Oxygen transport through laccase biocathodes for a membrane-less glucose/O2 biofuel cell

The present study reports the development of operational membrane-less glucose/O₂ biofuel cell based on oxygen contactor. Glucose oxidation was performed by glucose oxidase (GOx) co-immobilized with the mediator 8-hydroxyquinoline-5-sulfonic acid hydrate (HQS) at the anode, whereas oxygen was reduced by laccase co-immobilized with 2,2′-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS²⁻) at the cathode. Both enzymes and mediators were immobilized within electropolymerized polypyrrole polymers.Nevertheless, this system is limited by the secondary reaction of O₂ electro-reduction at the anode that reduces the electron flow through the anode and thus the output voltage. In order to avoid the loss of current at the anode in glucose/O₂ biofuel cell, we developed a strategy to supply dissolved oxygen separate from the electrolyte. Porous carbon tubes were used as electrodes and modified on the external surface by the couple enzyme/mediator. The inside of the cathode tube was continuously supplied with saturated dioxygen solution diffusing from the inner to the external surface of the porous tube. The assembled biofuel cell was studied under nitrogen at 37 °C in phosphate buffer at pH 5.0 and 7.0. The maximum power density reached 27 μW cm⁻² at a cell voltage of 0.25 V at pH 5.0 with 10 mM glucose. The power density was twice as high as compared to the same system with oxygen bubbling directly in the cell.     

Enhancement of the performances of a single concentric glucose/O2 biofuel cell by combination of bilirubin oxidase/Nafion cathode and Au–Pt anode

This work deals with a novel preparation method of bilirubin oxidase/2,2′-azinobis-3-ethylbenzothiazoline-6-sulfonic acid electrode. The enzyme and its mediator were adsorbed on carbon Vulcan XC-72R before their immobilization into a Nafion^® matrix. Promising results were obtained when this biocathode was associated with Au₇₀Pt₃₀ nanoparticles as anode in a single concentric glucose/O₂ biofuel cell (BFC). The latter BFC delivered at 37 °C a power density of 90 μW cm^?2 for a cell voltage of 0.4 V in phosphate buffer (pH 7.4) containing 0.01 M glucose. Moreover, the electrical performances were increased with the concentration of glucose by generating up to 190 μW cm^?2 for a cell voltage of 0.52 V when the concentration of the renewable fuel reached 0.7 M.     

Synthesis of Au/C and Au/Pani for anode electrodes in glucose microfluidic fuel cell

Gold nanoparticles have been prepared by two methods: chemical (ex-situ, Au/C) by two phase protocol, and electrochemical (in-situ, Au/Pani) by electroreduction of gold ions on a polyaniline film and compared as anode catalysts in a glucose microfluidic fuel cell. In this paper the structural characteristics and electrocatalytic properties were investigated by X-ray diffraction and electrochemical measurements. The catalytic behavior of both anodes was tested in a microfluidic fuel cell with a reference electrode incorporated, by means of linear sweep voltammetry (LSV), showing a cathodic shift in the glucose oxidation peak for Au/Pani. Results show a higher power density (0.5 mW cm^? 2) for Au/C anode compared with an already reported value, where a glucose microfluidic fuel cell was used in similar conditions.     

A novel single phase cathode material for a proton-conducting SOFC

A novel single phase BaCe_0.5Bi_0.5O_3 ? δ (BCB) was employed as a cathode material for a proton-conducting solid oxide fuel cell (SOFC). 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 BCB cathode layer, was assembled and tested from 600 to 700 °C with humidified hydrogen (～3% H₂O) as the fuel and the static air as the oxidant. An open-circuit potential of 0.96 V and a maximum power density of 321 mW cm^?2 were obtained for the single cell. A relatively low interfacial polarization resistance of 0.28Ω cm² at 700 °C indicated that the BCB was a promising cathode material for proton-conducting SOFCs.     

A direct borohydride–peroxide fuel cell using a Pd/Ir alloy coated microfibrous carbon cathode

A direct borohydride fuel cell with a Pd/Ir catalysed microfibrous carbon cathode and a gold-catalysed microporous carbon cloth anode is reported. The fuel and oxidant were NaBH₄ and H₂O₂, at concentrations within the range of 0.1–2.0 mol dm⁻³ and 0.05–0.45 mol dm⁻³, respectively. Different combinations of these reactants were examined at 10, 25 and 42 °C. At constant current density between 0 and 113 mA cm⁻², the Pd/Ir coated microfibrous carbon electrode proved more active for the reduction of peroxide ion than a platinised-carbon one. The maximum power density achieved was 78 mW cm⁻² at a current density of 71 mA cm⁻² and a cell voltage of 1.09 V.     

