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.     

Direct alkaline fuel cell for multiple liquid fuels: Anode electrode studies

A direct alkaline fuel cell with a liquid potassium hydroxide solution as an electrolyte is developed for the direct use of methanol, ethanol or sodium borohydride as fuel. Three different catalysts, e.g., Pt-black or Pt/Ru (40 wt.%:20 wt.%)/C or Pt/C (40 wt.%), with varying loads at the anode against a MnO₂ cathode are studied. The electrodes are prepared by spreading the catalyst slurry on a carbon paper substrate. Nickel mesh is used as a current-collector. The Pt–Ru/C produces the best cell performance for methanol, ethanol and sodium borohydride fuels. The performance improves with increase in anode catalyst loading, but beyond 1 mg cm⁻² does not change appreciably except in case of ethanol for which there is a slight improvement when using Pt–Ru/C at 1.5 mA cm⁻². The power density achieved with the Pt–Ru catalyst at 1 mg cm⁻² is 15.8 mW cm⁻² at 26.5 mA cm⁻² for methanol and 16 mW cm⁻² at 26 mA cm⁻² for ethanol. The power density achieved for NaBH₄ is 20 mW cm⁻² at 30 mA cm⁻² using Pt-black.     

Performance of a direct methanol alkaline membrane fuel cell

A study of a direct methanol fuel cell (DMFC) operating with hydroxide ion conducting membranes is reported. Evaluation of the fuel cell was performed using membrane electrode assemblies incorporating carbon-supported platinum/ruthenium anode and platinum cathode catalysts and ADP alkaline membranes. Catalyst loadings used were 1 mg cm⁻² Pt for both anode and cathode. The effect of temperature, oxidant (air or oxygen) and methanol concentration on cell performance is reported. The cell achieved a power density of 16 mW cm⁻², at 60 °C using oxygen. The performance under near ambient conditions with air gave a peak power density of approximately 6 mW cm⁻².     

Design, fabrication and performance evaluation of a miniature air breathing direct formic acid fuel cell based on printed circuit board technology

A miniature air breathing compact direct formic acid fuel cell (DFAFC), with gold covered printed circuit board (PCB) as current collectors and back boards, is designed, fabricated and evaluated. Effects of formic acid concentration and catalyst loading (anodic palladium loading and cathodic platinum loading) on the cell performance are investigated and optimized fuel concentration and catalyst loading are obtained based on experimental results. A maximum power density of 19.6 mW cm⁻² is achieved at room temperature with passive operational mode when 5.0 M formic acid is fed and 1 mg cm⁻² catalyst at both electrodes is used. The home-made DFAFC also displays good long-term stability at constant current density.     

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.     

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.     

Quaternized-chitosan membranes for possible applications in alkaline fuel cells

Novel crosslinked quaternized-chitosan membranes were fabricated and further investigated for possible applications in alkaline polyelectrolyte fuel cells. Impedance analysis indicated that some hydrated membranes could exhibit a conductivity close to 10⁻² S cm⁻¹. Several membranes were selected and integrated into unit fuel cells for the evaluations on their cell performance, using hydrogen as fuel, air as oxidant and platinum as the electrode catalyst, and a current density of 65 mA cm⁻² was already achieved with a flow rate of hydrogen at 50 mL min⁻¹ and air at 250 mL min⁻¹ at a relatively low running temperature of 50 °C.     

Study on the membrane electrode assembly fabrication with carbon supported cobalt triethylenetetramine as cathode catalyst for proton exchange membrane fuel cell

An improved fabrication technique for conventional hot-pressed membrane electrode assemblies (MEAs) with carbon supported cobalt triethylenetetramine (CoTETA/C) as the cathode catalyst is investigated. The V-I results of PEM single cell tests show that addition of glycol to the cathode catalyst ink leads to significantly higher electrochemical performance and power density than the single cell prepared by the traditional method. SEM analysis shows that the MEAs prepared by the conventional hot-pressed method have cracks between the cathode catalyst layer and Nafion membrane, and the contact problem between cathode catalyst layer and Nafion membrane is greatly suppressed by addition of glycol to the cathode catalyst ink. Current density-voltage curve and impedance studies illuminate that the MEAs prepared by adding glycol to the cathode catalyst ink have a higher electrochemical surface area, lower cell ohmic resistance, and lower charge transfer resistance. The effects of CoTETA/C loading, Nafion content, and Pt loading are also studied. By optimizing the preparation parameters of the MEA, the as-fabricated cell with a Pt loading of 0.15 mg cm⁻² delivers a maximum power density of 181.1 mW cm⁻², and a power density of 126.2 mW cm⁻² at a voltage of 0.4 V.     

