Investigation of fabrication of gas diffusion substrate for proton exchange membrane fuel cells

The gas diffusion substrate (GDS) is essential in the proton exchange membrane fuel cells. Its fabrication techniques affect the performance significantly and are worthy of investigation. In this study, a manufacturing process of the GDS is proposed to understand the formation process of GDS and promote its structure and performance more pertinently. Different states during the preparation process, raw carbon paper, pre-curing, curing, carbonation, and graphitization, are characterized and measured. Experimental and numerical methods are employed to determine the relationships between microstructure, transport, and mechanical performance variation with the fabricating processes. The results show that its porosity, average pore size, and effective diffusivity decrease first and increase after curing. These parameters after graphitization are lower than that of the carbon paper (CP). The electrical resistivity increases dramatically while pre-curing and decreases gradually after curing, carbonation, and graphitization, and it is much reduced after graphitization. Moreover, mechanical measurement results show that both the picks of tensile strength and flexural modulus occur after curing. Its tensile strength shows little change after graphitization compared to the initial paper's. In contrast, the flexural modulus is improved significantly.     

Zeolite-templated sub-nanometer carbon nanotube arrays and membranes for hydrogen storage and separation

Adsorbents and membranes consisting of carbon nanotube (CNT) pores with diameters of molecular dimensions are highly desirable for hydrogen storage and selective, high-flux membrane separation. However, fabrication of such materials with precise pore sizes and monodispersity as well as evaluation of the mechanisms associated to adsorption and molecular transport are challenging. Herein, we grew aluminophsphate zeolites (CoAPO-5, AFI crystal structure) consisting of one-dimensional, monodisperse parallel pores with diameter of ～7 Å, and utilized them as templates to grow singe-walled CNTs (SWNTs) inside the pores. The resulting materials were examined as adsorbents and membranes for hydrogen storage and separation, respectively, using single-gas and real mixture feeds. Detailed mechanistic analysis and fundamental investigation of permeance and adsorption behavior of the resulting CNT-in-zeolite systems via combined adsorption, equilibrium, and kinetic studies were carried out. A superior gravimetric hydrogen uptake of 1.2 wt% at 35 °C and 1 bar was achieved in the case of the SWNTs grown in the cobalt-richer AFI host. Permeability measurements were performed on the respective Co(x)APO@SWNT membranes with the Co-richAPO@SWNT membrane exhibiting the highest permeance for all studied gases as a consequence of larger and more densely packed AFI crystals along with higher number of SWNT-filled pores, assets attributed to the higher Co catalyst content. Notably, the produced composite membranes exhibited gas permeability values that were two orders of magnitude higher than what predicted by the Knudsen mechanism.     

One-step to prepare high-performance gas diffusion layer (GDL) with three different functional layers for proton exchange membrane fuel cells (PEMFCs)

Gas diffusion layer (GDL) is one of the most important components of fuel cells. In order to improve the fuel cell performance, GDL has developed from single layer to dual layers, and then to multiple layers. However, dual or multi layers in GDL are usually prepared by layer-by-layer methods, which cost too much time, energy, and resources. In this work, we successfully developed a facile one-step method to prepare a GDL with three functional layers by utilizing the different sedimentation rates and filtration rates of short carbon fiber (CF) and carbon nanotube (CNT). The treatment temperature for this GDL is much lower than that of traditional method. The thickness of the GDL can be effectively controlled from as thin as 50 μm to more than 200 μm by simply adjusting the content of CF. The GDL with high flexibility is suitable to develop high performance flexible electronics. The fuel cell with the GDL has the maximum power density 1021 mW cm^?2, which shows 19% improvement comparing to the conventional one. Therefore, this work breaks the traditional concept that GDL for fuel cells only can be prepared by very complex and high-cost procedure.     

