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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Synthesis of Platin/Carbon XC72R Nanocomposite Using as Electrocatalyst for Direct Methanol Fuel Cells

Platinum/Carbon XC72R （Pt/C） nanocomposite was synthesized in-situ by polyol method. Precursor of hexahydrated chloroplatinic acid H2PtCI6-6H2O was reduced by EG （ethylene glycol） so as to form Pt nanoparticles which were deposited on the surface of carbon. Pt/C composites （treated or untreated carbon） were synthesized at pH - 6.5 and pH = 11. The XRD pattern of Pt/C showed peaks assigned to the crystalline structure of Pt and carbon. TEM images showed that Pt nanoparticles on carbon were ultrafine spheres and the particles obtained sizes from 2 to 6 nm which are mostly concentrated on size of 3 nm. The electrocatalytic activity of Pt/C catalysts toward methanol oxidation was examined by CV （cyclic voltammetry）. Pt/treated XC72R （pH = 11） at potential （0.69 V） exhibited better electroactivity （628 mA/mg Pt）.

High Proton Conducting SPEEK/SiO_2/ PWA Composite Membranes for Direct Methanol Fuel Cells

Sulfonated polyether ether ketone （SPEEK） based composite membranes for direct methanol fuel cell （DMFC） application were prepared by sol-gel reaction of tetraethoxysilane （TEOS） in the SPEEK matrix and the incorporation of phosphotungstic acid （PWA）.The conductivity of the developed membranes was determined by impedance spectroscopy and the methanol permeability through the membranes was obtained from diffuseness experiments.The SEM images show that the addition of SiO2 and the covalent cross-linking structure lead to fine PWA particles and more uniformly dispersion.The swelling of composite membranes remains in the range of 5%-8% at 30-90 ℃ and the effusion of PWA reduces significantly.The composite membranes show a good balance in higher proton conductivity and lower methanol permeation.The cell with composite membrane has higher open circuit voltage（0.728 V） and higher peak power density（45 mW/cm2） than that with Nafion117.

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.

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.

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.

Synthesis and characterization of Pt-MoO_x-TiO_2 electrodes for direct ethanol fuel cells

To enhance the CO-tolerance performance of anode catalysts for direct ethanol fuel cells,carbon nanotubes were modified by titanium dioxide （donated as CNTs@TiO2） and subsequently served as the support for the preparation of Pt/CNTs@TiO2 and Pt-Mo/CNTs@TiO2 electrocatalysts via a UV-photoreduction method.The physicochemical characterizations of the catalysts were carried out by using X-ray diffraction （XRD）,transmission electron microscopy （TEM）,X-ray photoelectron spectroscopy （XPS）,and infrared spectroscopy of adsorbed probe ammonia molecules.The electrocatalytic properties of the catalysts for methanol oxidation were investigated by the cyclic voltammetry technique.The results show that Pt-Mo/CNTs@TiO2 electrode exhibits the highest performance in all the electrodes.It is explained that,the structure,the oxidation states,and the acid-base properties of the catalysts are influenced due to the strong interaction between Ti and Mo species by adding TiO2 and MoOx to the Pt-based catalysts.

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.

Performance evaluation of the incorporation of different wire meshes in between perforated current collectors and membrane electrode assembly on the Passive Direct methanol fuel cell

Passive Direct methanol fuel cells(DMFC)are more suitable for charging small capacity electronic devices.In passive DMFC,the fuel and oxidant are supplied by diffusion and natural convection process on the anode and cathode sides respectively.Current collectors(CC)play a vital importance in fuel cell performance.This paper presents the combined impact of perforated and wire mesh current collectors(WMCC)on passive DMFC performance.Three types of open ratios of perforated current collectors(PCC),such as 45.40%,55.40%and 63.40%and two types of wire mesh current collectors with open ratios of 38.70%and 45.40%were chosen for the experimental work.A combination of TaguchiL9 rule is considered.A combination of three PCC and two WMCC on both anode and cathode was used.Methanol concentration was varied from 1 mol·L^(-1)-5 mol·L^(-1)for nine combinations of PCC and WMCC.From the experimental results,it is noticed that the combination of PCC and WMCC with an open ratio of 55.40%and 38.70%incorporated passive DMFC produced peak power density at 5 mol·L^(-1)of methanol concentration.The passive DMFC performance was evaluated in terms of maximum power density and maximum current density.The combined current collectors of PCC and WMCC open ratios of 55.40%+38.70%have more stable voltage than single PCC of open ratio 63.40%at 4 mol·L^(-1)of methanol concentration.