A direct NaBH4–H2O2 fuel cell using Ni foam supported Au nanoparticles as electrodes

Au/Ni-foam electrodes with three dimensional network structures are prepared by simple spontaneous deposition of nano-sized Au particles onto nickel foam surface in an aqueous solution of AuCl₃. Their morphology and catalytic performance for NaBH₄ electrooxidation and H₂O₂ electroreduction in NaOH solution are investigated. Au particles with diameters smaller than 100 nm are uniformly deposited on the whole surface of all skeletons of the nickel foam substrate. The onset potential for NaBH₄ electrooxidation and H₂O₂ electroreduction is about −1.2 V and −0.1 V, respectively. A direct liquid feed alkaline NaBH₄–H₂O₂ fuel cell is constructed using Au/Ni-foam electrode as both the anode and the cathode. The effects of the concentration of NaBH₄ and H₂O₂ and operation temperature on the fuel cell performance are investigated. The fuel cell exhibits an open circuit voltage of about 1.07 V and a peak power density of 75 mW cm⁻² at a current density of 150 mA cm⁻² and a cell voltage of 0.5 V operating on 0.2 mol dm⁻³ NaBH₄ and 0.5 mol dm⁻³ H₂O₂ at 40 °C.     

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.     

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.     

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.     

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.     

A direct borohydride fuel cell based on poly(vinyl alcohol)/hydroxyapatite composite polymer electrolyte membrane

A new poly(vinyl alcohol)/hydroxyapatite (PVA/HAP) composite polymer membrane was synthesized using a solution casting method. Alkaline direct borohydride fuel cells (DBFCs), consisting of an air cathode based on MnO₂/C inks on Ni-foam, anodes based on PtRu black and Au catalysts on Ni-foam, and the PVA/HAP composite polymer membrane, were assembled and investigated for the first time. It was demonstrated that the alkaline direct borohydride fuel cell comprised of this low-cost PVA/HAP composite polymer membrane showed good electrochemical performance. As a result, the maximum power density of the alkaline DBFC based on the PtRu anode (45 mW cm⁻²) proved higher than that of the DBFC based on the Au anode (33 mW cm⁻²) in a 4 M KOH + 1 M KBH₄ solution at ambient conditions. This novel PVA/HAP composite polymer electrolyte membrane with high ionic conductivity at the order of 10⁻² S cm⁻¹ has great potential for alkaline DBFC applications.     

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.     

Performance of air-breathing direct methanol fuel cell with anion-exchange membrane

This report details development of an air-breathing direct methanol alkaline fuel cell with an anion-exchange membrane. The commercially available anion-exchange membrane used in the fuel cell was first electrochemically characterized by measuring its ionic conductivity, and showed a promising result of 1.0 × 10⁻¹ S cm⁻¹ in a 5 M KOH solution. A laboratory-scale direct methanol fuel cell using the alkaline membrane was then assembled to demonstrate the feasibility of the system. A high open-circuit voltage of 700 mV was obtained for the air-breathing alkaline membrane direct methanol fuel cell (AMDMFC), a result about 100 mV higher than that obtained for the air-breathing DMFC using a proton exchange membrane. Polarization measurement revealed that the power densities for the AMDMFC are strongly dependent on the methanol concentration and reach a maximum value of 12.8 mW cm⁻² at 0.3 V with a 7 M methanol concentration. A durability test for the air-breathing AMDMFC was performed in chronoamperometry mode (0.3 V), and the decay rate was approximately 0.056 mA cm⁻² h⁻¹ over 160 h of operation. The cell area resistance for the air-breathing AMDMFC was around 1.3 Ω cm² in the open-circuit voltage (OCV) mode and then is stably supported around 0.8 Ω cm² in constant voltage (0.3 V) mode.     

Electrochemical oxidation of borohydride at nano-gold-based electrodes: Application in direct borohydride fuel cells

Nano-particulate gold-based materials along with commercial gold supported over carbon were investigated as possible alternative electrocatalysts for the oxidation of borohydride in alkaline media. Cyclic voltammetry experiments conducted on these materials show very high activity for the nano-particulate materials compared to the commercial materials despite a lower loading of gold (0.8 mg cm⁻² compared to 1.0 mg cm⁻²) and lower interface area in the nano-particulate materials. The presence of BH₄⁻ appears to have detrimental effect on the performances of the air-electrode for oxygen reduction. The current density recorded at −0.6 V versus Hg/HgO has decreased by a factor of six for silver nitrate AC65 while for MnO₂ a reduction in the current density by a factor of two only was observed. The implementation of the nano-particulate gold-based materials and the air-electrodes along with a low-cost anionic membrane in QinetiQ's tubular cell design has led to power density exceeding 28 mW cm⁻² obtained at ambient temperature.     

