Electrooxidation of hydrogen peroxide and sodium borohydride on Ni deposited carbon fiber electrode for alkaline fuel cells

In this study, Ni deposited carbon fiber electrode (Ni/CF) prepared by electroless deposition method was examined for their redox process and electrocatalytic activities during the oxidation of hydrogen peroxide and sodium borohydride in alkaline solutions. The Ni/CF catalyst was characterized by X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), scanning electron microscopy (SEM) and electrochemical voltammetry analysis. The electrocatalytic activity of the Ni/CF for oxidation of hydrogen peroxide and sodium borohydride in alkaline solutions was investigated by cyclic voltammetry. The anodic peak current density is found to be three times higher on Ni/CF catalyst for sodium borohydride compared to that for hydrogen peroxide. Preliminary tests on a single cell of a direct borohydride/peroxide fuel cell (DBPFC) and direct peroxide/peroxide fuel cell (DPPFC) indicate that DBPFC with the power density of 5.9 mW cm⁻² provides higher performance than DPPFC (3.8 mWcm⁻²).     

Recovery of borohydride from metaborate solution using a silver catalyst for application of direct rechargable borohydride/peroxide fuel cells

This study aims at the investigation of a suitable catalyst for the electrochemical reduction mechanism of metaborate into borohydride with the hope of the construction of rechargeable direct borohydride/peroxide fuel cell. A passive direct borohydride/peroxide fuel cell with Ag anode and Pt/C cathode was constructed. Its maximum power density was calculated as 7 mW cm⁻² at a cell voltage of 0.5 and a current density of 11 mA cm⁻². Recycling of the metaborate, the co-product of the borohydride oxidation, to the borohydride is the major issue in order to achieve the rechargeable borohydride fuel cells. Accordingly, the NaBO₂ solution was electrolyzed with the use of Ag electrodes for this purpose. The converted borohydride were determined by the cyclic voltammetry using Au and Ag electrodes which are highly selective for this purpose. The cyclic voltammetric curves revealed the peaks which indicated the conversion of NaBO₂ into NaBH₄. The presence of NaBH₄ was also verified iodometrically after the electrolysis. It was observed that there was 10% conversion after 24 h of electrolysis which reached up to 17% after 48 h. These data are very promising in the quest of the construction of a rechargeable direct borohydride fuel cell.     

A direct borohydride fuel cell employing Prussian Blue as mediated electron-transfer hydrogen peroxide reduction catalyst

A direct borohydride-hydrogen peroxide fuel cell employing carbon-supported Prussian Blue (PB) as mediated electron-transfer cathode catalyst is reported. While operating at 30 °C, the direct borohydride-hydrogen peroxide fuel cell employing carbon-supported PB cathode catalyst shows superior performance with the maximum output power density of 68 mW cm⁻² at an operating voltage of 1.1 V compared to direct borohydride-hydrogen peroxide fuel cell employing the conventional gold-based cathode with the maximum output power density of 47 mW cm⁻² at an operating voltage of 0.7 V. X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray Analysis (EDAX) suggest that anchoring of Cetyl-Trimethyl Ammonium Bromide (CTAB) as a surfactant moiety on carbon-supported PB affects the catalyst morphology. Polarization studies on direct borohydride-hydrogen peroxide fuel cell with carbon-supported CTAB-anchored PB cathode exhibit better performance with the maximum output power density of 50 mW cm⁻² at an operating voltage of 1 V than the direct borohydride-hydrogen peroxide fuel cell with carbon-supported Prussian Blue without CTAB with the maximum output power density of 29 mW cm⁻² at an operating voltage of 1 V.     

