Copper oxide nanoparticle made by flame spray pyrolysis for photoelectrochemical water splitting - Part II. Photoelectrochemical study

A scalable method for hydrogen generation by splitting water via a photoelectrochemical cell was studied. Flame spray pyrolysis and spin coating processing methods were used for preparing copper oxide nanoparticles and copper oxide photocathodes. Copper oxide p-type semiconductor nanoparticles made by flame spray pyrolysis were spin coated on conducting ITO substrates and served as photocathodes for photoelectrochemical splitting of water. The film thickness was controlled by the concentration of the CuO suspension solution and numbers of layer deposited on the substrate. As sintering temperature increased to 600 °C, crystalline diameter increased from 28 nm (before sintering) to 110 nm and the bandgaps decreased from 1.68 eV to 1.44 eV. A 387 nm thickness CuO film with bandgap 1.44 eV was demonstrated to have 1.48% total conversion efficiency and 0.91% photon-to-hydrogen generation efficiency. The net photocurrent density (photocurrent - dark current) was measured to be 1.20 mA/cm² at applied voltage of −0.55 V vs. Ag/AgCl in 1 M KOH electrolyte with 1 sun (AM1.5G) illumination. Based on the Mott-Schottky plot, the carrier density was estimated to be 1.5 × 10²¹ cm⁻³ and the flatband potential to be 0.23 V vs. Ag/AgCl. Furthermore, the valence band edge and conduction band levels were found to lie at −5.00 eV and −3.56 eV respect to the vacuum respectively.     

Enhanced photoelectrochemical properties of WO3 thin films fabricated by reactive magnetron sputtering

Polycrystalline WO₃ thin films were fabricated by reactive magnetron sputtering at a substrate temperature of 350 °C under different Ar/O₂ gas pressures. In order to study the thickness dependence of photoelectrochemical (PEC) behavior of WO₃, the thickness-gradient films were fabricated and patterned using a micro-machined Si-shadow mask during the deposition process. The variation of the sputter pressure leads to the evolution of different microstructures of the thin films. The films fabricated at 2 mTorr sputter pressure are dense and show diminished PEC properties, while the films fabricated at 20 mTorr and 30 mTorr are less dense and exhibit enhanced water photooxidation efficiency. The enhanced photooxidation is attributed to the coexistence of porous microstructure and space charge region enabling improved charge carrier transfer to the electrolyte and back contact. A steady-state photocurrent as high as 2.5 mA cm⁻² at 1 V vs. an Ag/AgCl (3 M KCl) reference electrode was observed. For WO₃ films fabricated at 20 mTorr and 30 mTorr, the photocurrent increases continuously up to a thickness of 600 nm.     

Low-temperature ceria-electrolyte solid oxide fuel cells for efficient methanol oxidation

Low temperature anode-supported solid oxide fuel cells with thin films of samarium-doped ceria (SDC) as electrolytes, graded porous Ni-SDC anodes and composite La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF)-SDC cathodes are fabricated and tested with both hydrogen and methanol fuels. Power densities achieved with hydrogen are between 0.56 W cm⁻² at 500 °C and 1.09 W cm⁻² at 600 °C, and with methanol between 0.26 W cm⁻² at 500 °C and 0.82 W cm⁻² at 600 °C. The difference in the cell performance can be attributed to variation in the interfacial polarization resistance due to different fuel oxidation kinetics, e.g., 0.21 Ω cm² for methanol versus 0.10 Ω cm² for hydrogen at 600 °C. Further analysis suggests that the leakage current densities as high as 0.80 A cm⁻² at 600 °C and 0.11 A cm⁻² at 500 °C, resulting from the mixed electronic and ionic conductivity in the SDC electrolyte and thus reducing the fuel efficiency, can nonetheless help remove any carbon deposit and thereby ensure stable and coking-free operation of low temperature SOFCs in methanol fuels.     

