Effect of anode and cathode flow field depths on the performance of liquid feed direct methanol fuel cells (DMFCs)

The effect of the anode and cathode flow field depths on the performance of a single cell Direct methanol fuel cell (DMFC) of 45 cm² active area were experimentally investigated. Double serpentine flow fields (DSFFs) with varying channel depth namely, 0.2, 0.4, 0.6, 0.8, and 1 mm but with fixed channel and rib width each of 1 mm on both anode and cathode were designed, fabricated, and tested. The experimental study involved measurement of pressure drops across anode and cathode flow field plates, polarization, and carbon dioxide concentration measurements at various current densities. The mass transport at both anode and cathode were found to increase with increase in pressure drop across the flow field on account of reduced channel depth from 1.0 to 0.4 mm at all current densities. However, further decrease to a channel depth of 0.2 mm was found to be counter-productive with different phenomena operating on either side viz., increased CO₂ slug length on the anode flow channel and increased methanol crossover on the cathode side. Hence, the maximum performance for DMFCs was observed for a channel depth of 0.4 mm on anode and cathode flow fields. A decrease in flow field channel depth at cathode was found to increase the methanol crossover due to convective mass transfer effect.     

Effect of Serpentine Multi‐pass Flow Field Channel Orientation in the Liquid Water Distributions and Cell Performance

A commercial 50 cm² polymer electrolyte membrane (PEM) fuel cell with serpentine flow fields was operated at 2.0 bar and 60 °C with two orientations of the flow field channels with respect to gravity, i.e. horizontal and vertical channels. A 3 × 3 test matrix of anode and cathode reactants relative humidity was used for the performance assessment of the cell in both orientations. The cell performance and operating data, including cell voltage and resistance, were measured, and neutron radiographs were recorded during the entire operation in order to gain knowledge of the liquid water distributions within the cell for both orientations. A quantitative analysis of the results is presented in this work, comparing the cell operation for both flow field orientations. It is observed that the configuration with horizontal cathode flow field channels presents a better cell performance, and less amount of liquid water blocking the flow field channels. Thus, the results show that the selection of the cell orientation has an influence on the final performance, and it is therefore, a design parameter to be considered for a real application. The differences in the cell water content are quantitatively analyzed and discussed.     

Experimental study on the effect of reactant flow arrangements on the current distribution in proton exchange membrane fuel cells

Current distribution in a proton exchange membrane fuel cell (PEMFC) is significantly influenced by reactant flow configurations. In this study, the current distribution has been measured experimentally using a segmented flow-field plate and printed circuit board (PCB). Local current distributions for a PEMFC with serpentine flow field and three different flow arrangements including co-flow, cross-flow, and counter-flow arrangements for the anode and cathode streams are investigated along with the effect of flow channel orientation. It is shown that the counter-flow arrangement yields most uniform distribution for the current density, whereas the co-flow arrangement results in a considerable variation in the current density from the reactant gas stream inlet to exit. Flow channel orientation can also impact the cell performance and the current distribution appreciably. The limiting hydrogen concentration at the anode side due to the low stoichiometry condition can have a predominant effect on the current distribution and cell performance.     

A zinc–air cell employing a porous zinc electrode fabricated from zinc–graphite-natural biodegradable polymer paste

Porous zinc anodes have been fabricated from a mixture of zinc and graphite powder using gelatinized agar solution as the binding agent. Agar is a biodegradable polysaccharide polymer extracted from marine algae. The graphite content and the agar solution concentration were varied to find the best electrode composition. Zinc–air cells were fabricated using the porous zinc anode, a commercially available air cathode sheet and KOH electrolyte in the form of elastic jelly granules. The electrode performance was evaluated from the zinc–air cell galvanostatic discharge capability. In the cell design, a thin agar layer was introduced between the electrode-gelled electrolyte interfaces, resulting in substantially improved cell discharge performance. The inclusion of particulate graphite into the electrode did not enhance the electrode performance due to the formation of a graphite-rich layer, which obscured the electrode porosity. A zinc–air cell employing the optimized porous zinc electrode demonstrated a capacity of 2066 mA h and specific energy density of 443 Wh kg^–1.     