Influences of sodium borohydride concentration on direct borohydride fuel cell performance

In this work, the effects of sodium borohydride concentration on the performance of direct borohydride fuel cell, which consisted of Pd/C anode, Pt/C cathode and Na⁺ form Nafion^® membrane as the electrolyte, have been investigated in steady state/steady-flow and uniform state/uniform-flow systems. The experimental results have revealed that the power density increased as the sodium borohydride concentration increased in the SSSF system. Peak power densities of 7.1, 10.1 and 11.7 mW cm⁻² have been obtained at 0.5, 1 and 1.5 M, respectively. However, the performance has decreased when the sodium borohydride concentration has been increased, and the fuel utilization ratios of 29.8%, 21.6% and 20.4% have been obtained at 0.5, 1 and 1.5 M, respectively in the USUF system.     

Electrospray deposition of catalyst layers with ultra-low Pt loadings for PEM fuel cells cathodes

Suspensions of Pt/C catalyst nanoparticles in Nafion^®-alcohol solutions have been electrosprayed over carbon paper to prepare cathodes for proton exchange membrane fuel cells (PEMFC). Catalyst layers with platinum loading ranging from 0.1 mg_Pt cm⁻² down to 0.0125 mg_Pt cm⁻² and different Nafion^® contents were obtained by this method. Morphological studies of the catalyst layers by SEM inspection showed fractal structures with a high dispersion of catalyst. Fuel cell performance of membrane-electrode assemblies (MEAs) made from these cathodes revealed a strong dependence on the Nafion^® concentration in the electrosprayed suspension. In the platinum loading range 0.1-0.025 mg_Pt cm⁻² and optimal Nafion^® content, a linear relation between fuel cell power density and platinum loading has been found, such that a reduction of platinum content by a factor 4 only reduces the performance by roughly a factor 2. However for the lowest platinum loading investigated, 0.0125 mg_Pt cm⁻², a sharp drop in performance was noticed.     

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.     

Three-dimensional anode engineering for the direct methanol fuel cell

Catalyzed graphite felt three-dimensional anodes were investigated in direct methanol fuel cells (DMFCs) operated with sulfuric acid supporting electrolyte. With a conventional serpentine channel flow field the preferred anode thickness was 100 μm, while a novel flow-by anode showed the best performance with a thickness of 200-300 μm. The effects of altering the methanol concentration, anolyte flow rate and operating temperature on the fuel cell superficial power density were studied by full (2³ + 1) factorial experiments on a cell with anode area of 5 cm² and excess oxidant O₂ at 200 kPa(abs). For operation in the flow-by mode with 2 M methanol at 2 cm³ min⁻¹ and 353 K the peak power density was 2380 W m⁻² with a PtRuMo anode catalyst, while a PtRu catalyst yielded 2240 W m⁻² under the same conditions.     

An investigation of Pt alloy oxygen reduction catalysts in phosphoric acid doped PBI fuel cells

A study of a phosphoric acid doped polybenzimidazole (PBI) membrane fuel cell using commercial carbon supported, Pt alloy oxygen reduction catalysts is reported. The cathodes were made from PTFE bonded carbon supported Pt alloys without PBI but with phopshoric acid added to the electrode for ionic conductivity. Polarisation data for fuel cells with cathodes made with alloys of Pt with Ni, Co, Ru and Fe are compared with those with Pt alone as cathode at temperatures between 120 and 175 °C. With the same loading of Pt enhancement in cell performance was achieved with all alloys except Pt-Ru, in the low current density activation kinetics region of operation. The extent of enhancement depended upon the operating temperature and also the catalyst loading. In particular a Pt-Co alloy produced performance significantly better than Pt alone, e.g. a peak power, with low pressure air, of 0.25 W cm⁻² with 0.2 mg Pt cm⁻² of a 20 wt% Pt-Co catalyst.     

Electrochemical and fuel cell evaluation of Co based catalyst for oxygen reduction in anion exchange polymer membrane fuel cells

Co based catalyst were evaluated for oxygen reduction (ORR) in liquid KOH and alkaline anion exchange membrane fuel cells (AAEMFCs). In liquid KOH solution the catalyst exhibited good performance with an onset potential 120 mV more negative than platinum and a Tafel slope of ca. 120 mV dec⁻¹. The hydrogen peroxide generated, increased from 5 to 50% as the electrode potential decreased from 175 to −300 mV vs. SHE.In an AAEMFC environment, one catalyst (GP2) showed promising performance for ORR, i.e. at 50 mA cm⁻² the differences in cell potential between the stable performance for platinum (more positive) and cobalt cathodes with air and oxygen, were only 45 and 67 mV respectively. The second catalyst (GP4) achieved the same stable power density as with platinum, of 200 and 145 mW cm⁻², with air at 1 bar (gauge) pressure and air (atm) cathode feed (60 °C), respectively. However the efficiency was lower (i.e. cell voltage was lower) i.e. 40% in comparison to platinum 47.5%.     

