Well-Dispersed Na fi on Array Prepared by the Freeze-Drying Method to E ff ectively Improve the Performance of Proton Exchange Membrane Fuel Cells

: The ordered membrane electrode assembly (MEA) is currently the frontier research fi eld of proton exchange membrane fuel cells (PEMFCs). The ordered MEA is e ff ective in increasing the utilization of the Pt catalyst and reducing the Pt catalyst loading and cost. Due to a larger speci fi c surface area and faster rate of proton transfer, a Na fi on array was used to prepare a high-performance MEA. In order to realize the ideal performance, the critical mission is to make a well-dispersed Na fi on array. However, the pillars in the Na fi on array are prone to form bundles induced by surface tension of water, resulting in a severe reduction in the speci fi c surface area. In this work, we successfully prepared a well-dispersed Na fi on array by the freeze-drying method, which greatly improved the performance of the ordered MEA of a PEMFC. The percentage of isolated pillars in the Na fi on array is improved from about 0.8% after natural drying to about 90% after freeze-drying. The speci fi c surface area of the Na fi on array membrane after freeze-drying increases to 4.74, which is 2.1 times that after natural drying, and is close to the theoretical value of 4.99, indicating that the well-isolated array possesses a larger speci fi c surface area to load a catalyst. Consequently, the electrochemical surface area of the catalyst layer reaches as high as 131.5 m 2 g Pt − 1 , which is 1.6 or 2.5 times that with the Na fi on array after natural drying or without the Na fi on array. For the ordered MEA, a long-term stability is vital for PEMFC operation. In this work, the lifetime of the ordered MEA with the Na fi on array after freeze-drying is excellent compared to the Na fi on array after natural drying and without the array. Besides, the scanning electron microscopy characterization clearly shows that the Na fi on array remains a well-dispersed structure even after hot-pressing and plays a pivotal role in PEMFC operation. Therefore, this research proves that the freeze-drying method can e ff ectively solve the aggregation of the Na fi on array during drying and further proves that the well-dispersed Na fi on array could show much higher performance. More importantly, this work provides an ideal basic material for the preparation of the ordered MEA.

[1]  S. Du.  Recent Advances in Electrode Design Based on One-Dimensional Nanostructure Arrays for Proton Exchange Membrane Fuel Cell Applications , 2021, Engineering.

[2]  W. Shi,et al.  Photo-driven growth of a monolayer of platinum spherical-nanocrowns uniformly coated on a membrane toward fuel cell applications , 2020, Journal of Materials Chemistry A.

[3]  Yun-Jing Huang,et al.  Great improvement in the performance and lifetime of a fuel cell using a highly dense, well-ordered, and cone-shaped Nafion array , 2020, Journal of Materials Chemistry A.

[4]  W. Guo,et al.  Magnetron sputtering a high-performance catalyst for ultra-low-Pt loading PEMFCs , 2020 .

[5]  S. Liao,et al.  Enhancing membrane electrode assembly performance by improving the porous structure and hydrophobicity of the cathode catalyst layer , 2019 .

[6]  H. Bailung,et al.  Low loaded platinum (Pt) based binary catalyst electrode for PEMFC by plasma co-sputtered deposition method , 2019, Materials Chemistry and Physics.

[7]  R. Fiala,et al.  Optimization of ionomer-free ultra-low loading Pt catalyst for anode/cathode of PEMFC via magnetron sputtering , 2019, International Journal of Hydrogen Energy.

[8]  Zhichuan J. Xu,et al.  Approaches for measuring the surface areas of metal oxide electrocatalysts for determining their intrinsic electrocatalytic activity. , 2019, Chemical Society reviews.

[9]  Guoliang Wang,et al.  Multidimensional nanostructured membrane electrode assemblies for proton exchange membrane fuel cell applications , 2019, Journal of Materials Chemistry A.

[10]  P. He,et al.  Ultralow Loading and High-Performing Pt Catalyst for a Polymer Electrolyte Membrane Fuel Cell Anode Achieved by Atomic Layer Deposition , 2019, ACS Catalysis.

[11]  J. Bowen,et al.  Support-free nanostructured Pt Cu electrocatalyst for the oxygen reduction reaction prepared by alternating magnetron sputtering , 2019, Journal of Power Sources.

