Direct Fuel Cell Research Articles

Analysis of the Effect of Operating Conditions on the Performance of a Direct Ammonia Fuel Cell Using Multiphysics Modelling

Abstract Understanding the physical and chemical basis of device operation is important for their development. While hydrogen fuel cells are a widely studied topic, direct ammonia fuel cells (DAFCs) are a smaller field with fewer studies. Although the theoretical voltage of a DAFC is approximately equal to that of a hydrogen fuel cell, the slow kinetics of the ammonia oxidation reaction (AOR) hamper cell performance. Therefore, development of anode catalysts is especially needed for practical viability of the DAFCs. To study DAFC operation, specifically interactions between reaction kinetics and different transport phenomena, we developed a one-dimensional model of a DAFC and performed a sensitivity analysis for several parameters related to the cell operating conditions (e.g., temperature, relative humidity) and properties (e.g., catalyst loading). As expected, temperature and relative humidity were very important for cell power. However, while faster reaction kinetics improved the cell performance, simply increasing the catalyst loading did not always produce a comparable enhancement. These and other observations about the relative importance of the operating parameters should help to prioritize and guide future development of and research on DAFCs. Further studies are needed to understand and optimize e.g. humidity management in different scenarios.

Advancements in Noble Metal-Decorated Porous Carbon Nanoarchitectures: Key Catalysts for Direct Liquid Fuel Cells.

Noble-metal nanocrystals have emerged as essential electrode materials for catalytic oxidation of organic small molecule fuels in direct liquid fuel cells (DLFCs). However, for large-scale commercialization of DLFCs, adopting cost-effective techniques and optimizing their structures using advanced matrices are crucial. Notably, noble metal-decorated porous carbon nanoarchitectures exhibit exceptional electrocatalytic performances owing to their three-dimensional cross-linked porous networks, large accessible surface areas, homogeneous dispersion (of noble metals), reliable structural stability, and outstanding electrical conductivity. Consequently, they can be utilized to develop next-generation anode catalysts for DLFCs. Considering the recent expeditious advancements in this field, this comprehensive review provides an overview of the current progress in noble metal-decorated porous carbon nanoarchitectures. This paper meticulously outlines the associated synthetic strategies, precise microstructure regulation techniques, and their application in electrooxidation of small organic molecules. Furthermore, the review highlights the research challenges and future opportunities in this prospective research field, offering valuable insights for both researchers and industry experts.

Correction: Biomass Oxidation in Direct Biomass Redox Flow Fuel Cell: The Roles of Catalysts, Redox Couples, Mediators and Oxidants

Correction: Biomass Oxidation in Direct Biomass Redox Flow Fuel Cell: The Roles of Catalysts, Redox Couples, Mediators and Oxidants

Direct Ethanol Fuel Cell for Clean Electric Energy: Unravelling the Role of Electrode Materials for a Sustainable Future

Direct ethanol fuel cells (DEFCs) are better than others in commercially used FCs due to easy availability, less toxicity, and C‐2‐type alcohol. Ethanol has a high theoretical efficiency of 97% and is a safe, plentiful, and renewable resource that can be stored and controlled using the infrastructure that is in place now. Nevertheless, low functional efficiencies and the release of carbon dioxide (CO2), acetaldehyde, and byproducts of acetic acid must be addressed if DEFCs are to grow and become more commercially viable. To overcome these problems, new anode and cathode catalysts are needed, so this review article discusses the introduction of FCs with their structure, working and mechanism. Further, the report covers various types of FC catalysts, and their application in FC technology is explained. The role of the catalyst (such as anode and cathode), similarities and differences between Pt/Pd‐based catalysts, and the importance of supporting materials (such as carbon, transition metal dichalcogenides, MXene, and black phosphorus‐based materials) in DEFCs are described. In addition, the applications, advantages, and disadvantages of the DEFCs are discussed. Finally, the proposed theme is concluded with the existing challenges in this field and the future prospect of DEFCs.

Interface Engineering of PdPt Ultrafine Ethanol Electro-Oxidation Nanocatalysts by Bacterial Soluble Extracellular Polymeric Substances (s-EPS) to Break through Sabatier Principle.