Polydopamine hydrophilic modification of polypropylene separator for lithium ion battery

The modified polypropylene (PP) separators with self‐polymerization of dopamine on the surfaces are prepared by a simple solution‐immersion method to improve the interfacial hydrophilic and discharge performance. The contact angle test and the liquid electrolyte uptake capacity test results show that the wettability and the electrolyte‐retention ability of polydopamine‐modified separator are improved significantly. The robust and thin polydopamine layer on the surface also enhances thermal performance and tensile strength of the modified PP separator certified by DSC and tensile strength tests. The ionic conductivity of the modified PP separator is up to 3.08 mS·cm^?1, ～2.5 times of the bare separator. Good discharge capacity retention and C‐rate discharge performance are demonstrated by a 2025 coin half‐cell with the liquid electrolyte‐soaked polydopamine modified PP separator sandwiched between lithium metal anode and LiFePO₄ cathode. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40543.     

Performance and cycling of the iron-ion/hydrogen redox flow cell with various catholyte salts

A redox flow cell utilizing the Fe²⁺/Fe³⁺ and H₂/H⁺ couples is investigated as an energy storage device. A conventional polymer electrolyte fuel cell anode and membrane design is employed, with a cathode chamber containing a carbon felt flooded with aqueous acidic solution of iron salt. The maximum power densities achieved for iron sulfate, iron chloride, and iron nitrate are 148, 207, and 234 mW cm^?2, respectively. It is found that the capacity of the iron nitrate solution decreases rapidly during cycling. Stable cycling is observed for more than 100 h with iron chloride and iron sulfate solutions. Both iron sulfate and iron chloride solutions display moderate discharge polarization and poor charge polarization; therefore, voltage efficiency decreases dramatically with increasing current density. A small self-discharge current occurs when catholyte is circulating through the cathode chamber. As a result, a current density above 100 mA cm^?2 is required to achieve high Coulombic efficiency (>0.9).     

An electrochemical device for oxygen production avoiding the generation of hydrogen

An electrochemical device for oxygen production which makes oxygen on both cathode and anode from air has been developed. The electrolytic cell consists of an air cathode, a catalytic decomposition mesh and a nickel anode. The electrolyser is composed of six single cells. The working surface area of a single cell is 0.02 m². Performance depends on factors such as the basic electrolyte concentration, temperature, air flow rate, gas flow distribution and current density. When the device is operated with 7m KOH at room temperature and with an air flow rate of 0.4m³ h^–1 and current of 20 A, the oxygen evolution rate is 0.036m³ h^–1 and the oxygen purity is 99.5%. The current efficiency is 72.0%. The device has operated continuously for 12 months with stable performance.     

Effect of the geometry and pattern of the flow channel on the performance of polymer electrolyte membrane fuel cell

This research focuses on the effect of the geometry and patterns of the gas flow channel on the PEM fuel cell performance. Simulation was conducted and the results were verified by experiments. Three-dimensional, single phase, compressible and isothermal models of 5 cm² electrodes, anode and cathode, were developed and studied by utilizing a commercial Computational Fluid Dynamics (CFD) software, FLUENT 4.5. Two types of gas flow channel were investigated: conventional and interdigitated. The results showed that the flow channel pattern does not have a significant effect on the anode cell performance, whereas it has a strong effect/influence on the cathode cell performance. The interdigitated design provides a higher limiting current density and cell performance than the conventional design on the cathode side. Moreover, the cell performance does not depend on the inlet and outlet channel widths. On the contrary, for the interdigitated design, it was influenced by the shoulder width. Finally, experiments were conducted to validate the simulation results.     

Performance evaluation of printed LiCoO2 cathodes with PVDF-HFP gel electrolyte for lithium ion microbatteries

