The Effects of the Geometry of a Current Collector with an Equal Open Ratio on Output Power of a Direct Methanol Fuel Cell

The open ratio of a current collector has a great impact on direct methanol fuel cell(DMFC)performance.Although a number of studies have investigated the influence of the open ratio of DMFC current collectors,far too little attention has been given to how geometry(including the shape and feature size of the flow field)affects a current collector with an equal open ratio.In this paper,perforated and parallel current collectors with an equal open ratio of 50%and different feature sizes are designed,and the corresponding experimental results are shown to explain the geometry effects on the output power of the DMFC.The results indicate that the optimal feature sizes are between 2 and 2.5 mm for both perforated and parallel flow field in the current collectors with an equal open ratio of 50%.This means that for passive methanol fuel cells,to achieve the highest output power,the optimal feature size of the flow field in both anode and cathode current collectors is between 2 and 2.5 mm under the operating mode of this experiment.The effects of rib and channel position are also investigated,and the results indicate that the optimum pattern depends on the feature sizes of the flow field.

Upcycling end of lithium cobalt oxide batteries to electrocatalyst for oxygen reduction reaction in direct methanol fuel cell via sustainable approach

Recycling spent lithium-ion batteries(SLIBs)has become essential to preserve the environment and reclaim vital resources for sustainable development.The typical SLIBs recycling concentrated on separating valuable components had limitations,including high energy consumption and complicated separation processes.This work suggests a safe hydrometallurgical process to recover usable metallic cobalt from depleted LiCoO_(2)batteries by utilizing citric acid as leachant and hydrogen peroxide as an oxidizing agent,with ethanol as a selective precipitating agent.The anode graphite was also recovered and converted to graphene oxide(GO).The above components were directly resynthesized to cobaltintegrated nitrogen-doped graphene(Co@NG).The Co@NG showed a decent activity towards oxygen reduction reaction(ORR)with a half-wave potential of 0.880 V vs.RHE,almost similar to Pt/C(0.888 V vs.RHE)and with an onset potential of 0.92 V vs.RHE.The metal-nitrogen-carbon(Co-N-C)having the highest nitrogen content has decreased the barrier for ORR since the reaction was enhanced for Co@NG-800,as confirmed by density functional theory(DFT)simulations.The Co@NG cathode catalyst coupled with commercial Pt-Ru/C as anode catalyst exhibits excellent performance for direct methanol fuel cell(DMFC)with a peak power density of 34.7 mW cm^(-2)at a discharge current density of120 m A cm^(-2)and decent stability,indicating the promising utilization of spent battery materials in DMFC applications.Besides,lithium was recovered from supernatant as lithium carbonate by coprecipitation process.This work avoids sophisticated elemental separation by utilizing SLIBs for other renewable energy applications,lowering the environmental concerns associated with recycling.

Advances and challenges of methanol-tolerant oxygen reduction reaction electrocatalysts for the direct methanol fuel cell

Methanol cross-over effects from the anode to the cathode are important parameters for reducing catalytic performance in direct methanol fuel cells.A promising candidate catalyst for the cathode in direct methanol fuel cells must have excellent activity toward oxygen reduction reaction and resistance to methanol oxidation reaction.This review focuses on the methanol tolerant noble metal-based electrocatalysts,including platinum and palladium-based alloys,noble metal–carbon based composites,transition metal-based catalysts,carbon-based metal catalysts,and metal-free catalysts.The understanding of the correlation between the activity and the synthesis method,electrolyte environment and stability issues are highlighted.For the transition metal-based catalyst,their activity,stability and methanol tolerance in direct methanol fuel cells and comparisons with those of platinum are particularly discussed.Finally,strategies to enhance the methanol tolerance and hinder the generation of mixed potential in direct methanol fuel cells are also presented.This review provides a perspective for future developments for the scientist in selecting suitable methanol tolerate catalyst for oxygen reduction reaction and designing high-performance practical direct methanol fuel cells.

