Manganese dioxide as a cathode catalyst for a direct alcohol or sodium borohydride fuel cell with a flowing alkaline electrolyte

The oxygen reduction reaction at a manganese dioxide cathode in alkaline medium is studied using cyclic voltammetry and by measuring volume of oxygen consumed at the cathode. The performance of the manganese dioxide cathode is also determined in the presence of fuel and an alkali mixture with a standard Pt/Ni anode in a flowing alkaline-electrolyte fuel cell. The fuels tested are methanol, ethanol and sodium borohydride (1 M), while 3 M KOH is used as the electrolyte. The performance of the fuel cell is measured in terms of open-circuit voltage and current–potential characteristics. A single peak in the cyclic voltammogram suggests that a four-electron pathway mechanism prevails during oxygen reduction. This is substantiated by calculating the number of electrons involved per molecule of oxygen that are reacted at the MnO₂ cathode from the oxygen consumption data for different fuels. The results show that the power density of the fuel cell increases with increase in MnO₂ loading to a certain limit but then decreases with further loading. The maximum power density is obtained at 3 mg cm⁻² of MnO₂ for each of the three different fuels.     

Improving the direct borohydride fuel cell performance with thiourea as the additive in the sodium borohydride solution

In this study, the effects of the additive thiourea (TU) have been investigated under steady state/steady-flow and uniform state/uniform-flow systems with the aim of minimizing the anodic hydrogen evolution on Pd in order to increase the performance of a direct borohydride fuel cell. The fuel cell has consisted of Pd/C anode, Pt/C cathode and Na⁺ form Nafion membrane as the electrolyte. There has been a small improvement in peak power density and fuel utilization ratio by addition of TU (1.6 × 10⁻³ M) into the sodium borohydride solution; the peak power densities of 14.4 and 15.1 mW cm⁻², and fuel utilization ratios of 21.6% and 23.2% have been obtained without and with TU, respectively.     

Polymer electrolyte based on polyethylene glycol for quasi-solid state dye sensitized solar cells

A gel polymer electrolyte containing I⁻/I₃⁻ redox couple was prepared using polyethylene glycol (PEG) as polymer matrix and propylene carbonate (PC) as organic solvent by sol-gel method. A dye sensitized solar cell (DSSC) employing the gel polymer electrolyte gives an open-circuit voltage of 0.7 V and a short-circuit current of 8.1 mA cm⁻² at an incident light intensity of 100 mW cm⁻². Fourier transform infrared spectroscopy was utilized to examine the chemical properties of produced gel electrolytes. Unlike the conventional covalent bond that bridges the different polymer segments, in this study, it was observed that hydrogen bonds bridged polyethylene glycol and propylene carbonate. Influences of different synthetic parameters such as reaction time and temperature were also investigated. Optimal DSSC performance was observed at electrolyte reaction temperature and time of 100 °C and 24 h, respectively, with a maximum photoelectric energy conversion efficiency of 2.2%.     

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.     

Electrochemical and mechanical behavior of carbon composite bipolar plate for fuel cell

Composite bipolar plates for fuel cells were prepared by a compression molding technique using novolac type phenol formaldehyde resin as a binder and natural graphite, carbon black and carbon fiber as reinforcements. The plates were characterized for electrical conductivity, mechanical strength and corrosion resistance. The flexural strength of the bipolar plate for optimum composition (PF:30%; NG:60%; CB:5%; CF:5%) was 55.28 MPa, with a deflection of 5.2% at mid-span, while the in-plane and through-plane electrical conductivities were 286 and 92 S cm⁻¹, respectively. Corrosion analyses were conducted in normal and rigorous simulated polymer electrolyte membrane fuel cell and alkaline fuel cell environments. The corrosion current density was close to the limit set by the USA Department of Energy. The corrosion current density at the optimum composition was found to be 0.99 μA cm⁻² for polymer electrolyte membrane fuel cell and 17.62 μA cm⁻² for alkaline fuel cell environments.     

