Multi-objective optimization of the cathode catalyst layer micro-composition of polymer electrolyte membrane fuel cells using a multi-scale,two-phase fuel cell model and data-driven surrogates

Polymer electrolyte membrane fuel cells(PEMFCs)are considered a promising alternative to internal combustion engines in the automotive sector.Their commercialization is mainly hindered due to the cost and effectiveness of using platinum(Pt)in them.The cathode catalyst layer(CL)is considered a core component in PEMFCs,and its composition often considerably affects the cell performance(V_(cell))also PEMFC fabrication and production(C_(stack))costs.In this study,a data-driven multi-objective optimization analysis is conducted to effectively evaluate the effects of various cathode CL compositions on Vcelland Cstack.Four essential cathode CL parameters,i.e.,platinum loading(L_(Pt)),weight ratio of ionomer to carbon(wt_(I/C)),weight ratio of Pt to carbon(wt_(Pt/c)),and porosity of cathode CL(ε_(cCL)),are considered as the design variables.The simulation results of a three-dimensional,multi-scale,two-phase comprehensive PEMFC model are used to train and test two famous surrogates:multi-layer perceptron(MLP)and response surface analysis(RSA).Their accuracies are verified using root mean square error and adjusted R^(2).MLP which outperforms RSA in terms of prediction capability is then linked to a multi-objective non-dominated sorting genetic algorithmⅡ.Compared to a typical PEMFC stack,the results of the optimal study show that the single-cell voltage,Vcellis improved by 28 m V for the same stack price and the stack cost evaluated through the U.S department of energy cost model is reduced by$5.86/k W for the same stack performance.

膜内掺Pt含量对质子交换膜电解水性能与氢渗透的影响

针对质子交换膜电解水制氢中存在的氢渗透安全隐患,该文通过超声喷涂将纳米Pt颗粒负载到膜上,并经过热压制备掺Pt复合膜,以缓解运行中的氢渗透。在保持膜电极总Pt含量不变的条件下,研究膜内不同掺Pt含量对性能与氢渗透的影响。结果表明,通过超声喷涂和热压成功将纳米Pt颗粒负载到膜中,并有效缓解了氢渗透。随着膜内掺Pt含量的增加,氢渗透通量降低,同时由于阴极Pt含量降低、欧姆损失增大,电解性能呈现逐渐降低的趋势。综合考虑氢渗透和电解性能,最佳的掺Pt含量为0.01 mg/cm^(2),在0.1 A/cm^(2)时,氧中氢含量仅为0.82%,与无Pt复合膜相比,氢渗透降低了50.32%,而电解电压仅增加约20 mV。长时间运行电解电压和氧中氢浓度相对较稳定,氧中氢浓度低于氢气爆炸下限。

Pt/WO_3/C nanocomposite with parallel WO_3 nanorods as cathode catalyst for proton exchange membrane fuel cells

Pt/WO3/C nanocomposites with parallel WO3 nanorods were synthesized and applied as the cathode catalyst for proton exchange membrane fuel cells （PEMFCs）. Electrochemical results and single cell tests show that an enhanced activity for the oxygen reduction reaction （ORR） is obtained for the Pt/WO3/C catalyst compared with Pt/C. The higher catalytic activity might be ascribed to the improved Pt dispersion with smaller particle sizes. The Pt/WO3/C catalyst also exhibits a good electrochemical stability under potential cycling. Thus, the Pt/WO3/C catalyst can be used as a potential PEMFC cathode catalyst.

Carbon-supported ultrafine Pt nanoparticles modified with trace amounts of cobalt as enhanced oxygen reduction reaction catalysts for proton exchange membrane fuel cells

To accelerate the kinetics of the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells,ultrafine Pt nanoparticles modified with trace amounts of cobalt were fabricated and decorated on carbon black through a strategy involving modified glycol reduction and chemical etching.The obtained Pt36Co/C catalyst exhibits a much larger electrochemical surface area(ECSA)and an improved ORR electrocatalytic activity compared to commercial Pt/C.Moreover,an electrode prepared with Pt36Co/C was further evaluated under H2-air single cell test conditions,and exhibited a maximum specific power density of 10.27 W mgPt^-1,which is 1.61 times higher than that of a conventional Pt/C electrode and also competitive with most state-of-the-art Pt-based architectures.In addition,the changes in ECSA,power density,and reacting resistance during the accelerated degradation process further demonstrate the enhanced durability of the Pt36Co/C electrode.The superior performance observed in this work can be attributed to the synergy between the ultrasmall size and homogeneous distribution of catalyst nanoparticles,bimetallic ligand and electronic effects,and the dissolution of unstable Co with the rearrangement of surface structure brought about by acid etching.Furthermore,the accessible raw materials and simplified operating procedures involved in the fabrication process would result in great cost-effectiveness for practical applications of PEMFCs.

