Enhanced performance of solid oxide fuel cells with Ni/CeO2 modified La0.75Sr0.25Cr0.5Mn0.5O3−δ anodes

The optimization of electrodes for solid oxide fuel cells (SOFCs) has been achieved via a wet impregnation method. Pure La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCrM) anodes are modified using Ni(NO₃)₂ and/or Ce(NO₃)₃/(Sm,Ce)(NO₃)_x solution. Several yttria-stabilized zirconia (YSZ) electrolyte-supported fuel cells are tested to clarify the contribution of Ni and/or CeO₂ to the cell performance. For the cell using pure-LSCrM anodes, the maximum power density (P_max) at 850 °C is 198 mW cm⁻² when dry H₂ and air are used as the fuel and oxidant, respectively. When H₂ is changed to CH₄, the value of P_max is 32 mW cm⁻². After 8.9 wt.% Ni and 5.8 wt.% CeO₂ are introduced into the LSCrM anode, the cell exhibits increased values of P_max 432, 681, 948 and 1135 mW cm⁻² at 700, 750, 800 and 850 °C, respectively, with dry H₂ as fuel and air as oxidant. When O₂ at 50 mL min⁻¹ is used as the oxidant, the value of P_max increases to 1450 mW cm⁻² at 850 °C. When dry CH₄ is used as fuel and air as oxidant, the values of P_max reach 95, 197, 421 and 645 mW cm⁻² at 750, 800, 850 and 900 °C, respectively. The introduction of Ni greatly improves the performance of the LSCrM anode but does not cause any carbon deposit.     

Power generation using an activated carbon fiber felt cathode in an upflow microbial fuel cell

An activated carbon fiber felt (ACFF) cathode lacking metal catalysts is used in an upflow microbial fuel cell (UMFC). The maximum power density with the ACFF cathode is 315 mW m⁻², compared to lower values with cathodes made of plain carbon paper (67 mW m⁻²), carbon felt (77 mW m⁻²), or platinum-coated carbon paper (124 mW m⁻², 0.2 mg-Pt cm⁻²). The addition of platinum to the ACFF cathode (0.2 mg-Pt cm⁻²) increases the maximum power density to 391 mW m⁻². Power production is further increased to 784 mW m⁻² by increasing the cathode surface area and shaping it into a tubular form. With ACFF cutting into granules, the maximum power is 481 mW m⁻² (0.5 cm granules), and 667 mW m⁻² (1.0 cm granules). These results show that ACFF cathodes lacking metal catalysts can be used to substantially increase power production in UMFC compared to traditional materials lacking a precious metal catalyst.     

Synthesis and assessment of La0.8Sr0.2ScyMn1−yO3−δ as cathodes for solid-oxide fuel cells on scandium-stabilized zirconia electrolyte

Perovskite-type La_0.8Sr_0.2Sc_yMn_1−yO_3−δ oxides (LSSMy, y = 0.0–0.2) were synthesized and investigated as cathodes for solid-oxide fuel cells (SOFCs) containing a stabilized zirconia electrolyte. The introduction of Sc³⁺ into the B-site of La_0.8Sr_0.2MnO_3−δ (LSM) led to a decrease in the oxides’ thermal expansion coefficients and electrical conductivities. Among the various LSSMy oxides tested, LSSM0.05 possessed the smallest area-specific cathodic polarization resistance, as a result of the suppressive effect of Sc³⁺ on surface SrO segregation and the optimization of the concentration of surface oxygen vacancies. At 850 °C, it was only 0.094 Ω cm² after a current passage of 400 mA cm⁻² for 30 min, significantly lower than that of LSM (0.25 Ω cm²). An anode-supported cell with a LSSM0.05 cathode demonstrated a peak power density of 1300 mW cm⁻² at 850 °C. The corresponding value for the cell with LSM cathode was 450 mW cm⁻² under the same conditions. The LSSM0.05 oxide may potentially be a good cathode material for IT-SOFCs containing doped zirconia electrolytes.     

Stable, easily sintered BaCe0.5Zr0.3Y0.16Zn0.04O3−δ electrolyte-based protonic ceramic membrane fuel cells with Ba0.5Sr0.5Zn0.2Fe0.8O3−δ perovskite cathode

A stable, easily sintered perovskite oxide BaCe_0.5Zr_0.3Y_0.16Zn_0.04O_3−δ (BCZYZn) as an electrolyte for protonic ceramic membrane fuel cells (PCMFCs) with Ba_0.5Sr_0.5Zn_0.2Fe_0.8O_3−δ (BSZF) perovskite cathode was investigated. The BCZYZn perovskite electrolyte synthesized by a modified Pechini method exhibited higher sinterability and reached 97.4% relative density at 1200 °C for 5 h in air, which is about 200 °C lower than that without Zn dopant. By fabricating thin membrane BCZYZn electrolyte (about 30 μm in thickness) on NiO–BCZYZn anode support, PCMFCs were assembled and tested by selecting stable BSZF perovskite cathode. An open-circuit potential of 1.00 V, a maximum power density of 236 mW cm⁻², and a low polarization resistance of the electrodes of 0.17 Ω cm² were achieved at 700 °C. This investigation indicated that proton conducting electrolyte BCZYZn with BSZF perovskite cathode is a promising material system for the next generation solid oxide fuel cells.     

Power generation from furfural using the microbial fuel cell

Furfural is a typical inhibitor in the ethanol fermentation process using lignocellulosic hydrolysates as raw materials. In the literature, no report has shown that furfural can be utilized as the fuel to produce electricity in the microbial fuel cell (MFC), a device that uses microbes to convert organic compounds to generate electricity. In this study, we demonstrated that electricity was successfully generated using furfural as the sole fuel in both the ferricyanide-cathode MFC and the air-cathode MFC. In the ferricyanide-cathode MFC, the maximum power densities reached 45.4, 81.4, and 103 W m⁻³, respectively, when 1000 mg L⁻¹ glucose, a mixture of 200 mg L⁻¹ glucose and 5 mM furfural, and 6.68 mM furfural were used as the fuels in the anode solution. The corresponding Coulombic efficiencies (CE) were 4.0, 7.1, and 10.2% for the three treatments, respectively. For pure furfural as the fuel, the removal efficiency of furfural reached up to 95% within 12 h. In the air-cathode MFC using 6.68 mM furfural as the fuel, the maximum values of power density and CE were 361 mW m⁻² (18 W m⁻³) and 30.3%, respectively, and the COD removal was about 68% at the end of the experiment (about 30 h). Increase in furfural concentrations from 6.68 to 20 mM resulted in increase in the maximum power densities from 361 to 368 mW m⁻², and decrease in CEs from 30.3 to 20.6%. These results indicated that some toxic and biorefractory organics such as furfural might still be suitable resources for electricity generation using the MFC technology.     

Direct methanol fuel cell operation with pre-stretched recast Nafion

Direct methanol fuel cell operation with uniaxially pre-stretched recast Nafion^® membranes (draw ratio of 4) was investigated and compared to that with commercial (un-stretched) Nafion^®. The effects of membrane thickness (60–250 μm) and methanol feed concentration (0.5–10.0 M) on fuel cell power output were quantified for a cell temperature of 60 °C, ambient pressure air, and anode/cathode catalyst loadings of 4.0 mg cm⁻². Pre-stretched recast Nafion^® in the 130–180 μm thickness range produced the highest power at 0.4 V (84 mW cm⁻²), as compared to 58 mW cm⁻² for Nafion^® 117. MEAs with pre-stretched recast Nafion^® consistently out-performed Nafion^® 117 at all methanol feed concentrations, with 33–48% higher power densities at 0.4 V, due to a combination of low area-specific resistance (the use of a thinner pre-stretched membrane, where the conductivity was the same as that for commercial Nafion^®) and low methanol crossover (due to low methanol solubility in the membrane). Very high power was generated with a 180-μm thick pre-stretched recast Nafion^® membrane by increasing the cell temperature to 80 °C, increasing the anode/cathode catalyst loading to 8.0 mg cm⁻², and increasing the cathode air pressure to 25 psig. Under these conditions the power density at 0.4 V for a 1.0-M methanol feed solution was 240 mW cm⁻² and the maximum power density was 252 mW cm⁻².     