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.     

Preparation of nano-sized nickel as anode catalyst for direct urea and urine fuel cells

Nano-sized nickel with primary particle size of 2-3 nm has been successfully prepared for use as efficient anode catalysts in urea and urine fuel cells. XRD, SEM and TEM were used for characterisation of nano-sized nickel. Based on the previous communication, the performance of urea and urine fuel cells has been further improved when the relative humidity at the cathode was 100%. A maximum power density of 14.2 mW cm⁻² was achieved when 1 M urea was used as fuel, humidified air as oxidant. The performance of urine fuel cells operating above room temperature was also reported for the first time and a power density of 4.23 mW cm⁻² was achieved at 60 °C indicating potential application in urea-rich waste water treatment.     

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.     

Design,fabrication and testing of a PMMA-based passive single-cell and a multi-cell stack micro-DMFC

A passive, air-breathing polymethyl methacrylate (PMMA) based single-cell and a multi-cell stack micro-direct methanol fuel cell (DMFC) with 1.0 cm² active area with a novel cathode plate structure and assembly layer are designed, fabricated and tested. The fuel cell is completely passive with no auxiliary device such as pump or fan. Oxygen is taken from the surrounding air, and the methanol solution is stored in a built-in reservoir. The performance of the single cell is tested with different methanol concentrations ranging from 1.0 M to 5.0 M, and the optimum performance is achieved by using methanol at a concentration of 4.0 M. A stack with 6 cells is fabricated and tested with the optimum methanol concentration of 4.0 M, and power levels produced by different catalyst loadings on the anode are compared. Besides, this study also considers the cost analysis of micro-DMFC. The combination of a catalyst loading of 3.0 mg cm⁻² Pt/Ru on the anode and 2.0 mg cm⁻² Pt on the cathode yield the highest power of 12.05 mW at 1.08 V and 11.2 mA. The total cost for the micro-DMFC in this study is only about USD 2 mW⁻¹.     

Three-dimensional,gas phase fuel cell with a laccase biocathode

A fuel cell using an enzymatic biocathode operating in a gas phase mode is reported. The electrode was prepared using a three-dimensional conductive electrode matrix. An enzyme solution containing laccase and a mediator was distributed into a hydrophilic matrix of carbon felt fibers creating a porous gas-flowing electrode. A Pt-based gas diffusion electrode served as the anode. A maximum power density of 9.4 W m⁻² (2.9 kW m⁻³) was obtained with 15 U of enzyme cm⁻², with hydrogen as the fuel. Power density was found to be a function of the enzyme loading, air flow rate, volume of the liquid phase and the humidity of the air stream. The ability to use methanol and ethanol as vapors in gas phase was also shown. The introduction of three-dimensionality into the electrode architecture and operation of the fuel cell in a gas phase mode to supply the fuel and the oxidant demonstrates an avenue for improving the power density of EFCs.     

Performance of metal-supported SOFCs with infiltrated electrodes

Metal-supported solid oxide fuel cells (SOFCs) with thin YSZ electrolyte films and infiltrated Ni and LSM catalysts are operated in the temperature range 650–750 °C. A five-layer structure consisting of porous metal-support/porous YSZ interlayer/dense YSZ electrolyte film/porous YSZ interlayer/porous metal current collector is prepared at 1300 °C in reducing atmosphere. This cell structure is then sealed and joined to a cell housing/gas manifold using a commercially available braze. Finally, the porous YSZ interlayers are infiltrated with Ni and LSM catalyst precursor solutions at low temperature prior to cell testing. Infiltrating the catalysts after the high temperature sintering and brazing steps avoids undesirable decomposition of LSM, Ni coarsening, and interdiffusion between Ni catalyst and FeCr in the support. Maximum power densities of 233 and 332 mW cm⁻² were achieved at 650 and 700 °C, respectively, with air as oxidant. With pure oxygen as oxidant, power densities of 726, 993, and >1300 mW cm⁻² were achieved at 0.7 V at 650, 700, and 750 °C, respectively.