Ce0.85Fe3CoSb12/rGO热电纳米复合材料的制备及其力学性能

doi:10.15541/jim20160220

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

参考文献 21

[1]	CHEN L D, XIONG Z, BAI S Q.Recent progress of thermoelectric nano-composites.Journal of Inorganic Materials, 2010, 25(6): 561-568.
[2]	TANG Y S, BAI S Q, REN D D.Interface structure and electrical property of Yb0.3Co4Sb12/Mo-Cu element prepared by welding using Ag-Cu-Zn solder.Journal of Inorganic Materials, 2015, 3(30): 256-260.
[3]	ROGL G, ROGL P.Mechanical properties of skutterudites.Science of Advanced Materials, 2011, 3(4): 517-538.
[4]	RAVI V, FIRDOSY S, CAILLAT T, et al. Mechanical Properties of Thermoelectric Skutterudites. AIP Conference Proceedings, 2008, 969: 656-662.
[5]	SLACK G A, ROWE D M, ed. CRC Handbook of Thermoelectrics. Boca Raton: CRC Press, 1995.
[6]	CHEN L D, KAWAHARA T, TANG X F,et al.Anomalous barium filling fraction and n-type thermoelectric performance of BayCo4Sb12.Journal of Applied Physics, 2001, 90(4): 1864-1868.
[7]	SHI X, YANG J, SALVADOR R J,et al.Multiple-filled skutterudites: high thermoelectric figure of merit through separately optimizing electrical and thermal transports.Journal of the American Chemical Society, 2011, 133(20): 7837-7846.
[8]	DING J, LIU R H, GU H,et al.Study on the high temperature stability of YbyCo4Sb12/Yb2O3 composite thermoelctric material.Journal of Inorganic Materials, 2014, 29(2): 209-214.
[9]	ROGL G, GRYTSIV A, ROGL P,et al.N-type skutterudites (R,Ba,Yb)yCo4Sb12(R = Sr, La, Mm, DD, SrMm, SrDD) approaching ZT ≈ 2.0.Acta Materialia, 2014, 63: 30-43.
[10]	ROGL G, GRYTSIV A, ROGL P,et al.Nanostructuring of p- and n-type skutterudites reaching figures of merit of approximately 1.3 and 1.6, respectively.Acta Materialia, 2014, 76: 434-448.
[11]	ZHANG Q H, HUANG X Y, BAI S Q,et al.Thermoelectric devices for power generation: recent progress and future challenges.Advanced Engineering Materials, 2016, 18(2): 194-213.
[12]	GEIM A K.Graphene: status and prospects.Science, 2009, 324(5934): 1530-1534.
[13]	LI J L, CHEN B B, ZHANG W,et al.Recent progress in ceramic/graphene bulk composites.Journal of Inorganic Materials, 2014, 29(3): 225-236.
[14]	WALKER L S, MAROTTO V R, RAFIEE M A, et al.Toughening in graphene ceramic composites.ACS Nano, 2011, 5(4): 3182-3190.
[15]	RAMIREZA C, MIRANZO P, BELMONTE M,et al.Extraordinary toughening enhancement and flexural strength in Si3N4 composites using graphene sheets.Journal of the European Ceramic Society, 2014, 34(2): 161-169.
[16]	LIU J, YAN H X, JIANG K.Mechanical properties of graphene platelet-reinforced alumina ceramic composites.Ceramic International, 2013, 39(6): 6215-6221.
[17]	FAN Y C, IGARASHI G, JIANG W,et al.Highly strain tolerant and tough ceramic composite by incorporation of graphene.Carbon, 2015, 90: 274-283.
[18]	ZONG P A, CHEN X H, ZHU Y W,et al.Construction of a 3D-rGO network-wrapping architecture in a YbyCo4Sb12/rGO composite for enhancing the thermoelectric performance.Journal of Material Chemistry A, 2015, 3(16): 8643-8649.
[19]	STANKOVICH S, DIKIN D A, PINER R D,et al.Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide.Carbon, 2007, 45(7): 1558-1565.
[20]	MARCANO D C, KOSYNKIN D V, BERLIN J M,et al.Improved synthesis of graphene oxide.ACS Nano, 2010, 4(8): 4806-4814.
[21]	RAMÍREZ C, VEGA-DIAZ S M, MORELOS-GÓMEZ A,et al.Synthesis of conducting graphene/Si3N4 composites by spark plasma sintering.Carbon, 2013, 57: 425-432.