An enzymatic glucose/O2 biofuel cell: Preparation,characterization and performance in serum

This study demonstrates a new kind of single-walled carbon nanotubes (SWNT)-based compartment-less glucose/O₂ biofuel cell (BFC) with glucose dehydrogenase (GDH) and bilirubin oxidase (BOD) as the anodic and cathodic biocatalysts, respectively, and with poly(brilliant creysl blue) (BCB) adsorbed onto SWNT nanocomposite as the electrocatalyst for the oxidation of NADH. The prepared GDH-polyBCB-SWNT bioanode exhibits an excellent electrocatalytic activity toward the oxidation of glucose biofuel; in 0.10 M phosphate buffer containing 20 mM NAD⁺ and 100 mM glucose, the oxidation of glucose commences at −0.25 V and the current reaches its maximum of 310 μA/cm² at −0.05 V vs. Ag/AgCl. At the BOD-SWNT biocathode, a high potential output is achieved for the reduction of O₂ due to the direct electron transfer property of BOD at the SWNTs. In 0.10 M phosphate buffer, the electrocatalytic reduction of O₂ is observed at a high potential of 0.53 V vs. Ag/AgCl with an electrocatalytic current plateau of ca. 28 μA/cm² at 0.45 V under ambient air and ca. 102 μA/cm² under O₂-saturated atmosphere. In 0.10 M phosphate buffer containing 10 mM NAD⁺ and 40 mM glucose under O₂-saturated atmosphere, the power density of the assembled SWNT-based glucose/O₂ BFC reaches 53.9 μW/cm² at 0.50 V. The performance and the stability of the glucose/O₂ BFC are also evaluated in serum. This study could offer a new route to the development of new kinds of enzymatic BFCs with a high performance and provide useful information on future studies on the enzymatic BFCs as in vivo power sources.     

Methane-fueled SOFC with traditional nickel-based anode by applying Ni/Al2O3 as a dual-functional layer

Novel γ-Al₂O₃ supported nickel (Ni/Al₂O₃) catalyst was developed as a functional layer for Ni–ScSZ cermet anode operating on methane fuel. Catalytic tests demonstrated Ni/Al₂O₃ had high and comparable activity to Ru–CeO₂ and much higher activity than the Ni–ScSZ cermet anode for partial oxidation, steam and CO₂ reforming of methane to syngas between 750 and 850 °C. By adopting Ni/Al₂O₃ as a catalyst layer, the fuel cell demonstrated a peak power density of 382 mW cm^?2 at 850 °C, more than two times that without the catalyst layer. The Ni/Al₂O₃ also functioned as a diffusion barrier layer to reduce the methane concentration within the anode; consequently, the operation stability was also greatly improved without coke deposition.     

A glucose/O2 biofuel cell base on nanographene platelet-modified electrodes

This study demonstrated a novel nanographene platelets (NGPs)-based glucose/O₂ biofuel cell (BFC) with the glucose oxidase (GOD) as the anodic biocatalysts and the laccase as the cathodic biocatalysts. The GOD/NGPs-modified electrode exhibited good catalytic activity towards glucose oxidation and the laccase/NGPs-modified electrode exhibited good catalytic activity towards O₂ electroreduction. The maximum power density was ca. 57.8 μW cm^? 2 for the assembled glucose/O₂ NGPs-based BFC. These results indicated that the NGPs were very useful for the future development of novel carbon-based nanomaterials BFC device.     

A biofuel cell with enhanced power output by grape juice

Glucose oxidase and laccase immobilized at multiwalled carbon nanotubes-ionic liquid gel modified electrodes are used as the catalysts of anode and cathode of biofuel cells (BFCs), respectively. The BFC based on glucose and air is proposed. When ferrocene monocarboxylic acid is adopted as the mediator of anode, the power output of the BFC is ca. 4.1 μW (power density ca. 10.0 μW cm⁻²), which is higher than the value of 2.7 μW (power density ca. 6.6 μW cm⁻²) by taking ferrocene dicarboxylic acid as the mediator. This implies that the mediator with formal potential closing to that of the enzyme does improve the power output. Furthermore, the power output of the BFC is greatly improved by taking grape juice as the fuel of anode rather than glucose. This system also indicates that grape juice as a fuel of the BFC not only is feasible and can also enhances the power output of the BFCs. Besides, it greatly lowers the cost and simplifies the preparation procedure of the BFCs, making the BFC towards “green” bioenergy.     

