Ultrafine amorphous Co–W–B alloy as the anode catalyst for a direct borohydride fuel cell

The ultrafine amorphous Co–W–B alloy has been synthesized by chemical reduction and used as anode catalyst in direct borohydride fuel cell. The results show that the maximum power output of the cell is 101 mW cm⁻² at 15 °C, and the essential power density of this material can be up to 350 mW cm⁻² at 15 °C and 500 mW cm⁻² at 60 °C, respectively. The cell has also a good durability, with no attenuation observed after one week of operation.     

Combinatorial investigation of Pt–Ru–Sn alloys as an anode electrocatalysts for direct alcohol fuel cells

Low-temperature direct alcohol fuel cells fed with different kinds of alcohol (methanol, ethanol and 2-propanol) have been investigated by employing ternary electrocatalysts (Pt–Ru–Sn) as anode catalysts. Combinatorial chemistry has been applied to screen the 66-PtRuSn-anode arrays at the same time to reduce cost, time, and effort when we select the optimum composition of electrocatalysts for DAFCs (Direct Alcohol Fuel Cells). PtRuSn (80:20:0) showed the lowest onset potential for methanol electro-oxidation, PtRuSn (50:0:50) for ethanol, and PtRuSn (20:70:10) for 2-propanol in CV results respectively, and single cell performance test indicated that Ru is more suitable for direct methanol fuel cell system, Sn for direct ethanol fuel cell system, and 2-propanol could be applied as fuel with low platinum composition anode electrocatalyst. The single cell performance results and electrochemical results (CV) were well matched with the combinatorial electrochemical results. As a result, we could verify the availability of combinatorial chemistry by comparing the results of each extreme electrocatalysts compositions as follows: PtRuSn (80:20:0) for methanol, PtRuSn (50:0:50) for ethanol and PtRuSn (20:70:10) for 2-propanol.     

Effect of anode conditions on the performance of direct borohydride–hydrogen peroxide fuel cell system

Direct borohydride–hydrogen peroxide fuel cells (DBHPFCs) are attractive power sources for space applications. Although the cathode conditions are known to affect the system performance, the effect of the anode conditions is rarely investigated. Thus, in this study, a DBHPFC system was tested under various anode conditions, such as electrocatalyst, fuel concentration, and stabilizer concentration, to investigate their effects on the system performance. A virtual DBHPFC system was analyzed based on the experimental data obtained from fuel cell tests. The anode electrocatalyst had a considerable effect on the mass and electrochemical reaction rate of the fuel cell system, but had minimal effect on the decomposition reaction rate. The NaBH₄ concentration greatly influenced the mass and decomposition reaction rate of the fuel cell system; however, it had minimal impact on the electrochemical reaction rate. The NaOH concentration affected the electrochemical reaction rate, decomposition reaction rate, and mass of the fuel cell system. Therefore, the significant effects of the anode conditions on the electrochemical reaction rate, decomposition reaction rate, and mass of the fuel cell system prompt the need for their careful selection through fuel cell tests and system analysis.     

Endurance study of a solid polymer electrolyte direct ethanol fuel cell based on a Pt–Sn anode catalyst

The performance decay of a solid polymer electrolyte direct ethanol fuel cell (DEFC) based on a Pt₃Sn₁/C anode catalyst during an endurance test has been investigated. The effect of different cell shut-down procedures on the cycled behaviour of the DEFC has been studied. To get specific insights into the degradation mechanism, polarization and ac-impedance spectroscopy studies have been carried out. These analyses have been complemented by post-operation transmission electron microscopy and X-ray diffraction studies. The combination of these techniques has allowed to get information on recoverable and unrecoverable losses. This provides a basis for further improvement of DEFC components.     