Investigation of La0.6Sr0.4Co1-xNixO3-δ (x=0, 0.2, 0.4, 0.6, 0.8) catalysts on solid oxide fuel cells anode for biogas dry reforming

The introduction of catalyst on anode of solid oxide fuel cell (SOFC) has been an effective way to alleviate the carbon deposition when utilizing biogas as the fuel. A series of La_0.6Sr_0.4Co_1-xNi_xO_3-δ (x = 0, 0.2, 0.4, 0.6, 0.8) oxides are synthesized by sol-gel method and used as catalysts precursors for biogas dry reforming. The phase structure of La_0.6Sr_0.4Co_1-xNi_xO_3-δ oxides before and after reduction are characterized by X-ray diffraction (XRD). The texture properties, carbon deposition, CH₄ and CO₂ conversion rate of La_0.6Sr_0.4Co_1-xNi_xO_3-δ catalysts are evaluated and compared. The peak power density of 739 mW cm^?2 is obtained by a commercial SOFC with La_0.6Sr_0.4Co_0.4Ni_0.6O_3-δ catalyst at 850 °C when using a mixture of CH₄: CO₂ = 2:1 as fuel. This shows a great improvement from the cell without catalyst for internal dry reforming, which is attributed to the formation of NiCo alloy active species after reduction in H₂ atmosphere. The results indicate the benefits of inhibiting the carbon deposition on Ni-based anode through introducing the La_0.6Sr_0.4Co_0.4Ni_0.6O_3-δ catalyst precursor. Additionally, the dry reforming technology will also help to convert part of the exhaust heat into chemical energy and improve the efficiency of SOFC system with biogas fuel.     

Manufacturing catalyst-coated membranes by ultrasonic spray deposition for PEMFC: Identification of key parameters and their impact on PEMFC performance

This study deals with the manufacturing of catalyst-coated membranes (CCMs) for newcomers in the field of coating. Although there are many studies on electrode ink composition for improving the performance of proton-exchange membrane fuel cells (PEMFCs), there are few papers dealing with electrode coating itself. Usually, it is a know-how that often remains secret and constitutes the added value of scientific teams or the business of industrialists. In this paper, we identify and clarify the role of key parameters to improve coating quality and also to correlate coating quality with fuel cell performance via polarization curves and electrochemical active surface area measurements. We found that the coating configurations can affect the performance of lab-made CCMs in PEMFCs. After the repeatability of the performance obtained by our coating method has been proved, we show that: (i) edge effects, due to mask shadowing - cannot be neglected when the active surface area is low, (ii) a heterogeneous thickness electrode produces performance lower than a homogeneous thickness electrode, and (iii) the origin and storage of platinum on carbon powders are a very important source of variability in the obtained results.     

Electrochemical performance of spherical Li-rich LMNCO cathode materials prepared using a two-step spray-drying method

In this study we synthesized Li-rich Li_1.2Ni_0.13Mn_0.54Co_0.13O₂ (LMNCO) as a composite cathode material through a two-step spray-drying method, using transition metal (TM) acetates and citric acid (CA, as a chelating agent) at various molar ratios and then calcining at various temperatures for various periods of time. This two-step spray-drying method created hierarchical nano/micro-sphere structures of the LMNCO cathode material. The LMNCO cathode exhibited the best electrochemical performance when synthesized with a TM:CA ratio of 3:2, a calcination temperature of 900 °C, and a calcination time of 5 h. This as-prepared LMNCO composite was then modified with polyimide (PI) at various weight ratios (PI/LMNCO = 0.5, 1.0, and 1.5 wt%) to improve its electrochemical properties. Among the various structures, the LMNCO cathode material coated with 1.0 wt% of PI at a layer thickness of approximately 1.88 nm achieved the best initial discharge capacities. This modified electrode also displayed enhanced cycle stability, with over 93.3 and 87.9% of the capacity retained after 30 cycles at 0.1C and 100 cycles at 1C, respectively. In comparison, the capacity retention of the unmodified LMNCO electrode measured under the same conditions was no more than 91.3% at 0.1C and 70.1% at 1C. Thus, surface modification with PI was an effective method for improving the coulombic efficiency, discharge capacity, and long-term cycling performance of the LMNCO cathode. Such PI-coated LMNCO composite cathode materials appear to be potential candidates for use in next-generation high-performance lithium-ion batteries.     