Direct-methane solid oxide fuel cells with Cu1.3Mn1.7O4 spinel internal reforming layer

Cu_1.3Mn_1.7O₄ spinel oxide has been synthesized and characterized as anode internal reforming layer for Ni–SDC anode-supported solid oxide fuel cells (SOFCs) directly operating on methane fuel. XRD and Cu mapping image results of Cu_1.3Mn_1.7O₄ oxide after in-situ reduction by methane show that a highly dispersed nano-Cu metal network has been obtained. By adopting Cu_1.3Mn_1.7O₄ as an internal reforming layer, the cell demonstrated maximum power densities of 242 and 311 mW cm^?2 at 650 and 700 °C, respectively using methane as fuel and ambient air as oxidant. More importantly, Cu_1.3Mn_1.7O₄ internal reforming layer has significantly improved the cell performance stability. The cell with the Cu_1.3Mn_1.7O₄ internal reforming layer has demonstrated reasonably stable performance while the cell without it degraded very rapidly.     

Effects of CuO addition to anode on the electrochemical performances of cathode-supported solid oxide fuel cells

A cathode-supported electrolyte film was fabricated by tape casting and co-sintering techniques. (La_0.8Sr_0.2)_0.95MnO₃ (LSM95), LSM95/Zr_0.89Sc_0.1Ce_0.01O_2?x (SSZ), and SSZ were used as materials of cathode substrate, cathode active layer, and electrolyte, respectively. CuO–NiO–SSZ composite anode was deposited on SSZ surface by screen-printing and sintered at 1250 °C for 2 h. The effects of CuO addition to NiO–SSZ anode on the performance of cathode-supported SOFCs were investigated. CuO can effectively improve the sintering activity of NiO–SSZ. The assembled cells were electrochemically characterized with humidified H₂ as fuel and O₂ as oxidant. With 4 wt.% CuO addition, the ohmic resistance decreased from 3 to 0.46 Ω cm², and at the same time the polarization resistance decreased from 3.4 to 0.74 Ω cm². In comparison with the cell without CuO, the maximum power density at 850 °C increased from 0.054 to 0.446 W cm^?2 with 4 wt.% CuO addition.     

Cost-effective solid oxide fuel cell prepared by single step co-press-firing process with lithiated NiO cathode

A cost-effective cell fabrication process was developed for intermediate temperature solid oxide fuel cells (IT-SOFCs). Co-doped ceria Ce_0.8Gd_0.05Y_0.15O_1.9 (GYDC) was synthesized by carbonate co-precipitation method. Lithiated NiO was prepared by glycine-nitrate combustion method and adopted as cathode material for IT-SOFCs. Single cell was fabricated by one-step dry-pressing and co-firing anode, anode functional layer (AFL), electrolyte and cathode together at 1200 °C for 4 h. The cell presented decent performance and an overall electrode polarization resistance of 0.54 Ω cm² has been achieved at 600 °C. These results demonstrate the possibility of using lithiated NiO as cathode material for ceria-based IT-SOFCs and the development of affordable fuel cell devices is encouraged.     

Fabrication and characterization of large-size electrolyte/anode bilayer structures for low-temperature solid oxide fuel cell stack based on gadolinia-doped ceria electrolyte

Preliminary progress is reported in this communication in building a planar anode-supported low-temperature solid oxide fuel cell (SOFC) stack based on gadolinia-doped ceria (GDC) electrolyte, i.e. fabrication and characterization of a Ø80 planar bilayer structure composed of GDC electrolyte film and Ni–GDC anode substrate. The anode substrates were prepared from mixtures of NiO, GDC, and carbon black by die-pressing. After pre-firing to remove the carbon black, the anode substrates were deposited with a GDC layer using a spray coating technique. The green bilayers of anode substrate and electrolyte film were then co-sintered at 1500 °C for 3 h. Through proper control of the sintering process, bilayer structures with excellent flatness were achieved after co-sintering. Scanning electron microscopy (SEM) observation indicated that the electrolyte film was about 22 μm in thickness, highly dense, crack-free, and well-bonded to the anode substrate. Small disks which were cut out from the Ø80 bilayer structure were electrochemically examined in a single button-cell mode incorporating a (LaSr)(CoFe)O₃–GDC composite cathode. With humidified hydrogen as the fuel and air as the oxidant, the cell demonstrated an open-circuit voltage of 0.884 V and a maximum power density of 562 mW/cm² at 600 °C. The results imply that high-quality anode-supported electrolyte/anode bilayer structures were successfully fabricated. Based on them, planar anode-supported SOFC stacks will be assembled in the future.     