[12]  Shanfu Lu,et al.  Design of a Catalytic Layer with Hierarchical Proton Transport Structure: The Role of Nafion Nanofiber , 2019, ACS Sustainable Chemistry & Engineering.

[13]  Jie Zhu,et al.  Bio‐Inspired Superhydrophobic Closely Packed Aligned Nanoneedle Architectures for Enhancing Condensation Heat Transfer , 2018, Advanced Functional Materials.

[14]  Zehui Yang,et al.  Bottom‐up Design of High‐Performance Pt Electrocatalysts Supported on Carbon Nanotubes with Homogeneous Ionomer Distribution , 2017 .

[15]  X. Gong,et al.  Recent Progress in Bionic Condensate Microdrop Self‐Propelling Surfaces , 2017, Advanced materials.

[16]  Suli Wang,et al.  Ordered Nafion® ionomers decorated polypyrrole nanowires for advanced electrochemical applications , 2017 .

[17]  Meng Wang,et al.  High performance and durability of order-structured cathode catalyst layer based on TiO 2 @PANI core-shell nanowire arrays , 2017 .

[18]  B. Yi,et al.  Nanostructured ultrathin catalyst layer based on open-walled PtCo bimetallic nanotube arrays for proton exchange membrane fuel cells , 2017 .

[19]  B. Yi,et al.  Development of advanced catalytic layer based on vertically aligned conductive polymer arrays for thin-film fuel cell electrodes , 2016 .

[20]  Suli Wang,et al.  Bio-inspired Construction of Advanced Fuel Cell Cathode with Pt Anchored in Ordered Hybrid Polymer Matrix , 2015, Scientific Reports.

[21]  S. Litster,et al.  Vertically Oriented Polymer Electrolyte Nanofiber Catalyst Support for Thin Film Proton‐Exchange Membrane Fuel Cell Electrodes , 2015 .

[22]  Jie Zhu,et al.  Copper-Based Ultrathin Nickel Nanocone Films with High-Efficiency Dropwise Condensation Heat Transfer Performance. , 2015, ACS applied materials & interfaces.

[23]  Jie Zhu,et al.  Clustered ribbed-nanoneedle structured copper surfaces with high-efficiency dropwise condensation heat transfer performance. , 2015, ACS applied materials & interfaces.

[24]  B. Yi,et al.  Vertically aligned carbon-coated titanium dioxide nanorod arrays on carbon paper with low platinum for proton exchange membrane fuel cells , 2015 .

[25]  Jiun‐Tai Chen,et al.  Wetting in nanopores of cylindrical anodic aluminum oxide templates: Production of gradient polymer nanorod arrays on large-area curved surfaces , 2015 .

[26]  B. Yi,et al.  An Oriented Ultrathin Catalyst Layer Derived from High Conductive TiO2 Nanotube for Polymer Electrolyte Membrane Fuel Cell , 2015 .

[27]  Xiaochun Zhou,et al.  Insights into the promotion effect of macrocycle molecule on HCOOH electro-oxidation , 2014 .

[28]  N. Nakashima,et al.  A polymer-coated carbon black-based fuel cell electrocatalyst with high CO-tolerance and durability in direct methanol oxidation , 2014 .

[29]  A. Weber,et al.  Unexplained transport resistances for low-loaded fuel-cell catalyst layers , 2014 .

[30]  Jie Zhu,et al.  Energy-effective frost-free coatings based on superhydrophobic aligned nanocones. , 2014, ACS applied materials & interfaces.

[31]  S. Bashir,et al.  Functionalization of Aligned Carbon Nanotubes to Enhance the Performance of Fuel Cell , 2013 .

[32]  R. Besser,et al.  Fabrication and performance evaluation of an in-membrane micro-fuel cell , 2013 .

[33]  J. Kozlova,et al.  Sputter-deposited Pt nanoparticle/multi-walled carbon nanotube composite catalyst for oxygen reduction reaction , 2013 .

[34]  Lin Jiang,et al.  Morphology Controlled Synthesis and Characterization of Vertically Aligned Carbon Nanofibers Supported Platinum Catalysts for Polymer Electrolyte Fuel Cells , 2013 .

[35]  Chi-Yeong Ahn,et al.  Effects of ionomer content on Pt catalyst/ordered mesoporous carbon support in polymer electrolyte membrane fuel cells , 2013 .