3D-nano-hetero-structured n/n junction,CuO/Ru–ZnO thin films,for hydrogen generation with enhanced photoelectrochemical performances

Hydrogen, derived from solar-water splitting, is a clean and renewable fuel for which per gram energy storage capacity is even higher than fossil fuels. Towards the development of a viable technology for above conversion, this report describes enhanced performance in photoelectrochemical water splitting using uniquely evolved nano-hetero-structured bilayered thin films, CuO/Ru–ZnO as photoanode. Grown over ITO (In:SnO₂) glass substrates by using low-cost and easily up-scalable wet chemical methods, films were characterized for microstructure, optical behaviour and surface characteristics, using XRD and other spectral measurements viz. FESEM, AFM, TEM, UV–Visible Spectroscopy, EDX and XPS. Against monolayered pristine films of CuO and ZnO, bilayered films yielded a major gain in PEC water splitting photocurrent, on being used as working electrode in PEC cell, in conjunction with platinum counter electrode and saturated calomel reference electrode (electrolyte solution 0.1 M NaOH solution, pH 13, temperature 30 ± 3.6 °C). Films with 1% Ru-incorporation yielded highest photocurrent (2.04 mA/cm²). Enhanced photoactivity of bilayered films was found correlated with increments in light absorption, charge carrier density and film surface area, coupled with reduced electrical resistivity. The study highlights an important role played by Ru added in ZnO overlayer, apparently existing as RuO₂ nanoparticles dispersed in ZnO lattice, in hole-transfer from valence band of CuO underlayer to electrolyte, thereby imparting a significant boost on photocurrent generation.     

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.     

Microstructural modification of the anode/electrolyte interface of SOEC for hydrogen production

The microstructure of the anode/electrolyte interface is one of key factors to affect the hydrogen production performance of solid oxide electrolysis cells (SOECs). In this paper, a novel interfacial modification method was developed to enhance the active electrode area and the electrolysis performance via preparing a porous YSZ layer on the surface of the dense electrolyte. The effects of YSZ electrolyte pre-sintering temperature, the thickness of dense YSZ electrolyte film and preparation of porous YSZ on the microscopic morphology and the performance of single button cells were investigated. After optimization, a 9 μm porous YSZ layer was successfully prepared on the surface of a 4 μm dense YSZ electrolyte film with an OCV of 1.072 V at the temperature of 850 °C. The results of electrochemical tests showed that the current densities could elevate from −0.681 A cm⁻² to −1.118 A cm⁻² when electrolyzed at 1.5 V under SOEC mode after microstructural modification.     

High-performance anode-supported Solid Oxide Fuel Cells based on Ba(Zr0.1Ce0.7Y0.2)O3−δ (BZCY) fabricated by a modified co-pressing process

A modified co-pressing process was developed to fabricate anode-supported dense and uniform Ba(Zr_0.1Ce_0.7Y_0.2)O_3−δ (BZCY) electrolyte films (∼20 μm thick) from BZCY powders with different characteristics; the powders derived from a glycine nitrate process was used for the anode whereas the powders from solid state reaction for the electrolyte. The BZCY electrolyte films sintered at 1350 °C for 6 h reached a conductivity of ∼0.025 S cm⁻¹ at 700 °C, similar to that of BZCY pellet sintered at 1550 °C for 10 h. Further, a test cell based on such an anode-supported BZCY electrolyte demonstrated peak power densities of ∼780 and ∼490 mW cm⁻² at 700 and 600 °C, respectively.     

High performance metal-supported solid oxide fuel cells fabricated by thermal spray

