质子交换膜燃料电池微孔层浆液微观结构与流变性

doi:10.16085/j.issn.1000-6613.2021-1856

摘要/Abstract

摘要：

微孔层（MPL）是质子交换膜燃料电池（PEMFC）水管理的重要部件。本文系统性选择了4种典型炭黑[ACET、XC-72R、BP2000、天然气裂解炭黑（NG）]，借助原子力显微镜（AFM）、场发射透射电镜（TEM）和动态光散射粒度分析仪（DLS PSD）对浆液微观结构的研究，给出团聚性这一浆液评价标准，并结合流变性揭示了定量标准。研究结果表明，不同炭黑的团聚程度大小依次为ACET>XC-72R>BP2000>NG。剪切稀化指数n越大，MPL浆液团聚程度越低，颗粒分散越均匀；n越小，团聚程度越高。具体而言，固含量α=6%时，添加NG、BP2000、XC-72R、ACET炭黑的MPL浆液的剪切稀化指数n分别为0.554、0.320、0.118、0.039；测得的ACET、XC-72R、BP2000、NG的团聚体粒径分别为1.358μm、1.149μm、0.732μm、0.406μm，所以浆液的剪切稀化指数与其团聚程度成反比。总之，NG-MPL剪切稀化程度最低，NG更加适合作为MPL的碳材料，也为今后MPL的制备和优化提供指导。

关键词: 燃料电池, 微孔层, 炭黑, 微观结构, 流变性

Abstract:

The microporous layer (MPL) is an important component of water management in proton exchange membrane fuel cells (PEMFC). It is crucial to gain an in-depth understanding of MPL ink, which determines MPL's structure and performance. In this paper, four typical carbon blacks [ACET, XC-72R, BP2000, and natural gas cracking carbon black (NG)] were selected to systematically study the microstructure of the slurry by using atomic force microscopy (AFM), field emission transmission electron microscopy (TEM) and dynamic light scattering particle size analyzer (DLS PSD). Agglomeration was proposed as an ink evaluation criterion, and quantitative criteria were also given by combining rheology study. The results showed that the agglomeration degree of different carbon blacks was in the following order: ACET>XC-72R>BP2000>NG. The larger the shear thinning index n, the lower the agglomeration degree of MPL slurry and the more uniform the particle dispersion, and the smaller the n, the higher the agglomeration degree. Specifically, for the solid content α=6%, n_NG-MPL=0.554, n_BP2000-MPL=0.320, n_XC-72R-MPL=0.118, and n_ACET-MPL=0.039. The measured agglomerates particle sizes of ACET, XC-72R, BP2000 and NG were 1.358μm, 1.149μm, 0.732μm and 0.406μm, respectively. So the shear thinning index of the ink should be inversely proportional to the degree of agglomeration. In conclusion, NG-MPL has the lowest shear thinning degree and is a more suitable carbon material for MPL, which also provides guidance for the preparation and optimization of MPL in the future.

Key words: fuel cell, microporous layer, carbon black, microstructure, rheology

中图分类号:

陈哲坤, 潘伟童, 姚顶松, 丁路, 王辅臣. 质子交换膜燃料电池微孔层浆液微观结构与流变性[J]. 化工进展, 2022, 41(7): 3808-3815.

CHEN Zhekun, PAN Weitong, YAO Dingsong, DING Lu, WANG Fuchen. Microstructure and rheology of microporous layer ink for proton exchange membrane fuel cells[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3808-3815.

