Direct Fuel Cell Research Articles

10-Cell Direct Ammonia Solid Oxide Fuel Cell Stack Design Development with Improved Efficiency and Resilience to Thermal Shock

Hydrogen's potential as a green fuel faces a storage challenge, which has prompted recent studies to explore methods to advance solid and liquid storage, with a particular focus on utilizing ammonia. Employing hydrogen in the form of ammonia has shown considerable promise as it capitalizes on well-established and mature technologies. Nevertheless, establishing effective and resilient direct ammonia Solid Oxide Fuel Cell (SOFC) stacks demands a high degree of congruence with stack design, uniform species distribution, and temperature regulation. This research compared the conventional simple cross flow configuration with a novel approach involving two alternating fuel and air flow configurations within a 10-cell direct ammonia SOFC stack. An experimentally validated model of the direct ammonia SOFC was utilized for multi-physics modeling. The results revealed that the alternating fuel and air stacking method creates a superior ammonia decomposition profile compared to simple cross flow stacking. Moreover, the results demonstrate a lower temperature difference of 55 K within the stack. The implementation of the alternating fuel flow and air flow method enhanced the stack's efficiency by 0.74%, primarily due to its improved thermal management capabilities within the stack. This study achieved its goal of optimizing a 10-cell direct ammonia SOFC stack by refining the design while maximizing performance and durability.

The Effect of Saccharin on SnNi Alloy: the Electrodeposition and its Electrocatalytic Activity in Ethanol Oxidation Reaction

The development of Direct Ethanol Fuel Cell (DEFC) has attracted much attention, as alternative energy sources due to its various advantages. However, among its various advantages, DEFC has several problems, such as the kinetics of the ethanol oxidation reaction. Transition metal-based catalysts such as nickel and tin are considered as potential catalysts for DEFC due to their oxophilic properties that can improve catalytic activity. In this study, the effect of saccharin on SnNi bimetallic alloy catalyst synthesized by electrodeposition method on copper wire substrate was investigated. SnNi samples were characterized by several techniques, including X-ray diffraction, Scanning electron microscopy, and energi dispersive X-ray spectrocopy. Saccharin addition had a significant effect on the morphology, crystallite size, and composition of the catalyst. The presence of saccharin causes the formation of more uniform particles and has a smaller size. The sample with the addition of saccharin had a smaller charge transfer resistance value 4.82 Ω, lower tafel slope by 115 mV/dec, and show higher jf/jb ratio by 0.55. Furthermore, as the current density decreases, the SnNi catalyst with saccharin has a slow decrease rate and higher stability than the SnNi catalyst without saccharin.

Pd Nanoparticles-Decorated Three-Dimensional Hierarchical Structure SnO2/rGO@Ni Foam Self-Supporting Electrode for Direct Borohydride-Hydrogen Peroxide Fuel Cells

Pd Nanoparticles-Decorated Three-Dimensional Hierarchical Structure SnO₂/rGO@Ni Foam Self-Supporting Electrode for Direct Borohydride-Hydrogen Peroxide Fuel Cells

Outstanding Activity and Durability of Supported NiCo2O4 Nanoparticles for Direct Ethanol Fuel Cells