β-FeOOH modified carbon monolith anode derived from wax gourd for microbial fuel cells

The preparation of high-performance anode materials is of significance for enhanced power generation in microbial fuel cells (MFCs). Herein, porous carbon monolith was prepared by simple freeze drying of wax gourd and subsequent pyrolysis (WGC). β-FeOOH was coated on WGC to further improve the performance of the anode (β-FeOOH/WGC). The maximum power density of the MFCs with WGC and β-FeOOH/WGC anode was 913.9 and 1355.1 mW/m² respectively, which was much higher than that of the control (558.2 mW/m²). WGC possessed three-dimensional pore structure, nitrogen and oxygen-containing functional groups, which endowed it with satisfactory bacterial loading. Improved MFC performance after β-FeOOH modification could be ascribed to two aspects: β-FeOOH enhanced the electrochemical activity and decrease the transfer resistance; β-FeOOH was conducive to exoelectrogens formation. This study demonstrated that the synthesis of β-FeOOH modified carbon monolith anode offered an efficient route to enhance the power generation of MFCs.     

The impact of the thermal treatment during ink preparation on the ionomer-supported catalyst interactions in the catalyst layers

Catalyst slurries (inks) were prepared with and without thermal treatment to determine the support/ionomer structures and interactions in the catalyst layer (CL) which impact on membrane electrode performance and durability. The thermal treatment of the ink has a nominal effect on the ionomer/support structure in which the carbon support is non-graphitised. The agglomerate/aggregate structures have a high degree of support/ionomer interface and sufficient macroporosity for water movement in the CL. This improves the membrane electrode assembly (MEA) performance, but also accelerates electrochemical carbon degradation. Thermal treatment of graphitised support-containing inks resulted in increased performance facilitated by a larger support/ionomer interface. Without thermal treatment, the more hydrophobic support would form aggregate structures in which water contact was restricted, limiting proton transfer, isolating catalyst, decreasing performance. The water limited access, would however, prolong stability during accelerates carbon degradation. The electrochemical properties were studied using full and half MEA cells.     

Facile synthesis of black phosphorus directly grown on carbon paper as an efficient OER Electrocatalyst: Role of Interfacial charge transfer and induced local charge distribution

Black phosphorus (BP), as a new 2D material, is normally synthesized by a high-pressure and high-temperature (HPHT) method from white and red phosphorus, which severely hinders the further development of BP for any potential applications and leads to search for other potential applications of BP with big challenge. Herein, we develop a facile and efficient Thermal-Vaporization-Transformation (TVT) approach to prepare a highly active BP directly grown on carbon paper as the electrode for Oxygen evolution reaction (OER), showing a low onset potential of 1.45 V versus RHE. Simultaneously, the current density of BP-CP illustrates the excellent electro-catalysis stability only decreases by 3.4% after continuous operation for 10000 s. Meanwhile, the density functional theory (DFT) calculations further illustrates the P-doped carbon layer in the upper side of BP layer is actually responsible for its enhanced OER property, and the adjacent carbon atoms of the embedded P atoms are actually the active sites due to the induced local change distribution by intramolecular change transfer. Considering the facile, but efficient and scalable, TVT approach can directly synthesize BP-CP with excellent OER performance, which is promising for BP electrocatalysts used for OER in metal-air batteries, fuel cells, water-splitting devices, even other key renewable energy.     

Anodic corrosion of heteroatom doped graphene oxide supports and its influence on the electrocatalytic oxygen evolution reaction

Transition metal-based electrocatalysts supported on carbon substrates face the challenges of anodic corrosion of carbon during oxygen evolution reaction at high oxidation potential. The role of electrophilic functional groups (carbonyl, pyridinic, thiol, etc.) incorporated in graphene oxide has been studied towards the anodic corrosion resistance. Heteroatom functionalized carbon supports possess modified electronic properties, surface oxygen content, and hydrophilicity, which are crucial in governing electrochemical corrosion in the alkaline oxidative environment. Evidently, electron-withdrawing groups in NGO support (pyridinic, cyano, nitro, etc) and its lower oxygen content impart maximum corrosion resistance and anodic stability in comparison to the other sulfur-doped and co-doped graphene oxide support. In this report, we establish the baseline evaluation of carbon-supported OER electrocatalysts by a systematic analysis of activity and substrate corrosion resistance. The result of this study establishes the role of surface composition of the doped supports while for designing a stable, corrosion-resistant OER electrocatalyst.