In order to improve the discharge capacity in lithium ion microbatteries, a thick-film cathode was fabricated by a screen printing using LiCoO₂ pastes. The printed cathode showed a different discharge curves when the cell was tested using various (liquid, gel and solid-state) electrolytes. When a cell test was performed with organic liquid electrolyte, the maximum discharge capacity was 200 μAh cm⁻², which corresponded to approximately 133 mAh g⁻¹ when the loading weight of LiCoO₂ was calculated. An all-solid-state microbattery could be assembled using sputtered LiPON electrolyte, an evaporated Li anode, and printed LiCoO₂ cathode films without delamination or electrical problems. However, the highest discharge capacity showed a very small value (7 μAh cm⁻²). This problem could be improved using a poly(vinylidene fluoride-hexafluoro propylene) (PVDF-HFP) gel electrolyte, which enhanced the contact area and adhesion force between cathode and electrolyte. The discharge value of this cell was measured as approximately 164 μAh cm⁻² (≈110 mAh g⁻¹). As the PVDF-HFP electrolyte had a relatively soft contact property with higher ionic conductance, the cell performance was improved. In addition, the cell can be fabricated in a leakage-free process, which can resolve many safety problems. According to these results, there is a significant possibility that a film prepared using the aforementioned paste with screen printing and PVDF-HFP gel electrolyte is feasible for a microbattery.     

The electrochemical performance of lithium–sulfur batteries with LiClO4 DOL/DME electrolyte

The electrochemical performance of lithium–sulfur batteries with LiClO₄ DOL/DME as electrolyte was investigated. Impedance and SEM analysis indicated that too high content of DME(Dimethoxy ethane) in electrolyte could raise the interfacial resistance of battery due to the impermeable layer formed on the surface of the sulfur cathode, which led to bad cycle performance, while the increase of DOL(1,3-dioxolane) could change those phenomena. The optimal composition of electrolyte was DME:DOL = 2:1 (v/v). With this electrolyte, the lithium–sulfur battery obtained a high initial discharge capacity of 1,200 mA h g^?1 and still remained 800 mA h g^?1 after 20 cycles.     

MnO2 cathode in an aqueous Li2SO4 solution for battery applications

A manganese dioxide (MnO₂) cathode with zinc (Zn) as the anode has been investigated using lithium sulphate (Li₂SO₄) as an electrolyte. Previously we demonstrated that cells comprising MnO₂ and lithium hydroxide (LiOH) as an electrolyte can be made rechargeable to over one-electron capacity with a discharge capacity of 150 mAh g⁻¹. Here we have extended our work to assess Li₂SO₄ as an electrolyte and have found that the battery is not rechargeable. Based on the electrochemical (discharge/charge) performance and the products formed following discharge and charge, the mechanism proposed for the sulphate-based media is one of proton insertion into the MnO₂ cathode, rather than the lithium ion insertion observed for the LiOH electrolyte. The addition of bismuth species to the Li₂SO₄-based cell results in a transition to rechargeable behaviour. This is believed to be due to the influence of Bi ions on the formation of soluble Mn³⁺ soluble intermediates. However, the coulombic efficiency of the cell diminishes rapidly with repeated charge/discharge cycles. This confirms that the nature of the Li-containing electrolyte has a marked influence on the electrochemistry of the cell.     

A printed circuit board approach to measuring current distribution in a fuel cell

A new method of measuring current distribution in a polymer electrolyte fuel cell of active area 100cm2 has been demonstrated, using a printed circuit board (PCB) technology to segment the current collector and flow field. The PCB technique was demonstrated to be an effective approach to fabricating a segmented electrode and provide a useful tool for analysing cell performance at different reactant gas flow rates and humidification strategies. In this initial chapter of work with the segmented cell, we describe measured effects on current distribution of cathode and anode gas stream humidification levels in a hydrogen/air cell, utilizing a NafionTM 117 membrane and single serpentine channel flow fields, and operating at relatively high gas flow rates. Effects of the stoichiometric flow of air are also shown. A clear trend is seen, apparently typical for a thick ionomeric membrane, of lowering in membrane resistance down the flow channel, bringing about the highest local current density near the air outlet. This trend is reversed at low stoichiometric flows of air. At an air flow rate less than three times stoichiometry, the local performance starts to drop significantly from inlet to outlet, as local oxygen concentration drop overshadows the lowering in resistance along the direction of flow.     