Co-free, iron perovskites as cathode materials for intermediate-temperature solid oxide fuel cells

We have developed a Co-free solid oxide fuel cell (SOFC) based upon Fe mixed oxides that gives an extraordinary performance in test-cells with H₂ as fuel. As cathode material, the perovskite Sr_0.9K_0.1FeO_3−δ (SKFO) has been selected since it has an excellent ionic and electronic conductivity and long-term stability under oxidizing conditions; the characterization of this material included X-ray diffraction (XRD), thermal analysis, scanning microscopy and conductivity measurements. The electrodes were supported on a 300-μm thick pellet of the electrolyte La_0.8Sr_0.2Ga_0.83Mg_0.17O_3−δ (LSGM) with Sr₂MgMoO₆ as the anode and SKFO as the cathode. The test cells gave a maximum power density of 680 mW cm⁻² at 800°C and 850 mW cm⁻² at 850 °C, with pure H₂ as fuel. The electronic conductivity shows a change of regime at T ≈ 350 °C that could correspond to the phase transition from tetragonal to cubic symmetry. The high-temperature regime is characterized by a metallic-like behavior. At 800 °C the crystal structure contains 0.20(1) oxygen vacancies per formula unit randomly distributed over the oxygen sites (if a cubic symmetry is assumed). The presence of disordered vacancies could account, by itself, for the oxide-ion conductivity that is required for the mass transport across the cathode. The result is a competitive cathode material containing no cobalt that meets the target for the intermediate-temperature SOFC.     

Effect of precursor nature on the performance of palladium–cobalt electrocatalysts for direct methanol fuel cells

The performance of platinum-free palladium–cobalt catalysts in oxygen reduction was investigated for a direct methanol fuel cell. The dependence of catalytic activity on precursor nature was determined for two classes of precursors; namely, palladium chloride and palladium nitrate. The nitrate precursor exhibits much higher catalytic performance than the chloride precursor. X-ray absorption fine structure (XAFS) spectra indicate that the structure of palladium catalyst prepared from nitrate is much closer to Pd₃Co structure that can explain high catalytic activity. The MEA prepared from the nitrate catalyst achieved the peak power density of 125 mW cm⁻², which is much higher than 19 mW cm⁻² measured on the cell prepared from the chloride catalyst.     

A novel bifunctional electrocatalyst for unitized regenerative fuel cell

5 wt.% of platinum (Pt) nanoparticles are highly dispersed on the surface of IrO₂ by chemical reduction, and the catalyst is mixed with Pt black to be used as a novel bifunctional oxygen electrocatalyst for the unitized regenerative fuel cell (URFC). The novel cell has been evaluated in the hydrogen and oxygen fuel cell and water electrolysis modes, and compared to a similar cell with an oxygen electrode using conventional mixed Pt black and IrO₂ catalyst. With the novel oxygen electrode catalyst, the highest fuel cell power density is 1160 mW cm⁻² at 2600 mA cm⁻²; the overall performance is close to that with the commercial Pt supported on carbon catalyst and about 1.8 times higher than that with the conventional mixed Pt black and IrO₂ catalyst. Additionally, the cell performance for water electrolysis is also slightly improved, which is probably the result of lower interparticle catalyst resistance with 5 wt.% Pt on IrO₂ compared to no Pt on IrO₂.     