Unsatisfactory performance of ethanol oxidation reaction (EOR) catalysts hinders the application of direct ethanol fuel cells (DEFCs), while traditional alloy catalysts (like PdPt) is cursed by Sabatier principle due to countable active site types. However, bacterial soluble extracellular polymeric substances (s-EPS) owning abundent functional groups may help breacking through it by contrusting different active sites on PdPt and inducing them to play synergy effect, which is called interface engineering. Using s-EPS to engineer catalysts is more green and consumes lower energy compared to chemical reagents. Herein, PdPt alloy nanoparticles (≈2.1nm) are successfully in situ synthesized by/on s-EPS of Bacillus megaterium, an ex-holotype. Tryptophan residuals are proved as the main reductant. In EOR, PdPt@s-EPS shows higher activity (3.89mAcm-2 ) than Pd@s-EPS, Pt@s-EPS, Pt/C and most reported akin catalysts. Its stability and durability are excellent, too. DFT modelling further demonstrates that, interface engineering by s-EPS breaks through Sabatier principle, by the synergy of diverse sites owning different degrees of d-p orbital hybridization. This work not only makes DEFCs closer to practice, but provides a facile and green strategy to design more catalysts.

Toward High-Energy-Density Fuels for Direct Liquid Organic Hydrogen Carrier Fuel Cells: Electrooxidation of 1-Cyclohexylethanol.

Electrochemically active liquid organic hydrogen carriers (EC-LOHCs) can be used directly in fuel cells; so far, however, they have rather low hydrogen storage capacities. In this work, we study the electrooxidation of a potential EC-LOHC with increased energy density, 1-cyclohexylethanol, which consists of two storage functionalities (a secondary alcohol and a cyclohexyl group). We investigated the product spectrum on low-index Pt single-crystal surfaces in an acidic environment by combining cyclic voltammetry, chronoamperometry, and in situ infrared spectroscopy, supported by density functional theory. We show that the electrooxidation of 1-cyclohexylethanol is a highly structure-sensitive reaction with activities Pt(111) ≫ Pt(100) > Pt(110). Most importantly, we demonstrate that 1-cyclohexylethanol can be directly converted to acetophenone, which desorbs from the electrode surface. However, decomposition products are formed, which lead to poisoning. If the latter side reactions could be suppressed, the electrooxidation of 1-cyclohexylethanol would enable the development of EC-LOHCs with greatly increased hydrogen storage capacities.

Urine Treatment in a Stacked Membraneless Direct Urea Fuel Cell with Honeycomb-like Nickel–Molybdenum Bimetal Phosphide as the Anodic Electrocatalyst

Urine Treatment in a Stacked Membraneless Direct Urea Fuel Cell with Honeycomb-like Nickel–Molybdenum Bimetal Phosphide as the Anodic Electrocatalyst

Development of a smart powering system with ammonia fuel cells and internal combustion engine for submarines

The current limitations of hydrogen storage technology in submarines have prompted the need for alternative solutions. One promising option is the use of ammonia, a readily stored fuel. This paper presents an innovative, integrated system that runs on ammonia and does not rely on atmospheric air. The system combines Direct Ammonia Fuel Cell (DAFC) stack and an Internal Combustion Engine (ICE) technology to generate power, freshwater, and cooling. The system also recovers waste heat and utilizes it efficiently to produce these useful outputs. The study further aims to assess the system's performance using energy and exergy analysis methods and to conduct a parametric analysis to examine the impact of parameters and operating conditions on system efficiency. In the developed integrated system, the quantities of net power produced, cooling provided, and freshwater flow rate produced under specified conditions are 4069 kW, 589.5 kW, and 1.269 kg/s, respectively. Its energy and exergy efficiency were found to be 38.58% and 44.77%, respectively. The analysis study also obtains that increasing the ammonia flow rate supplied to the ICE and the steam flow rate provided to the turbine, as well as the reference temperature, could potentially improve both energetic and exergetic efficiencies.

Biomass Oxidation in Direct Biomass Redox Flow Fuel Cell: The Roles of Catalysts, Redox Couples, Mediators and Oxidants

Biomass Oxidation in Direct Biomass Redox Flow Fuel Cell: The Roles of Catalysts, Redox Couples, Mediators and Oxidants

Advancements in Ni‐based Catalysts for Direct Urea Fuel Cells: A Comprehensive Review

AbstractThe growing demand for sustainable energy sources has spurred significant studies to optimize the potency of fuel cell technology. Direct urea fuel cell (DUFC) has gained attention due to their energy density, eco‐friendliness, and potential applications in power generation using urea from various sources, including wastewater and urine. Efficient electrocatalysts are pivotal in DUFCs, and nickel‐based catalysts, particularly in the form of NiOOH, have demonstrated cost effectiveness, excellent stability in alkaline media, and good activity for urea oxidation reaction. However, low‐density and durability are still the major limitation in the overall DUFC performance. This review provides a comprehensive analysis of the latest development in Ni‐based catalysts, covering synthesis methods, factors influencing the catalytic activity as well as their implications for DUFC performance durability and commercial viability. In addition, another important factor including the use of different oxidant and electrolyte medium is also elaborated. Based on this review, 2D‐3D Ni‐based materials with the addition of other metals and the use of non‐oxide nickel binary compound are predicted to be the future evolution of the effective nickel‐based catalysts.

