A stabilized NiO cathode prepared by sol-impregnation of LiCoO2 precursors for molten carbonate fuel cells

Layers of LiCoO₂ were formed on the internal surface of a porous NiO cathode to reduce the rate of NiO dissolution into the molten carbonate. A sol-impregnation technique assisted by acrylic acid (AA) was used to deposit gel precursors of LiCoO₂ on the pore surface of the Ni plate. Thermal treatment of the gel-coated cathode above 400 °C produced LiCoO₂ layers on the porous cathode. A number of bench-scale single cells were fabricated with LiCoO₂-coated cathodes and the cell performance was examined at atmospheric pressure for 1000 h. With the increase in the LiCoO₂ content in the cathode, the initial cell voltage decreased, but the cell performance gradually improved during the cell test. It was found from symmetric cathode cell test that the cathode was initially flooded with electrolyte, but redistribution of the electrolyte took place during the test and cell performance became comparable to that of a conventional NiO cathode. The amount of Ni precipitated in the matrix during the cell operation for 1000 h was significantly reduced by the LiCoO₂ coating. For instance, coating 5 mol% of LiCoO₂ in the cathode led to a 56% reduction of Ni precipitation in the matrix. The results obtained in this study strongly suggest that LiCoO₂ layers formed on the internal surface of the porous NiO cathode effectively suppress the rate of NiO dissolution for 1000 h.     

Mechanical strength of porous nickel plates containing lithium and their performance as the cathode for MCFC

To improve the mechanical properties of MCFC cathode materials, pre-lithiated porous nickel plates containing 1–5 mol% of lithium were fabricated by the tape casting method, and the microstructures, mechanical properties, and performance was examined. The microstructure and pore distribution was not changed until the lithum content reached 3 mol%. The sample containing 5 mol% of lithium had patch structure on the skeleton and a smaller volume of primary pores. XRD analysis showed that lithium-containing porous nickel plates can easily form solid solutions without any undesirable byproducts after the oxidation. Both the bending strength and Young’s modulus of the porous plates increased with the increase of lithium content. The average bending strengths of the samples containing 1, 3, and 5 mol% of lithium were 1.29, 1.33, and 1.49 kgf/mm² which were 2.9, 3.0, and 3.4 times higher than that of pure porous nickel plate. The Young’s modulus increased up to 1.35 kgf/mm in the case of the 5 mol% lithium containing sample that is 5.4 times higher than that of pure porous nickel plate. The OCV of single cells using pre-lithiated cathodes were between 1.065 and 1.067 V, and comparable cell performance was obtained for 500 h of single cell operation.     

Study of cobalt-doped lithium–nickel oxides as cathodes for MCFC

Cobalt substituted lithium–nickel oxides were synthesized by a solid-state reaction procedure using lithium nitrate, nickel hydroxide and cobalt oxalate precursor and were characterized as cathodes for molten carbonate fuel cell (MCFC). LiNi_0.8Co_0.2O₂ cathodes were prepared using non-aqueous tape casting technique followed by sintering in air. The X-ray diffraction (XRD) analysis of sintered LiNi_1−xCo_xO₂ indicated that lithium evaporation occurs during heating. The lithium loss decreases with an increase of the cobalt content in the mixed oxides. The stability studies showed that dissolution of nickel into the molten carbonate melt is smaller in the case of LiNi_1−xCo_xO₂ cathodes compared to the dissolution values reported in the literature for state-of-the-art NiO. Pore volume analysis of the sintered electrode indicated a mean pore size of 3 μm and a porosity of 40%. A current density of 160 mA/cm² was observed when LiNi_0.8Co_0.2O₂ cathodes were polarized at 140 mV. The electrochemical impedance spectroscopy (EIS) studies done on LiNi_0.8Co_0.2O₂ cathodes under different gas conditions indicated that the rate of the cathodic discharge reaction depends on the O₂ and CO₂ partial pressures.     