Structural optimization and performance trade-off strategies for semi-crystalline sulfonated poly(arylene ether ketone) membranes in high-concentration direct methanol fuel cells

Direct methanol fuel cells(DMFCs) have attracted extensive attention as promising next-generation energy conversion devices. However, commercialized proton exchange membranes(PEMs) hardly fulfill the demand of methanol tolerance for DMFCs employing high-concentration methanol solutions.Herein, we report a series of semi-crystalline poly(arylene ether ketone) PEMs with ultra-densely sulfonic-acid-functionalized pendants linked by flexible alkyl chains, namely, SL-SPEK-x(where x represents the molar ratio of the novel monomer containing multiple phenyl side chain to the bisfluoride monomers). The delicate structural design rendered SL-SPEK-x membranes with high crystallinity and well-defined nanoscale phase separation between hydrophilic and hydrophobic phases. The reinforcement from poly(ether ketone) crystals enabled membranes with inhibited dimensional variation and methanol penetration. Furthermore, microphase separation significantly enhanced proton conductivity. The SL-SPEK-12.5 membrane achieved the optimum trade-off between proton conductivity(0.182 S cm^(-1), 80 ℃), water swelling(13.6%, 80 ℃), and methanol permeability(1.6 × 10^(-7)cm~2 s^(-1)). The DMFC assembled by the SL-SPEK-12.5 membrane operated smoothly with a 10 M methanol solution, outputting a maximum power density of 158.3 mW cm^(-2), nearly twice that of Nafion 117(94.2 mW cm^(-2)). Overall, the novel structural optimization strategy provides the possibility of PEMs surviving in high-concentration methanol solutions, thus facilitating the miniaturization and portability of DMFC devices.

Stable NiPt-Mo_(2)C active site pairs enable boosted water splitting and direct methanol fuel cell

Sluggish kinetics of methanol oxidation reaction(MOR)and alkaline hydrogen evolution reaction(HER)even on precious Pt catalyst impede the large-scale commercialization of direct methanol fuel cell(DMFC)and water electrolysis technologies.Since both of MOR and alkaline HER are related to water dissociation reaction(WDR),it is reasonable to invite secondary active sites toward WDR to pair with Pt for boosted MOR and alkaline HER activity on Pt.Mo_(2)C and Ni species are therefore employed to engineer NiPt-Mo_(2)C active site pairs,which can be encapsulated in carbon cages,via an in-situ self-confinement strategy.Mass activity of Pt in NiPt-Mo_(2)C@C toward HER is boosted to11.3 A mg_(pt)^(-1),33 times higher than that of Pt/C.Similarly,MOR catalytic activity of Pt in NiPt-Mo_(2)C@C is also improved by 10.5 times and the DMFC maximum power density is hence improved by 9-fold.By considering the great stability,NiPt-Mo_(2)C@C exhibits great practical application potential in DMFCs and water electrolysers.

Preparation of high active Pt/C cathode electrocatalyst for direct methanol fuel cell by citrate-stabilized method

Platinum nanoparticles supported on carbons（Pt/C,60%,mass fraction） electrocatalysts for direct methanol fuel cell（DMFC） were prepared by citrate-stabilized method with different reductants and carbon supports.The catalysts were characterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM） and cyclic voltammetry（CV）.It is found that the size of Pt nanoparticles on carbon is controllable by citrate addition and reductant optimization,and the form of carbon support has a great influence on electrocatalytic activity of catalysts.The citrate-stabilized Pt nanoparticles supported on BP2000 carbon,which was reduced by formaldehyde,exhibit the best performance with about 2 nm in diameter and 66.46 m2/g（Pt） in electrocatalytic active surface（EAS） area.Test on single DMFC with 60%（mass fraction） Pt/BP2000 as cathode electrocatalyst showed maximum power density at 78.8 mW/cm2.

Nanostructured electrocatalytic materials and porous electrodes for direct methanol fuel cells

Direct methanol fuel cells （DMFCs） are promising for use in portable devices because of advantages such as high fuel energy density, low working temperature and low emission of pollutants. Nanotechnology has been used to improve the performance of DMFCs. Catalytic materials composed of small, metallic particles with unique nanostructure supparted on carbons or metal oxides have been widely investigated for use in DMFCs. Despite our increased understanding of this type of fuel cell, many challenges still remain. This paper reviews the current developments of nanostructured elec- trocatalytic materials and porous electrodes for use in DMFCs. In particular, this review focuses on the synthesis and characterization of nanostructured catalysts and supporting materials. Both computational and experimental approaches to optimize mass transportation in porous electrodes of DMFCs, such as theoretical modeling of internal transfer processes and preparation of functional structures in membrane electrode assemblies, are introduced.