Trimetallic PdRhPt Porous Nanooctahedra as Highly Active and Cost‐Effective Electrocatalysts for Ethanol Electrooxidation

AbstractThe development of highly active and cost‐effective electrocatalysts for the ethanol oxidation reaction (EOR) is imperative for the prospective application of direct ethanol fuel cells (DEFCs). In this study, we successfully synthesized porous octahedral nanoarchitectures comprising Pd, Rh, and Pt, through a straightforward one‐step co‐reduction aided by additional Ag precursors and other surface capping agents. The in‐situ galvanic replacement played a pivotal role in shaping hollow structures within the prepared PdRhPt porous octahedra, designated as PdRhPt‐POct. By strategically employing both composition and structure engineering, PdRhPt‐POct exhibited remarkably enhanced activity and stability toward EOR. Specifically, the mass activity of PdRhPt‐POct, reaching 8.11 A mg−1Pd+Pt, surpassed that of the majority of state‐of‐the‐art EOR electrocatalysts, owing to increased efficiency in C−C bond breaking and enhanced anti‐poisoning properties. This work introduces new prospects for designing and producing unique hollow‐structured multi‐metal nanocrystals as high‐performance EOR catalysts.

Defect-rich Pt-Ru metallic aerogels for highly efficient ethanol oxidation reaction

Direct ethanol fuel cells (DEFCs) are a new type of green and efficient energy conversion devices, but the slow anodic reaction kinetics limit their application. Herein, a series of Pt-Ru metallic aerogels (MAs) with controllable composition, rich surface defects, and large specific surface area were prepared for ethanol oxidation reaction (EOR) by freeze–thaw method. Pt6Ru MAs exhibit the highest mass activity (1.264 A mgPt−1) toward EOR among all the catalysts we have prepared, which is 2.0, 1.8, and 3.7 times higher than those of Pt MAs (0.632 A mgPt−1), the commercial Pt/C (0.696 A mgPt−1), Pt6Ru NPs (0.339 A mgPt−1). 1H nuclear magnetic resonance spectroscopy confirms that only acetic acid was the liquid product of Pt6Ru MAs during EOR catalysis. Furthermore, Pt6Ru MAs show little attenuation and satisfactory reactivation abilities in stability assessment, demonstrating their good stability. This proves that the introduction of Ru makes feasible adjustments to the electronic structure of Pt in MAs, improving the electrocatalysis activity of Pt6Ru MAs in EOR. Mechanistic investigations reveal that the optimal electronic structure is the intrinsic reason for the excellent EOR performance of Pt6Ru MAs. The findings open a new way to develop high-performance Pt-based materials electrocatalysts.

Insight into the ordering process and ethanol oxidation performance of Au-Pt-Cu ternary alloys

Direct ethanol fuel cell (DEFC), which has been widely recognized as nontoxic and green energy conversion device, shows attractive application prospect in liquid hydrogen-carrier, due to the higher specific energy...

Analysis and Modeling of Direct Ammonia Fuel Cells for Solar and Wind Power Leveling in Smart Grid Applications

Analysis and Modeling of Direct Ammonia Fuel Cells for Solar and Wind Power Leveling in Smart Grid Applications

Silver and Silver Alloy on Carbon-supported Catalysts for Cathodes in Proton Exchange Membrane Fuel Cell and Direct Ethanol Fuel Cell

This research was focused on the synthesis of 20 %wt silver, silver platinum alloy, and silver-copper alloy catalysts on carbon Vulcan XC-72 supporter for proton exchange membrane fuel cell (PEMFC) and direct ethanol fuel cell (DEFC) cathode using sodium borohydride method. Herein, the ratio of silver and platinum or copper sources was 1:1 by weight. The obtained catalysts were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and the electro-activity performance was investigated on single-cell testing. XRD and TEM results confirmed the catalytic products of the Ag metal, AgPt alloy, and silver copper oxide (AgxCu2-xO). Therefore, the particle size of the catalytic 20 %wt AgPt/C was observed in the smallest size of about 4.71±1.03 nm. The catalyst was selected for PEMFC and DEFC cathode testing. It showed high power density of 14.68 and 1.26 W/cm2.g(M), respectively.