ABSTRACTThe rational design of noble metal‐free electrocatalysts represents one of the basic stones for fuel cell development. With the exploration of eco‐friendly nanomaterials for the investigated alcohol oxidation process, nickel‐based electrodes have been recognized as the most auspicious anodes with promoted activity and stability. In this work, a series of NiCo2O4 nanoparticles were deposited onto graphite sheets (NiCo2O4/T) introducing varied proportions of cobalt oxide species. Co‐precipitation protocol of the respective metallic hydroxides onto the carbonaceous support was followed with consecutive annealing in an air atmosphere at 400°C. The fabricated mixed metallic oxide nanopowder was physically studied using X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X‐ray analysis (EDX), X‐ray photoelectron spectroscopy (XPS), and selected area electron diffraction (SAED). Uniformly arranged nanoparticles were observed on graphite surface as evidenced by SEM and TEM. The cubic lattice structure of formed NiCo2O4 crystals was also confirmed by XRD through the defined peaks of binary metallic oxides clarifying their successful preparation scheme. The electrocatalytic properties of these NiCo2O4/T nanocatalysts were evaluated for oxidizing ethanol molecules in basic solution. Pronounced oxidation current densities were remarkably measured at NiCo2O4/T electrodes in relation to that at NiO/T. Differing the introduced cobalt oxide content into the synthesized nanocatalyst significantly controlled its catalytic performance. NiCo2O4/T‐20 exhibited the highest activity and stability among the prepared nanomaterials. Much decreased charge transfer resistances were also recorded at this electrode demonstrating its promoted electron transfer characteristics. This work could provide a reasonable route for the simple synthesis of comparable transition metallic oxides with promising attitudes for energy generation purposes.

Breaking the Pt Electron Symmetry and OH Spillover towards PtIr Active Center for Performance Modulation in Direct Ammonia Fuel Cell.

The growing interest in low-temperature direct ammonia fuel cells (DAFCs) arises from the utilization of a carbon-neutral ammonia source; however, DAFCs encounter significant electrode overpotentials due to the substantial energy barrier of the *NH2 to *NH dehydrogenation, compounded by the facile deactivation by *N on the Pt surface. In this work, a unique catalyst, Pt4Ir@AlOOH/NGr i.e., Pt4Ir/ANGr, is introduced composed of PtIr alloy nanoparticles controllably decorated on the pseudo-boehmite phase of AlOOH-supported nitrogen-doped reduced graphene (AlOOH/NGr) composite, synthesized via the polyol reduction method. The detailed studies on the structural and electronic properties of the catalyst by XAS and VB-XPS reveal the possible electronic modulations. The optimized Pt4Ir/ANGr composition exhibits a significantly improved onset potential and mass activity for AOR. The DFT study confirms the OHad species spillover by AlOOH and Pt4Ir (100) facilitates the conversion of the *NH2 to *NH with minimal energy barriers. Finally, testing of DAFC at the system level using a membrane electrode assembly (MEA) with Pt4Ir/ANGr as the anode catalyst, demonstrating the suitability of the catalyst for its practical applications. This study thus uncovers the potential of the Pt4Ir catalyst in synergy with ANGr, largely addressing the challenges in hydrogen transportation, storage, and safety within DAFCs.

PtCu-a-SnO2 interface engineering on PtCu-SnO2 aerogels for ethanol oxidation electrocatalysis

Designing catalysts with high activity and stability to boost their ethanol oxidation reaction (EOR) performance is one of the central targets in the development of direct ethanol fuel cells (DEFCs). However, how to design the EOR catalysts in a rational way is still challenging, needing more efforts put in. Herein, we have synthesized a catalyst of PtCu-SnO2 aerogel via ingeniously introducing Cu into Pt-SnO2 system, resulting in the formation of a main phase of alloy (PtCu)-amorphous oxide (a-SnO2) interface. Benefiting from the optimized structures, the PtCu-SnO2 aerogel displays excellent acidic EOR performance with 4.5 times promotion in activity compared to pure Pt aerogel. In-depth investigations through electrochemical in-situ Fourier transform infrared spectroscopy and density functional theory calculations have shown that the absorbed OH on a-SnO2 surface together with the greatly-modified electronic structure of the alloy surface atoms can facilitate the C1 pathway and the oxidation of *CO intermediates for ethanol oxidation reaction. The resulting affinity of surface OH and the modification of reaction energies both in turn contribute to the improvement of EOR performance with high activity, stability, and anti-poisoning ability, proving interfacial engineering an effective strategy for the rational design of EOR catalyst.