Electrodeposition of Pt–Ru and Pt–Ru–Ni nanoclusters on multi-walled carbon nanotubes for direct methanol fuel cell

A full-electrochemical method is developed to deposit three dimension structure (3D) flowerlike platinum-ruthenium (PtRu) and platinum-ruthenium-nickel (PtRuNi) alloy nanoparticle clusters on multi-walled carbon nanotubes (MWCNTs) through a three-step process. The structure and elemental composition of the PtRu/MWCNTs and PtRuNi/MWCNTs catalysts are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray polycrystalline diffraction (XRD), IRIS advantage inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). The presence of Pt(0), Ru(0), Ni(0), Ni(OH)₂, NiOOH, RuO₂ and NiO is deduced from XPS data. Electrocatalytic properties of the resulting PtRu/MWCNTs and PtRuNi/MWCNTs nanocomposites for oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) are investigated. Compared with the Pt/MWCNTs, PtNi/MWCNTs and PtRu/MWCNTs electrodes, an enhanced electrocatalytic activity and an appreciably improved resistance to CO poisoning are observed for the PtRuNi/MWCNTs electrode, which are attributed to the synergetic effect of bifunctional catalysis, three dimension structure, and oxygen functional groups which generated after electrochemical activation treatment on MWCNTs surface. The effect of electrodeposition conditions for the metal complexes on the composition and performance of the alloy nanoparticle clusters is also investigated. The optimized ratios for PtRu and PtRuNi alloy nanoparticle clusters are 8:2 and 8:1:1, respectively, in this experiment condition. The PtRuNi catalyst thus prepared exhibits excellent performance in the direct methanol fuel cells (DMFCs). The enhanced activity of the catalyst is surely throwing some light on the research and development of effective DMFCs catalysts.     

Electrocatalysts supported on multiwalled carbon nanotubes for direct borohydride–hydrogen peroxide fuel cell

Electrocatalysts of Rh, Ru, Pt, Au, Ag, Pd, Ni, and Cu supported on multiwalled carbon nanotubes for direct borohydride–hydrogen peroxide fuel cells are investigated. Metal/γ-Al₂O₃ catalysts for NaBH₄ and H₂O₂ decomposition tests are manufactured and their catalytic activities upon decomposition are compared. Also, the effects of XC-72 and multiwalled carbon nanotube (MWCNT) carbon supports on fuel cell performance are determined. The performance of the catalyst with MWCNTs is better than that of the catalyst with XC-72 owing to a large amount of reduced Pd and the good electrical conductivity of MWCNTs. Finally, the effect of electrodes with various catalysts on fuel cell performance is investigated. Based on test results, Pd (anode) and Au (cathode) are selected as catalysts for the electrodes. When Pd and Au are used together for electrodes, the maximum power density obtained is 170.9 mW/cm² (25 °C).     

Evaluation of Pt–Ru–Ni and Pt–Sn–Ni catalysts as anodes in direct ethanol fuel cells

In this study, the electrooxidation of ethanol on carbon supported Pt–Ru–Ni and Pt–Sn–Ni catalysts is electrochemically studied through cyclic voltammetry at 50 °C in direct ethanol fuel cells. All electrocatalysts are prepared using the ethylene glycol-reduction process and are chemically characterized by energy-dispersive X-ray analysis (EDX). For fuel cell evaluation, electrodes are prepared by the transfer-decal method. Nickel addition to the anode improves DEFC performance. When Pt₇₅Ru₁₅Ni₁₀/C is used as an anode catalyst, the current density obtained in the fuel cell is greater than that of all other investigated catalysts. Tri-metallic catalytic mixtures have a higher performance relative to bi-metallic catalysts. These results are in agreement with CV results that display greater activity for PtRuNi at higher potentials.     