Controllable fabrication of ordered Pt nanorod array as catalytic electrode for passive direct methanol fuel cells

The nanostructure of the catalytic electrode has a great effect on the performance of direct metha- nol fuel cells （DMFCs）, including catalyst utilization, precious metal loading, water balance, and oxygen mass transfer. In this work, ordered arrays of platinum nanorods with different diameters were directly grown onto microporous layers by electrodeposition via a sacrificial template, and were used as the catalytic cathode for passive DMFCs. The use of these ordered electrodes led to a dramatic decrease in cathode polarization behavior. The maximum power density of passive DMFCs fabricated with catalytic electrodes of 200 and 100 am Pt nanorod arrays were 17.3 and 12.0 mW/cm2, respectively. The obtained improvement in performance was ascribed to the fact that the ordered nanostructured electrode not only increased the electrochemically active surface area and the catalyst utilization, but also enhanced oxygen mass transfer and water balance in the system.

A Fe-N-C catalyst with highly dispersed iron in carbon for oxygen reduction reaction and its application in direct methanol fuel cells

Exploring non‐precious metal catalysts for the oxygen reduction reaction （ORR） is essential for fuel cells and metal–air batteries. Herein, we report a Fe‐N‐C catalyst possessing a high specific surface area （1501 m2/g） and uniformly dispersed iron within a carbon matrix prepared via a two‐step pyrolysis process. The Fe‐N‐C catalyst exhibits excellent ORR activity in 0.1 mol/L NaOH electrolyte （onset potential, Eo=1.08 V and half wave potential, E1/2=0.88 V vs. reversible hydrogen electrode） and 0.1 mol/L HClO4 electrolyte （Eo=0.85 V and E1/2=0.75 V vs. reversible hydrogen electrode）. The direct methanol fuel cells employing Fe‐N‐C as the cathodic catalyst displayed promising per‐formance with a maximum power density of 33 mW/cm2 in alkaline media and 47 mW/cm2 in acidic media. The detailed investigation on the composition–structure–performance relationship by X‐ray diffraction, X‐ray photoelectron spectroscopy and Mo-ssbauer spectroscopy suggests that Fe‐N4, together with graphitic‐N and pyridinic‐N are the active ORR components. The promising direct methanol fuel cell performance displayed by the Fe‐N‐C catalyst is related to the intrinsic high catalytic activity, and critically for this application, to the high methanol tolerance.

Proton-Exchange Sulfonated Poly （ether ether ketone） （SPEEK）/SiOx-S Composite Membranes in Direct Methanol Fuel Cells

A sulfonated poly（ether ether ketone） （SPEEK） membrane with a fairly high degree of sulfonation （DS） can swell excessively and even dissolve at high temperature. To solve these problems, insolvable functionalized silica powder with sulfonic acid groups （SiOx-S） was added into the SPEEK matrix （DS = 55.1%） to prepare SPEEK/ SiOx-S composite membranes. The decrease in both the swelling degree and the methanol permeability of the membranes was a dose-dependent result of addition of the SiOx-S powder. Pure SPEEK membrane swelled 52.6% at 80℃, whereas the SPEEK/SiOx-S （15%, by mass） membrane swelled only 27.3% at the same temperature. From room temperature to 80℃, all SPEEK/SPEEK/SiOx-S composite membranes had methanol permeability of about one order of magnitude lower than that ofNafion115. Compared with pure SPEEK membranes, the addition of the SiOx-S powder not only leads to higher proton conductivity, but also increases the dimensional stability at higher temperatures, and greater proton conductivity can be achieved at higher temperature. The SPEEK/SiO4-S （20%, by mass） membrane could withstand temperature up to 145℃, at which in 100% relative humidity （RH） its proton conductivity exceeded slightly that of Nafion 1 15 membrane and reached 0.17 S·cm^-1, while pure SPEEK membrane dissolved at 90℃. The SPEEK/SiOx-S composite membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.