AlF3-modified LiCoPO4 for an advanced cathode towards high energy lithium-ion battery

Surface-interface reaction between the electrode and electrolyte plays a key role in lithium-ion storage properties, especially for high voltage cathode such as LiCoPO₄ and Ni-riched cathode. Generally, surface modification is an effective method to improve the electrochemical performance of electrode materials. Herein, in order to revise the LiCoPO₄ cathode with desirable properties, uniform AlF₃-modified LiCoPO₄ (LiCoPO₄@AlF₃) cathode materials in nano-sized distribution are synthesized. XRD result indicates that there is no structural transformation observed after AlF₃ coating. TEM characterization and XPS analysis reveal that the surface of LiCoPO₄ particle is coated by a nano-sized uniform AlF₃ layer. Further, the electrochemical results indicate that AlF₃ layer significantly improves the cycling and rate performances of LiCoPO₄ cathode within the voltage range of 3.0–5.0 V. After a series of optimization, 4 mol% AlF₃-coated LiCoPO₄ material exhibits the best properties including an initial discharge capacity of 159 mA h g^?1 at 0.1 C with 91% capacity retention after 50 cycles, especially a discharge capacity of 90 mA h g^?1 can be obtained at 1 C rate. CV curves indicate that the polarization of cathode is reduced by AlF₃ layer and EIS curves reveal that AlF₃ layer relieves the increase of resistance to facilitate Li-ion transfer at the interface between electrode and electrolyte during the cycling process. The enhanced electrochemical performances are attributed to that the AlF₃ layer can stabilize the interface between the cathode and electrolyte, form steady SEI film and suppress the electrolyte continuous decomposition at 5 V high voltages. This feasible strategy and novel characteristics of LiCoPO₄@AlF₃ could promise the prospective applications in the stat-art of special lithium-ion battery with high energy and/or power density.     

A parametric study of a platinum ruthenium anode in a direct borohydride fuel cell

Data on the performance of a direct borohydride fuel cell (DBFC) equipped with an anion exchange membrane, a Pt–Ru/C anode and a Pt/C cathode are reported. The effect of oxidant (air or oxygen), borohydride and electrolyte concentrations, temperature and anode solution flow rate is described. The DBFC gives power densities of 200 and 145 mW cm⁻² using ambient oxygen and air cathodes respectively at medium temperatures (60 °C). The performance of the DBFC is very good at low temperatures (ca. 30 °C) using modest catalyst loadings of 1 mg cm⁻² for anode and cathode. Preliminary data indicate that the cell will be stable over significant operating times.     

Hexagonal boron nitride nanosheet/carbon nanocomposite as a high-performance cathode material towards aqueous asymmetric supercapacitors

The two-dimensional hexagonal boron nitride (h-BN) has garnered tremendous interest due to its unique mechanical, thermal and electronic properties. However, the application of h-BN has been restricted as electrode materials for supercapacitors because of its wide band gap and rather low conductivity. Herein, a carbon-modified hexagonal boron nitride nanosheet (h-BN/C) nanocomposite is prepared through a facile and scalable solid-state reaction. Interestingly, the h-BN/C nanocomposite as cathode material exhibits a pair of distinct and reversible redox peaks in 2?M KOH aqueous electrolyte. Because of the enhanced electrical conductivity derived from the modified carbon and the increased specific surface area, the h-BN/C nanocomposite presents a high specific capacitance of 250?F?g^?1 at the current density of 0.5?A?g^?1. More importantly, the fabricated aqueous asymmetric supercapacitor with the h-BN/C as cathode and activated carbon as anode displays an operating voltage of 1.45?V, an energy density of 17?Wh?kg^?1 at a power density of 245?W?kg^?1, and high stability up to 1000 cycles. Therefore, h-BN/C nanocomposite would promisingly be a cathode material for aqueous asymmetric supercapacitors.     

A high-capacity lithium–air battery with Pd modified carbon nanotube sponge cathode working in regular air

We report a lithium–air battery with a free-standing, highly porous Pd-modified carbon nanotube (Pd–CNT) sponge cathode. The Pd-CNT sponge was synthesized through a chemical vapor deposition growth followed with an electrochemical deposition process. To build a whole lithium–air battery, the air cathode is integrated with a ceramic electrolyte-protected lithium metal anode and non-volatile ionic liquid electrolyte. The lithium anode is stable during the operation and long-time storage and the ionic liquid is chemically inert. By controlling the amount of ionic liquid electrolyte, the sponge is wet but not fulfilled by the electrolyte. Such configuration offers a tricontinuous passage for lithium ions, oxygen and electrons, which is propitious to the discharge reaction. In addition, the existence of Pd nanoparticles improves the catalytic reactivity of the oxygen reduction reaction. The battery is durable to any humidity level and delivers a capacity as high as 9092 mA h g⁻¹.     