Enhanced low-humidity performance of proton exchange membrane fuel cell by incorporating phosphoric acid-loaded covalent organic framework in anode catalyst layer

Developing self-humidifying membrane electrode assembly (MEA) is of great significance for the practical use of proton exchange membrane fuel cell (PEMFC). In this work, a phosphoric acid (PA)-loaded Schiff base networks (SNW)-type covalent organic framework (COF) is proposed as the anode catalyst layer (CL) additive to enhance the PEMFC performance under low humidity conditions. The unique polymer structure and immobilized PA endow the proposed COF network with not only excellent water retention capacity but also proton transfer ability, thus leading to the superior low humidity performance of the PEMFC. The optimization of the additive content, the effect of relative humidity (RH) and PEMFC operating temperature are investigated by means of electrochemical characterization and single cell test. At a normal operation temperature of 60 °C and 38% RH, the MEA with optimized COF content (10 wt%) showes the maximum power density of 582 mW cm^?2, which is almost 7 times higher than that of the routine MEA (85 mW cm^?2). Furthermore, a preliminary durability test demonstrates the potential of the proposed PEMFC for practice operation under low humidity environment.     

An alkaline direct NaBH4–H2O2 fuel cell with high power density

A high performance alkaline direct borohydride–hydrogen peroxide fuel cell with Pt–Ru catalyzed nickel foam as anode and Pd–Ir catalyzed nickel foam as cathode is reported. The electrodes were prepared by electrodeposition of the catalyst components on nickel foam. Their morphology and composition were analyzed by SEM–EDX. The effects of concentrations of NaBH₄ and H₂O₂ as well as operation temperature on the cell performance were investigated. The cell exhibited an open circuit voltage of about 1.0 V and a peak power density of 198 mW cm⁻² at a current density of 397 mA cm⁻² and a cell voltage of 0.5 V using 0.2 mol dm⁻³ NaBH₄ as fuel and 0.4 mol dm⁻³ H₂O₂ as oxidant operating at room temperature. Electrooxidation of NaBH₄ on Pt–Ru nanoparticles was studied using a rotating disk electrode and complete 8e⁻ oxidation was observed in 2 mol dm⁻³ NaOH solution containing 0.01 mol dm⁻³ NaBH₄.     

Fabrication and electrochemical performance of thin-film solid oxide fuel cells with large area nanostructured membranes

Thin-film solid oxide fuel cells (SOFCs) with large (5-mm square) membranes and ultra-thin La_0.6Sr_0.4Co_0.8Fe_0.2O_3−δ (LSCF) cathodes have been fabricated and their electrochemical performance was measured up to 500 °C. A grid of plated nickel on the cathode with 5–10 μm linewidth and 25–50 μm pitch successfully supported a roughly 200-nm-thick LSCF/yttria-stabilized zirconia/platinum membrane while covering less than 20% of the membrane area. This geometry yielded a maximum performance of 1 mW cm⁻² and 200 mV open-circuit voltage at 500 °C. Another approach toward realizing large area fuel cell junctions consists of depositing the membrane on a smooth substrate, covering it with a high-porosity material formed in situ, then removing the substrate. We have used a composite of silica aerogel and carbon fiber as the support, and show that this material can be created in flow channels etched into the underside of a silicon chip bonded to the top of the SOFC membrane. We anticipate these integrated fuel cell devices and structures to be of relevance to advancing low-temperature SOFCs for portable applications.     

Highly efficient,cell reversal resistant PEMFC based on PtNi/C octahedral and OER composite catalyst

In order to obtain a fuel cell with both enhanced power generation performance and cell reversal resistance, the composite catalyst consisting of the self-made PtNi/C octahedral and the oxygen evolution reaction (OER) catalyst IrO₂ and RuO₂ is mixed and applied in the anode, and the only octahedral catalyst is employed as the cathode to prepare the membrane electrode assembly (MEA). The electrochemical activity of the composite catalyst decreases slightly, but its performance retention after the accelerated durability test (ADT) is higher. In the single cell test, the MEA fabricated using the composite catalyst maintains good single cell power generation performance. Compared with the control fabricated with Pt/C (JM), the cell voltage at 1 A cm⁻² and the maximum power density are increased by 23 mV and 119 mW cm⁻², respectively. Especially, its durability under continuous cell reversal condition is also improved significantly, and the holding time is prolonged by 1 h. This work realizes the transformation of the octahedral catalyst from the laboratory research to the actual application, and solves the difficulties in fuel cell application, and promotes its commercialization.     