Cathode catalytic dependency behavior on ionomer content in direct methanol fuel cells

Cathode catalyst layers （CLs） with varying ionomer （Nation） contents were prepared and the direct methanol fuel cell structure and catalytic behavior were investigated as a function of ionomer content. CL roughness and thickness increased with increasing Nation content. Contact angle measurements determined that CL hydrophilicity also increased as a function of Nation content. Poor bonding between the CL, microporous layer, and the proton exchange membrane was obtained when the ionomer content was too low. The electrochemical surface areas （ESAs） were found to increase with increasing Nation content before reaching an asymptote at elevated loading levels. However, upon increasing the ionomer content above 30 wt.%, the water and oxygen mass transler properties were difficult to control. Considering the above conditions, N30 （：30 wt.% Nation） was found to be the optimal level to effectively extend the three-phase boundaries and enhance cell performance.

On-line Measurement for Ohmic Resistance in Direct Methanol Fuel Cell by Current Interruption Method

Electrochemical impedance spectroscopy (EIS) is widely used in fuel cell impedance analysis. However, for ohmic resistance (R Ω), EIS has some disadvantages such as long test period and complex data analysis with equivalent circuits. Therefore, the current interruption method is explored to measure the value of RΩ in direct methanol fuel cells (DMFC) at different temperatures and current densities. It is found that RΩ decreases as temperature increase, and decreases initially and then increases as current density increases. These results are consistent with those measured by the EIS technique. In most cases, the ohmic resistances with current interruption (R iR ) are larger than those with EIS (R EIS ), but the difference is small, in the range from –0.848% to 5.337%. The errors of R iR at high current densities are less than those of R EIS . Our results show that the R iR data are reliable and easy to obtain in the measurement of ohmic resistance in DMFC.

Performance analysis and fuzzy neural networks modeling of direct methanol fuel cell

This paper introduces the effects of cell operating temperature, methanol concentration and airflow rate, respectively, on the performance of direct methanol fuel cell （DMFC）. A novel method based on fuzzy neural networks identification technique is proposed to establish the performance model of DMFC. Three dynamic performance models of DMFC under the influences of cell operating temperature, methanol concentration, and airflow rate are identified and established separately. Simulation results show that modeling using fuzzy neural networks identification is satisfactory with high accuracy. It is applicable to DMFC control systems.

Effects of environmental factors on corrosion behaviors of metal-fiber porous components in a simulated direct methanol fuel cell environment

Abstract： To enable the use of metallic components in direct methanol fuel cells （DMFCs）, issues related to corrosion resistance must be considered because of an acid environment induced by the solid electrolyte. In this study, we report the electrochemical behaviors of metal-fiber-based porous sintered components in a simulated corrosive environment of DMFCs. Three materials were evaluated： pure copper, AISI304, and AISI316L. The environmental factors and related mechanisms affecting the corrosion behaviors were analyzed. The results demonstrated that AISI316L exhibits the best performance. A higher SO4^2- concentration increases the risk of material corrosion, whereas an increase in methanol concentration inhibits corrosion. The morphological features of the corroded samples were also characterized in this study.

Pt-Ru Catalysts Prepared by a Modified Polyol Process for Direct Methanol Fuel Cells

Supported PtRu/C catalysts used in direct methanol fuel cells (DMFCs) were prepared by a new modified polyol method. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and cyclic voltammograms (CVs) were carried out to characterize the morphology, composition and the electrochemical properties of the PtRu/C catalyst. The results revealed that the PtRu nanoparticles with small average particle size (≈2.5 nm), and highly dispersed on the carbon support. The PtRu/C catalyst exhibited high catalytic activity and anti poisoned performance than that of the JM PtRu/C. It is imply that the modified polyol method is efficient for PtRu/C catalyst preparation.

The Catalysis of NAD^+ on Methanol Anode Oxidation Electrode for Direct Methanol Fuel Cell

A tentative idea of developing a liquid-catalytic system on methanol anode oxidation was proposed by analyzing the characteristics of methanol anode oxidation in direct methanol fuel cell. The kinetics of methanol oxidation at a glassy carbon electrode in the presence of nicotinamide adenine dinucleotide (NAD +) was investigated. It is found that the current density of methanol oxidation increases greatly and the electrochemical reaction impedance reduces obviously in the presence of NAD + compared with those in the absence of NAD +. The catalytic activity of NAD + is sensitive to temperature. When the temperature preponderates over 45℃, NAD + is out of function of catalysis for methanol oxidation, which is probably due to the denaturation of NAD + at a relatively high temperature.