Effect of components in electrodes on sintering characteristics of Ce0.9Gd0.1O1.95 electrolyte in intermediate-temperature solid oxide fuel cells during fabrication

The effects of anode and cathode components on solid-state reaction and sintering characteristics of Ce_0.9Gd_0.1O_1.95 (CGO) electrolyte were investigated in the temperature range from 900 to 1200 °C. The solubility limit of components in the anode was <4 mol% for 1/2Fe₂O₃, <1 mol% for NiO, and <3 mol% for CuO. The solubility limit of components in the cathode was <4 mol% for 1/2La₂O₃, <4 mol% for SrO, and <1 mol% for 1/3Co₃O₄. A small amount of addition of Fe₂O₃, Co₃O₄ or CuO remarkably enhanced the sintering characteristics of the CGO nanopowder. NiO, La₂O₃ or SrO addition lowered. In the case of the mixture of the CGO and La_0.6Sr_0.4CoO₃, enhancement of sintering characteristics of the CGO and no reaction products were observed. From scanning electron microscopy observation, the sintered CGO samples with Fe₂O₃ showed the feature by solid-state sintering mechanism. For the CGO with CuO, the samples showed the trace of liquid-phase sintering. The samples of CGO with Co₃O₄ included large grains, which seem to relate to cobalt vapor from the cobalt oxide particles.     

Comparative studies of nickel oxide films on different substrates for electrochemical supercapacitors

Thin nickel oxide (NiO) films were obtained by post-heating of the corresponding precursor films of nickel hydroxide (Ni(OH)₂) cathodically deposited onto different substrates, i.e., nickel foils, and graphite at 25 °C from a bath containing 1.5 mol L⁻¹ Ni(NO₃)₂ and 0.1 mol L⁻¹ NaNO₃ in a solvent of 50% (v/v) ethanol. The surface morphology of the obtained films was observed by scanning electron microscope (SEM). Electrochemical characterization was performed using cyclic voltammetrty (CV), chronopotentiometry (CP) and electrochemical impedance analysis (EIS). When heated at 300 °C for 2 h in air, the specific capacitance of the prepared NiO films on nickel foils and graphite, with a deposition charge of 250 mC cm⁻², were 135, 195 F g⁻¹, respectively. When the deposition charge is less than 280 mC cm⁻², the capacitance of both appears to keep the linear relationship with the deposition charge. The specific capacitance, cyclic stability of the NiO/graphite hybrid electrodes in 1 mol L⁻¹ KOH solution were superior to those on nickel foils mainly due to the favorable adhesion, the good interface behavior between graphite and the NiO films, and the extra pseudo-capacitance of the heated graphite substrates.     

Synthesis and electrochemical properties of LiNi0.80(Co0.20−xAlx)O2 (x = 0.0 and 0.05) cathodes for Li ion rechargeable batteries

The effect of simultaneous cobalt as well as aluminum doping was studied to understand their effect on the phase formation behavior and electrochemical properties of solution derived lithium nickel oxide cathode materials for rechargeable batteries. The discharge capacities of LiNi_0.80Co_0.20O₂ and LiNi_0.80Co_0.15Al_0.05O₂ cathodes, measured at constant current densities of 0.45 mA cm⁻² in the cut-off voltage range of 4.3–3.2 V, were 100 and 136 mAh g⁻¹, respectively. LiNi_0.80Co_0.15Al_0.05O₂ had better cycleability than the LiNi_0.80Co_0.20O₂ cathodes. The retention of undesirable Li₂CO₃ phase both in LiNi_0.80Co_0.20O₂ and LiNi_0.80Co_0.15Al_0.05O₂ cathodes was argued to be responsible for the relatively lower discharge capacity of these materials.     

X-ray diffractometric study of in situ oxidation of Ni in Li/K and Li/Na carbonate eutectic

The formation of NiO, particularly the lithiation process, in molten carbonate at 923 K under oxidizing condition has been investigated by open circuit potential (OCP), AC impedance, and X-ray diffraction (XRD) measurements. Thin film electrodes of Ni were exposed to the Li/K and Li/Na carbonate eutectic and subjected to in situ oxidation. Quantification of lithium in the lithiated NiO with XRD revealed that the lithiation reaction continues even after the electrode potential reached the oxygen electrode potential. Lithium content, x in Li_xNi_1-xO, of the sample immersed in molten carbonate reached 0.041 and 0.033 in Li/K and Li/Na melt, respectively after 200 h of immersion. Difference observed in OCP decay and electrode impedance at 1 kHz for Ni oxidation in the Li/K and Li/Na carbonate has been also interpreted based on XRD data.     

Growth mechanism of thin films of yttria-stabilized zirconia by chemical vapor infiltration using NiO–ceria substrate as oxygen source

The deposition of yttria-stabilized zirconia films on a NiO–ceria substrate by chemical vapor infiltration (CVI) using ZrCl₄ and YCl₃ as metal sources and NiO–ceria as oxygen source was studied. The resultant films were cubic YSZ with a Y₂O₃ content of 3.7–4.2 mol%, and were transparent and strong. A NiO content of NiO–ceria above 60 mol% increases the growth rate of the YSZ film from about 5 to 25 μm over 2 h, indicating that chemical vapor deposition (CVD) occurred in addition to electrochemical vapor deposition (EVD), whereas NiO contents below 60 mol% does not affect the growth rate, indicating that only electrochemical vapor deposition occurred. The growth mechanism of the YSZ film is determined and a YSZ thin film is successfully fabricated on NiO–ceria to improve mechanical strength.     

Characterization and performance of high power iron(VI) ferrate batteries

In this paper we report on the high power discharge performance and impedance characteristics of potassium ferrate (K₂FeO₄) and barium ferrate (BaFeO₄) cathodes in zinc alkaline dry cells. The results show that if ferrate materials can be packaged to maximize the cathode surface area, they may offer superior performance over electrolytic manganese dioxide at operating voltages exceeding 1.6 V and currents as high as 100 mA/g of active material.     

NiO–YSZ cermets supported low temperature solid oxide fuel cells

Solid oxide fuel cells with thin electrolyte of two types, Sm_0.2Ce_0.8O_1.9 (SDC) (15 μm) single-layer and 8 mol% Yttria stabilized zirconia (YSZ) (5 μm) + SDC (15 μm) bi-layer on NiO–YSZ cermet substrates were fabricated by screen printing and co-firing. A Sm_0.5Sr_0.5CoO₃ cathode was printed, and in situ sintered during a cell performance test. The SDC single-layer electrolyte cell showed high electrochemical performance at low temperature, with a 1180 mW cm⁻² peak power density at 650 °C. The YSZ + SDC bi-layer electrolyte cell generated 340 mW cm⁻² peak power density at 650 °C, and showed good performance at 700–800 °C, with an open circuit voltage close to theoretical value. Many high Zr-content micro-islands were found on the SDC electrolyte surface prior to the cathode preparation. The influence of co-firing temperature and thin film preparation methods on the Zr-islands’ appearance was investigated.     

Layered Li(Ni0.5−xMn0.5−xM2x′)O2 (M′=Co,Al, Ti; x=0, 0.025) cathode materials for Li-ion rechargeable batteries

Layered Li(Ni_0.5−xMn_0.5−xM_2x′)O₂ materials (M′=Co, Al, Ti; x=0, 0.025) were synthesized using a manganese-nickel hydroxide precursor, and the effect of dopants on the electrochemical properties was investigated. Li(Ni_0.5Mn_0.5)O₂ exhibited a discharge capacity of 120 mAh/g in the voltage range of 2.8–4.3 V with a slight capacity fade up to 40 cycles (0.09% per cycle); by doping of 5 mol% Co, Al, and Ti, the discharge capacities increased to 140, 142, and 132 mAh/g, respectively, and almost no capacity fading was observed. The cathode material containing 5 mol% Co had the lowest impedance, 47 Ω cm², while undoped, Ti-doped, and Al-doped materials had impedance of 64, 62, and 99 Ω cm², respectively. Unlike the other dopants, cobalt was found to improve the electronic conductivity of the material. Further improvement in the impedance of these materials is needed to meet the requirement for powering hybrid electric vehicle (HEV, <35 Ω cm²). In all materials, structural transformation from a layered to a spinel structure was not observed during electrochemical cycling. Cyclic voltammetry and X-ray photoelectron spectroscopy (XPS) data suggested that Ni and Mn exist as Ni²⁺ and Mn⁴⁺ in the layered structure. Differential scanning calorimetry (DSC) data showed that exothermic peaks of fully charged Li_1−y(Ni_0.5−xMn_0.5−xM_2x′)O₂ appeared at higher temperature (270–290 °C) than LiNiO₂-based cathode materials, which indicates that the thermal stability of Li(Ni_0.5−xMn_0.5−xM_2x′)O₂ is better than those of LiNiO₂-based cathode materials.     