Novel cobalt-free cathode materials BaCexFe1−xO3−δ for proton-conducting solid oxide fuel cells

A series of cobalt-free and low cost BaCe_xFe_1−xO_3−δ (x = 0.15, 0.50, 0.85) materials are successful synthesized and used as the cathode materials for proton-conducting solid oxide fuel cells (SOFCs). The single cell, consisting of a BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7)-NiO anode substrate, a BZCY7 anode functional layer, a BZCY7 electrolyte membrane and a BaCe_xFe_1−xO_3−δ cathode layer, is assembled and tested from 600 to 700 °C with humidified hydrogen (3% H₂O) as the fuel and the static air as the oxidant. Within all the cathode materials above, the cathode BaCe_0.5Fe_0.5O_3−δ shows the highest cell performance which could obtain an open-circuit potential of 0.99 V and a maximum power density of 395 mW cm⁻² at 700 °C. The results indicate that the Fe-doped barium cerates can be promising cathodes for proton-conducting SOFCs.     

Quasi-solid-state dye-sensitized solar cells based on a sol–gel organic–inorganic composite electrolyte containing an organic iodide salt

An organic–inorganic composite gel electrolyte based on TiO₂ gel, γ-butyrolactone (γ-BL) and N-methyl pyridine iodide was prepared by the sol–gel method. This gel electrolyte shows high ambient ionic conductivity of 7.63 mS cm⁻¹, which is close to the data of liquid electrolyte with the same organic iodide salt and γ-butyrolactone. Based on the gel electrolyte, a quasi-solid-state dye-sensitized solar cell was fabricated and the highest overall energy conversion efficiency of light-to-electricity of 3.06% was achieved under irradiation of 60 mW cm⁻².     

Sulfonated poly(fluorenyl ether ketone nitrile) electrolyte membrane with high proton conductivity and low water uptake

High molecular weight sulfonated poly(fluorenyl ether ketone nitrile)s with different equivalent weight (EW) from 681 to 369 g mequiv.⁻¹ are synthesized by the nucleophilic substitution polycondensation of various amounts of sulfonated difluorobenzophenone (SDFBP) and 2,6-difluorobenzonitrile (DFBN) with bisphenol fluorene (BPF). The synthesized copolymers are characterized by ¹H NMR, FT-IR, TGA, and DSC techniques. The membranes cast from the corresponding copolymers exhibit superior thermal stability, good oxidative stability and high proton conductivity, but low water uptake due to the strong nitrile dipole interchain interactions that combine to limit swelling. Among all the membranes, the membrane with EW of 441 g mequiv.⁻¹ shows optimum properties of both high proton conductivity of 41.9 mS cm⁻¹ and low water uptake of 42.6%. Accordingly, That membrane is fabricated into a membrane electrode assembly (MEA) and evaluated in a single proton exchange membrane fuel cell (PEMFC). The experimental results indicate its similar cell performance as that of Nafion^® 117 at 70 °C, but much better cell performance at higher temperatures. At the potential of 0.6 V, the current density of fuel cell using the prepared membrane and Nafion^® 117 is 0.46 and 0.25 A cm⁻², respectively. The highest current density of the former reaches as high as 1.25 A cm⁻².     