图/表 8

参考文献 34

1	符冠云, 赵吉诗, 龚娟, 等. 2019年国内外氢能发展形势回顾及展望[J]. 中国能源, 2020, 42(3): 30-33.
	FU Guanyun, ZHAO Jishi, GONG Juan, et al. Review of the development of hydrogen energy at home and abroad in 2019 and outlook for 2020[J]. Energy of China, 2020, 42(3): 30-33.
2	OZDEN A, SHAHGALDI S, LI X G, et al. A review of gas diffusion layers for proton exchange membrane fuel cells—With a focus on characteristics, characterization techniques, materials and designs[J]. Progress in Energy and Combustion Science, 2019, 74: 50-102.
3	焦魁, 王博文, 杜青. 质子交换膜燃料电池水热管理[M]. 北京: 科学出版社, 2020.
	JIAO Kui, WANG Bowen, DU Qing. Proton exchange membrane fuel cell hydrothermal management[M]. Beijing: Science Press, 2020.
4	PAN W T, WANG P H, CHEN X L, et al. Combined effects of flow channel configuration and operating conditions on PEM fuel cell performance[J]. Energy Conversion and management, 2020, 220: 113046.
5	PARK S, LEE J W, POPOV B N. A review of gas diffusion layer in PEM fuel cells: materials and designs[J]. International Journal of Hydrogen Energy, 2012, 37(7): 5850-5865.
6	毛林昌, 金俊宏, 杨胜林, 等. 多孔纳米碳纤维作为质子交换膜燃料电池微孔层的性能[J]. 化工进展, 2020, 39(10): 3995-4001.
	MAO Linchang, JIN Junhong, YANG Shenglin, et al. Performance of porous carbon nanofibers as microporous layer for proton exchange membrane fuel cells[J]. Chemical Industry and Engineering Progress, 2020, 39(10): 3995-4001.
7	罗马吉, 张鑫, 罗志平, 等. 微孔层对质子交换膜燃料电池水传输的影响[J]. 华中科技大学学报(自然科学版), 2010, 38(7): 36-39.
	LUO Maji, ZHANG Xin, LUO Zhiping, et al. Effects of micro-porous layer on the water transport of PEMFC[J]. Journal of Huazhong University of Science and Technology (Natural Science Edition), 2010, 38(7): 36-39.
8	YANG Y G, ZHOU X Y, LI B, et al. Recent progress of the gas diffusion layer in proton exchange membrane fuel cells: material and structure designs of microporous layer[J]. International Journal of Hydrogen Energy, 2021, 46(5): 4259-4282.
9	SADEGHIFAR H, DJILALI N, BAHRAMI M. Effect of polytetrafluoroethylene (PTFE) and micro porous layer (MPL) on thermal conductivity of fuel cell gas diffusion layers: modeling and experiments[J]. Journal of Power Sources, 2014, 248: 632-641.
10	KIM T, LEE S, PARK H. A study of water transport as a function of the micro-porous layer arrangement in PEMFCs[J]. International Journal of Hydrogen Energy, 2010, 35(16): 8631-8643.
11	WEBER A Z, NEWMAN J. Effects of microporous layers in polymer electrolyte fuel cells[J]. Journal of the Electrochemical Society, 2005, 152(4): A677.
12	ANTONACCI P, CHEVALIER S, LEE J, et al. Feasibility of combining electrochemical impedance spectroscopy and synchrotron X-ray radiography for determining the influence of liquid water on polymer electrolyte membrane fuel cell performance[J]. International Journal of Hydrogen Energy, 2015, 40(46): 16494-16502.
13	BLANCO M, WILKINSON D P. Investigation of the effect of microporous layers on water management in a proton exchange membrane fuel cell using novel diagnostic methods[J]. International Journal of Hydrogen Energy, 2014, 39(29): 16390-16404.
14	LI B, XIE M, JI H, et al. Optimization of cathode microporous layer materials for proton exchange membrane fuel cell[J]. International Journal of Hydrogen Energy, 2021, 46(27): 14674-14686.
15	李超明, 康敬欣, 刘勇. 质子交换膜燃料电池微孔层研究进展[J]. 化工新型材料, 2020, 48(9): 256-259.
	LI Chaoming, KANG Jingxin, LIU Yong. Research progress on MPL of proton exchange membrane fuel cell[J]. New Chemical Materials, 2020, 48(9): 256-259.
16	YAN W M, WU D K, WANG X D, et al. Optimal microporous layer for proton exchange membrane fuel cell[J]. Journal of Power Sources, 2010, 195(17): 5731-5734.
17	FAN C C, CHANG M H. Improving proton exchange membrane fuel cell performance with carbon nanotubes as the material of cathode microporous layer[J]. International Journal of Energy Research, 2016, 40(2): 181-188.
18	XU F, ZHANG H Y, HO D, et al. Investigation of catalyst ink dispersion using small angle X-ray and small angle neutron scattering[J]. ECS Transactions, 2019, 33(1): 1335-1345.
19	GALLO STAMPINO P, CRISTIANI C, DOTELLI G, et al. Effect of different substrates, inks composition and rheology on coating deposition of microporous layer (MPL) for PEM-FCs[J]. Catalysis Today, 2009, 147: S30-S35.
20	LATORRATA S, STAMPINO P G, AMICI E, et al. Effect of rheology controller agent addition to micro-porous layers on PEMFC performances[J]. Solid State Ionics, 2012, 216: 73-77.
21	TAKAHASHI S, MASHIO T, HORIBE N, et al. Analysis of the microstructure formation process and its influence on the performance of polymer electrolyte fuel-cell catalyst layers[J]. ChemElectroChem, 2015, 2(10): 1560-1567.
22	PAN W T, CHEN Z K, YAO D S, et al. Microstructure and macroscopic rheology of microporous layer nanoinks for PEM fuel cells[J]. Chemical Engineering Science, 2021, 246: 117001.
23	LONG C M, NASCARELLA M A, VALBERG P A. Carbon black vs. black carbon and other airborne materials containing elemental carbon: physical and chemical distinctions[J]. Environmental Pollution, 2013, 181: 271-286.
24	KHANDAVALLI S, PARK J H, KARIUKI N N, et al. Rheological investigation on the microstructure of fuel cell catalyst inks[J]. ACS Applied Materials & Interfaces, 2018, 10(50): 43610-43622.
25	张宇. 纳米颗粒增强气液传质的实验和模型研究[D]. 北京: 清华大学, 2016.
	ZHANG Yu. Experimental and model study of gas-liquid mass transfer enhancement by nanoparticles[D]. Beijing: Tsinghua University, 2016.
26	张胜寒, 韩晓雪. 纳米颗粒表面修饰对纳米流体黏度的影响[J]. 科学技术与工程, 2018, 18(21): 168-174.
	ZHANG Shenghan, HAN Xiaoxue. Effect of different surface properties of nanoparticles on the viscosity of nanofluids[J]. Science Technology and Engineering, 2018, 18(21): 168-174.
27	吴瑞娟. 中性墨水稳定性影响因素研究[D]. 太原: 太原理工大学, 2014.
	WU Ruijuan. The study on the factors of stability of gel ink[D]. Taiyuan: Taiyuan University of Technology, 2014.
28	AOKI Y, HATANO A, WATANABE H. Rheology of carbon black suspensions. I. Three types of viscoelastic behavior[J]. Rheologica Acta, 2003, 42(3): 209-216.
29	SOBOLEVA T, ZHAO X, MALEK K, et al. On the micro-, meso-, and macroporous structures of polymer electrolyte membrane fuel cell catalyst layers[J]. ACS Applied Materials & Interfaces, 2010, 2(2): 375-384.
30	SOCHI T. Non-Newtonian flow in porous media[J]. Polymer, 2010, 51(22): 5007-5023.
31	NEGI A S, OSUJI C O. New insights on fumed colloidal rheology—shear thickening and vorticity-aligned structures in flocculating dispersions[J]. Rheologica Acta, 2009, 48(8): 871-881.
32	AOKI Y, CO A, LEAL G L, et al. Rheology of carbon black suspensions: effect of carbon black structure[C]//AIP Conference Proceedings. Monterey, 2008.
33	郭宇蓉. 锂电池浆料搅拌与涂布工艺的仿真及实验研究[D]. 太原: 太原科技大学, 2019.
	GUO Yurong. Simulation and experimental study on stirring and coating process of lithium battery slurry[D]. Taiyuan: Taiyuan University of Science and Technology, 2019.
34	KUMANO N, KUDO K, AKIMOTO Y, et al. Influence of ionomer adsorption on agglomerate structures in high-solid catalyst inks[J]. Carbon, 2020, 169: 429-439.