Effects of NaOH addition on performance of the direct hydrazine fuel cell

In this work, we suggested a figuration of the direct hydrazine fuel cell (DHFC) using non-precious metals as the anode catalyst, ion exchange membranes as the electrolyte and alkaline hydrazine solutions as the fuel. NaOH addition in the anolyte effectively improved the open circuit voltage and the performance of the DHFC. A power density of 84 mW cm⁻² has been achieved when operating the cell at room temperature. It was found that the cell performance was mainly influenced by anode polarization when using alkaline N₂H₄ solutions with low NaOH concentrations. However, when using alkaline N₂H₄ solutions with high NaOH concentrations as the fuel, the cell performance was mainly influenced by cathode polarization.     

Effects of operation conditions on direct borohydride fuel cell performance

In this study, the influences of different operational conditions such as cell temperature, sodium hydroxide concentration, oxidant conditions and catalyst loading 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 were investigated. The experimental results showed that the power density increased by increasing the temperature and increasing the flow rate of oxidant. Furthermore, it was found that 20 wt.% of NaOH concentration was optimum for DBFC operation. When oxygen was used as oxidant instead of air, better performance was observed. Experiments also showed that electrochemical performance was not considerably affected by humidification levels. An enhanced power density was found by increasing the loading of anodic catalyst. In the present study, a maximum power density of 27.6 mW cm⁻² at a cell voltage of 0.85 V was achieved at 55 mA cm⁻² at 60 °C when humidified air was used.     

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.     

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%.     

A direct borohydride fuel cell employing a sago gel polymer electrolyte

The electrochemistry of a direct borohydride fuel cell based on a gel polymer electrolyte was studied. Sago is a type of natural polymer, was employed as the polymer host for the electrolyte. An electrolyte with a composition of sago + 6 M KOH + 2 M NaBH₄ was prepared and evaluated as a novel gel polymer electrolyte for a direct borohydride fuel cell system because it exhibited a high electrical conductivity of 0.270 S cm⁻¹. The rate at which oxygen was consumed at the cathode can be related to the electric current by comparing the calculated number of electrons reacted per molecule of oxygen for different currents supplied to the fuel cell. From the oxygen consumption data, it was deduced that four electrons reacted per molecule of oxygen. The performance of the fuel cell was measured in terms of its current–voltage, discharge and open circuit voltage measurements. The maximum power density obtained was 8.818 mW cm⁻² at a discharge performance of ∼230 mA h and nominal voltage of 0.806 V. The open circuit voltage of the cells was about 0.900 V and sustained for 23 h.     

Rotating ring-disc electrode (RRDE) investigation of borohydride electro-oxidation

Rotating ring-disc electrode (RRDE) voltammetry is applied for the in situ determination of hydroxy borohydride (BH₃(OH)⁻) formation during borohydride (BH₄⁻) electro-oxidation on a gold (Au) electrode in 6.0 M NaOH solution. The BH₃(OH)⁻ is detected at the ring electrode due to its further oxidation to BH₂(OH)₂⁻ by maintaining its potential in the range of −0.800 to −0.600 V vs. normal hydrogen electrode (NHE) while oxidizing BH₄⁻ on the disc electrode. The study reveals that the generation of BH₃(OH)⁻ increases if the anodic polarization of the disc electrode is increased. The RRDE ring-shielding experiments show that the electro-oxidation of BH₄⁻ occurs over a wide potential range of −0.500 to 0.400 V on the Au electrode under hydrodynamic conditions. Chronoamperometry is also used to study the BH₃(OH)⁻ oxidation in the potential range of −0.800 to −0.600 V with 0.33 M NaBH₄ in three different buffer solutions of pH 10.2, 11.0 and 11.70, respectively. The chronoamperometric studies indicate that the formation and stability of BH₃(OH)⁻ depends on the pH value.     

Development of high performance carbon composite catalyst for oxygen reduction reaction in PEM Proton Exchange Membrane fuel cells

Highly active and stable carbon composite catalysts for oxygen reduction in PEM fuel cells were developed through the high-temperature pyrolysis of Co–Fe–N chelate complex, followed by the chemical post-treatment. A metal-free carbon catalyst was used as the support. The carbon composite catalyst showed an onset potential for oxygen reduction as high as 0.87 V (NHE) in H₂SO₄ solution, and generated less than 1% H₂O₂. The PEM fuel cell exhibited a current density as high as 0.27 A cm⁻² at 0.6 V and 2.3 A cm⁻² at 0.2 V for a catalyst loading of 6.0 mg cm⁻². No significant performance degradation was observed over 480 h of continuous fuel cell operation with 2 mg cm⁻² catalyst under a load of 200 mA cm⁻² as evidenced by a resulting cell voltage of 0.32 V with a voltage decay rate of 80 μV h⁻¹. Materials characterization studies indicated that the metal–nitrogen chelate complexes decompose at high pyrolysis temperatures above 800 °C, resulting in the formation of the metallic species. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface doped with nitrogen groups is catalytically active for oxygen reduction.     