Novel high-performance nanocomposite proton exchange membranes based on poly (ether sulfone)

In the present research, proton exchange membranes based on partially sulfonated poly (ether sulfone) (S-PES) with various degrees of sulfonation were synthesized. It was found that the increasing of sulfonation degree up to 40% results in the enhancement of water uptake, ion exchange capacity and proton conductivity properties of the prepared membranes to 28.1%, 1.59 meq g⁻¹, and 0.145 S cm⁻¹, respectively. Afterwards, nanocomposite membranes based on S-PES (at the predetermined optimum sulfonation degree) containing various loading weights of organically treated montmorillonite (OMMT) were prepared via the solution intercalation technique. X-ray diffraction patterns revealed the exfoliated structure of OMMT in the macromolecular matrices. The S-PES nanocomposite membrane with 3.0 wt% of OMMT content showed the maximum selectivity parameter of about 520,000 S s cm⁻³ which is related to the high conductivity of 0.051 S cm⁻¹ and low methanol permeability of 9.8 × 10⁻⁸ cm² s⁻¹. Furthermore, single cell DMFC fuel cell performance test with 4 molar methanol concentration showed a high power density (131 mW cm⁻²) of the nanocomposite membrane at the optimum composition (40% of sulfonation and 3.0 wt% of OMMT loading) compared to the Nafion^®117 membrane (114 mW cm⁻²). Manufactured nanocomposite membranes thanks to their high selectivity, ease of preparation and low cost could be suggested as the ideal candidate for the direct methanol fuel cell applications.     

ZnO-doped BaZr0.85Y0.15O3−δ proton-conducting electrolytes: Characterization and fabrication of thin films

ZnO-doped BaZr_0.85Y_0.15O_3−δ perovskite oxide sintered at 1500 °C has bulk conductivity of the order of 10⁻² S cm⁻¹ above 650 °C, which makes it an attractive proton-conducting electrolyte for intermediate-temperature solid oxide fuel cells. The structure, morphology and electrical conductivity of the electrolyte vary with sintering temperature. Optimal electrochemical performance is achieved when the sintering temperature is about 1500 °C. Cathode-supported electrolyte assemblies were prepared using spin coating technique. Thin film electrolytes were shown to be dense using SEM and EDX analyses.     

A liquid–gas phase mixed-reactant fuel cell with a RuSeW cathode electrocatalyst

Some data in mixed-reactant fuel cells (MRFC) at Newcastle using formic acid, methanol and ethanol are reported. The importance of using a fuel-tolerant selective cathode catalyst has been identified. The influence of fuel and oxidant conditions and feeding patterns has been evaluated. The cell performance using air, oxygen and hydrogen peroxide is reported. The highest peak power density of 16 mW cm⁻² was obtained with formic acid. The MRFC gave power densities approximately half those of a conventional, un-mixed-reactant fuel cell.     

Influence of electrolyte on the photovoltaic performance of a dye-sensitized TiO2 solar cell based on a Ru(II) terpyridyl complex photosensitizer

We have investigated the influence of electrolyte composition on the photovoltaic performance of a dye-sensitized nanocrystalline TiO₂ solar cell (DSSC) based on a Ru(II) terpyridyl complex photosensitizer (the black dye). We have also spectroscopically investigated the interaction between the electrolyte components and the adsorbed dye. The absorption peaks attributed to the metal-to-ligand charge transfer transitions of the black dye in solution and adsorbed on a TiO₂ film, were red-shifted in the presence of Li cations, which led to an expansion of the spectral response of the solar cell toward the near-IR region. The photovoltaic performance of the DSSC based on the black dye depended remarkably on the electrolyte composition. We developed a novel efficient organic liquid electrolyte containing an imidazolium iodide such as 1,2-dimethyl-3-n-propylimidazolium iodide or 1-ethyl-3-methylimidazolium iodide (EMImI) for a DSSC based on the black dye. A high solar energy-to-electricity conversion efficiency of 9.2% (J_sc=19.0 mA cm⁻², V_oc=0.67 V, and FF=0.72) was attained under AM 1.5 irradiation (100 mW cm⁻²) using a novel electrolyte consisting of 1.5 M EMImI, 0.05 M iodine, and acetonitrile as a solvent with an antireflection film.