In Situ Real-Time Simultaneous NMR Analyses of Anode and Cathode Exhausts of Direct Ethanol and Methanol Fuel Cells

Understanding the electrochemical reaction mechanisms of energy conversion and storage systems is essential for improving their performance. Nuclear magnetic resonance (NMR) spectroscopy is excellent for probing electrochemical reactions due to its capability to provide quantitative and qualitative information. For the in situ simultaneous acquisition of the anode and cathode exhaust spectra of direct alcohol fuel cells such as a direct methanol fuel cell (DMFC) or direct ethanol fuel cell (DEFC), real-time flow-NMR spectroscopy using a toroid cavity detector was developed in our laboratory. In the cathode exhaust of DMFC, the CD3OH crossed over from the anode as well as HOD was observed. Ex situ NMR spectroscopy cannot detect gas products because they are lost during sample preparation. On the other hand, the amount of CO2 gas detected in the anode exhaust using our in situ detection method was proportional to the HOD amount. It was also proportional to the cell current generated. This explains differences in the fuel cell performance by identifying generated and consumed chemicals and their pathways in the cells at respective conditions. Analyses of DEFC exhausts showed various reaction products such as acetic acid and acetaldehyde but CO2 gas detected was negligible. Our results show that this in situ real-time analysis could identify and quantify the exhaust components, including the gaseous products. Therefore, our results demonstrate that this in situ real-time analysis is appropriate to study the reaction mechanisms of diverse other liquid-flowing electrochemical systems in addition to fuel cells. Furthermore, it may be applicable to designing advanced materials for the systems.

Au-Based MOFs as Anodic Electrocatalysts for Direct Borohydride Fuel Cells

Researchers are exploring direct liquid fuel cells (DLFCs) as alternatives to proton-exchange membrane fuel cells because of their higher energy density and ease of storing and transporting the fuel. Direct borohydride fuel cells (DBFCs) are of particular interest as they offer a sustainable energy source with their high-power density output and the use of a highly alkaline NaBH4 medium [1]. Ensuring efficient and cost-effective catalysts for DBFCs is crucial for their commercial viability. Metal-organic frameworks (MOFs) have demonstrated significant potential as anodic electrocatalysts for BOR in DBFCs [2]. However, research should explore various modifications to MOFs, such as the incorporation of alternative metal ions or functional groups, to improve their catalytic efficiency and reduce cost. This study evaluated the performance of newly developed MOF-based electrocatalysts for DBFCs. Specifically, six MOF-based materials were synthesized and analyzed for their ability to facilitate borohydride oxidation (BOR) using cyclic voltammetry and chronoamperometry in alkaline media. MIL-101_Au@NH2 and MOF-808_Au@NH2 were found to be highly effective for BOR. The kinetic parameters for BOR with MOF-based electrocatalysts, including activation energy, reaction order, exchanged electrons, and anodic charge transfer coefficient, were determined. The activation energy for BOR was found to be 13.6 kJ mol−1 and 15.3 kJ mol−1 for MIL-101_Au@NH2 and MOF-808_Au@NH2, respectively. The number of transferred electrons, n, was found to be 7.0 and 3.1 for MIL-101_Au@NH2 and MOF-808_Au@NH2, respectively. This study demonstrates that MOF-based electrocatalysts can enhance DBFCs' performance, while offering insight into the potential usage of MOFs in other fuel cell technologies.[1] B. Šljukić, D.M.F. Santos, "Direct borohydride fuel cells", in: "Direct Liquid Fuel Cells: Fundamentals, Advances, and Future", 1st ed., R.G. Akay, A.B. Yurtcan (eds.), Academic Press, USA, 203-232 (2021)[2] G. Backovic, B. Šljukić, G.S. Kanberoglu, M. Yurderi, A. Bulut, M. Zahmakiran, D.M.F. Santos, Ruthenium (0) nanoparticles stabilized by the metal-organic framework as an efficient electrocatalyst for borohydride oxidation reaction, International Journal of Hydrogen Energy, 45, 27056-27066 (2020).

Electrochemical Impedance Analysis of Direct Ammonia Fuel Cell Operation and Clamping Effects

