Synthesis and Optimization of Chalcogenides Quantum Dots Thermoelectric Materials

124 Pages·2016·5.778 MB·English

by  Chong Xiao (auth.)

Springer Theses
Recognizing Outstanding Ph.D. Research
Chong Xiao

Synthesis and
Optimization of
Chalcogenides
Quantum Dots
Thermoelectric
Materials
Springer Theses
Recognizing Outstanding Ph.D. Research
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Chong Xiao
Synthesis and Optimization
of Chalcogenides Quantum
Dots Thermoelectric
Materials
Doctoral Thesis accepted by
University of Science and Technology of China, China
123
Author Supervisor
Dr. ChongXiao Prof. YiXie
University of Science andTechnology University of Science andTechnology
ofChina ofChina
Hefei Hefei
China China
ISSN 2190-5053 ISSN 2190-5061 (electronic)
SpringerTheses
ISBN978-3-662-49615-2 ISBN978-3-662-49617-6 (eBook)
DOI 10.1007/978-3-662-49617-6
LibraryofCongressControlNumber:2016933110
©Springer-VerlagBerlinHeidelberg2016
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Parts of this thesis have been published in the following journal articles:
1. Chong Xiao, Zhou Li, Kun Li, Pengcheng Huang, and Yi Xie* (2014)
Decoupling Interrelated Parameters for Designing High Performance
Thermoelectric Materials. Acc. Chem. Res. 47:1287−1295
2. Chong Xiao, Jie Xu, Kun Li, Jun Feng, Jinlong Yang, and Yi Xie* (2012)
Superionic Phase Transition in Silver Chalcogenide Nanocrystals Realizing
Optimized Thermoelectric Performance. J. Am. Chem. Soc. 134:4287–4293
3. Chong Xiao, Jie Xu, Boxiao Cao, Kun Li, Mingguang Kong, and Yi Xie*
(2012) Solid-Solutioned Homojunction Nanoplates with Disordered Lattice: a
Promising Approach toward “Phonon Glass Electron Crystal” Thermoelectric
Materials. J. Am. Chem. Soc. 134:7971–7977
4. Chong Xiao, Xinming Qin, Jie Zhang, Ran An, Jie Xu, Kun Li, Boxiao Cao,
Jinlong Yang*, Bangjiao Ye, and Yi Xie* (2012) High Thermoelectric and
Reversible p-n-p Conduction Type Switching Integrated in Di-metal
Chalcogenide. J. Am. Chem. Soc. 134:18460–18466
5. Chong Xiao, Kun Li, Jiajia Zhang, Wei Tong, Youwen Liu, Zhou Li,
Pengcheng Huang, Bicai Pan,HaibinSu,andYi Xie*(2012) Magnetic Ions in
Wide Band Gap Semiconductor Nanocrystals for Optimized Thermoelectric
Property. Mater. Horiz. 1:81–86
’
Supervisor s Foreword
Thermoelectric materials have attracted widespread research interest, since they
mayprovideanoptimizedsolutionformitigationofenergyandenvironmentcrisis
due to their capability of reversibly converting heat and electricity with the
advantages of being reliable, lightweight, robust, and environmentally friendly.
However, the energy conversion efficiency of thermoelectric devices is far below
the theoretical predictions, which suffers from their strongly inverse interrelated
electrical and thermal parameters. This Ph.D. thesis study focuses on the
long-standingandcrucialissueinthermoelectricmaterials:“Canwesynergistically
or individually optimize the electrical and thermal transport properties in thermo-
electric materials? And how?”
Dr. Xiao first proposed a universal and effective strategy to optimize the ther-
moelectric performance based on phase transition, a widespread phenomenon that
occurs in inorganic compounds, which takes advantage of modulated electronic
structure and phonon scattering across the phase transitions to decouple the power
factor and thermal conductivity. Furthermore, he found a novel phenomenon that
integrates of high thermoelectric performance and reversible p−n−p semiconduct-
ing switching in dimetal chalcogenides semiconductors, which may open a new
avenue todesignmultifunctional materials and devices.Then,he developed anew
approachtomeetthe“phononglasselectroncrystal”bydesigningsolid-solutioned
homojunction nanoplates in semiconductors with disordered lattices, which can
significantlyreducethermal conductivitywithoutthedeterioration ofthermopower
and electrical conductivity.
Itisnotexaggeratedtostatethatthisthesisstudyishighlyoriginalanditsresults
significantly deepen our understanding of the thermoelectric materials. This thesis
has paved a way for further development of both design and characterization of
materials science.
Hefei, China Prof. Yi Xie
August 2015
vii
Acknowledgments
Overtimeandwithage,fouryearsofPh.D.studycametoanendandanewstarting
pointisinfrontofus;inthismoment,thewordof“gratitude”staysforefrontinmy
mind throughout the day.
Firstly, I owe my deepest gratitude to my respected supervisor Prof. Yi Xie.
Without her enthusiasm, encouragement, continuous support, and optimism in my
whole Ph.D. study, this thesis would hardly have been completed. From the
selection of topics, data collection, and discussion about writing papers, in every
steps of my progress, I got a lot of enthusiastic help from my supervisor. Think