[36]  衣宝廉,et al.  Highly stable ternary tin–palladium–platinum catalysts supported on hydrogenated TiO2 nanotube arrays for fuel cells , 2013 .

[37]  Mark K. Debe,et al.  Tutorial on the Fundamental Characteristics and Practical Properties of Nanostructured Thin Film (NSTF) Catalysts , 2013 .

[38]  M. Jobbágy,et al.  Mesoporous Pt electrocatalyst for methanol tolerant cathodes of DMFC , 2012 .

[39]  Haiqun Chen,et al.  Graphene nanoplate-Pt composite as a high performance electrocatalyst for direct methanol fuel cells , 2012 .

[40]  Pei Kang Shen,et al.  A Highly Order‐Structured Membrane Electrode Assembly with Vertically Aligned Carbon Nanotubes for Ultra‐Low Pt Loading PEM Fuel Cells , 2011 .

[41]  R. Besser,et al.  Electron Beam Assisted Patterning and Dry Etching of Nafion Membranes , 2011 .

[42]  Wei Li,et al.  Resolving the HUPD and HOPD by DEMS to determine the ECSA of Pt electrodes in PEM fuel cells , 2011 .

[43]  Everett B. Anderson,et al.  Initial Performance and Durability of Ultra-Low Loaded NSTF Electrodes for PEM Electrolyzers , 2011 .

[44]  Jun Chen,et al.  Integrated High‐Efficiency Pt/Carbon Nanotube Arrays for PEM Fuel Cells , 2011 .

[45]  L. Qian,et al.  Controlled freezing and freeze drying: a versatile route for porous and micro‐/nano‐structured materials , 2011 .

[46]  M. Aizawa,et al.  Pillar Structured Membranes for Suppressing Cathodic Concentration Overvoltage in PEMFCs at Elevated Temperature/Low Relative Humidity , 2010 .

[47]  S. Du,et al.  A Facile Route for Polymer Electrolyte Membrane Fuel Cell Electrodes with in situ Grown Pt Nanowires , 2010 .

[48]  Lei Jiang,et al.  Designing Superhydrophobic Porous Nanostructures with Tunable Water Adhesion , 2009 .

[49]  B. Fang,et al.  Homogeneous deposition of platinum nanoparticles on carbon black for proton exchange membrane fuel cell. , 2009, Journal of the American Chemical Society.

[50]  Y. Elabd,et al.  Nafion® nanofibers and their effect on polymer electrolyte membrane fuel cell performance , 2009 .

[51]  Jun Shen,et al.  A review of PEM fuel cell durability: Degradation mechanisms and mitigation strategies , 2008 .

[52]  Patrick T. Mather,et al.  Nanofiber Network Ion-Exchange Membranes , 2008 .

[53]  S. Leea,et al.  Effect of Nafion gradient in dual catalyst layer on proton exchange membrane fuel cell performance , 2008 .

[54]  S. Soper,et al.  Free-standing, erect ultrahigh-aspect-ratio polymer nanopillar and nanotube ensembles. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[55]  Lei Jiang,et al.  The Dry‐Style Antifogging Properties of Mosquito Compound Eyes and Artificial Analogues Prepared by Soft Lithography , 2007 .

[56]  Toshiaki Kondo,et al.  Antireflection polymer surface using anodic porous alumina molds with tapered holes , 2007 .

[57]  Ashish A. Pandya,et al.  Molded, high surface area polymer electrolyte membranes from cured liquid precursors. , 2006, Journal of the American Chemical Society.

[58]  D. Aurbach,et al.  The dependence of the electronic conductivity of carbon molecular sieve electrodes on their charging states. , 2006, The journal of physical chemistry. B.

[59]  D. Gruber,et al.  Sputter-deposited ultra-low catalyst loadings for PEM fuel cells , 2005 .

[60]  Hubert A. Gasteiger,et al.  Dependence of PEM fuel cell performance on catalyst loading , 2004 .

[61]  K. Jeng,et al.  Modeling and simulation of a direct methanol fuel cell anode , 2002 .

[62]  F. Prinz,et al.  A sharp peak in the performance of sputtered platinum fuel cells at ultra-low platinum loading , 2002 .