Advanced mathematical model for the passive direct borohydride/peroxide fuel cell

In the literature a mathematical model has been developed for the direct borohydride fuel cells by Verma et al. [1]. This model simply simulates the fuel cell system via kinetic mechanisms of the borohydride and oxygen. Their mathematical expression contains the activation losses caused by the oxidation of the borohydride and the concentration overpotential increased by the reduction of oxygen. In this study a direct borohydride/peroxide fuel cell has been constructed using hydrogen peroxide (H₂O₂) as oxidant instead of the oxygen. Therefore we created an advanced model for peroxide fuel cells, including the activation overpotential of the peroxide. The goal of our model is to provide the information about the peroxide reduction effect on the cell performance. Our comprehensive mathematical model has been developed by taking Verma’s model into account. KH₂O₂ used in the advanced model was calculated as 6.72 × 10⁻⁴ mol cm⁻² s⁻¹ by the cyclic voltammogram of Pt electrode in the acidic peroxide solution.     

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.     

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.     

Samarium doped ceria-(Li/Na)2CO3 composite electrolyte and its electrochemical properties in low temperature solid oxide fuel cell

A composite of samarium doped ceria (SDC) and a binary carbonate eutectic (52 mol% Li₂CO₃/48 mol% Na₂CO₃) is investigated with respect to its morphology, conductivity and fuel cell performances. The morphology study shows the composition could prevent SDC particles from agglomeration. The conductivity is measured under air, argon and hydrogen, respectively. A sharp increase in conductivity occurs under all the atmospheres, which relates to the superionic phase transition in the interface phases between SDC and carbonates. Single cells with the composite electrolyte are fabricated by a uniaxial die-press method using NiO/electrolyte as anode and lithiated NiO/electrolyte as cathode. The cell shows a maximum power density of 590 mW cm⁻² at 600 °C, using hydrogen as the fuel and air as the oxidant. Unlike that of cells based on pure oxygen ionic conductor or pure protonic conductor, the open circuit voltage of the SDC-carbonate based fuel cell decreases with an increase in water content of either anodic or cathodic inlet gas, indicating the electrolyte is a co-ionic (H⁺/O²⁻) conductor. The results also exhibit that oxygen ionic conductivity contributes to the major part of the whole conductivity under fuel cell circumstances.     

Effects of Pt/C, Pd/C and PdPt/C anode catalysts on the performance and stability of air breathing direct formic acid fuel cells

Pt/C, Pd/C and PdPt/C catalysts are potential anodic candidates for electro-oxidation of formic acid. In this work we designed a miniature air breathing direct formic acid fuel cell, in which gold plated printed circuit boards are used as end plates and current collectors, and evaluated the effects of anode catalysts on open circuit voltage, power density and long-term discharging stability of the cell. It was found that the cell performance was strongly anode catalyst dependent. Pd/C demonstrated good catalytic activity but poor stability. A maximum power density of 25.1 mW cm⁻² was achieved when 5.0 M HCOOH was fed as electrolyte. Pt/C and PdPt/C showed poor activity but good stability, and the cell can discharge for about 10 h at 0.45 V (Pt/C anode) and 15 h at 0.3 V (PdPt/C) at 20 mA.     

Silver-modified Ba0.5Sr0.5Co0.8Fe0.2O3−δ as cathodes for a proton conducting solid-oxide fuel cell

Electrochemical performance of silver-modified Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF-Ag) as oxygen reduction electrodes for a protonic intermediate-temperature solid-oxide fuel cell (SOFC-H⁺) with BaZr_0.1Ce_0.8Y_0.1O₃ (BZCY) electrolyte was investigated. The BSCF-Ag electrodes were prepared by impregnating the porous BSCF electrode with AgNO₃ solution followed by reducing with hydrazine and then firing at 850 °C for 1 h. The 3 wt.% silver-modified BSCF (BSCF-3Ag) electrode showed an area specific resistance of 0.25 Ω cm² at 650 °C in dry air, compared to around 0.55 Ω cm² for a pure BSCF electrode. The activation energy was also reduced from 119 kJ mol⁻¹ for BSCF to only 84 kJ mol⁻¹ for BSCF-3Ag. Anode-supported SOFC-H⁺ with a BZCY electrolyte and a BSCF-3Ag cathode was fabricated. Peak power density up to 595 mW cm⁻² was achieved at 750 °C for a cell with 35 μm thick electrolyte operating on hydrogen fuel, higher than around 485 mW cm⁻² for a similar cell with BSCF cathode. However, at reduced temperatures, water had a negative effect on the oxygen reduction over BSCF-Ag electrode, as a result, a worse cell performance was observed for the cell with BSCF-3Ag electrode than that with pure BSCF electrode at 600 °C.     