In addition to being an essential chemical for fertilizers, ammonia can also be used as a hydrogen carrier or directly as a fuel. Compared to hydrogen, the main advantages are that ammonia can be liquefied in mild conditions and the technology for ammonia shipping and pipelines already exists. Compared to carbon-based synthetic fuels, no carbon dioxide is produced by the oxidation, only water and nitrogen. The theoretical voltage of a direct ammonia fuel cell (DAFC) is 1.17 V, nearly equal to the 1.23 V of hydrogen fuel cells (HFC) but a central drawback is the slow kinetics of the ammonia oxidation reaction (AOR). The AOR is even slower than the oxygen reduction reaction (ORR) at the cathode, which in turn is the main voltage loss component in HFCs. Consequently, due to the AOR kinetics, DAFCs typically require significantly higher platinum group metal (PGM) catalyst loadings than HFCs for the same power output.To improve the performance of our aqueous-feed DAFC, especially using non-PGM catalysts, we carried out comparisons of catalysts and anion exchange membranes (AEM), and supplemented the comparison of power, voltage, and current parameters with electrochemical impedance spectroscopy (EIS). Additionally, we also compared measurements in two different test cells to try to identify the cause of measurement repeatability issues that we had when using one of the cells.Initially, we assumed that the reproducibility of catalyst deposition (or lack of it) and AEM or catalyst degradation in the ammonia-containing electrolyte had caused our repeatability problems. However, following a preliminary analysis of measurement statistics, we consider problems with the cell itself a more likely cause. The maximum power of the cell depended almost inversely on the series resistance (R S, i.e., the high-frequency resistance/real-axis intercept of the EIS spectrum), and the current at given voltage varied more than the differences in the resistance alone could explain when most measurement parameters were not varied (e.g., ammonia and hydroxide concentrations, liquid and gas flow rates). The general inverse dependence on R S remained also when measuring the same electrodes in different cells, and the performance did not necessarily degrade over time so, clearly, degradation and differences between electrodes could not explain everything. When testing different screw torques and gaskets in our AEM electrolyser, we had noticed that the voltage differences were often high compared to the R S differences, and it is known that clamping torque can affect the operation of fuel cells and electrolysers significantly. Nevertheless, more detailed analysis is ongoing to determine possible other contributing factors, to optimize the use of the cell(s) in measurements, and to guide future work.This research was done under the TELEGRAM project. This project has received funding from the European Union’s Horizon 2020 Research and Innovation programme under grant agreement No 101006941. The project started on the 1st of November 2020 with a duration of 42 months. The authors acknowledge support from the Federal Ministry of Education and Research in the framework of the project Catlab (03EW0015A). Figure 1

Trimetallic Alloy as an Electrocatalyst for Direct Low Temperature Fuel Cells: The Case of MF Oxidation on Pt3Pd3Sn2

Methyl formate (MF) has been considered an attractive hydrogen carrier alternative fuel due to its high energy density, ease of storage and transport, and low boiling point (32o C @ 1 atmosphere) liquid. However, the low number of publications on efficient anodic catalysts is impeding the development of a direct methyl formate fuel cell (DMFFC).In this study, a first-principles density functional theory (DFT) calculation was performed to study the MF electro-oxidation on the surface of the Pt3Pd3Sn2 (111) alloy. This surface was proven to be the most active in the anodic oxidation of other small organic molecules1,2. A detailed thermochemistry and kinetics study of MF oxidation was carried out to determine the active sites, most probable reaction pathway for the oxidation of CH3OCHO to CO2, and analyzed the dehydrogenation steps via direct (HCOOH pathway) and indirect (CO pathway) mechanisms.The potential required for complete oxidation of MF to CO2 is 0.66 V. The study revealed that Sn plays an essential role in the mitigation of CO poisoning through water activation and surface oxide reaction mechanisms in a bifunctional manner. Furthermore, based on our findings, Pt and Pd work synergistically to enhance the utilization of active sites for the initiation of MF oxidation and promote HCOOH oxidation, which accelerates the kinetics of the electrochemical reaction.

A Hybrid Direct Ammonia Fuel Cell

Ammonia has emerged as a highly promising energy carrier [1], primarily because it offers a noticeable economic benefit over hydrogen in terms of source-to-tank expenses, owing to reduced transmission, distribution, and dispensation costs [2]. Direct ammonia fuel cells (DAFCs) are capable of directly converting the chemical energy stored in ammonia into electrical energy. With its quick start-up advantage, this fuel cell technology holds great potential in the field of zero-emission transportation [3]. Although promising, this fuel cell performance needs to be much improved before the widespread commercialization becomes possible. The limiting factors include the sluggish kinetics of ammonia oxidation and the poor conductivity of anion exchange membranes. In addition, another important factor that limits the cell performance is that thermodynamically, its theoretical voltage is low (1.17 V). In this work, a hybrid direct ammonia fuel cell is developed, which consists of an alkaline anode, a cation exchange membrane, and an acid cathode. This hybrid fuel cell offers a theoretical voltage of as high as 2.55 V. The experimental results have shown that it exbibits an open-circuit voltage of 1.35 V and a peak power density of 437.1 mW cm−2 at 90 °C. Acknowledgement This work was fully supported by a grant from the National Natural Science Foundation of China (Project No. 52022003).