Impact of reforming catalyst on the anodic polarisation resistance in single-chamber SOFC fed by methane

This paper emphasises the electrochemical and catalytic properties of a Ni–10% GDC (10% gadolinium-doped ceria) cermet anode of a single-chamber solid oxide fuel cell (SC-SOFC). Innovative coupling of electrochemical impedance spectroscopy with gas chromatography measurements was carried out to characterise the anode material using an operando approach. The experiments were conducted in a symmetric anode/electrolyte/anode cell prepared by slurry coating resulting in 100 μm-thick anode layers. The electrochemical performance was assessed using a two-electrode arrangement between 400 °C and 650 °C, in a methane-rich atmosphere containing CH₄, O₂ and H₂O in a 14:2:6 volumetric ratio. The insertion of a Pt–CeO₂ based catalyst with high specific surface area inside the cermet layer was found to promote hydrogen production from the Water Gas Shift reaction and consequently to improve the electrochemical performances. Indeed, a promising polarisation resistance value of 12 Ω cm² was achieved at 600 °C with a catalytic loading of only 15 wt.%.     

High performance cathode-supported SOFC with perovskite anode operating in weakly humidified hydrogen and methane

A high performance cathode-supported solid oxide fuel cell (SOFC), suitable for operating in weakly humidified hydrogen and methane, has been developed. The SOFC is essentially made up by a YSZ/LSM composite supporting cathode, a thin YSZ film electrolyte, and a GDC-impregnated La_0.75Sr_0.25Cr_0.5Mn_0.5O₃ (LSCM) anode. A gas tight thin YSZ film (∼27 μm) was formed during the co-sintering of cathode/electrolyte bi-layer at 1200 °C. The cathode-supported SOFC developed in this study showed encouraging performance with maximum power density of 0.182, 0.419, 0.628 and 0.818 W cm⁻² in air/3% H₂O–97% H₂ (and 0.06, 0.158, 0.221 and 0.352 W cm⁻² in air/3% H₂O–97% CH₄) at 750, 800, 850 and 900 °C, respectively. Such performance is close to that of the cathode-supported cell (0.42 W cm⁻² vs. 0.455 W cm⁻² in humidified H₂ at 800 °C) developed by Yamahara et al. [Solid State Ionics 176 (2005) 451–456] with a Co-infiltrated supporting LSM-YSZ cathode, a (Sc₂O₃)_0.1(Y₂O₃)_0.01(ZrO₂)_0.89 (SYSZ) electrolyte of 15 μm in thickness and a SYSZ/Ni anode, indicating that the performance of the GDC-impregnated LSCM anode is comparable to that made of Ni cermet while stable in weakly humidified methane fuel.     

Bioelectrocatalytic oxidation of glucose by hexose oxidase directly wired to graphite

Glucose-oxidizing enzymes are widely used in electrochemical biosensors and biofuel cells; in most applications glucose oxidase, an enzyme with non-covalently bound FAD and low capability of direct electronic communications with electrodes, is used. Here, we show that another glucose-oxidizing enzyme with a covalently bound FAD center, hexose oxidase (HOX), adsorbed on graphite, exhibits a pronounced non-catalytic voltammetric response from its FAD, at − 307 mV vs. Ag/AgCl, pH 7, characterized by the heterogeneous electron transfer (ET) rate constant of 29.2 ± 4.5 s^− 1. Direct bioelectrocatalytic oxidation of glucose by HOX proceeded, although, with a 350 mV overpotential relative to FAD signals, which may be connected with a limiting step in biocatalysis under conditions of the replacement of the natural redox partner, O₂, by the electrode; mediated bioelectrocatalysis was consistent with the potentials of a soluble redox mediator used. The results allow development of HOX-based electrochemical biosensors for sugar monitoring and biofuel cells exploiting direct ET of HOX, and, not the least, fundamental studies of ET non-complicated by the loss of FAD from the protein matrix.     