High-performance proton exchange membrane fuel cell with ultra-low loading Pt on vertically aligned carbon nanotubes as integrated catalyst layer

Reducing a Pt loading with improved power output and durability is essential to promote the large-scale application of proton exchange membrane fuel cells(PEMFCs).To achieve this goal,constructing optimized structure of catalyst layers with efficient mass transportation channels plays a vital role.Herein,PEMFCs with order-structured cathodic electrodes were fabricated by depositing Pt nanoparticles by Ebeam onto vertically aligned carbon nanotubes(VACNTs)growth on Al foil via plasma-enhanced chemical vapor deposition.Results demonstrate that the proportion of hydrophilic Pt-deposited region along VACNTs and residual hydrophobic region of VANCTs without Pt strongly influences the cell performance,in particular at high current densities.When Pt nanoparticles deposit on the top depth of around 600 nm on VACNTs with a length of 4.6μm,the cell shows the highest performance,compared with others with various lengths of VACNTs.It delivers a maximum power output of 1.61 W cm^(-2)(H_(2)/O_(2),150 k Pa)and 0.79 W cm^(-2)(H_(2)/Air,150 k Pa)at Pt loading of 50μg cm^(-2),exceeding most of previously reported PEMFCs with Pt loading of<100μg cm^(-2).Even though the Pt loading is down to 30μg cm^(-2)(1.36 W cm^(-2)),the performance is also better than 100μg cm^(-2)(1.24 W cm^(-2))of commercial Pt/C,and presents better stability.This excellent performance is critical attributed to the ordered hydrophobic region providing sufficient mass passages to facilitate the fast water drainage at high current densities.This work gives a new understanding for oxygen reduction reaction occurred in VACNTs-based ordered electrodes,demonstrating the most possibility to achieve a substantial reduction in Pt loading<100μg cm^(-2) without sacrificing in performance.

Synthesis of Nafion^(■)-stabilized Pt nanoparticles to improve the durability of proton exchange membrane fuel cell

Nafion-stabilized Pt nanoparticle colloidal solution is synthesized through ethylene glycol reduction.Pt/Nafion added with carbon black as electric conduction material（labeled Pt/Nafion-XC72） shows excellent electrochemical property compared with Pt/C.After a 300-cycle discharging durability test,the cell performance of membrane electrode assembly（MEA） with the Pt/Nafion-XC72 and Pt/C catalysts indicates a 29.9% and 92.2% decrease,respectively.The charge transfer resistances of Pt/Nafion-XC72 and Pt/C increase by 27.2% and 101.9%,respectively.The remaining electrochemically active surface area of Pt is about 61.7% in Pt/Nafion-XC72 and about 38.1% in Pt/C after the durability test.The particle size of Pt/C increases from about 5.1 nm to about 10.8 nm but only from 3.6 nm to 5.8 nm in the case of Pt/Nafion-XC72.These data suggest that Pt/Nafion-XC72 as a catalyst can enhance the durability of PEMFCs compared with Pt/C.

Preparation and Optimization of Porous Membrane Electrodes via Gradient Coating in Hydrogen Fuel Cell

Fuel cells are considered to be one of the ideal alternatives to traditional fossil energy conversion devices.Membrane electrodes are the core components in the hydrogen fuel cells.Our work reported the synthesis of the Pt/C catalysts with different Pt loading,and by changing the Nafion content,hot pressing temperature and hot pressing pressure,the catalyst coated membrane(CCM)spraying process was optimized.Moreover,the three-dimensional structure model of the single battery membrane electrode was studied quantitatively,and the porous membrane electrode with gradient distribution was fabricated under optimized processing conditions,with excellent electrical performance.

Electrochemical Study of Lincomycin on Au-PtNPs/nanoPAN/ Chitosan Nanocomposite Membrane and Its Determination in Injections

The Au-Pt alloy nanoparticles（Au-PtNPs） were electrochemically deposited on the surface of polyaniline nanotube（nanoPAN） and chitosan（CS） modified glassy carbon electrode（GCE）. The electrochemical behavior of lincomycin at Au-PtNPs/nanoPAN/CS modified GCE was investigated by cyclic voltammetry, linear sweep voltammetry and chronocoulometry. Cyclic voltammetric experiments show that lincomycin at the nanocomposite membrane modified electrode exhibited a pair of quasi-reversible redox peaks in pH=6.0 PBS. The membrane could accelerate the electron transfer of lincomycin on the electrode and significantly enhance the peak current. In a range of 3.0-100.0 mg/L, the reductive peak current of lincomycin at 0.42 V was linearly related to its concentration and the linear regression equation was ip,c=0.2703ρ-0.0042（ip, c： μA; ρ： mg/L; r=0.998, n=7） with a detection limit of 1.0 mg/L（S/N =3）. Compared with other methods, this method exhibited many advantages such as high sensitivity, selectivity, wide linear range and low detection limit. The method was used to determine the content of lincomycin in injections commercially available with satisfactory results. