Ce0.85Fe3CoSb12/rGO热电纳米复合材料的制备及其力学性能

doi:10.15541/jim20160220

无机材料学报 ›› 2017, Vol. 32 ›› Issue (1): 33-38.DOI: 10.15541/jim20160220 CSTR: 32189.14.10.15541/jim20160220

Ce_0.85Fe₃CoSb₁₂/rGO热电纳米复合材料的制备及其力学性能

宗鹏安^1,2, 陈立东¹

(1. 中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海200050; 2. 中国科学院大学, 北京100864)

收稿日期:2016-04-01 修回日期:2016-05-31 出版日期:2017-01-20 网络出版日期:2016-12-15
作者简介:宗鹏安(1989–), 男, 博士研究生. E-mail: zongpengan@student.sic.ac.cn
基金资助:
国家自然科学基金重点项目(51222209, 11234012);国家重点基础研究发展计划(973)项目(2013CB632503)

Preparation and Mechanical Properties of Ce_0.85Fe₃CoSb₁₂/rGO Thermoelectric Nanocomposite

ZONG Peng-An^1,2, CHEN Li-Dong¹

(1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China; 2. University of Chinese Academy of Sciences, Beijing 100864, China)

Received:2016-04-01 Revised:2016-05-31 Published:2017-01-20 Online:2016-12-15
About author:ZONG Peng-An. E-mail: zongpengan@student.sic.ac.cn
Supported by:
National Science Foundation of China (51222209, 11234012);National Key Basic Research (973) Program of China (2013CB632503)

摘要/Abstract

摘要：

p型填充方钴矿材料的力学性能相对于n型较差, 成为方钴矿热电器件集成设计的薄弱环节。本工作利用氧化石墨烯(GO)良好的润湿性和亲水性, 通过液相分散实现了GO对Ce_0.85Fe₃CoSb₁₂基体颗粒的网状包覆与均匀分散。利用放电等离子烧结技术同时实现了致密化和对GO的原位还原, 获得了2~5 nm厚还原氧化石墨烯(rGO)三维网状包覆的Ce_0.85Fe₃CoSb₁₂基纳米复合材料。该三维网状结构利用桥接作用增加了裂纹扩展额外功, 实现了对基体材料的增强增韧。当rGO含量为2.8vol%时, Ce_0.85Fe₃CoSb₁₂/rGO复合材料的抗弯强度和断裂韧性相对于纯基体材料分别提高40%和33%。但进一步提高rGO含量会增加基体晶界处的rGO厚度, 进而弱化其增强增韧效果。

关键词: 热电材料, 方钴矿, 石墨烯, 纳米复合, 力学性能

Abstract:

Comparing to n-type filled skutterudite, p-type one owns poorer mechanical propertities, which becomes the weak link of integration and the design of skutterudite based thermoelectric devices. By utilizing outstanding wettability and hydrophily of graphene oxide (GO), network wrapping and homogeneous dispersion of GO were realized in Ce_0.85Fe₃CoSb₁₂matrix particles via liquid dispersion. Spark plasma sintering was adopted to realize coherent densification and in-situ reduction of GO to rGO. Thus a 2-5 nm thick three dimensional reduced graphene oxide (rGO) wrapping structure in Ce_.85Fe₃CoSb₁₂/rGO nanocomposite was obtained, which would enhance the flexural strength and toughness by additional crack-expanding work with bridging effect. Comparing to the pure Ce_0.85Fe₃CoSb₁₂material, flexural strength and toughness of Ce_.85Fe₃CoSb₁₂/rGO nanocomposite with 2.8vol% rGO were enhanced by up to 40% and 33%, respectively. Reinforcing and toughening effects were weakened when rGO content farther increased, due to the thickened rGO layers in the matrix grain boundaries.

Key words: thermoelectric materials, skutterudite, graphene, nanocomposite, mechanical properties

中图分类号:

TQ174

宗鹏安, 陈立东. Ce_0.85Fe₃CoSb₁₂/rGO热电纳米复合材料的制备及其力学性能[J]. 无机材料学报, 2017, 32(1): 33-38.

ZONG Peng-An, CHEN Li-Dong. Preparation and Mechanical Properties of Ce_0.85Fe₃CoSb₁₂/rGO Thermoelectric Nanocomposite[J]. Journal of Inorganic Materials, 2017, 32(1): 33-38.

图/表 8

图1 氧化石墨烯的热重分析曲线

Fig. 1 Thermogravimetric (TG) analysis curves of GO

图2 GO及rGO (GO 850K-SPS烧结所得)的拉曼图谱

Fig. 2 Raman spectra of GO and rGO (850K-SPSed GO)

图3 Ce0.85Fe3CoSb12/y vol% rGO (y = 0, 0.56, 1.4, 2.8) 复合材料的粉末XRD图谱

Fig. 3 Powder XRD patterns of the sintered Ce0.85Fe3 CoSb12/ yvol% rGO (y = 0, 0.56, 1.4, 2.8)

图4 (a) GO片层边缘高分辨透射电镜照片, (b) Ce0.85Fe3 CoSb12/1.4vol% GO混合粉末透射电镜照片, (c) SPS烧结所得Ce0.85Fe3CoSb12/1.4vol% rGO块体表面HADDF-STEM照片和(d) Ce0.85Fe3CoSb12/1.4vol% rGO块体界面高分辨HADDF- STEM照片

Fig. 4 (a) High resolution TEM image of fold GO sheet edge, (b) TEM image of Ce0.85Fe3CoSb12/1.4vol% GO mixed powder, (c) HADDF-STEM image of the SPSed Ce0.85Fe3CoSb12/ 1.4vol% rGO bulk surface and (d) Local high resolution HADDF-STEM image of the Ce0.85Fe3CoSb12/1.4vol% rGO bulk interface

图5 Ce0.85Fe3CoSb12/2.8vol% rGO 复合材料块体表面能谱图

Fig. 5 Surface EDS patterns of the sintered Ce0.85Fe3CoSb12/2.8vol% rGO bulk nanocomposite

图6 Ce0.85Fe3CoSb12/y vol% rGO (y = 0, 0.56, 1.4, 2.8) 复合块体材料三点抗弯强度(σ)及断裂韧性(KIC)随rGO含量的变化关系图

Fig. 6 Three-point flexural strength (σ) and fracture toughness (KIC) of the Ce0.85Fe3CoSb12/yvol% rGO (y = 0, 0.56, 1.4, 2.8) composites as a function of rGO content

图7 (a) Ce0.85Fe3CoSb12/1.4vol% rGO复合材料块体断面扫描电镜照片; (b) Ce0.85Fe3CoSb12/1.4vol% rGO复合材料块体裂纹扩展扫描电镜照片和(c,d) 裂纹扩展拉断rGO图例

Fig. 7 (a) Fracture SEM image of the Ce0.85Fe3CoSb12/ 1.4vol% rGO bulk nanocomposite; (b) SEM image of the expanded crack of the Ce0.85Fe3CoSb12/1.4vol% rGO bulk nanocomposite and (c,d) TEM images of failed crack with breaked rGO (example I, II)

图8 石墨烯增韧机理示意图

Fig. 8 Schematic toughing mechanism by rGO

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Ce_0.85Fe₃CoSb₁₂/rGO热电纳米复合材料的制备及其力学性能

Preparation and Mechanical Properties of Ce_0.85Fe₃CoSb₁₂/rGO Thermoelectric Nanocomposite

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