A microbial fuel cell using manganese oxide oxygen reduction catalysts

Microbial fuel cells (MFCs) are a potential method for enhanced water and waste treatment, which offer the additional benefit of energy generation. Manganese oxide was prepared by a simple chemical oxidation using potassium permanganate. Carbon-supported manganese oxide nanoparticles were successfully characterised as cathode materials for MFCs. The manganese oxide particles when used in a two-chamber MFC, using inoculum from an anaerobically digested sewage sludge, were found to exhibit similar oxygen reduction performance to that in separate electrochemical tests. MFC tests were conducted in a simple two chamber cell using aqueous air-saturated catholytes separated from the anode chamber by a Nafion membrane. MFC peak power densities were ca. 161 mW m^?2 for MnO _x /C compared to 193 mW m^?2 for a benchmark Pt/C, in neutral solution at room temperature. The catalyst materials demonstrated good stability in the 7.0–10.0 pH range. Theoretical (IR free) peak power densities were 937 mW m^?2 for MnO _x /C compared with 1037 mW m^?2 for Pt/C in the same experimental conditions: showing the MFCs performances can easily be improved by using more favourable conditions (more conductive electrolyte, improved cathode catalyst etc.). Our studies indicated that the use of our low cost MnO _x /C catalysts is of potential interest for the future application of MFC systems.     

High speed zinc electrowinning system using a hydrogen anode and a rotating aluminium disc cathode

The performance of a novel high speed zinc electrowinning system using a hydrogen anode and an aluminium rotating disc cathode (1 m diam.) was investigated under various experimental conditions. This new type of zinc electrowinning system was continuously operated at a current density of 70 A dm^–2, which is twelve times higher than that usually employed. Current efficiency is 90% at 50 A dm^–2 in an electrolyte containing 60 g dm^–3 Zn + 160 g dm^–3 H₂SO₄, the zinc purity being at least 99.999%. The energy usage of the system is 1650 kWh per tonne of zinc, 380 m³ of H₂ gas being required.     

Zinc deposition and dissolution in sulfuric acid onto a graphite–resin composite electrode as the negative electrode reactions in acidic zinc-based redox flow batteries

Electrodeposition and dissolution of zinc in sulfuric acid were studied as the negative electrode reactions in acidic zinc-based redox flow batteries. The zinc deposition and dissolution is a quasi-reversible reaction with a zinc ion diffusion coefficient of 4.6 × 10^?6 cm² s^?1 obtained. The increase of acid concentration facilitates an improvement in the kinetics of zinc electrodeposition–dissolution process. But too high acid concentration would result in a significant decrease in charge efficiency. The performance of the zinc electrode in a three-electrode system with magnetic stirring was also studied as a function of Zn(II) ion concentration, sulfuric acid concentration, current density, and the addition of additives in 1 M H₂SO₄ medium. The optimum electrolyte composition is suggested at high zinc(II) concentration (1.25 M) and moderate sulfuric acid concentration (1.0–1.5 M) at a current density range of 20–30 mA cm^?2. Whether in acid-free solution or in sulfuric acid solution with or without additives, no dendrite formation is observed after zinc electrodeposition for 1 h at 20 mA cm^?2. The energy efficiency is improved from 77 % in the absence of additives in 1 M H₂SO₄ medium to over 80 % upon the addition of indium oxide or SLS–Sb(III) combined additive as hydrogen suppressants.     

Optimization of operating parameters of a direct methanol fuel cell and physico-chemical investigation of catalyst–electrolyte interface

A physico-chemical investigation of catalyst–Nafion® electrolyte interface of a direct methanol fuel cell (DMFC), based on a Pt–Ru/C anode catalyst, was carried out by XRD, SEM-EDAX and TEM. No interaction between catalyst and electrolyte was detected and no significant interconnected network of Nafion micelles inside the composite catalyst layer was observed. The influence of some operating parameters on the performance of the DMFC was investigated. Optimal conditions were 2 M methanol, 5 atm cathode pressure and 2–3 atm anode pressure. Power densities of 110 and 160 mW cm⁻² were obtained for operation with air and oxygen, respectively, at temperatures of 95–100°C and with 1 mg cm⁻² Pt loading.