Development of a power management unit for small portable direct borohydride fuel cell–NiMH battery hybrid system

In this study, a small portable fuel cell/battery hybrid system has been developed. The system consists of a single portable direct borohydride/peroxide fuel cell (DBPFC), NiMH battery and power management unit (PMU). The battery has been used as a primary power source and has been discharged at constant load. When its state of charge is reduced, the DBPFC charges the battery and powers the load simultaneously. A DC–DC Boost converter has been used as a PMU. The DBPFC has provided the total power of 0.21 Wh into the system during the charge. During this experimental study fuel (NaBH₄) efficiency of 37% has been achieved in the hybrid system, while the system efficiency has been calculated as 34.5%.     

Nanostructured Pt–Fe/C cathode catalysts for direct methanol fuel cell: The effect of catalyst composition

A series of carbon supported Pt–Fe bimetallic nanocatalysts (Pt–Fe/C) with varying Pt:Fe ratio were prepared by a modified ethylene glycol (EG) method, and then heat-treated under H₂–Ar (10 vol%-H₂) atmosphere at 900 °C. The Pt–Fe/C catalysts were characterized by X-ray diffraction (XRD), transmission electron spectroscopy (TEM), energy dispersive analysis by X-rays (EDX) and induced coupled plasma-atomic emission spectroscopy (ICP-AES). XRD analysis shows that Pt–Fe/C catalysts have small crystalline particles and form better Pt–Fe alloy structure with Fe amount increasing. TEM images evidence that small Pt–Fe nanoparticles homogeneously deposited on carbon support and addition of Fe can effectively prevent Pt particles agglomeration. EDX and ICP-AES show that Fe precursor cannot be fully reduced and deposited on carbon support through the adopted EG reduction approach. The electrochemical surface area of Pt–Fe/C catalyst obtained through hydrogen desorption areas in the CV curve increases with Fe atomic percentage increasing from 0 to ca. 50%, and then decreases with more Fe in the Pt–Fe/C catalyst. RDE tests show that the Pt–Fe/C with a Pt:Fe ratio of 1.2:1 and an optimized lattice parameter of around 3.894 Å has the highest mass activity and specific activity to oxygen reduction reaction (ORR). As cathode catalyst, this Pt–Fe/C (Pt:Fe ratio of 1.2:1) exhibits higher direct methanol fuel cell performance at 90 °C than Pt/C and other Pt–Fe/C catalysts, this could be attributed to its smaller particle size and better Pt–Fe alloy structure.     

Catalytic activity of Ni–YSZ–CeO2 anode for the steam reforming of methane in a direct internal-reforming solid oxide fuel cell

As one of the key technologies in the development of a direct internal-reforming solid oxide fuel cell, catalytic activity and stability of a Ni–YSZ–CeO₂ anode on a zirconia electrolyte for the steam reforming of methane was investigated by experiments using a differential fuel cell reactor. The effects of the partial pressure of CH₄, H₂O and H₂, and temperature as well as the electrochemical oxidation on the catalytic activity were analyzed. It was found that the catalytic activity of the Ni–YSZ–CeO₂ anode was higher than that of the Ni–YSZ reported especially at low temperature. A deterioration of the catalytic activity of the anode was observed at low P_H2 and high P_H2O atmosphere, and also at high current densities. This might be caused by the oxidation of the Ni surface by H₂O in the reaction gas and that produced by the anodic reaction. A rate equation for a fractional function for the steam reforming on open circuit was also proposed.     

Preparation of a high performance Pt–Co/C electrocatalyst for oxygen reduction in PEM fuel cell via a combined process of impregnation and seeding

The preparation of a Pt–Co/C electrocatalyst for the oxygen reduction reaction in PEM fuel cells was achieved via a combined process of impregnation and seeding. The effects of initial pH of the precursor solution and Pt loading were all found to have a significant effect on both the electrocatalyst morphology and the cell performance when tested in a single PEM fuel cell. The optimum condition found for preparing the Pt–Co/C electrocatalyst was from an initial precursor solution pH of 2 at the metal loading of 23.6–30.3% (w/w). The Pt–Co/C electrocatalysts, formed under these optimal conditions, tested in a single PEM fuel cell with the carbon sub-layer, gave a cell performance of 772 mA/cm² or 460 mW/cm² at 0.6 V in a H₂/O₂ system. An electron pathway of oxygen reduction on the prepared Pt–Co/C electrocatalyst was also determined using a rotating disk electrode.     