炭黑类型	V_总孔/m³·g^－1	V_{介孔+大孔}/ m³·g^－1	V_微孔/m³·g^－1
ACET	0.168	0.167	0.001
XC-72R	0.441	0.410	0.031
NG	0.951	0.941	0.010

炭黑类型	V_总孔/m³·g^－1	V_{介孔+大孔}/ m³·g^－1	V_微孔/m³·g^－1
ACET	0.168	0.167	0.001
XC-72R	0.441	0.410	0.031
NG	0.951	0.941	0.010

炭黑类型	平均粒径/nm	多分散性指数
ACET	443.6	0.403
XC-72R	374.3	0.062
NG	209.5	0.040

炭黑类型	平均粒径/nm	多分散性指数
ACET	443.6	0.403
XC-72R	374.3	0.062
NG	209.5	0.040

炭黑类型	α/%	k	n	R²
ACET	3	1.807	0.213	0.993
	4	2.781	0.188	0.996
	5	10.478	0.076	0.999
	6	55.951	0.039	0.998
	7	79.806	0.015	1.000
XC-72R	3	1.149	0.340	0.963
	4	1.359	0.310	0.974
	5	1.843	0.276	0.983
	6	8.023	0.118	0.992
	7	14.300	0.067	0.996
BP2000	3	0.732	0.396	0.937
	4	0.961	0.389	0.962
	5	1.059	0.355	0.978
	6	1.218	0.320	0.978
	7	1.521	0.295	0.973
NG	3	0.052	1.000	—
	4	0.057	1.000	—
	5	0.070	1.000	—
	6	0.125	0.554	0.981
	7	0.674	0.233	0.981