Direct borohydride fuel cell using Ni-based composite anodes

In this study, nickel-based composite anode catalysts consisting of Ni with either Pd on carbon or Pt on carbon (the ratio of Ni:Pd or Ni:Pt being 25:1) were prepared for use in direct borohydride fuel cells (DBFCs). Cathode catalysts used were 1 mg cm⁻² Pt/C or Pd electrodeposited on activated carbon cloth. The oxidants were oxygen, oxygen in air, or acidified hydrogen peroxide. Alkaline solution of sodium borohydride was used as fuel in the cell. High power performance has been achieved by DBFC using non-precious metal, Ni-based composite anodes with relatively low anodic loading (e.g., 270 mW cm⁻² for NaBH₄/O₂ fuel cell at 60 °C, 665 mW cm⁻² for NaBH₄/H₂O₂ fuel cell at 60 °C). Effects of temperature, oxidant, and anode catalyst loading on the DBFC performance were investigated. The cell was operated for about 100 h and its performance stability was recorded.     

Platinum-plated nanoporous gold: An efficient,low Pt loading electrocatalyst for PEM fuel cells

Platinum-plated nanoporous gold leaf (Pt-NPGL) is made by coating a conformal, atomically thin skin of platinum over the high surface area pores of a thin membrane of nanoporous gold. Because Pt loading in Pt-NPGL can be controlled down to 0.01 mg cm⁻² using only simple benchtop chemistry, the material holds promise as a low Pt loading, carbon-free electrocatalyst. Here, we report successful use of Pt-NPGL as a catalyst in proton exchange membrane (PEM) fuel cells. Stable and high performance Pt-NPGL/Nafion membrane electrode assemblies (MEAs) were made using a stamping technique. The performance of Pt-NPGL MEAs is comparable to conventional carbon-supported nanoparticles-based MEAs with much higher loading, generating an output power density of up to 4.5 kW g⁻¹ Pt in our non-optimized test configuration. Correlations between the performance of Pt-NPGL MEAs, the electrochemically accessible surface area, and material microstructure are discussed. Our success in using Pt-NPGL as a fuel cell catalyst suggests that creating precious metals skins over nanoporous metal supports is a viable strategy for designing new catalysts for PEM fuel cells. This promising approach allows tailoring catalytic activity by engineering precious metal/substrate interactions, employs materials with dual functionality acting both as current collector and catalyst, and may avoid the sintering problems plaguing conventional nanoparticle-based catalysts.     

Influence of operation conditions on direct NaBH4/H2O2 fuel cell performance

Although hydrogen fuel cells have attracted so much attentions in these years because of the application prospect in electric vehicles, some obstacles have not been solved yet, among which hydrogen storage is one of the biggest. Direct borohydride fuel cell (DBFC) is another choice without hydrogen storage problem because borohydride is used as reactant directly in the fuel cell. In this paper, DBFC performance under different operation conditions was studied including electrolyte membrane type, operation temperature, borohydride concentration, supporting electrolyte and oxidant. Results showed that, with Pt/C and MnO₂ as anode and cathode electrocatalyst, respectively, Nafion^® 117 membrane as electrolyte, 1.0 M, 3.0 M and 6.0 M NaBH₄ and H₂O₂ solution in NaOH as reactant solution, 80 °C operation, the peak power density could reach 130 mW/cm².     

Optimized hydrogen generation in a semicontinuous sodium borohydride hydrolysis reactor for a 60 W-scale fuel cell stack

Catalyzed hydrolysis of sodium borohydride (SBH) is a promising method for the hydrogen supply of fuel cells. In this study a system for controlled production of hydrogen from aqueous sodium borohydride (SBH) solutions has been designed and built. This simple and low cost system operates under controlled addition of stabilized SBH solutions (fuel solutions) to a supported CoB catalyst. The system works at constant temperature delivering hydrogen at 1 L min⁻¹ constant rate to match a 60-W polymer electrolyte membrane fuel cell (PEMFC). For optimization of the system, several experimental conditions were changed and their effect was investigated. A simple model based only on thermodynamic considerations was proposed to optimize system parameters at constant temperature and hydrogen evolution rate. It was found that, for a given SBH concentration, the use of the adequate fuel addition rate can maximize the total conversion and therefore the gravimetric storage capacity. The hydrogen storage capacity was as high as 3.5 wt% for 19 wt% SBH solution at 90% fuel conversion and an operation temperature of 60 °C. It has been demonstrated that these optimized values can also be achieved for a wide range of hydrogen generation rates. Studies on the durability of the catalyst showed that a regeneration step is needed to restore the catalytic activity before reusing.     

