石墨烯材料热学和电学性能研究——从非简谐效应视角

本书是学术著作，反映了作者科研团队在石墨烯材料热力学和电学性质，特别是非简谐效应理论领域的研究成果。该书在介绍石墨烯材料的有关概念、分类和制备方法、普遍的物理化学性质以及石墨烯的结构和晶体结合的基础上，论述非简谐效应理论的有关概念、基本观点、研究问题的基本方法及其在三维、二维、纳米系统热学和电学性能等方面的一些应用。该书基于石墨烯、外延石墨烯、类石墨烯等石墨烯材料的结构以及组成粒子相互作用和运动特点，对石墨烯材料的热力学和电学性能的变化规律及其非简谐效应，从理论上进行深入的定量研究。该书突出了石墨烯材料的热学和电学性能非简谐效应在高蓄热材料器件、新能源、新器件、微电子、太赫兹、新型环境响应材料等方面的应用。该书的研究成果对石墨烯材料的研究和应用具有重要的理论和实际意义。

目  录

1  石墨烯材料简介·································································· 001

1.1  石墨烯材料的起源及分类··············································· 001

1.1.1  石墨烯材料的起源················································ 001

1.1.2  石墨烯材料的分类················································ 004

1.2  石墨烯材料的基本性质·················································· 007

1.2.1  石墨烯的力学性质················································ 007

1.2.2  石墨烯的光学性质················································ 008

1.2.3  石墨烯的化学性质················································ 008

1.2.4  石墨烯的导电性··················································· 009

1.2.5  石墨烯的导热性··················································· 010

1.2.6  石墨烯的阻隔性··················································· 010

1.3  石墨烯材料的制备方法简介············································· 011

1.3.1  机械剥离法························································· 011

1.3.2  外延生长法························································ 013

1.3.3  氧化还原法························································ 014

1.3.4  溶剂热法··························································· 019

1.3.5  有机合成法························································ 020

1.3.6  化学气相沉积法··················································· 021

1.3.7  电弧放电法························································ 024

1.3.8  等离子增强合成法················································ 025

1.3.9  火焰法······························································ 027

参考文献········································································· 029

2  石墨烯的结构和晶体结合······················································· 035

2.1  石墨烯的结构和显微形貌以及电子结构······························· 035

2.1.1  石墨烯的晶体结构················································ 035

2.1.2  石墨烯的电子结构················································ 036

2.1.3  多层石墨烯的晶体结构和电子结构···························· 038

2.2  石墨烯的晶体结合························································ 041

2.2.1  石墨烯的原子相互作用能········································ 041

2.2.2  石墨烯的结合能··················································· 042

2.2.3  温度对石墨烯原子相互作用能的影响·························· 043

2.3  石墨烯与吸附原子的结合··············································· 044

2.3.1  石墨烯的吸附模型················································ 045

2.3.2  吸附引起的石墨烯态密度的改变······························· 046

2.3.3  吸附原子性质对石墨烯吸附系统结合强弱的影响············ 048

2.3.4  吸附原子覆盖度随温度的变化·································· 049

2.4  石墨烯与吸附原子的键能随温度的变化······························· 051

2.4.1  石墨烯与吸附原子之间的相互作用能·························· 051

2.4.2  吸附原子性质对石墨烯与吸附原子键能的影响·············· 052

2.4.3  温度对吸附键能的影响·········································· 055

参考文献········································································· 056

3 
非简谐效应理论及其在晶体热学性质上的应用······························ 057

3.1  非简谐效应理论的有关概念和基本方法······························· 057

3.1.1  简谐近似与非简谐效应的概念·································· 057

3.1.2  描述非简谐效应的特征量········································ 058

3.1.3  非简谐效应理论的基本观点和基本方程······················· 061

3.1.4  非简谐效应理论研究问题的方法······························· 062

3.2  三维晶体的物理模型和声子谱·········································· 062

3.2.1  三维晶体的物理模型············································· 063

3.2.2  三维晶体的声子谱················································ 064

3.2.3  德拜温度和格林乃森参量与简谐系数和非简谐系数的
关系································································· 066