Stability of supported Pd-based ethanol oxidation reaction electrocatalysts in alkaline media

This study evaluates the dissolution of the supported electrocatalysts Pd/C, PdSn/C, PdNb/C, and PdFe3O4/C during ethanol oxidation reaction for Alkaline Direct Liquid Fuel Cells (ADLFC) applications. A scanning flow cell (SFC) combined to an inductively coupled plasma mass spectrometry (online ICP-MS) is used to assess the dissolution stability in a broad potential window. Accelerated stress tests with and without ethanol are developed using a rotating disk electrode (RDE) with dissolution products analysis by ex-situ ICP-MS. Potential profiles simulating those experienced by the catalyst during regular fuel cell operation were used. Sn and Fe catalysts demonstrate improved activity and stability compared with the material with Pd alone. For these reasons, PdSn/C and PdFe3O4/C are suitable for ADLFC applications. Severe Nb dissolution destabilizes Pd, increasing its leaching. This work demonstrates that while additional metals and oxides can improve the alcohol oxidation kinetics of Pd, these additives’ dissolution stability must already be considered at the catalyst design stage.

Development and experimental investigation of a new direct urea fuel cell

This study concerns the development and experimental investigation of Direct Urea-Hydrogen Peroxide Fuel Cells (DUHPFC), with a particular emphasis on electrode preparation using nickel zinc iron oxide coated on stainless steel foil via the electrochemical deposition method, and the performance evaluation of single cells under varying operational conditions is also performed. This electrochemical deposition helps achieve a uniform and stable anode coating, which exhibits the high catalytic activity and stability, resulted in significantly enhanced urea oxidation reaction. The research further identifies an optimal performance for a single cell at 25 °C with 9 M KOH and 0.5 M urea, achieving a peak power density of 46.38 mW/cm2. The single cell demonstrates an open circuit voltage (OCV) of 0.72 V. Both energy and exergy efficiencies are further investigated for the cell performance and found to be 58% and 24%, respectively, at 5 M KOH. The electrochemical impedance spectroscopy (EIS) results reveal a significant reduction in impedance, from 30-Ωcm2 at 25 °C to 15-Ωcm2 at 65 °C, indicating an enhanced ionic conductivity and a reduced resistance. The present study results suggest that optimizing the electrode composition and operational parameters significantly improves the DUHPFC's performance, offering valuable insights for future fuel cell development.

Enhancing the Catalytic Activity of Pd Nanocatalysts for Anion Exchange Membrane Direct Ethanol Fuel Cells by Functionalizing Vulcan XC-72 with Cu Organometallic Compounds.

The most widely used support in low-temperature fuel cell applications is the commercially available Vulcan XC-72. Herein, we report its functionalization with the home-obtained mesityl copper (Cu-mes) and Cu coordinate (Cu(dmpz)L2) organometallic compounds. Pd nanoparticles are anchored on the supports obtaining Pd/CCu-mes, Pd/CCu(dmpz)L2, and Pd/C (on nonfunctionalized support). The polarization curves of the ethanol oxidation reaction (EOR) show that Pd/CCu-mes and Pd/CCu(dmpz)L2 promote the reaction at a more negative onset potential, i.e., E onset = 0.38 V/reversible hydrogen electrode (RHE), compared to 0.41 V/RHE of Pd/C. The mass current density (j m) delivered by Pd/CCu-mes is considerably higher (1231.3 mA mgPd -1), followed by Pd/CCu(dmpz)L2 (1001.8 mA mgPd -1), and Pd/C (808.3 mA mgPd -1). The enhanced performance of Pd/CCu-mes and Pd/CCu(dmpz)L2 for the EOR (and tolerance to CO poisoning) is attributed to a shift of their d-band center toward more negative values, compared to Pd/C, because of the formation of PdCu alloyed phases arising from the functionalization. In addition, laboratory-scale tests of the anion exchange membrane-direct ethanol fuel cell assembled with Pd/CCu-mes show the highest open circuit voltage (OCV = 0.60 V) and cell power density (P cell = 0.14 mW cm-2). As a result of its high catalytic activity, Pd/CCu-mes can find application as an anode nanocatalyst in AEM-DEFCs.

