z, Liu Y, Li J 2011 Chem. Commun. 47 12697Google Scholar

    [16]

    Dennler G, Chmielowski R, Jacob S, Capet F, Roussel P, Zastrow S, Nielsch K, Opahle I, Madsen G K H 2014 Adv. Energy Mater. 4 1301581Google Scholar

    [17]

    Qin P, Qian X, Ge Z H, Zheng L, Feng J, Zhao L D 2017 Inog. Chem. Front. 4 1192Google Scholar

    [18]

    Ge Z, Liu X, Feng D, Lin J, He J 2016 Adv. Energy Mater. 6 1600607Google Scholar

    [19]

    Ge Z H, Chong X, Feng D, Zhang Y X, Qiu Y, Xie L, Guan P W, Feng J, He J 2019 Mater. Today Phys. 8 71Google Scholar

    [20]

    Zou L, Zhang B, Ge Z, Gao C, Zhang D, Liu Y 2013 Phys. Status Solidi A. 210 2550Google Scholar

    [21]

    Qin P, Ge Z, Feng J 2017 J. Alloys Compd. 696 782Google Scholar

    [22]

    Yao Y, Zhang B, Pei J, Han Y, Zhou M 2016 Ceram. Int. 42 17518Google Scholar

    [23]

    Liang D, Ge Z, Li H, Zhang B, Li F 2017 J. Alloys Compd. 708 169Google Scholar

    [24]

    Ge Z, Zhang Y, Song D, Chong X, Qin P, Zheng F, Feng J, Zhao L 2018 J. Mater. Chem. A 6 14440Google Scholar

    [25]

    Tang H, Zhuang H, Cai B, Asfandiyar A, Dong J, Sun F, Li J 2019 J. Mater. Chem. C 7 4026Google Scholar

    [26]

    Bayikadi K S, Wu C T, Chen L, Chen K, Chou F, Sankar R 2020 J. Mater. Chem A 8 5332Google Scholar

    [27]

    Chen T, Zhang K, Wang H, Su W, Mehmood F, Wang T, Zhai J, Wang X, Huo T, Wang C 2020 J. Mater. Chem. C 8 1679Google Scholar

    [28]

    Zhao K, Qiu P, Song Q, Blichfeld A B, Eikeland E, Ren D, Ge B, Iversen B B, Shi X, Chen L 2017 Mater. Today Phys. 1 14Google Scholar

    [29]

    Poudel B, Hao Q, Ma Y, Lan Y, Minnich A, Yu B, Yan X, Wang D, Muto A, Vashaee D, Chen X, Liu J, Dresselhaus M S, Chen G, Ren Z 2008 Science 320 634Google Scholar

    [30]

    Li J, Zhang X, Chen Z, Lin S, Li W, Shen J, Witting I T, Faghaninia A, Chen Y, Jain A, Chen L, Snyder G J, Pei Y 2018 Joule 2 976Google Scholar

    [31]

    Zhao L D, Wu H J, Hao S Q, Wu C I, Zhou X Y, Biswas K, He J Q, Hogan T P, Uher C, Wolverton C, Dravid V P, Kanatzidis M G 2013 Energy Environ. Sci. 6 3346Google Scholar

    [32]

    Xu Q, Huang B, Zhao Y F, Yan Y F, Noufi R, Wei S H 2012 Appl. Phys. Lett. 100 061906Google Scholar

    [33]

    Chakrabarti D J, Laughlin D E 1983 Bull. Alloy Phase Diagrams 4 254Google Scholar

    [34]

    Tang C, Liang D, Li H, Luo K, Zhang B 2019 J. Adv. Ceram. 8 209Google Scholar

    [35]

    Zhou Y, Ge Z, Gan G, Song P, Feng J 2019 Solid State Sci. 95 105953Google Scholar

    [36]

    Zhang Y, Ma Z, Ge Z, Qin P, Zheng F, Feng J 2018 J. Alloys Compd. 764 738Google Scholar

    [37]

    Qin P, Ge Z, Feng J 2017 J. Mater. Res. 32 3029Google Scholar

  • [1] 李桑丫, 张艾霖, 徐欣, 吕涛, 王世康, 罗箐. 基于强流离子源的离子束溅射镀膜设备均匀性优化. 物理学报, 2024, 73(5): 058101. doi: 10.7498/aps.73.20231491
    [2] 雷照康, 武耀蓉, 黄晨阳, 莫润阳, 沈壮志, 王成会, 郭建中, 林书玉. 驻波场中环状空化泡聚集结构的稳定性分析. 物理学报, 2024, 0(0): . doi: 10.7498/aps.73.20231956
    [3] 程秋振, 黄引, 李玉辉, 张凯, 冼国裕, 刘鹤元, 车冰玉, 潘禄禄, 韩烨超, 祝轲, 齐琦, 谢耀锋, 潘金波, 陈海龙, 李永峰, 郭辉, 杨海涛, 高鸿钧. 准一维层状半导体Nb4P2S21单晶的面内光学各向异性. 物理学报, 2023, 72(21): 218102. doi: 10.7498/aps.72.20231539
    [4] 刘远峰, 李斌成, 赵斌兴, 刘红. SiC光学材料亚表面缺陷的光热辐射检测. 物理学报, 2023, 72(2): 024208. doi: 10.7498/aps.72.20221303
    [5] 蒋东镔, 张颖, 姜大朋, 朱斌, 李纲, 孙立, 黄征, 卢峰, 谢娜, 周凯南, 粟敬钦. Nd, Gd:SrF2晶体材料在宽带放大中的光谱增益特性. 物理学报, 2023, 72(22): 224208. doi: 10.7498/aps.72.20230972
    [6] 刘瑛, 郭斯琳, 张勇, 杨鹏, 吕克洪, 邱静, 刘冠军. 1/f噪声及其在二维材料石墨烯中的研究进展. 物理学报, 2023, 72(1): 017302. doi: 10.7498/aps.72.20221253
    [7] 孙颖慧, 穆丛艳, 蒋文贵, 周亮, 王荣明. 金属纳米颗粒与二维材料异质结构的界面调控和物理性质. 物理学报, 2022, 71(6): 066801. doi: 10.7498/aps.71.20211902
    [8] 徐强, 司雪, 佘维汉, 杨光敏. 超电容储能电极材料的密度泛函理论研究. 物理学报, 2021, 70(10): 107301. doi: 10.7498/aps.70.20201988
    [9] 郑丽仙, 胡剑峰, 骆军. 铜掺杂Cu2SnSe4的热电输运性能. 物理学报, 2020, 69(24): 247102. doi: 10.7498/aps.69.20200861
    [10] 何寿杰, 周佳, 渠宇霄, 张宝铭, 张雅, 李庆. 氩气空心阴极放电复杂动力学过程的模拟研究. 物理学报, 2019, 68(21): 215101. doi: 10.7498/aps.68.20190734
    [11] 马堃, 陈展斌, 黄时中. 等离子体屏蔽效应对Ar16+基态和激发态能级的影响. 物理学报, 2019, 68(2): 023102. doi: 10.7498/aps.68.20181915
计量
  • 文章访问数:  3192
  • PDF下载量:  89
  • 被引次数: 0
出版历程
  • 收稿日期:  2020-11-05
  • 修回日期:  2021-02-03
  • 上网日期:  2021-06-07
  • 刊出日期:  2021-06-20

/

返回文章
返回