Investigation of amorphous CoB alloy as the anode catalyst for a direct borohydride fuel cell

Co-B amorphous alloy powders have been synthesized by chemical reduction of cobalt chloride with potassium borohydride in an aqueous solution. We find that this alloy can be used as an anode catalyst for a direct borohydride fuel cell (DBFC). This catalyst exhibits excellent electrocatalytic activity. An essential power output of 220 mW cm⁻² has been achieved at 15 °C, and a life test last for 160 h with no attenuation has been observed. The amorphous structure of the CoB alloy is still stable after the life test.     

LaNi4.5Al0.5 alloy doped with Au used as anodic materials in a borohydride fuel cell

Fuel cells using borohydride as the fuel have received much attention because of their high thermodynamic cell voltage. Using rare-earth hydrogen storage alloys as the anodic catalyst materials instead of noble metals showed high catalytic activity both in the electrochemical oxidation and the hydrolysis of borohydride. In this work, we doped Au to modify the surface structure of LaNi_4.5Al_0.5 alloy by a self-reduction reaction method. The surface of the alloy particles was evenly covered with Au after treatment. The largest discharge current density increased from about 150 mA cm⁻² (discharge to −0.6 V versus Hg/HgO electrode) with the parent alloy to 250 mA cm⁻² with the Au-doped alloy. This finding suggested that the electrochemical catalytic activity of the alloy was enhanced after modification with Au. Fuel utilization also increased after modification with Au.     

Iron phthalocyanine as a cathode catalyst for a direct borohydride fuel cell

A direct borohydride fuel cell (DBFC) is constructed using a cathode based on iron phthalocyanine (FePc) catalyst supported on active carbon (AC), and a AB₅-type hydrogen storage alloy (MmNi_3.55Co_0.75Mn_0.4Al_0.3) was used as the anode catalyst. The electrochemical properties are investigated by cyclic voltammetry (CV), linear sweep voltammetry (LSV), etc. methods. The electrochemical experiments show that FePc-catalyzed cathode not only exhibits considerable electrocatalytic activity for oxygen reduction in the BH₄⁻ solutions, but also the existence of BH₄⁻ ions has almost no negative influences on the discharge performances of the air-breathing cathode. At the optimum conditions of 6 M KOH + 0.8 M KBH₄ and room temperature, the maximal power density of 92 mW cm⁻² is obtained for this cell with a discharge current density of 175 mA cm⁻² at a cell voltage of 0.53 V. The new type alkaline fuel cell overcomes the problem of the conventional fuel cell in which both noble metal catalysts and expensive ion exchange membrane were used.     

High utilization of Pt nanocatalysts fabricated using a high-pressure sputtering technique

Pt nanocatalysts formed on a gas diffusion layer substrate for use in proton exchange membrane fuel cells were fabricated by using a high-pressure sputtering technique in a gaseous mixture of Ar and He. Rather than the dense film deposited by conventional sputtering techniques, the resulting structure was comprised of a porous Pt nanocatalyst layer with an average particle size of 8.9 nm. The porous Pt nanocatalysts were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray absorption near edge spectroscopy. Compared with the dense Pt catalyst layer, the electrochemical activated surface of the porous Pt nanocatalyst layer, measured using cyclic voltammetry, was enhanced about 250%. Polarization characteristics of the membrane electrode assembly, which utilized the porous Pt nanocatalyst layer in the proton exchange membrane fuel cells, showed that the maximum power density per unit area increased with an increase in the sputtering pressure. The high performance of Pt nanocatalysts fabricated at a sputtering pressure of 200 mTorr (Ar/He = 1) was due to miniaturization of the Pt particles and formation of the porous catalyst layer.     