back, these past several years have not been an easy ride, both academically and
personally. I truly thank Prof. Yi Xie for sticking by my side, even when I was
irritableanddepressed.Prof.YiXiewasthereasonwhyIdecidedtogotopursuea
career in research. Her profound knowledge, acute insights, modesty and rigorous
scholarship,andenthusiasmandloveforteaching arecontagious.Sheshowedand
stimulatedmeindifferent waystoapproacharesearchproblemandtheneedtobe
persistenttoaccomplishanygoal.Here,Ipaymyhighrespectandgratitudetomy
respected supervisor Prof. Yi Xie.
It is a pleasure to thank Mr. Xiaobo Tian for his support in the experimental
installation and routine business and for creating a cordial working environment.
I thankfully acknowledge the help come from Prof. Jinlong Yang (Department of
Chemical Physics), Prof. Bangjia Ye (Department of Modern Physics), and Prof.
Changzheng Wu (Department of Chemistry). Thanks to my collaborators: Jie Xu,
Kun Li, Youwen Liu, Zhou Li, Pengcheng Huang and other students for their
assistance and cooperation during the completion of this theses, which made me
feelfuninscientificresearchwork.Ialsothanktheseniorfellowapprenticesinthe
laboratory:Dr.ZhenyuYao,Dr.NinaYe,Dr.ShudongZhang,Dr.YanZheng,Dr.
FangDuan,Dr.YangXu,Dr.LeiZheng,Dr.YongfuSun,Dr.LiangLiu,Dr.Min
Zhou,Dr.YanXue,andDr.JianWu;graduatesofthesameyear:XiaodongZhang,
Haiou Zhu, Liangfei Bai, and Jinbao Zhu; and also junior fellow apprentices:
Junfeng Xie, Lin Liang, Ran Long, Xiao Gang, Chengming Wang, Meili Guan,
Hangmin Guan, Conghai Deng, Jian Bao, Xu Sun, Feng Feng, Wentuan Bi, Kun
ix
x Acknowledgments
Xu, HuXin, Jiajia Zhang, Shan Gao, Zejun Li, Xiao Xie, Xiaojiao Zhu, Xiuli Lu,
FengcaiLei,QinLiu,HuiWang,ShuangLi,JingLiang,andPengzuoChen.Ialso
thank the wonderful staff in the USTC for always being so helpful and friendly.
People here are genuinely nice and want to help you out and I am glad to have
interacted with many.
Theauthorwouldalsoliketothankallthepresentmembersofthephysicaland
chemical test center, especially Guien Zhou, Shuyuan Zhang, Xianming Liu,
Tanwei Li, Xiaoming Feng, Yunbo Jia, Shengquan Fu, Ming Li, Jianliu Huang,
Yanwei Ding, Jian Zuo, Yi Jin, Minghua Yu, Bo Pan, Jiyin Zhao, and Wanqun
Zhang,fortheirhelpinmaterialtestingandforcompletingthisthesis.Thanksgoto
Xinming Qin from the department of chemical physics and Jie Zhang, Shaojuan
Fan,andRanAnfromthedepartmentofmodernphysics,fortheirpowerfulhelpin
theoretical calculation and special material characterization.
I would never have got to the position of being able to do a Ph.D. without my
parents, wife, and sister, who always encouraged me to achieve my full potential
andprovidedgenerouscareandmoralsupportineverypossiblewaythroughoutmy
education. The warmth offamily has been and will always be the strong backing
behind my life. It is difficult to pay them back with simply words. Without them,
I would not have remained as motivated as I did throughout various stages of the
work, and I dedicate this thesis to them.
Finally, I would like to express my gratitude to all those who have cared,
embosomed,andhelpedmeinmystudy.Thisthesiswouldnothavebeenpossible
without the inspiration and support of a number of wonderful individuals—my
thanks and appreciation to all of them for being part of this journey.
Hefei, China Chong Xiao
May 2013
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Thermoelectric Effect and Applications. . . . . . . . . . . . . . . . . . . 2
1.3 Performance Parameters of Thermoelectric Materials . . . . . . . . . 4
1.4 Progress in Optimization of the Thermoelectric Parameters. . . . . 6
1.4.1 Individual Parameter Modulation. . . . . . . . . . . . . . . . . . 6
1.4.2 Two Parameters Synergistic Modulation. . . . . . . . . . . . . 11
1.4.3 Three Parameters Synergistic Modulation. . . . . . . . . . . . 21
1.5 Our Main Goals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2 Superionic Phase Transition Optimizing Thermoelectric
Performance in Silver Chalcogenide Nanocrystals . . . . . . . . . . . . . 35
2.1 Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.2 Results and Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3 Two Metal Ion Exchange Realizing Efficient Thermoelectric
Properties and p–n–p Conduction Type Transition . . . . . . . . . . . . 51
3.1 Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.2 Results and Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.3 Conculsion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
4 Toward “Phonon Glass Electron Crystal” in Solid-Solutioned
Homojunction Nanoplates with Disordered Lattice . . . . . . . . . . . . 65
4.1 Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.2 Results and Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.3 Conculsion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
xi