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

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 21

相关文章 15

编辑推荐

Metrics

本文评价

[1]	贺丹琪, 魏明旭, 刘蕤之, 汤志鑫, 翟鹏程, 赵文俞. 一步法制备重费米子YbAl₃热电材料及其性能提升[J]. 无机材料学报, 2023, 38(5): 577-582.
[2]	陈赛赛, 庞雅莉, 王娇娜, 龚䶮, 王锐, 栾筱婉, 李昕. 绿-黄可逆电热致变色织物的制备及其性能[J]. 无机材料学报, 2022, 37(9): 954-960.
[3]	安文然, 黄晶琪, 卢祥荣, 蒋佳宁, 邓龙辉, 曹学强. 热处理温度对LaMgAl₁₁O₁₉涂层热/力学性能的影响[J]. 无机材料学报, 2022, 37(9): 925-932.
[4]	张叶, 曾宇平. 自蔓延高温合成氮化硅多孔陶瓷的研究进展[J]. 无机材料学报, 2022, 37(8): 853-864.
[5]	王鹏将, 康慧君, 杨雄, 刘颖, 程成, 王同敏. 熵调控抑制ZrNiSn基half-Heusler热电材料的晶格热导率[J]. 无机材料学报, 2022, 37(7): 717-723.
[6]	程成, 李建波, 田震, 王鹏将, 康慧君, 王同敏. In₂O₃/InNbO₄复合材料的热电性能研究[J]. 无机材料学报, 2022, 37(7): 724-730.
[7]	孙铭, 邵溥真, 孙凯, 黄建华, 张强, 修子扬, 肖海英, 武高辉. RGO/Al复合材料界面性质第一性原理研究[J]. 无机材料学报, 2022, 37(6): 651-659.
[8]	洪督, 牛亚然, 李红, 钟鑫, 郑学斌. 等离子喷涂TiC-Graphite复合涂层摩擦磨损性能[J]. 无机材料学报, 2022, 37(6): 643-650.
[9]	徐谱昊, 张相召, 刘桂武, 张明芬, 桂新易, 乔冠军. Al-Ti合金钎焊SiC陶瓷接头界面微观结构与力学性能[J]. 无机材料学报, 2022, 37(6): 683-690.
[10]	夏乾, 孙是昊, 赵义亮, 张翠萍, 茹红强, 王伟, 岳新艳. 碳化硼颗粒级配对硅反应结合碳化硼复合材料结构与性能的影响[J]. 无机材料学报, 2022, 37(6): 636-642.
[11]	丁健翔, 张凯歌, 柳东明, 郑伟, 张培根, 孙正明. Ti₃AlC₂陶瓷及其衍生物Ti₃C₂T_x增强的Ag基电接触材料[J]. 无机材料学报, 2022, 37(5): 567-573.
[12]	王虹力, 王男, 王丽莹, 宋二红, 赵占奎. 功能化石墨烯担载型AuPd纳米催化剂增强甲酸制氢反应[J]. 无机材料学报, 2022, 37(5): 547-553.
[13]	安琳, 吴淏, 韩鑫, 李耀刚, 王宏志, 张青红. 非贵金属Co_5.47N/N-rGO助催化剂增强TiO₂光催化制氢性能[J]. 无机材料学报, 2022, 37(5): 534-540.
[14]	董淑蕊, 赵笛, 赵静, 金万勤. 离子化氨基酸对氧化石墨烯膜渗透汽化过程中水选择性渗透的影响[J]. 无机材料学报, 2022, 37(4): 387-394.
[15]	蒋丽丽, 徐帅帅, 夏宝凯, 陈胜, 朱俊武. 缺陷调控石墨烯复合催化剂在氧还原反应中的作用[J]. 无机材料学报, 2022, 37(2): 215-222.