Influences of fuel crossover on cathode performance in a micro borohydride fuel cell

Influences of borohydride crossover on cathode performance were studied in a micro direct borohydride fuel cell (DBFC). The results showed that fuel crossover resulted in decreases in open circuit potentials of cathodes. On the other hand, effects of fuel crossover on cathode overpotentials strongly depended on the cathode material. The Pt/C cathode demonstrated a small potential drop of 0.11 V, while the Ag/C cathode had a much larger potential drop of 0.26 V under the same condition. Fuel crossover was found to be depressed during current operations. It is possible that fuel depletion happened around the anode during operation, resulting in a decrease of fuel concentration gradient across the membrane and thus less crossover. Experiments also showed that a balance in wet-proof property is essential for the cathode in the direct borohydride fuel cell and the stability of cell performance was mainly dependent on wet-proof durability of the cathode.     

Response to Disselkamp: Direct peroxide/peroxide fuel cell as a novel type fuel cell

Besides hydrogen peroxide is known as conventionally oxidizer, it is both a fuel and a source of ignition. Platinum is not suitable catalyst for oxidation and reduction of hydrogen peroxide, because it directly converts the hydrogen peroxide to oxygen gas. In this study, the oxidation mechanism of peroxide is investigated and a fuel cell operating with acidic peroxide as oxidant and basic peroxide as fuel is constructed. The peroxide oxidation reaction in novel alkaline direct peroxide/peroxide fuel cell (DPPFC), shown feasible here using less expensive carbon supported Nickel catalyst, makes the alkaline direct peroxide/peroxide fuel cell a potentially low cost technology compared to PEM fuel cell technology, which employs platinum catalysts. The power density of 3.75 mW cm⁻² at a cell voltage of 0.55 V and a current density of 14 mA cm⁻² was achieved in our fuel cell.     

Ni–Pt/C as anode electrocatalyst for a direct borohydride fuel cell

In this study, a series of Ni–Pt/C and Ni/C catalysts, which were employed as anode catalysts for a direct borohydride fuel cell (DBFC), were prepared and investigated by XRD, TEM, cyclic voltammetry, chronopotentiometry and fuel cell test. The particle size of Ni₃₇–Pt₃/C (mass ratio, Ni:Pt = 37:3) catalyst was sharply reduced by the addition of ultra low amount of Pt. And the electrochemical measurements showed that the electro-catalytic activity and stability of the Ni₃₇–Pt₃/C catalysts were improved compared with Ni/C catalyst. The DBFC employing Ni₃₇–Pt₃/C catalyst on the anode (metal loading, 1 mg cm⁻²) showed a maximum power density of 221.0 mW cm⁻² at 60 °C, while under identical condition the maximum power density was 150.6 mW cm⁻² for Ni/C. Furthermore, the polarization curves and hydrogen evolution behaviors on all the catalysts were investigated on the working conditions of the DBFC.     

Study of CoO as an anode catalyst for a membraneless direct borohydride fuel cell

In this paper, cobalt(II) oxide (CoO) has been used as an anode catalyst in a direct borohydride fuel cell (DBFC). The microstructure of CoO has been characterised by X-ray diffraction. The cell performance and short-term performance stability of the DBFC using the CoO as anode catalyst have been investigated. At the optimum conditions, the maximum power density of 80 mW cm⁻² has been achieved at 30 °C for this cell without using any precious metals and ion exchange membranes. Results from XRD, TEM, and XPS analysis confirm that the good performance of the fuel cell is attributed to the co-operation of CoO and CoB which formed from CoO during the operation.     

Borohydride electrochemical oxidation on carbon-supported Pt-modified Au nanoparticles

The carbon-supported Pt-modified Au nanoparticles were prepared by two different chemical reduction processes, the simultaneous chemical reduction of Pt and Au on carbon process (A-AuPt/C) and the successive reduction of Au then Pt (B-AuPt/C) on carbon process. These two catalysts were investigated as the anode catalysts for a direct borohydride fuel cell (DBFC) and Au nanoparticles on carbon (Au/C) were also prepared for comparison. The DBFC with B-AuPt/C as the anode catalyst shows the best anode and fuel cell performance. The maximum power density with the B-AuPt/C catalyst is 112 mW cm⁻² at 40 °C, compared to 97 mW cm⁻² for A-AuPt/C and 65 mW cm⁻² for Au/C. In addition, the DBFC with the B-AuPt/C catalyst shows the best fuel utilization with a maximum apparent number of electrons (N_app) equal to 6.4 in 1 M NaBH₄ and 7.2 in 0.5 M NaBH₄ as compared to the value of N_app of 8 for complete utilization of borohydride.     