A Miniature glucose/O2 biofuel cell with single-walled carbon nanotubes-modified carbon fiber microelectrodes as the substrate

This study demonstrates a new kind of miniature glucose/O₂ biofuel cells (BFCs) based on carbon fiber microelectrodes (CFMEs) modified with single-walled carbon nanotubes (SWNTs). SWNTs are used as a support both for stably confining the electrocatalyst (i.e., methylene green, MG) for the oxidation of NADH and the anodic biocatalyst (i.e., NAD⁺-dependent glucose dehydrogenase, GDH) for the oxidation of glucose and for efficiently facilitating direct electrochemistry of the cathodic biocatalyst (i.e., laccase) for the O₂ reduction. The prepared micro-sized GDH-based bioanode and laccase-based biocathode exhibit good bioelectrocatalytic activity toward the oxidation of glucose and the reduction of oxygen, respectively. In 0.10 M phosphate buffer containing 10 mM NAD⁺ and 45 mM glucose under ambient air, the power density of the assembled miniature compartment-less glucose/O₂ BFC reaches 58 μW cm⁻² at 0.40 V. The stability of the miniature glucose/O₂ BFC is also evaluated.     

Preparation of an extremely dense BaCe0.8Sm0.2O3−δ thin membrane based on an in situ reaction

The thin membrane of BaCe_0.8Sm_0.2O_3−δ (BCS) with high quality was successfully fabricated on porous NiO–BCS anode substrate through a novel in situ reaction method. The key part of this method is to directly spray well-mixed suspension of BaCO₃, CeO₂ and Sm₂O₃ instead of pre-synthesized BCS ceramic powder on the anode substrate. After sintering at 1400 °C for 5 h, the extremely dense electrolyte membrane in the thickness of 10 μm is obtained. A single cell was assembled with La_0.7Sr_0.3FeO_3−σ as cathode and tested with humidified hydrogen as fuel at 650 °C. The open circuit voltage (OCV) and maximum power density respectively reach 1.04 V and 535 mW/cm². Interface resistance of cell under open circuit condition was also investigated.     

A completely spray-coated membrane electrode assembly

We present a proton exchange membrane fuel cell (PEMFC) manufacturing route, in which a thin layer of polymer electrolyte solution is spray-coated on top of gas diffusion electrodes (GDEs) to work as a proton exchange membrane. Without the need for a pre-made membrane foil, this allows inexpensive, fast, large-scale fabrication of membrane-electrode assemblies (MEAs), with a spray-coater comprising the sole manufacturing device. In this work, a catalyst layer and a membrane layer are consecutively sprayed onto a fibrous gas diffusion layer with applied microporous layer as substrate. A fuel cell is then assembled by stacking anode and cathode half-cells with the membrane layers facing each other. The resultant fuel cell with a low catalyst loading of 0.1 mg Pt/cm² on each anode and cathode side is tested with pure H₂ and O₂ supply at 80 °C cell temperature and 92% relative humidity at atmospheric pressure. The obtained peak power density is 1.29 W/cm² at a current density of 3.25 A/cm². By comparison, a lower peak power density of 0.93 W/cm² at 2.2 A/cm² is found for a Nafion NR211 catalyst coated membrane (CCM) reference, although equally thick membrane layers (approx. 25 μm), and identical catalyst layers and gas diffusion media were used. The superior performance of the fuel cell with spray-coated membrane can be explained by a decreased low frequency (mass transport) resistance, especially at high current densities, as determined by electrochemical impedance spectroscopy.     

Fabrication by Co-extrusion and electrochemical characterization of micro-tubular hollow fibre solid oxide fuel cells

A phase inversion process was used to co-extrude cerium–gadolinium oxide (Ce_0.9Gd_0.1O_1.95)/NiO–CGO dual-layer hollow fibres (HF), which were then sintered to form, respectively, the electrolyte and high porosity anode precursor of a solid oxide fuel cell (SOFC) with anode inner diameter of 0.8 mm. Graded CGO–lanthanum strontium cobalt ferrite (La_0.6Sr_0.4Fe_0.8Co_0.2O₃) cathode layers were then painted onto the CGO electrolyte to form a micro-tubular HF-SOFC. With a carefully designed anode current collector, this produced maximum power densities of 1186–5864 W m^? 2 at 450–570 °C. High magnification imaging analysis revealed large three-phase boundary regions within the anode, a dense electrolyte layer and clearly highlighted the multiple CGO–LSCF cermet and pure LSCF cathode layers. The performance of the HF-SOFC with a twenty millimetre active length showed no degradation after four thermal cycles between 300 °C and 570 °C.