Pd decorated Co–Ni nanowires as a highly efficient catalyst for direct ethanol fuel cells

The storage and conversion of energy necessitates the use of appropriate electrochemical systems and chemical reaction catalysts. This work presents newly developed catalysts for electrooxidation of ethanol in an alkaline medium. Nanocatalysts composed of Co–Ni nanowires (Co–Ni NWs) decorated with Pd nanoparticles (Pd NPs) were made at varying metal ratios and their chemical composition and structure was investigated in detail. The synthesis involved a wet chemical reduction assisted by a magnetic field, which led to the generation of NWs, followed by the deposition of spherical Pd NPs on their surface. The best catalytic activity was obtained for the catalyst made of Co₃–Ni₇ decorated with Pd NPs, which exhibited EOR of 8003 mA/mg_Pd for only 0.86 wt% of Pd loading. The results can be explained by the synergistic effect between the morphology of the bimetallic support and the favorable interaction of oxophilic Co, Ni with catalytic Pd.     

A direct borohydride–peroxide fuel cell–LiPO battery hybrid motorcycle prototype – II

In this study, a direct borohydride–peroxide fuel cell (DBPFC)–LiPo battery hybrid motorcycle, called HYBROTO, was developed. The hybrid system was designed using a 10-cell DBPFC stack with 120 W of maximum power as the main power source, a 12 LiPo battery pack with 6300 mAh and 65 C for energy storage and as auxiliary power source, and a brushless DC (BLDC) motor. In addition, a voltage-monitoring integrated circuit for fuel cells, a battery management unit, and a motor control circuit were developed to command the DBPFC, LiPo battery, and BLDC motor, respectively. The hybrid system was managed and synchronized by a main control unit (MCU) containing a synchronous bidirectional buck–boost converter and a boost converter. For performance tests, the DBPFC–battery system and BLDC motor were installed in an electric motorcycle body. Performance tests were carried out in the hybrid system under a constant load of 60 W. The hybrid system showed a satisfactory performance under the constant load with an efficiency of 67%. However, the MCU requires further improvement to provide more stable power output. The motorcycle prototype was tested at the 2016 International Symposium on Sustainable Aviation organized by the Sustainable Aviation Research Society.     

Performance of supported Au–Co alloy as the anode catalyst of direct borohydride-hydrogen peroxide fuel cell

Au–Co alloys supported on Vulcan XC-72R carbon were prepared by the reverse microemulsion method and used as the anode electrocatalyst for direct borohydride-hydrogen peroxide fuel cell (DBHFC). The physical and electrochemical properties were investigated by energy dispersive X-ray (EDX), X-ray diffraction (XRD), cyclic voltammetry, chronamperometry and chronopotentiometry. The results show that supported Au–Co alloys catalysts have higher catalytic activity for the direct oxidation of BH₄⁻ than pure nanosized Au catalyst, especially the Au₄₅Co₅₅/C catalyst presents the highest catalytic activity among all as-prepared Au–Co alloys, and the DBHFC using the Au₄₅Co₅₅/C as anode electrocatalyst shows as high as 66.5 mW cm⁻² power density at a discharge current density of 85 mA cm⁻² at 25 °C.     

