碳分子筛的优化设计及其I3-还原性能研究

doi:10.11949/0438-1157.20191533

摘要/Abstract

摘要：

研究对比了商业化碳分子筛(CMS)、多壁碳纳米管、活性炭和还原氧化石墨烯四种碳材料的I₃^-还原性能。采用场发射扫描电镜、高倍率透射电镜、X射线衍射等技术手段表征了材料的微观结构特征，结合循环伏安(CV)和光电转换测试(I-V)结果，解耦了材料的构效关系。结果发现，以CMS为对电极组装的DSSCs的光电转换效率最高，达7.46%。在此基础上，研究考察了高温退火处理对CMS的微观结构、性质和性能的影响，揭示了影响I₃^-还原性能的关键因素。结果表明，800℃处理的样品CMS800光电转换效率高达8.56%，明显优于贵金属Pt对电极，同时表现出优于Pt的电化学稳定性。

关键词: 染料敏化太阳能电池, 碳分子筛, 光电转换效率, 催化活性, I₃^-还原

Abstract:

The study compared the I₃^- reduction properties of four carbon materials, commercial carbon molecular sieve (CMS), multi-walled carbon nanotubes, activated carbon and reduced graphene oxide. The morphology and structure of the materials were characterized by FESEM, TEM and XRD, and their catalytic performance for $I 3 -$ reduction was evaluated by cyclic voltammetry, electrochemical impedance spectroscopy and Tafel polarization test. Compared with other materials, CMS possesses the highest power conversion efficiency of 7.46% as the CE materials in DSSCs. The effects of annealing temperatures on themorphology, structure and electrocatalytic activity of CMS were also investigated. The as-made CMS800 via thermal annealing at 800^oC achieves a high power conversion efficiency of 8.56%, which is significantly better than the precious metal Pt counter electrode, and at the same time shows better electrochemical stability than that of Pt.

Key words: dye-sensitized solar cells, carbon molecular sieves, power conversion efficiency, catalytic activity, triiodide reduction

中图分类号:

TM 914.4

姚春, 黄龙龙, 常江伟, 丁一旺, 于畅, 邱介山. 碳分子筛的优化设计及其I₃^-还原性能研究[J]. 化工学报, 2020, 71(6): 2696-2704.

Chun YAO, Longlong HUANG, Jiangwei CHANG, Yiwang DING, Chang YU, Jieshan QIU. Optimization design of carbon molecular sieves and its I₃^- reduction performance[J]. CIESC Journal, 2020, 71(6): 2696-2704.

图/表 10

图1 CMS(a)，MWCNT(b)，AC(c)，RGO(d)的FESEM图；CMS的HRTEM图(e)和热重曲线(f)

Fig.1 FESEM images of CMS(a), MWCNT (b), AC (c) and RGO (d); HRTEM image (e) and thermogravimetric analysis curve (f) of CMS

图2 CMS、AC、MWCNT和RGO的XRD谱图(a)，拉曼谱图(b)，氮气吸附/脱附等温线(c)和孔径分布图(d)

Fig.2 XRD patterns (a), Raman spectra (b), nitrogen adsorption and desorption isotherms (c) and the pore size distribution (d) of CMS, AC, MWCNT and RGO

图3 AC、MWCNT、RGO、CMS对电极的CV曲线(a)，EIS谱图(插图是放大图和等效电路图)(b)，Tafel曲线(c)和J-V曲线(d)

Fig.3 CV curves of various CEs(a); Nyquist plots curves (inset is the magnified plots and equivalent circuits) (b); Tafel curves of the symmetrical dummy cells assembled by various CEs (c) and J-V curves of DSSCs based on various CEs (d)

表1 不同对电极的电化学参数(源于EIS谱)

Table 1 Electrochemical parameters derived from EIS measurements for various CEs

对电极	R_s /(Ω·cm²)	R_ct/(Ω·cm²)
AC	5.76	5.81
MWCNT	5.24	0.41
RGO	4.88	5.90
CMS	5.12	2.23

表2 不同对电极的光伏性能参数

Table 2 Photovoltaic parameters for various CEs

对电极	V_oc/V	J_sc/(mA·cm^-2)	FF	PCE/%
AC	0.77	14.79	0.61	6.88
MWCNT	0.71	13.78	0.66	6.41
RGO	0.78	14.92	0.61	7.13
CMS	0.74	16.59	0.61	7.46

图4 CMS(a)和CMS800(b)的FESEM图；CMS、CMS600、CMS800和CMS1000的XRD谱图(c)和拉曼谱图(d)

Fig.4 FESEM images of CMS (a) and CMS800 (b) samples; XRD patterns (c) and Raman spectra (d) of CMS, CMS600, CMS800 and CMS1000 samples

图5 CMS800和Pt对电极的CV曲线(a)；CMS600、CMS800、CMS1000和Pt对电极的EIS谱图(插图是放大图和等效电路图)(b)，Tafel曲线(c)和J-V曲线(d)

Fig.5 CV curves for CMS800 and Pt CEs(a); Nyquist plots curves (inset is the magnified plots and equivalent circuits) (b) and Tafel curves (c) of the symmetrical dummy cells assembled by various CEs; J-V curves of DSSCs based on various CEs (d)

表3 不同对电极的电化学参数(源于EIS谱)

Table 3 Electrochemical parameters derived from EIS measurements for various CEs

对电极	R_s /(Ω·cm²)	R_ct /(Ω·cm²)
CMS600	5.56	2.02
CMS800	5.00	1.03
CMS1000	5.01	1.31
Pt	9.78	1.08

表4 不同对电极的光伏性能参数

Table 4 Photovoltaic parameters for various CEs

对电极	V_oc/V	J_sc/(mA·cm^-2)	FF	PCE/%
CMS600	0.73	16.01	0.65	7.65
CMS800	0.75	17.03	0.67	8.56
CMS1000	0.74	15.56	0.69	8.04
Pt	0.71	13.31	0.69	6.53

图6 CMS800(a)和Pt(b)对电极组装成假电池的电化学稳定性测试图；基于EIS测试的两种电极的Rct变化曲线(c)

Fig.6 Electrochemical stability of CMS800 (a) and Pt (b) dummy cells, the EIS tests were repeated for 10 times (inset is the equivalent circuits); Rct changes of CMS800 and Pt CEs versus the EIS scan number (c)

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碳分子筛的优化设计及其I₃^-还原性能研究

Optimization design of carbon molecular sieves and its I₃^- reduction performance

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