Determination of optimal operating conditions for bioelectrolyte fuel cells using ADH as anode catalyst and solidification of fuel

Enzyme-based direct ethanol fuel cells (DEFCs) have the potential to become the next generation of energy devices without platinum catalysts. However, the development of DEFCs requires the search for new electrolytes that are compatible with ethanol fuel and enzymes. In this study, DEFCs with a combination of chitin electrolytes and ADH were fabricated and characterized. DEFCs using chitin electrolyte were also investigated for various ethanol fuel concentrations, and it was found that DEFCs using 50 mM ethanol achieved the highest power density. In addition, enzyme activity was measured and showed a maximum value when 50 mM ethanol was used, suggesting that the proton production reaction catalyzed by the enzyme determines the maximum power density of the bioelectrolyte DEFC. Furthermore, we successfully fabricated a highly portable solid bio-electrolyte DEFC and found that it achieved a maximum power density of 0.11 mW/cm2 at an ethanol concentration of 25 %.

Mechanistic Insights on Direct Ammonia Solid Fuel Cell Using Ni-YSZ Anode: Experimental and Density Functional Theory Studies

While Ni-Yttria-stabilized zirconia (Ni-YSZ) cermet exhibits a great potential to realize high-efficiency ammonia to power using direct ammonia solid oxide fuel cell (DA-SOFC), the mechanisms of NH3 cracking and H2 oxidation reactions as well as direct electro-oxidation of ammonia are still unclear. In this context, with the motivation, the DA-SOFC performance of fuel electrode (Ni-YSZ) using conventional anode-supported cell (Ni-YSZ|YSZ|GDC-LSCF) is studied through microscale observation coupled with density functional theory (DFT) calculations to unravel the reaction mechanisms on Ni-YSZ(111) anode. The performance of DA-SOFC is examined using NH3, H2 and N2/H2 mixture as fuel at the temperature range of 700-800℃. In addition to XRD and SEM-EDX characterizations, the electrochemical characterization is performed using the impedance spectroscopy (EIS) measurements at three different temperatures of 700, 750 and 800 °C. Interestingly, the experimentally observed trend in Open-circuit voltage (OCV) implies that direct electro-oxidation of ammonia is the dominant reaction mechanism. Notably, polarization resistance is primarily contributed by ammonia anodic reaction and secondarily by the gas diffusion impedance. DFT results revealed that ammonia adsorbs favorably on the Ni cluster, and hydrogen follows a dissociative mode of adsorption on the Ni cluster. The activation barriers of elementary steps involved in the proposed mechanisms for fuel cracking and oxidation reactions are computed. This work is anticipated to provide valuable insights into the rational design of Ni-YSZ-based fuel electrodes. Keywords: ammonia, hydrogen, SOFC, fuel cells, DFT, reaction mechanism

Direct Hydroquinone Fuel Cells

The Increasing interest and need to shift to sustainable energy give rise to the utilization of fuel cell technologies in various applications. The challenging task of hydrogen storage and transport led to the development of liquid hydrogen carriers (LHC) as fuels for direct LHC fuel cells, such as methanol in direct methanol fuel cells (DMFC). Although simpler to handle, most direct LHC fuel cells suffer from durability and price issues, derived from high catalysts’ loadings and by-products of the oxidation reaction of the fuel. Herein, we report on the development of direct hydroquinone fuel cells (DQFC) based on anthraquinone-2,7-disulfonic acid (AQDS) as an LHC. We have shown that DQFC can operate with continues flow of quinone as a hydrogen carrier, outperforming the incumbent state-of-the-art DMFC by a factor of three in peak power density, while completely removing the need for any catalyst at the anode. In addition, we demonstrate that the quinone can be charged with protons in the same system, making it a reversible fuel cell system. We optimized the operating conditions and will discuss the governing conditions to reach best performance.