3.3  三维晶体热力学性质的非简谐效应···································· 067

3.3.1  简谐近似下三维晶体的热力学性质···························· 068

3.3.2  三维晶体的热膨胀、热压强、压缩系数随温度的变化······ 069

3.3.3  三维晶体的定容热容量随温度的变化·························· 071

3.3.4  三维晶体的热导率随温度的变化······························· 073

3.4  非简谐振动对二维系统的临界点与玻意耳线的影响················· 075

3.4.1  Collins模型························································ 075

3.4.2  二维系统的吉布斯函数·········································· 076

3.4.3  二维系统的状态方程和临界点·································· 078

3.4.4  非简谐振动对玻意耳温度和玻意耳线的影响················· 079

3.5  二维晶体热力学性质的非简谐效应···································· 082

3.5.1  简谐近似下二维晶体的热力学函数···························· 082

3.5.2  简谐近似下二维晶格热容理论·································· 083

3.5.3  非简谐振动对二维二元系统溶解限曲线的影响·············· 085

3.5.4  二维晶体的定压热膨胀系数和等温压缩系数················· 087

3.6  纳米晶热力学性质的非简谐效应······································· 088

………

7.4.1  类石墨烯的弹性模量············································· 265

7.4.2  类石墨烯的形变··················································· 267

7.4.3  形变对类石墨烯极性的影响····································· 268

7.4.4  形变对类石墨烯有效电荷的影响······························· 270

7.5  类石墨烯的介电性质····················································· 274

7.5.1  类石墨烯的极化率················································ 274

7.5.2  类石墨烯的介电常数随化合物的变化·························· 277

7.5.3  类石墨烯的介电常数随温度的变化···························· 278

参考文献········································································· 280

 

前  言

自2004年Geim和Novoselov采用机械剥离法获得石墨烯并于2010年获得诺贝尔物理学奖以来，石墨烯作为一种新兴的二维材料，它的完美晶体结构和独特的电学、光学、热学、力学等性能，使其在电子器件、能量储存、环境科学等领域具有广泛的应用前景和科学价值，对石墨烯材料的研究，已成为当前最受关注的研究领域之一，目前已有许多学者对石墨烯材料（包括石墨烯、外延石墨烯、类石墨烯、氧化石墨烯、石墨烯复合材料等）的制备、性能、应用等展开研究，主要是性能实验和定性分析。但缺乏理论上的深入研究，特别是对石墨稀材料各种性质的非简谐效应的研究较少，缺乏这方面的具有一定理论深度的著作。为了深入对石墨烯材料的研究，使其更好地应用于生产、科技、生活等领域，需要一部有关石墨烯材料热、电性能及其应用的著作，期望从实验和理论上更深入地揭示石墨烯材料的电学、热学和力学等非简谐性质遵从的规律以及这些性质的应用。

重庆文理学院新型储能器件及应用工程研究中心，长期以来对三维、二维、纳米等各类材料的电学、热学和力学性质及其原子振动的非简谐效应进行研究，提出了非简谐效应理论。特别是2004年Novoselov等首次用机械剥离法得到单原子厚度的石墨烯以来，该科研团队紧跟世界科技发展，对石墨烯材料的制备、性能等进行了大量的实验和理论研究，采取实验和理论相结合的方法，在实验基础上，构建物理模型，应用固体物理理论，采用格林函数法、密度泛函方法等方法，对石墨烯材料热、电和力学性能的非简谐效应及其变化规律进行较深入的研究，并取得成效。为了将已有的研究成果深入化、系统化及理论化，使我们对石墨烯材料的研究更深入，再上新台阶；为新器件、新材料的应用提供可靠的理论和实验支撑；使读者较系统和深入地了解石墨烯材料的制备、结构、热力学和电学性质的变化规律，特别是非简谐效应及其应用；了解主要的理论研究方法和采用的理论模型以及基本研究过程，并由此发现新现象；也为了使我们的研究被同行所了解，促进学术交流，我们将所做的工作进行总结，撰写了一本有关石墨烯材料热学和电学性能非简谐效应及其应用的著作。

本书共8章，第1、2章分别介绍石墨烯材料的有关概念、分类和制备方法、物理化学性质以及石墨烯的结构和晶体结合；第3章论述非简谐效应理论的有关概念、基本观点、研究问题的基本方法和它在研究三维、二维、纳米系统的热学、电学和光学等性质方面的一些应用；从第4章起，按照石墨烯、外延石墨烯、类石墨烯材料的顺序，依次论述了石墨烯材料的热力学、电学性质的非简谐效应；第8章论述了石墨烯的热电效应及其应用。

本书第1章、第8章由杨文耀撰写，第2章、第6章由夏继宏撰写，第3、4、5、7章由郑瑞伦撰写。全书经郑瑞伦、夏继宏统一修改，保证了各章内容的协调和风格的一致性。

本书的出版得到重庆文理学院的资助。著者衷心感谢重庆文理学院领导的热情鼓励和大力支持、帮助，感谢电子科技大学杨邦朝教授对本书撰写的策划组织并审阅全书，感谢西南科技大学彭同江教授的热情指导。在所写的内容中，许多是我们科研团队的老师，如程正富、任晓霞、申凤娟、杜一帅、周虹君、高君华、李杰、杨保亮等老师的研究成果，在修改和整理的过程中，还得到学校许多老师的热情帮助，在此向他们表示衷心感谢。

限于作者水平，书中难免存在错误和不妥之处，敬请读者指正。