A cobalt polypyrrole composite catalyzed cathode for the direct borohydride fuel cell

A cobalt polypyrrole carbon (Co-PPY-C) composite has been attempted for use as a cathode catalyst in a direct borohydride fuel cell (DBFC). A Co-PPY-C composite has been fabricated in laboratory and characterized by the field emission scanning electron microscopy, transmission electron microscopy, as well as X-ray photoemission spectroscopy. Fabricated Co-PPY-C catalyst demonstrates good short-term durability and activity which are comparable to those obtained from the Pt/C catalyst. A maximum power density of 65 mW cm⁻² has been achieved at ambient conditions. This research concludes that metallo-organic coordination compounds would be potential candidates for use as cathode catalysts in the DBFC.     

Studies of electrochemical performance of carbon supported Pt-Cu nanoparticles as anode catalysts for direct borohydride-hydrogen peroxide fuel cell

Carbon supported Pt-Cu bimetallic nanoparticles are prepared by a modified NaBH₄ reduction method in aqueous solution and used as the anode electrocatalyst of direct borohydride-hydrogen peroxide fuel cell (DBHFC). The physical and electrochemical properties of the as-prepared electrocatalysts are investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammetry (CV), chronoamperometry (CA), chronopotentiometry (CP) and fuel cell test. The results show that the carbon supported Pt-Cu bimetallic catalysts have much higher catalytic activity for the direct oxidation of BH₄⁻ than the carbon supported pure nanosized Pt catalyst, especially the Pt₅₀Cu₅₀/C catalyst presents the highest catalytic activity among all as-prepared catalysts, and the DBHFC using Pt₅₀Cu₅₀/C as anode electrocatalyst and Pt/C as cathode electrocatalyst shows as high as 71.6 mW cm⁻² power density at a discharge current density of 54.7 mA cm⁻² at 25 °C.     

Influences of hydrogen evolution on the cell and stack performances of the direct borohydride fuel cell

To scale up power generation of the direct borohydride fuel cell (DBFC), 10-cell and 20-cell stacks have been constructed based on the single cell achievements. It has been found that the stacking loss of the DBFC is mainly caused by hydrogen evolution which leads to uneven fuel distribution in each cell of the stack. To reduce stacking loss, several efforts have been made to decrease hydrogen evolution influence on the stack performance. The anode preparation method has been modified from a dry-method to a wet-method. The influence of hydrogen evolution on stack performance can be alleviated by altering fuel supply manner. When hydrogen evolution is suppressed, an even distribution of cell voltage can be obtained and the maximum power of 10-cell stack reaches up to 229 W.     

Sulfated zirconia as a proton conductor for fuel cells: Stability to hydrolysis and influence on catalysts

Sulfated zirconia is an inorganic solid superacid having sulfate groups covalently bonded to its surface. In this work, sulfated zirconia is synthesized by a solvent-free method to obtain it in the nanoparticle form. This nanostructured sulfated zirconia has been evaluated in terms of (i) chemical stability to hydrolysis and to hydrogen peroxide by thermogravimetric analysis, and (ii) influences on Pt catalyst activity by cyclic voltammetry using sulfated-zirconia dispersion as a supporting electrolyte solution. The results demonstrate that our sulfated zirconia is stable almost perfectly to hydrolysis but partly decomposed by a Fenton reagent containing hydrogen peroxide and Fe²⁺. In addition, we show that oxygen reduction activity of Pt catalyst in a sulfated-zirconia dispersion is comparatively high (specific activity at 0.9 V vs. RHE, i_0.9: ca. 17 μA cm⁻²) compared to that in a 0.5 M sulfuric acid solution (i_0.9: ca. 15 μA cm⁻²). Finally, we demonstrate that sulfated zirconia does not influence hydrogen oxidation reaction. These results lead us to conclude that sulfated zirconia is a promising proton conductor for fuel cells.