Preparation and characterization of polyvinylchloride membrane embedded with Cu nanoparticles for electrochemical oxidation in direct methanol fuel cell

Copper nanoparticles were prepared by the chemical reduction method.These copper particles were embedded into the polyvinylchloride(PVC)matrix as support and used as an electrode(PVC/Cu)for the oxidation of methanol fuel for improving the current response.The PVC/Cu electrodes were characterized by thermal gravimetric analysis(TGA)for thermal stability of the electrode,X-ray diffraction(XRD)for identification of copper nanoparticles in the electrode,Fourier transform infrared spectroscopy(FTIR)to identify the interaction between PVC and Cu and scan electron microscopy(SEM)with EDAX for the morphology of the electrode.The electrocatalytic activity of the electrode was characterized by the cyclic voltammetry,linear sweep voltammetry,and chronoamperometry techniques.An increase in the electrode activity was observed with the increase of copper quantity from 0.18 g(PVC/Cu-0.18 g)to 0.24 g(PVC/Cu-0.24 g)and the maximum was found at 0.24 g of copper in the electrode.Also,it was observed that the electrode achieved the maximum catalytic current in 0.5 mol/L CH3OH+1 mol/L Na OH solution.FTIR identified that water molecules,C—H group,copper nanoparticle and its oxide were available in the electrode.SEM images with EDAX showed that copper particles were properly embedded in the polyvinylchloride matrix.

A comparison of hydrocarbons emission from engine running 85￣＃gasoline and M－100 methanol fuel

Increasing global interest in methanoi fuel has led us to investigate the exhaust emissionsof its engine. Analysis of its inorganic and organic emissions. such as CO. NO_x and hydrocarbons(total HC) have been widely reported. This paper presents an analysis of more than 20 kinds ofhydrocarbons in the emissions obtained from a spark-ignition Shanghai car running 85# gasoline anda comparison with emission from a Santana test car running M-100 methanol fuel. A set ofenrichment method has also been described. Test results show that at the current stage of methanolengine development the concentration of individual hydrocarbon including some poisonous substancesis lower than those of normal gasoline engine.

Effects of Sputtering Parameters on the Performance of Sputtered Cathodes for Direct Methanol Fuel Cells

Plasma sputtering deposition techniques are good candidates for the fabrication of electrodes used for direct methanol fuel cells （DMFCs）. A house-made plasma sputtering system was used to deposit platinum of 0.1 mg/cm^2 onto un-catalyzed gas diffusion layers （GDLs） to form a Pt catalyzed cathode at different radio frequency （RF） powers and sputtering-gas pressures. The sputtered cathodes were assembled in custom-made membrane electrode assemblies （MEAs） with a commercial anode and tested for the electrical performance of the single cell. A custommade MEA with a sputtering prepared cathode was compared with that of a reference membrane electrode assembly made of commercial JM （Johnson Mattey） catalysts （Pt loading per electrode of 0.5 mg/cm^2） under passive methanol supply, ambient temperature and air-breathing conditions. The results showed that the cathode prepared at an input power of 110 W and sputtering-gas pressure of 5.3 Pa exhibited the best cell performance and highest Pt utilization efficiency, which was due to the miniaturization of the Pt particles and formation of the porous catalyst layer. Although the single cell performance of the commercial cathode was better than all the sputtering fabricated cathodes, the Pt utilization efficiency of all the sputtered cathodes was higher than that of the commercial cathode.

Carbon Nanotubes Supported Pt-Ru-Ni as Methanol Electro-Oxidation Catalyst for Direct Methanol Fuel Cells

Carbon nanotubes （CNTs） supported Pt-Ru and Pt-Ru-Ni catalysts were prepared by chemical reduction of metal precursors with sodium borohydride at room temperature. The crystallographic properties and composition of the catalysts were characterized by X-ray diffraction （XRD） and energy dispersive X-ray （EDX） analysis, and the catalytic activity and stability for methanol electro-oxidation were measured by electrochemical impedance spectroscopy （EIS）, linear sweep voltammetries （LSV）, and chronoamperometry （CA）. The results show that the catalysts exhibit face-centered cubic （fcc） structure. The particle size of Pt-Ru-Ni/CNTs catalyst is about 4.8 nm. The catalytic activity and stability of the Pt-Ru-Ni/CNTs catalyst are higher than those of Pt-Ru/CNTs catalyst.