Non-stoichiometric tungsten-carbide-oxide-supported Pt–Ru anode catalysts for PEM fuel cells – From basic electrochemistry to fuel cell performance

Durability and cost of Proton Exchange Membrane fuel cells (PEMFCs) are two major factors delaying their commercialization. Cost is associated with the price of the catalysts, while durability is associated with degradation and poisoning of the catalysts, primarily by CO. This motivated us to develop tungsten-carbide-oxide (W_xC_yO_z) as a new non-carbon based catalyst support for Pt–Ru–based anode PEMFC catalyst. The aim was to improve performance and obtain higher CO tolerance compared to commercial catalysts. The performance of obtained PtRu/W_xC_yO_z catalysts was investigated using cyclic voltammetry, linear scan voltammetry and rotating disk electrode voltammetry. Particular attention was given to the analysis of CO poisoning, to better understand how W_xC_yO_z species can contribute to the CO tolerance of PtRu/W_xC_yO_z. Improved oxidation of CO_ads at low potentials (E < 0.5 V vs. RHE) was ascribed to OH provided by the oxide phase at the interfacial region between the support and the PtRu particles. On the other hand, at high potentials (E > 0.5 V vs. RHE) CO removal proceeds dominantly via OH provided from the oxidized metal sites. The obtained catalyst with the best performance (30% PtRu/W_xC_yO_z) was tested as an anode catalyst in PEM fuel cell. When using synthetic reformate as a fuel in PEMFC, there is a significant power drop of 35.3 % for the commercial 30% PtRu/C catalyst, while for the PtRu/W_xC_yO_z anode catalyst this drop is around 16 %.     

A study on novel combined processes for preparation of high performance Pt–Co/C electrocatalyst for oxygen reduction in PEM fuel cell

The preparation of a Pt–Co/C electrocatalyst for the oxygen reduction reaction in PEM fuel cells was achieved via a novel combined process of impregnation and seeding. The effect of seeding and non-seeding approaches on the morphologies and activities of the electrocatalyst was explored. The results indicated that the seeding or non-seeding approaches provided the similar results of Pt structure and phase composition in the Pt–Co/C electrocatalyst. However, the seeding approach provided a more uniform dispersion and smaller particle size of electrocatalyst compared with that of the non-seeding approach. Also, higher values of kinetic parameters including i₀, E₀, i_0.9V and E_10mA/cm2 were obtained in case of seeding electrocatalyst. Finally, the rotating disk electrode experimental results showed that the mechanism of oxygen reduction involved the four-electron pathway.     

Bipolar polymer electrolyte interfaces for hydrogen–oxygen and direct borohydride fuel cells

Direct borohydride fuel cells (DBFCs) using liquid hydrogen peroxide as the oxidant are safe and attractive low temperature power sources for unmanned underwater vehicles (UUVs) as they have excellent energy and power density and do not feature compressed gases or a flammable fuel stream. One challenge to this system is the disparate pH environment between the anolyte fuel and catholyte oxidant streams. Herein, a bipolar interface membrane electrode assembly (BIMEA) is demonstrated for maintaining pH control of the anolyte and catholyte compartments of the fuel cell. The prepared DBFC with the BIMEA yielded a promising peak power density of 110 mW cm⁻². This study also investigated the same BIMEA for a hydrogen–oxygen fuel cell (H₂–O₂ FC). The type of gas diffusion layer used and the gas feed relative humidity were found to impact fuel cell performance. Finally, a BIMEA featuring a silver electrocatalyst at the cathode in a H₂–O₂ FC was successfully demonstrated.     

Alloy-free amorphous Pt–B–P/C electrocatalyst for enhanced methanol electro-oxidation

This study reports the first known demonstration of amorphous Pt–B–P/C achieved via electroless reduction without the need for additional unstable transition metals. The amorphous structure was induced by simultaneous dual doping of both B and P by electroless reduction of Pt ion solution using a simple and facile process at ambient conditions. Amorphous Pt–B–P/C exhibited superior specific, mass activity compared to both commercial PtRu/C and crystalline Pt–B–P/C. Durability and CO poisoning resistance were also found to be better. XPS and annealing results suggest that synergistic effect of both doping and amorphous structure of Pt–B–P/C led to its overall enhanced catalytic performance.