Investigation of A-site deficient Ba0.9Co0.7Fe0.2Nb0.1O3−δ cathode for proton conducting electrolyte based solid oxide fuel cells

A novel cathode material for proton conducting electrolyte based solid oxide fuel cells (SOFCs) of A-site deficient Ba_0.9Co_0.7Fe_0.2Nb_0.1O_3−δ (BCFN) has been synthesized and characterized. The A-site deficient BCFN has demonstrated a thermal expansion coefficient (TEC) similar to that of BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY) electrolyte, enhanced oxygen reduction activity and chemical stability. The application of BCFN in proton-conducting electrolyte-based SOFCs has been investigated, and the SOFCs with Ni-BZCY|BZCY|BCFN configuration demonstrate maximum cell power outputs of 180, 240 and 300 mW cm⁻² at 600, 650 and 700 °C, respectively. The cell polarization resistance is as low as 0.951, 0.387 and 0.201 Ω cm² under open circuit voltage (OCV) at 600, 650 and 700 °C, respectively. The cell maximum power density increases from 300 to 356 mW cm⁻² at 700 °C after over 118 h operating under a constant current of 300 mA cm⁻².     

Performance of a hybrid direct ethylene glycol fuel cell

In this work, a hybrid fuel cell is developed and tested, which is composed of an alkaline anode, an acid cathode, and a cation exchange membrane. In this fuel cell, ethylene glycol and hydrogen peroxide serve as fuel and oxidant, respectively. Theoretically, this fuel cell exhibits a theoretical voltage reaching 2.47 V, whereas it is experimentally demonstrated that the hybrid fuel cell delivers an open‐circuit voltage of 1.41 V at 60°C. More impressively, this fuel cell yields a peak power density of 80.9 mW cm^?2 (115.3 mW cm^?2 at 80°C). Comparing to an open‐circuit voltage of 0.86 V and a peak power density of 67 mW cm^?2 previously achieved by a direct ethylene glycol fuel cell operating with oxygen, this hybrid direct ethylene glycol fuel cell boosts the open‐circuit voltage by 62.1% and the peak power density by 20.8%. This significant improvement is mainly attributed not only to the high‐voltage output of this hybrid system design but also to the faster kinetics rendered by the reduction reaction of hydrogen peroxide.     

Preparation and characterization of nanocrystalline Ce0.8Sm0.2O1.9 for low temperature solid oxide fuel cells based on composite electrolyte

Nanocrystalline Ce_0.8Sm_0.2O_1.9 (SDC) has been synthesized by a combined EDTA–citrate complexing sol–gel process for low temperature solid oxide fuel cells (SOFCs) based on composite electrolyte. A range of techniques including X-ray diffraction (XRD), and electron microscopy (SEM and TEM) have been employed to characterize the SDC and the composite electrolyte. The influence of pH values and citric acid-to-metal ions ratios (C/M) on lattice constant, crystallite size and conductivity has been investigated. Composite electrolyte consisting of SDC derived from different synthesis conditions and binary carbonates (Li₂CO₃–Na₂CO₃) has been prepared and conduction mechanism is discussed. Water was observed on both anode and cathode side during the fuel cell operation, indicating the composite electrolyte is co-ionic conductor possessing H⁺ and O²⁻ conduction. The variation of composite electrolyte conductivity and fuel cell power output with different synthesis conditions was in accordance with that of the SDC originated from different precursors, demonstrating O²⁻ conduction is predominant in the conduction process. A maximum power density of 817 mW cm⁻² at 600 °C and 605 mW cm⁻² at 500 °C was achieved for fuel cell based on composite electrolyte.     