Metal-supported solid oxide fuel cells (SOFCs) have been fabricated and characterized in this work. The cells consist of porous NiO-SDC as anode, thin SDC as electrolyte, and SSCo as cathode on porous stainless steel substrate. The anode and electrolyte layers were consecutively deposited onto porous metal substrate by thermal spray, using standard industrial thermal spray equipment, operated in an open-air atmosphere. The cathode materials were applied to the as-sprayed half-cells by screen-printing and heat-treated at 800 °C for 2 h. The cell components and performance were examined by scanning electron microscopy (SEM), X-ray diffraction, leakage test, ac impedance and electrochemical polarization at temperatures between 500 and 700 °C. The half-inch button cells exhibit a maximum power density in excess of 0.50 W cm⁻² at 600 °C and 0.92 W cm⁻² at 700 °C operated with humidified hydrogen fuel, respectively. The half-inch button cell was run at 0.5 A cm⁻² at 603 °C for 100 h. The cell voltage decreased from 0.701 to 0.698 V, giving a cell degradation rate of 4.3% kh⁻¹. Impedance analysis indicated that the cell degradation included 4.5% contribution from ohmic loss and 1.4% contribution from electrode polarization. The 5 cm × 5 cm cells were also fabricated under the same conditions and showed a maximum power density of 0.26 W cm⁻² at 600 °C and 0.56 W cm⁻² at 700 °C with dry hydrogen as fuel, respectively. The impedance analysis showed that the ohmic resistance of the cells was the major polarization loss for all the cells, while both ohmic and electrode polarizations were significantly increased when the operating temperature decreased from 700 to 500 °C. This work demonstrated the feasibility for the fabrication of metal-supported SOFCs with relatively high performance using industrially available deposition techniques. Further optimization of the metal support, electrode materials and microstructure, and deposition process is ongoing.     

SrCo0.7Fe0.2Ta0.1O3−δ perovskite as a cathode material for intermediate-temperature solid oxide fuel cells

Perovskite oxide SrCo_0.7Fe_0.2Ta_0.1O_3−δ (SCFT) was synthesized by a solid–state reaction and investigated as a potential cathode material for intermediate-temperature solid oxide fuel cell (IT-SOFC). The single phase SCFT having a cubic perovskite structure was obtained by sintering the sample at 1200 °C for 10 h in air. Introduction of Ta improved the phase stability of SCFT. The SCFT exhibited a good chemical compatibility with the La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) electrolyte at 950 °C for 10 h. The average thermal expansion coefficient was 23.8 × 10⁻⁶ K⁻¹ between 30 and 1000 °C in air. The electrical conductivities of the SCFT sample were 71–119 S cm⁻¹ in the 600−800 °C temperature range in air, and the maximum conductivity reached 247 S cm⁻¹ at 325 °C. The polarization resistance of the SCFT cathode on the LSGM electrolyte was 0.159 Ω cm² at 700 °C. The maximum power density of a single-cell with the SCFT cathode on a 300 μm-thick LSGM electrolyte reached 652.9 mW cm⁻² at 800 °C. The SCFT cathode had shown a good electrochemical stability over a period of 20 h short-term testing. These findings indicated that the SCFT could be a suitable alternative cathode material for IT-SOFCs.     

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.     

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.     

Electrical conductivity of epitaxial La0.6Sr0.4Co0.2Fe0.8O3−δ thin films grown by pulsed laser deposition

Epitaxial La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) thin films have been grown successfully on single crystal LaAlO₃ substrate by pulsed laser deposition (PLD). AFM micrographs have shown a rms roughness of 5Å for the 550 °C deposited films. The films further exhibited electrical conductivities of as high as 2.3 × 10³ S cm⁻¹ at 600 °C, with an activation energy of 0.09 eV. The surface exchange coefficient (k_chem$k_{chem}$) of the epitaxial LSCF thin film, determined by electrical conductivity relaxation (ECR) technique, increased with the increasing temperature, and reached a value of ∼5.1 × 10⁻⁶ S cm⁻¹ at temperatures above 620 °C.     

Metal-supported solid oxide fuel cells with in-situ sintered (Bi2O3)0.7(Er2O3)0.3–Ag composite cathode

Metal-supported solid oxide fuel cells (SOFCs) containing porous 430L stainless steel support, Ni-YSZ anode and YSZ electrolyte were fabricated by tape casting, laminating and co-firing in a reduced atmosphere. (Bi₂O₃)_0.7(Er₂O₃)_0.3–Ag composite cathode was applied by screen printing and in-situ sintering. The polarization resistances of the composite cathode were 1.18, 0.48, 0.18, 0.09 Ω cm² at 600, 650, 700 and 750 °C, respectively. A promissing maximum power density of 568 mW cm⁻² at 750 °C was obtained of the single cell. Short-term stability was measured as well.     