Development and testing of anode-supported solid oxide fuel cells with slurry-coated electrolyte and cathode

A laboratory setup was designed and put into operation for the development of solid oxide fuel cells (SOFCs). The whole project consisted of the preparation of the component materials: anode, cathode and electrolyte, and the buildup of a hydrogen leaking-free sample chamber with platinum leads and current collectors for measuring the electrochemical properties of single SOFCs. Several anode-supported single SOFCs of the type (ZrO₂:Y₂O₃ + NiO) thick anode/(ZrO₂:Y₂O₃) thin electrolyte/(La_0.65Sr_0.35MnO₃ + ZrO₂:Y₂O₃) thin cathode have been prepared and tested at 700 and 800 °C after in situ H₂ anode reduction. The main results show that the slurry-coating method resulted in single-cells with good reproducibility and reasonable performance, suggesting that this method can be considered for fabrication of SOFCs.     

In situ screen-printed BaZr0.1Ce0.7Y0.2O3−δ electrolyte-based protonic ceramic membrane fuel cells with layered SmBaCo2O5+x cathode

In order to develop a simple and cost-effective route to fabricate protonic ceramic membrane fuel cells (PCMFCs) with layered SmBaCo₂O_5+x (SBCO) cathode, a dense BaZr_0.1Ce_0.7Y_0.2O_3?δ (BZCY) electrolyte was fabricated on a porous anode by in situ screen printing. The porous NiO–BaZr_0.1Ce_0.7Y_0.2O_3?δ (NiO–BZCY) anode was directly prepared from metal oxide (NiO, BaCO₃, ZrO₂, CeO₂ and Y₂O₃) by a simple gel-casting process. An ink of metal oxide (BaCO₃, ZrO₂, CeO₂ and Y₂O₃) powders was then employed to deposit BaZr_0.1Ce_0.7Y_0.2O_3?δ (BZCY) thin layer by an in situ reaction-sintering screen printing process on NiO–BZCY anode. The bi-layer with 25 μm dense BZCY electrolyte was obtained by co-sintering at 1400 °C for 5 h. With layered SBCO cathode synthesized by gel-casting on the bi-layer, single cells were assembled and tested with H₂ as fuel and the static air as oxidant. A high open-circuit potential of 1.01 V, a maximum power density of 382 mW cm^?2, and a low polarization resistance of the electrodes of 0.15 Ω cm² was achieved at 700 °C.     

Electrochemical properties of LSM–CBO composite cathode

In order to develop a cathode that can be used in intermediate temperature solid oxide fuel cells (ITSOFC), the composite materials La_0.8Sr_0.2MnO₃–Ce_0.7Bi_0.3O₂ (LSM–CBO) has been prepared and its electrode performances are investigated below 700 °C by AC impedance spectroscopy and dc polarization measurements. Results indicate that the oxygen adsorption process is the reaction rate limiting step. The polarization resistance decreases with the increasing of CBO contents. The optimum value of 50 wt.% CBO in LSM results in 1.78 Ω cm² area specific resistivity (ASR), which indicates that the LSM–CBO composite electrode is a promising cathode material in ITSOFC.     

High power BaFe(VI)O4/MnO2 composite cathode alkaline super-iron batteries

This short communication demonstrates that not only pure Fe(VI) cathodes, but also MnO₂/Fe(VI) composite cathodes can substantially enhance the high power discharge of alkaline batteries. The 2.8 Ω and 0.7 W high power discharge of alkaline cells are investigated for 3:1 and 1:1 composite MnO₂/BaFeO₄ cathode cells, provide discharge energies intermediate to that found in the (non-composite) BaFeO₄ cathode cell. At a constant 2.8 Ω load, the 1:1 composite MnO₂/BaFeO₄ cell delivers up to 40% higher energy capacity than the MnO₂ pure cathode alkaline cell, and up to three-fold the capacity of the constant 0.7 W power MnO₂ discharge.     

Synthesis and electrochemical properties of mesoporous nickel oxide

Mesoporous Ni(OH)₂ is synthesized using sodium dodecyl sulfate as a template and urea as a hydrolysis-controlling agent. Mesoporous NiO with a centralized pore-size distribution is obtained by calcining Ni(OH)₂ at different temperatures. The BET specific surface area reaches 477.7 m² g⁻¹ for NiO calcined at 250 °C. Structure characterizations indicate a good mesoporous structure for the nickel oxide samples. Cyclic voltammetry shows the NiO to have good capacitive behaviour due to its unique mesoporous structure when using a large amount of NiO to fabricate the electrode. Compared with NiO prepared by dip-coating and cathodic precipitation methods, mesoporous NiO with a controlled pore structure can be used in much larger amounts to fabricate electrodes and still maintain a high specific capacitance and good capacitive behaviour.     