Improving durability and efficiency in passive direct ethanol fuel cells using a biodegradable polyvinyl alcohol/epoxidized natural rubber membrane

AbstractIn this study, a novel biodegradable polymer electrolyte membrane with reduced fuel crossover, high selectivity, and high conductivity compared with Nafion 117 membrane in direct ethanol fuel cells (DEFCs) has been reported. Herein, polyvinyl alcohol/epoxidized natural rubber (PVA/ENR) blend membranes were synthesized via a simple solution casting method and applied in DEFCs. The structural and physicochemical features of the PVA/ENR blend membranes were examined using FESEM, FTIR, XRD, water absorption, ethanol uptake, swelling ratio and oxidative stability. ENR enhances the chemical, structural, and mechanical characteristics of PVA, making it a valuable material in fuel cell applications. The incorporation of ENR into the PVA matrix results in a compact morphology, excessive multifunctional groups, low fuel crossover, and high selectivity. The optimum membrane thickness achieves the highest selectivity, reaching up to 12.32 × 104 S s cm−3 at 30°C. Additionally, the maximum power density achieved is 19.52 mW cm−2, surpassing that of the Nafion membrane, which is only 14.55 mW cm−2 at 90°C. Furthermore, this biodegradable membrane can sustain operation for 1000 h at 90°C, owing to its ability to maintain hydration for an extended period. This study represents the first attempt to combine PVA and ENR in fuel cells.

High-Performance Fluorinated Poly(aryl piperidinium) Membranes for Direct Ammonia Fuel Cells

High-Performance Fluorinated Poly(aryl piperidinium) Membranes for Direct Ammonia Fuel Cells

Investigating the Effects of the Physicochemical Properties of Cellulose-Derived Biocarbon on Direct Carbon Solid Oxide Fuel Cell Performance.

This paper presents a study of the characteristic effects of the physicochemical properties of microcrystalline cellulose and a series of biocarbon samples produced from this raw material through thermal conversion at temperatures ranging from 200 °C to 850 °C. Structural studies revealed that the biocarbon samples produced from cellulose had a relatively low degree of graphitization of the carbon and an isometric shape of the carbon particles. Based on thermal investigations using the differential thermal analysis/differential scanning calorimeter method, obtaining fully formed biocarbon samples from cellulose feedstock was possible at about 400 °C. The highest direct carbon solid oxide fuel cell (DC-SOFC) performance was found for biochar samples obtained via thermal treatment at 400-600 °C. The pyrolytic gases from cellulose decomposition had a considerable impact on the achieved current density and power density of the DC-SOFCs supplied by pure cellulose samples or biochars derived from cellulose feedstock at a lower temperature range of 200-400 °C. For the DC-SOFCs supplied by biochars synthesised at higher temperatures of 600-850 °C, the "shuttle delivery mechanism" had a substantial effect. The impact of the carbon oxide concentration in the anode or carbon bed was important for the performance of the DC-SOFCs. Carbon oxide oxidised at the anode to form carbon dioxide, which interacted with the carbon bed to form more carbon oxide. The application of biochar obtained from cellulose alone without an additional catalyst led to moderate electrochemical power output from the DC-SOFCs. The results show that catalysts for the reverse Boudouard reactions occurring in a biocarbon bed are critical to ensuring high performance and stable operation under electrical load, which is crucial for DC-SOFC development.

Direct Liquid Fuel Cell Using Cyclohexanol as Regenerative Fuel for Emission-Free Energy Generation

Direct Liquid Fuel Cell Using Cyclohexanol as Regenerative Fuel for Emission-Free Energy Generation

Impact of a Novel Nickel-Based Catalyst and Phenyl-Acrylate-Based Anion-Exchange Membrane in a Direct Urea Fuel Cell

Impact of a Novel Nickel-Based Catalyst and Phenyl-Acrylate-Based Anion-Exchange Membrane in a Direct Urea Fuel Cell

Candle Soot as a Novel Support for Nickel Nanoparticles in the Electrocatalytic Ethanol Oxidation.

