单壁碳纳米管复合增强二维平面聚酞菁铜的热电性能

doi:10.15541/jim20250089

无机材料学报 ›› 2026, Vol. 41 ›› Issue (1): 63-69.DOI: 10.15541/jim20250089 CSTR: 32189.14.10.15541/jim20250089

单壁碳纳米管复合增强二维平面聚酞菁铜的热电性能

胡宇晨¹^,²(), 徐子硕²^,³, 胡悦娟²^,³, 陈立东²^,³, 姚琴²^,³()

1.上海科技大学物质科学与技术学院, 上海 201210
2.中国科学院上海硅酸盐研究所, 上海 200050
3.中国科学院大学材料科学与光电工程中心, 北京 100049

收稿日期:2025-02-27 修回日期:2025-04-17 出版日期:2026-01-20 网络出版日期:2025-04-27
通讯作者: 姚琴, 正高级工程师. E-mail: yaoqin@mail.sic.ac.cn
作者简介:胡宇晨(2000-), 女, 硕士研究生. E-mail: huych2022@shanghaitech.edu.cn
基金资助:
国家自然科学基金(U23A20685)

Enhanced Thermoelectric Properties of Two-dimensional Planar Copper Polyphthalocyanine by Dispersing Single-walled Carbon Nanotubes

HU Yuchen¹^,²(), XU Zishuo²^,³, HU Yuejuan²^,³, CHEN Lidong²^,³, YAO Qin²^,³()

1. School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
3. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2025-02-27 Revised:2025-04-17 Published:2026-01-20 Online:2025-04-27
Contact: YAO Qin, professor. E-mail: yaoqin@mail.sic.ac.cn
About author:HU Yuchen (2000-), female, Master candidate. E-mail: huych2022@shanghaitech.edu.cn
Supported by:
National Natural Science Foundation of China(U23A20685)

摘要/Abstract

摘要：

二维平面金属聚酞菁具有独特的分子结构和高载流子迁移率, 是一种很有发展前景的有机热电材料。但是本征金属聚酞菁的载流子浓度和电导率低, 热电性能提升困难。本研究采用原位聚合法和机械球磨法分别制备了聚酞菁铜/单壁碳纳米管(CuPPc/SWCNTs)复合材料。与机械球磨样品(BM-CuPPc/SWCNTs)相比, 原位聚合样品(IS-CuPPc/SWCNTs)中的CuPPc和SWCNTs间存在强的π-π共轭效应, 能有效降低CuPPc和SWCNTs间的界面电阻。因此, 在SWCNTs浓度较高的情况下, IS-CuPPc/SWCNTs的电导率高于BM-CuPPc/SWCNTs。80%(质量分数)SWCNTs的IS-CuPPc/SWCNTs的电导率达1.31×10⁴ S·m^-1, 比BM-CuPPc/SWCNTs高30%, 比纯CuPPc提高了6个数量级。同时, IS-CuPPc/SWCNTs的最大热电功率因子达到18.24 μW·m^-1·K^-2, 高于BM-CuPPc/SWCNTs, 较纯CuPPc高出6个数量级。本研究为提升金属聚酞菁的热电性能提供了有效途径。

关键词: 聚酞菁铜, 碳纳米管, 复合材料, 热电性能

Abstract:

Two-dimensional planar metal polyphthalocyanine is considered a kind of promising organic thermoelectric material due to its unique molecular structure and high carrier mobility, but its low carrier concentration and low electrical conductivity impede improvement of thermoelectric performance. In this work, copper polyphthalocyanine/single-walled carbon nanotubes (CuPPc/SWCNTs) composites were prepared by in-situ polymerization and mechanical ball-milling, respectively. As compared with ball-milled sample (BM-CuPPc/SWCNTs), in-situ polymerized sample (IS-CuPPc/SWCNTs) presents strong π-π conjugation between CuPPc and SWCNTs, which can effectively reduce the interfacial resistance between CuPPc and SWCNTs. Therefore, IS-CuPPc/SWCNTs shows higher electrical conductivity than BM-CuPPc/SWCNTs at high SWCNTs concentration. With 80% (in mass) SWCNTs, the electrical conductivity of IS-CuPPc/SWCNTs reaches 1.31×10⁴ S·m^-1, 30% higher than that of BM-CuPPc/SWCNTs, and six orders of magnitude higher than that of pure CuPPc. Meanwhile, the maximum thermoelectric power factor of IS-CuPPc/SWCNTs reaches 18.24 μW·m^-1·K^-2, which is higher than that of BM-CuPPc/SWCNTs and surpasses that of pure CuPPc by six orders of magnitude. This study provides an effective way to enhance the thermoelectric properties of metallic polyphthalocyanine.