A single-component fuel cell reactor

We report here a single-component reactor consisting of a mixed ionic and semi-conducting material exhibiting hydrogen-air (oxygen) fuel cell reactions. The new single-component device was compared to a conventional three-component (anode/electrolyte/cathode) fuel cell showing at least as good performance. A maximum power density of 300-600 mW cm⁻² was obtained with a LiNiZn-oxide and ceria-carbonate nanocomposite material mixture at 450-550 °C. Adding a redox catalyst element (Fe) resulted in an improvement reaching 700 mW cm⁻² at 550 °C.     

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.     

Double cross-linked polyetheretherketone proton exchange membrane for fuel cell

The proton exchange membrane based on polyetheretherketone was prepared via two steps of cross-linking. The properties of the double cross-linked membrane (water uptake, proton conductivity, methanol permeability and thermal stability) have been investigated for fuel cell applications. The prepared membrane exhibited relatively high proton conductivity, 3.2 × 10⁻² S cm⁻¹ at room temperature and 5.8 × 10⁻² S cm⁻¹ at 80 °C. The second cross-linking significantly decreased the water uptake of the membrane. The performance of direct methanol fuel cell was slightly improved as compared to Nafion^® 117 due to its low methanol permeability. The results indicated that the double cross-linked membrane is a promising candidate for the polymer electrolyte membrane fuel cell, especially for the direct methanol fuel cell due to its low methanol permeability and high stability in a methanol solution.     

Performance evaluation of an anode-supported solid oxide fuel cell with Ce0.8Sm0.2O1.9 impregnated GdBaCo2O5+δ cathode

The performance of an anode-supported solid oxide fuel cell with nanosized Ce_0.8Sm_0.2O_1.9 (SDC) impregnated GdBaCo₂O_5+δ (GBCO) cathode is evaluated under various operation conditions. An SDC interlayer is applied between 8 mol% yttria-stabilized zirconia (8YSZ) electrolyte and cathode to prevent undesired chemical reaction. At 700 °C, the fuel cell yields a maximum power density of 790 mW cm⁻² when using simulated air as oxidant, which is promoted to 1100 mW cm⁻² in oxygen flow. The activation energies of ohmic resistance are smaller than that of bulk YSZ due to non-YSZ contribution. Electrode polarization resistance changes with fuel cell voltage while ohmic resistance nearly remains constant. The fuel cell output is mainly determined by the electrode polarization.     

Quasi solid state polymer electrolyte with binary iodide salts for photo-electrochemical solar cells

Quasi-solid-state polymer electrolytes can be used in dye sensitized solar cells (DSSCs) in order to overcome various problems associated with liquid electrolytes. Prior to fabricating commercially viable solar cells, the efficiency of quasi solid state DSSCs needs to be improved. Using electrolytes with a binary iodide mixture is a novel technique used to obtain such efficiency enhancement. In this work we report both conductivity and solar cell performance enhancements due to incorporation of a mixture containing LiI and tetrahexylammonium iodide in a quasi-solid-state electrolyte. The conductivity of the electrolyte increases with added amounts of LiI and thus the highest conductivity, 3.15 × 10⁻³ S cm⁻¹ at 25 °C, is obtained for the electrolyte 100 wt% LiI. The predominantly ionic behavior of the electrolytes was established from dc polarization measurements. The iodide ion conductivity, measured using iodine pellet electrodes decreased somewhat with increasing amount of LiI even though the overall conductivity increased. However, the highest efficiency was obtained for the DSSC containing a polymer electrolyte with Hex₄N⁺I^¯:LiI = 1:2 mass ratio. This cell had the largest short circuit current density of about 13 mA cm⁻² and more than 4% overall energy conversion efficiency. The results thus show that electrolytes with Hex₄N⁺I^¯/LiI mixed iodide system show better DSSC performance than single iodide systems.     

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.