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.     

Fabrication of porous Co–Ni–P catalysts by electrodeposition and their catalytic characteristics for the generation of hydrogen from an alkaline NaBH4 solution

Porous Co–Ni–P catalysts were made on Cu substrates by electrodeposition in order to generate hydrogen from an alkaline sodium borohydride (NaBH₄) solution. We investigated the effects of the cathodic current density and the electrodeposition time on the surface morphology and chemical composition of the Co–Ni–P catalysts. The hydrogen generation characteristics from an alkaline NaBH₄ solution using these catalysts in an alkaline NaBH₄ solution were then investigated. The cathodic current density significantly affected the growth behavior and catalytic properties of the Co–Ni–P electrodeposits. Co–Ni–P catalysts grew two-dimensionally at a low cathodic current density of 0.01 A cm⁻². By contrast, at a cathodic current density of more than 0.05 A cm⁻², three-dimensional growth of the catalysts occurred due to the large cathodic overpotential. In addition, the rates of hydrogen generation were found to be higher for the three-dimensional catalysts than the two-dimensional catalysts. Three-dimensional growth of the Co–Ni–P catalysts continued as the electrodeposition time increased from 1 to 10 min at a cathodic current density of 0.1 A cm⁻². The surface areas of the three-dimensional Co–Ni–P catalysts increased gradually with electrodeposition time, resulting in their catalytic efficiency for the hydrolysis of NaBH₄ being improved. The hydrogen generation rate was also influenced by the concentrations of the NaOH and NaBH₄ in the alkaline NaBH₄ solution. The hydrogen generation rate increased gradually with increasing NaOH concentration. By contrast, there was an optimum concentration of NaBH₄, above which the hydrogen generation rate decreased. Finally, the hydrogen generation rate from Co–Ni–P catalysts was found to decrease due to the precipitation of by-products.     

Cathode development for alkaline fuel cells based on a porous silver membrane

Porous silver membranes were investigated as potential substrates for alkaline fuel cell cathodes by the means of polarization curves and electrochemical impedance spectroscopy measurements. The silver membranes provide electrocatalytic function, mechanical support and a means of current collection. Improved performance, compared to a previous design, was obtained by increasing gas accessibility (using Teflon AF instead of PTFE suspension) and by adding a catalyst (MnO₂ or Pt) in the membrane structure to increase the cathode activity. This new cathode design performed significantly better (∼55 mA cm⁻² at 0.8 V, ∼295 mA cm⁻² at 0.6 V and ∼630 mA cm⁻² at 0.4 V versus RHE) than the previous design (∼30 mA cm⁻² at 0.8 V, ∼250 mA cm⁻² at 0.6 V and ∼500 mA cm⁻² at 0.4 V) in the presence of 6.9 M KOH and oxygen (1 atm(abs)) at room temperature. The hydrophobisation technique of the porous structure and the addition of an extra catalyst appeared to be critical and necessary to obtain high performance. A passive air-breathing hydrogen-air fuel cell constructed from the membranes achieves a peak power density of 65 mW cm⁻² at 0.40 V cell potential when operating at 25 °C showing a 15 mW cm⁻² improvement compared to the previous design.     

Effect of the porous carbon layer in the cathode gas diffusion media on direct methanol fuel cell performances

The effect of cathode gas diffusion media with microporous layers (MPLs) on direct methanol fuel cell (DMFC) performances is studied by combining electrochemical analysis and physicochemical investigation. The membrane electrode assemblies (MEAs) using MPL-modified cathode gas diffusion layers (GDLs, GDL-1) showed slightly better performances (117 mW cm⁻²) at 0.4 V and 70 °C than commercial GDL (SIGRACET^® product version: GDL-35BC, SGL Co.) DMFC MEAs (110 mW cm⁻²). This might be due to high gas permeability, uniform pore distributions, and low water transport coefficient including methanol crossover. For GDL-1, the air permeability was 31.0 cm³ cm⁻² s⁻¹, while the one for SGL 35BC GDLs was 21.7 cm³ cm⁻² s⁻¹. Also, the GDL-1 in the pore-size distribution diagrams had distinct peaks due to more uniform distributions of macropores and micropores with smaller holes between aggregates of carbon particles compared to GDL-35 BC as confirmed by SEM images. Furthermore, the MEA using GDL-1 for the cathode had a lower water transfer coefficient compared to an MEA with a commercial 35 BC GDL.