Key words: copper polyphthalocyanine, carbon nanotube, composite, thermoelectric property

中图分类号:

TB34

胡宇晨, 徐子硕, 胡悦娟, 陈立东, 姚琴. 单壁碳纳米管复合增强二维平面聚酞菁铜的热电性能[J]. 无机材料学报, 2026, 41(1): 63-69.

HU Yuchen, XU Zishuo, HU Yuejuan, CHEN Lidong, YAO Qin. Enhanced Thermoelectric Properties of Two-dimensional Planar Copper Polyphthalocyanine by Dispersing Single-walled Carbon Nanotubes[J]. Journal of Inorganic Materials, 2026, 41(1): 63-69.

图/表 8

图1 金属聚酞菁的分子结构式

Fig. 1 Molecular structural formula of metal polyphthalocyanine

图2 CuPPc/SWCNTs复合材料的制备工艺示意图

Fig. 2 Schematic diagrams of the preparation process of CuPPc/SWCNTs composites (a) In-situ polymerization method; (b) Mechanical ball-milling method

图3 IS-CuPPc/SWCNTs和BM-CuPPc/SWCNTs复合材料的TEM和SEM照片

Fig. 3 TEM and SEM images of IS-CuPPc/SWCNTs and BM-CuPPc/SWCNTs composites (a-d) TEM images of (a, b) IS-CuPPc/40%SWCNTs powder and (c, d) BM-CuPPc/60%SWCNTs powder; (e-g) SEM images of cross-sections of (e) IS-CuPPc/10%SWCNTs, (f) IS-CuPPc/60%SWCNTs and (g) IS-CuPPc/80%SWCNTs composite block; (h-j) SEM images of cross-sections of (h) BM-CuPPc/10%SWCNTs, (i) BM-CuPPc/60%SWCNTs and (j) BM-CuPPc/80%SWCNTs composite block

图4 不同SWCNTs质量分数的IS-CuPPc/SWCNTs和BM-CuPPc/SWCNTs样品的电输运性能

Fig. 4 Electrical transport properties of IS-CuPPc/SWCNTs and BM-CuPPc/SWCNTs samples with different SWCNTs mass fractions (a) Electrical conductivity; (b) Seebeck coefficient; (c) Thermoelectric power factor

图5 CuPPc、IS-CuPPc/xSWCNTs(x=40%, 60%, 80%)和BM-CuPPc/ySWCNTs(y=40%, 60%, 80%)的Cu2p XPS高分辨谱图

Fig. 5 High-resolution Cu2p XPS spectra of CuPPc, IS-CuPPc/xSWCNTs (x=40%, 60%, 80%) and BM-CuPPc/ySWCNTs (y=40%, 60%, 80%) (a) CuPPc; (b) CuPPc and IS-CuPPc/xSWCNTs (x=40%, 60%, 80%); (c) CuPPc and BM-CuPPc/ySWCNTs (y=40%, 60%, 80%)

图6 CuPPc、SWCNTs、IS-CuPPc/20%SWCNTs和BM-CuPPc/ 20%SWCNTs样品的Raman谱图

Fig. 6 Raman spectra of CuPPc, SWCNTs, IS-CuPPc/ 20%SWCNTs, and BM-CuPPc/20%SWCNTs samples

图7 IS-CuPPc/SWCNTs的电输运机制示意图

Fig. 7 Schematic diagram of the electrical transport mechanism of IS-CuPPc/SWCNTs

图S1 纯CuPPc粉末的FT-IR谱图

Fig. S1 FT-IR spectra of pure CuPPc powder

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单壁碳纳米管复合增强二维平面聚酞菁铜的热电性能

Enhanced Thermoelectric Properties of Two-dimensional Planar Copper Polyphthalocyanine by Dispersing Single-walled Carbon Nanotubes

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