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

doi:10.11949/0438-1157.20191533

Abstract

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

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

CLC Number:

TM 914.4

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.

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.

Figures/Tables 10

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

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

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)

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

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

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

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)

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

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

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)

References 25

26	Yu C, Liu Z Q, Chen Y W, et al. CoS nanosheets-coupled graphene quantum dots architectures as a binder-free counter electrode for high-performance DSSCs [J]. Science China Materials, 2016, 59(2): 104-111.
27	Rungta M, Wenz G B, Zhang C, et al. Carbon molecular sieve structure development and membrane performance relationships [J]. Carbon, 2017, 115: 237-248.
1	Mahmoud M S, Akhtar M S, Mohamed I M A, et al. Demonstrated photons to electron activity of S-doped TiO₂ nanofibers as photoanode in the DSSC [J]. Materials Letters, 2018, 225: 77-81.
2	Chen J, Li X, Wu W J, et al. A fast approach to optimize dye loading of photoanode via ultrasonic technique for highly efficient dye-sensitized solar cells [J]. Journal of Energy Chemistry, 2015, 24(6): 750-755.
28	Zhou Y W, Wang Y C, Ban Y J, et al. Carbon molecular sieving membranes for butane isomer separation [J]. AIChE Journal, 2019, 65(11): 16749.
29	Zhang S W, Lv W, Luo C, et al. Commercial carbon molecular sieves as a high performance anode for sodium-ion batteries [J]. Energy Storage Materials, 2016, 3: 18-23.
3	Mathew S, Yella A, Gao P, et al. Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers [J]. Nature Chemistry, 2014, 6: 242-247.
4	Soman S, Pradhan S C, Yoosuf M, et al. Probing recombination mechanism and realization of marcus normal region behavior in DSSCs employing cobalt electrolytes and triphenylamine dyes [J]. The Journal of Physical Chemistry C, 2018, 122(25): 14113-14127.
5	Freitag M, Teuscher J, Saygili Y, et al. Dye-sensitized solar cells for efficient power generation under ambient lighting [J]. Nature Photonics, 2017, 11: 372-378.
6	Wu K Z, Chen L, Cui W Z, et al. The effect of transition metal ions (M²⁺=Mn²⁺, Ni²⁺, Co²⁺, Cu²⁺) on the chemical synthesis polyaniline as counter electrodes in dye-sensitized solar cells [J]. Chinese Journal of Chemical Engineering, 2017, 25(5): 671-675.
30	Meng X T, Yu C, Song X D, et al. Scrutinizing defects and defect density of selenium-doped graphene for high-efficiency triiodide reduction in dye-sensitized solar cells [J]. Angewandte Chemie International Edition, 2018, 57(17): 4682-4686.
31	Sarkar A, Chakraborty A K, Bera S. NiS/rGO nanohybrid: an excellent counter electrode for dye sensitized solar cell [J]. Solar Energy Materials and Solar Cells, 2018, 182: 314-320.
7	Yu C, Meng X T, Song X D, et al. Graphene-mediated highly-dispersed MoS₂ nanosheets with enhanced triiodide reduction activity for dye-sensitized solar cells [J]. Carbon, 2016, 100: 474-483.
8	Wu J H, Lan Z, Lin J M, et al. Counter electrodes in dye-sensitized solar cells [J]. Chemical Society Reviews, 2017, 46(19): 5975-6023.
9	Fang H Q, Yu C, Ma T L, et al. Boron-doped graphene as a high-efficiency counter electrode for dye-sensitized solar cells [J]. Chemical Communications, 2014, 50(25): 3328-3330.
10	Meng X T, Yu C, Song X D, et al. Nitrogen-doped graphene nanoribbons with surface enriched active sites and enhanced performance for dye-sensitized solar cells [J]. Advanced Energy Materials, 2015, 5(11): 1500180.
11	Regan B O, Grätzel M. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO₂ films [J]. Nature, 1991, 353(6346): 737-740.
12	Meng X T, Yu C, Lu B, et al. Dual integration system endowing two-dimensional titanium disulfide with enhanced triiodide reduction performance in dye-sensitized solar cells [J]. Nano Energy, 2016, 22: 59-69.
13	Yao Z Y, Zhang M, Wu H, et al. Donor/acceptor indenoperylene dye for highly efficient organic dye-sensitized solar cells [J]. Journal of the American Chemical Society, 2015, 137(11): 3799-3802.
14	Yu C, Fang H Q, Liu Z Q, et al. Chemically grafting graphene oxide to B, N co-doped graphene via ionic liquid and their superior performance for triiodide reduction [J]. Nano Energy, 2016, 25: 184-192.
15	Meng X T, Yu C, Son X D, et al. Rational design and fabrication of sulfur-doped porous graphene with enhanced performance as a counter electrode in dye-sensitized solar cells [J]. Journal of Materials Chemistry A, 2017, 5(5): 2280-2287.
16	徐顺建. 9种树叶生物炭作为染料敏化太阳电池对电极的光电性能 [J]. 化工学报, 2016, 67(11): 4851-4857.
	Xu S J. Photovoltaic properties of 9 natural leaves derived biochars as counter electrodes for dye-sensitized solar cells [J]. CIESC Journal, 2016, 67(11): 4851-4857.
17	Xing Y D, Zheng X J, Wu Y H, et al. Nitrogen-doped carbon nanotubes with metal nanoparticles as counter electrode materials for dye-sensitized solar cells [J]. Chemical Communications, 2015, 51(38): 8146-8149.
18	Yu C, Liu Z Q, Meng X T, et al. Nitrogen and phosphorus dual-doped graphene as a metal-free high-efficiency electrocatalyst for triiodide reduction [J]. Nanoscale, 2016, 8(40): 17458-17464.
19	Meng X T, Yu C, Zhang X P, et al. Active sites-enriched carbon matrix enables efficient triiodide reduction in dye-sensitized solar cells: an understanding of the active centers [J]. Nano Energy, 2018, 54: 138-147.
20	Chang P J, Cheng K Y, Chou S W, et al. Tri-iodide reduction activity of shape- and composition-controlled PtFe nanostructures as counter electrodes in dye-sensitized solar cells [J]. Chemistry of Materials, 2016, 28(7): 2110-2119.
21	Liu T S, Zhao Y Y, Duan J L, et al. Transparent ternary alloy counter electrodes for high-efficiency bifacial dye-sensitized solar cells [J]. Solar Energy, 2018, 170: 762-768.
22	Zhang J B, Hao Y, Yang L, et al. Electrochemically polymerized poly (3, 4-phenylenedioxythiophene) as efficient and transparent counter electrode for dye sensitized solar cells [J]. Electrochimica Acta, 2019, 300: 482-488.
23	Nemala S S, Kartikay P, Agrawal R K, et al. Few layers graphene based conductive composite inks for Pt free stainless steel counter electrodes for DSSC [J]. Solar Energy, 2018, 169: 67-74.
24	Ren H, Shao H, Zhang L J, et al. A new graphdiyne nanosheet/Pt nanoparticle-based counter electrode material with enhanced catalytic activity for dye-sensitized solar cells [J]. Advanced Energy Materials, 2015, 5(12): 1500296.
25	Wang Z H, Lu B, Meng X T, et al. Graphene oxide induced fabrication of pillared and double-faced polyaniline arrays with enhanced triiodide reduction capability [J]. Electrochimica Acta, 2017, 252: 84-90.

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

碳分子筛的优化设计及其I₃^-还原性能研究

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