Potential low-temperature application and hybrid-ionic conducting property of ceria-carbonate composite electrolytes for solid oxide fuel cells

Ceria-carbonate composite materials have been widely investigated as candidate electrolytes for solid oxide fuel cells operated at 300-600 °C. However, fundamental studies on the composite electrolytes are still in the early stages and intensive research is demanded to advance their applications. In this study, the crystallite structure, microstructure, chemical activity, thermal expansion behavior and electrochemical properties of the samaria doped ceria-carbonate (SCC) composite have been investigated. Single cells using the SCC composite electrolyte and Ni-based electrodes were assembled and their electrochemical performances were studied. The SCC composite electrolyte exhibits good chemical compatibility and thermal-matching with Ni-based electrodes. Peak power density up to 916 mW cm⁻² was achieved at 550 °C, which was attributed to high electrochemical activity of both electrolyte and electrode materials. A stable discharge plateau was obtained under a current density of 1.5 A cm⁻² at 550 °C for 120 min. In addition, the ionic conducting property of the SCC composite electrolyte was investigated using electrochemical impedance spectroscopy technique. It was found that the hybrid-ionic conduction improves the total ionic conductivity and fuel cell performance. These results highlight potential low-temperature application of ceria-carbonate composite electrolytes for solid oxide fuel cells.     

An ion-plasma technique for formation of anode-supported thin electrolyte films for IT-SOFC applications

This paper describes a preparation method and structural and electrochemical properties of a thin bilayer anode-electrolyte structure for a solid oxide fuel cell operating at intermediate temperatures (IT-SOFC). Thin anode-supported yttria-stabilized zirconia electrolyte films were prepared by reactive magnetron sputtering of a Zr-Y target in an Ar-O₂ atmosphere. Porous anode surfaces of IT-SOFCs were modified by a pulsed low-energy high-current electron beam prior to film deposition; the influence of this pretreatment on the performance of both the deposited films and a single cell was investigated. The optimal conditions of the pulsed electron beam pretreatment were obtained. For the electrolyte thickness about 2.5 μm and the value of gas permeability of the anode/electrolyte structure 1.01 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹, the maximum power density achieved for a single cell at 800 °C and 650 °C was found to be 620 and 220 mW cm⁻² in air, respectively.     

Effects of a current treatment for an in-situ sintered cathode in a Ni-supported solid oxide fuel cell

Metal-supported solid oxide fuel cells (SOFCs) are one of the most promising candidates for applications in power plants as well as in portable applications due to their good mechanical and thermal properties. A Ni-supported SOFC that consists of a metal support (Ni, ∼180 μm), an anode functional layer (Ni-yttrium stabilized zirconia YSZ, ∼15 μm), an electrolyte (YSZ, ∼5 μm), and a nanocrystalline La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) cathode is prepared. A nanocrystalline LSCF synthesized with ethylenediaminetetraacetic acid, citric acid, and inorganic nanodispersants, is used as an in situ sinterable cathode. The Ni-supported SOFC with nanocrystalline LSCFs is operated without a high temperature treatment for cathode sintering. The cell exhibits the maximum power density of 580 mW cm⁻² at 780 °C. A current treatment for 8 h (0.5 A cm⁻² at 780 °C) enhances the interfacial contact between the cathode and the electrolyte. After the current treatment, the maximum power density at 730 °C increase by 1.6 times from 260 mW cm⁻² to 390 mW cm⁻². The ohmic resistance (R_ohm) at 730 °C decreases from 0.43 Ω cm² to 0.21 Ω cm² and the charge transfer polarization at 0.7 V decreases from 0.42 Ω cm² to 0.30 Ω cm² due to lowered interfacial resistance between the cathode and the electrolyte. However, the mass transfer polarization increases from 0.09 Ω cm² to 0.17 Ω cm², which may result from the morphological change in the porous microstructure of the Ni support. The current treatment of the Ni-supported SOFC with in situ sintered LSCFs exhibit an increment in fuel cell performance due to the lowered ohmic resistance, which is beneficial for simple and mechanically improved fabrication and operation of metal-supported SOFCs.     