The enhancement of carbon-supported components is a crucial factor in augmenting the interplay between carbon-supported and metal-active components in the utilization of catalysts for direct ethanol fuel cells (DEFCs). Here, we propose a strategy for designing a catalyst by modifying candle soot (CS) and loading nickel onto ordered carbon soot. The present study aimed to investigate the effect of the Ni nanoparticles content on the electrocatalytic performance of Ni-CS, ultimately leading to the identification of a maximum composition. The presence of an excessive quantity of nickel particles leads to a decrease in the number of active sites within the material, resulting in sluggishness of the electron transfer pathway. The electrocatalyst composed of nickel and carbon support, with a nickel content of 20 wt%, has demonstrated a noteworthy current activity of 18.43 mA/cm2, which is three times that of the electrocatalyst with a higher nickel content of 25 wt%. For example, the 20 wt% Ni-CS electrocatalytic activity was found to be good, and it was approximately four times higher than that of 20 wt% Ni-CB (nickel-carbon black). Moreover, the chronoamperometry (CA) test demonstrated a reduction in current activity of merely 65.80% for a 20 wt% Ni-CS electrocatalyst, indicating electrochemical stability. In addition, this demonstrates the great potential of candle soot with Ni nanoparticles to be used as a catalyst in practical applications.

Overall Design of a Gradient‐Ordered Membrane Electrode Assembly for Direct Liquid Fuel Cells

AbstractThe direct liquid fuel cell (DLFC) constitutes a promising energy conversion system that directly conveys the chemical energy of liquid fuels into electrical energy. In certain DLFCs, gas is produced as a product of electrochemical reactions during operation. However, the accumulation of gas inside the porous electrode can significantly hinder the transport of reactants, leading to the failure of active sites and severe concentration loss. To address this issue, a gradient‐ordered membrane electrode assembly (MEA) is designed and fabricated, consisting of a dual‐gradient diffusion layer that comprises a pore‐size gradient and a wettability gradient as well as a catalyst layer constructed by nanoneedle catalyst. This MEA promptly removes the produced gas and delivers the fresh solution, thereby enhancing the cell power output and stability. The fuel cell with the gradient‐ordered MEA achieves a remarkable peak power density of 177 mW cm−2 and a discharging time of 19 h, which are more than four times and 30 times, respectively, higher than those of the conventional MEA.

PdSnW Ternary Alloy Nanoparticle with Excellent CO Anti‐Poisoning Activity for Boosting Alkaline Ethanol Oxidation Reaction

AbstractEfficient ethanol oxidation reaction (EOR) catalysts with anti‐poisoning ability and high selectivity are in high demand for the widespread application of direct ethanol fuel cells (DEFCs). Here, the PdSnW ternary alloy nanoparticles are synthesized by a facile solvothermal method and exhibit an enhanced EOR catalytic performance. CO stripping experiment, X‐ray photoelectron spectroscopy and in situ Fourier transform infrared are employed to study the correlation between catalyst structure and EOR catalytic performance. The oxyphilic Sn and W not only provide dangling O−H bond, accelerating the subsequent oxidation of adsorbed intermediate CO species, but also moderate the electron state of Pd, enhancing the adsorption of CH3CH2OH, thus resulting in the promotion of C−C bond cleavage and an increased C1 selectivity. As a consequence, PdSnW alloy nanoparticle catalyst exhibit a better stability and a higher mass activity than those of Pd/C, PdSn and PdW, respectively. This work not only offers novel insights to strategically design highly efficient electrocatalysts for ethanol oxidation, but also further clarifies the inherent structure‐activity relationship.