CO2 adsorption on porous NiO as a cathode material for molten carbonate fuel cells

Molten carbonate fuel cells (MCFC) are the systems suitable for large-scale energy production. The cathode material used in these cells is NiO. In this study the NiO cathode was synthesized by tape-casting method and the adsorption of CO₂, one of the cathode feeding gases, was investigated on it. The adsorption studies were carried out by the use of packed column and the adsorption analysis were performed using pulse response technique. There were two 1/4 in. diameter and 5 and 10 cm length columns prepared for the experiments and they were packed with 3 mm average particle sized NiO. The experiments were carried out with gas chromatography using He as a carrier gas. The response curves were taken after pulsing the columns with CO₂. The equilibrium constants and heat of adsorption of CO₂ on NiO were determined by the use of the first absolute moment equations corresponding to retention times. It was observed that the adsorption was physical in nature. From the adsorption constants determined at different temperatures and the heat of adsorption, ΔH⁰, was found as −1299 cal mol⁻¹.     

Modifying the cathodes of intermediate-temperature solid oxide fuel cells with a Ce0.8Sm0.2O2 sol–gel coating

To increase the performance of solid oxide fuel cells operated at intermediate temperatures (<700 °C), we used the electronic conductor La_0.8Sr_0.2MnO₃ (LSM) and the mixed conductor La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) to modify the cathode in the electrode microstructure. For both cathode materials, we employed a Sm_0.2Ce_0.8O₂ (SDC) buffer layer as a diffusion barrier on the yttria-stabilized zirconia (YSZ) electrolyte to prevent the interlayer formation of SrZrO₃ and La₂Zr₂O₇, which have a poor ionic conductivity. These interfacial reaction products were formed only minimally at the electrolyte–cathode interlayer after sintering the SDC layer at high temperature; in addition, the degree of cathode polarization also decreased. Moreover to extend the triple phase boundary and improve cell performance at intermediate temperatures, we used sol–gel methods to coat an SDC layer on the cathode pore walls. The cathode resistance of the LSCF cathode cell featuring SDC modification reached as low as 0.11 Ω cm² in air when measured at 700 °C. The maximum power densities of the cells featuring the modified LSCF and LSM cathodes were 369 and 271 mW/cm², respectively, when using O₂ as the oxidant and H₂ as the fuel.     

Improvement of electrochemical properties of LiNi0.5Mn1.5O4 spinel

LiNi_0.5Mn_1.5O₄ material with a spinel structure is prepared by a sol–gel method. The material is initially fired at 850 °C and then subjected to a post-reaction annealing at 600 °C in order to minimize the nickel deficiency. The elevated firing temperature produces materials with a small surface-area which is beneficial for good capacity retention. Indeed, the spinel LiNi_0.5Mn_1.5O₄ not only shows a good cycle performance, but exhibits an excellent discharge capacity, i.e. 114 mAh g⁻¹ at 4.66 V plateau and 127 mAh g⁻¹ in total. Cyclic voltammetry and ac impedance spectroscopy are employed to characterize the reactions of lithium insertion and extraction in the LiNi_0.5Mn_1.5O₄ electrode. Excellent electrochemical performance and low material cost make this compound an attractive cathode for advanced lithium batteries.     

Improvement of anode performance by surface modification for solid oxide fuel cell running on hydrocarbon fuel

A Ni/ yttria-stabilized zirconia (YSZ) cermet anode was modified by coating with samaria-doped ceria (SDC, Sm_0.2Ce_0.8O₂) sol within the pores of the anode for a solid oxide fuel cell (SOFC) running on hydrocarbon fuel. The surface modification of Ni/YSZ anode resulted in an increase of structural stability and enlargement of the triple phase boundary (TPB), which can serve as a catalytic reaction site for oxidation of carbon or carbon monoxide. Consequently, the SDC coating on the pores of anode made it possible to have good stability for long-term operation due to low carbon deposition and nickel sintering.The maximum power density of an anode-supported cell (electrolyte; 8 mol% YSZ and thickness of 30 μm, and cathode; La_0.85Sr_0.15MnO₃) with the modified anode was about 0.3 W/cm² at 700 °C in the mixture of methane (25%) and air (75%) as the fuel and air as the oxidant. The cell was operated for 500 h without significant degradation of cell performance.