Infiltrated multiscale porous cathode for proton-conducting solid oxide fuel cells

A Sm_0.5Sr_0.5CoO_3−δ (SSC)-BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY) composite cathode with multiscale porous structure was successfully fabricated through infiltration for proton-conducting solid oxide fuel cells (SOFCs). The multiscale porous SSC catalyst was coated on the BZCY cathode backbones. Single cells with such composite cathode demonstrated peak power densities of 0.289, 0.383, and 0.491 W cm⁻² at 600, 650, 700 °C, respectively. Cell polarization resistances were found to be as low as 0.388, 0.162, and 0.064 Ω cm² at 600, 650 and 700 °C, respectively. Compared with the infiltrated multiscale porous cathode, cells with screen-printed SSC-BZCY composite cathode showed much higher polarization resistance of 0.912 Ω cm² at 600 °C. This work has demonstrated a promising approach in fabricating high performance proton-conducting SOFCs.     

La0.6Sr0.4Fe0.8Cu0.2O3−δ perovskite oxide as cathode for IT-SOFC

A La_0.6Sr_0.4Fe_0.8Cu_0.2O_3−δ (LSFCu) perovskite was investigated as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFC). The LSFCu material exhibited chemical compatibility with the Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte up to a temperature of 1100 °C. The electrical conductivity of the sintered sample was measured as a function of temperature from 100 to 800 °C. The highest conductivity of about 238 S cm⁻¹ was observed for LSFCu. The average thermal-expansion coefficient (TEC) of LSFCu was 14.6 × 10⁻⁶ K⁻¹, close to that of typical CeO₂ electrolyte material. The investigation of electrical properties indicated that the LSFCu cathode had lower interfacial polarization resistance of 0.070 Ω cm² at 800 °C and 0.138 Ω cm² at 750 °C in air. An electrolyte-supported single cell with 300 μm thick SDC electrolyte and LSFCu as cathode shows peak power densities of 530 mW cm⁻² at 800 °C.     

A comparative study of Sm0.5Sr0.5MO3−δ (M = Co and Mn) as oxygen reduction electrodes for solid oxide fuel cells

Sm_0.5Sr_0.5MO_3−δ (M = Co and Mn) materials are synthesized, and their properties and performance as cathodes for solid oxide fuel cells (SOFCs) on Sm_0.2Ce_0.8O_1.9 (SDC) and Y_0.16Zr_0.92O_2.08 (YSZ) electrolytes are comparatively studied. The phase structure, thermal expansion behavior, oxygen mobility, oxygen vacancy concentration and electrical conductivity of the oxides are systematically investigated. Sm_0.5Sr_0.5CoO_3−δ (SSC) has a much larger oxygen vacancy concentration, electrical conductivity and TEC than Sm_0.5Sr_0.5MnO_3−δ (SSM). A powder reaction demonstrates that SSM is more chemically compatible with the YSZ electrolyte than SSC, while both are compatible with the SDC electrolyte. EIS results indicate that the performances of SSC and SSM electrodes depend on the electrolyte that they are deposited on. SSC is suitable for the SDC electrolyte, while SSM is preferred for the YSZ electrolyte. A peak power density as high as 690 mW cm⁻² at 600 °C is observed for a thin-film SDC electrolyte with SSC cathode, while a similar cell with YSZ electrolyte performs poorly. However, SSM performs well on YSZ electrolyte at an operation temperature of higher than 700 °C, and a fuel cell with SSM cathode and a thin-film YSZ electrolyte delivers a peak power density of ∼590 mW cm⁻² at 800 °C. The poor performances of SSM cathode on both YSZ and SDC electrolytes are obtained at a temperature of lower than 650 °C.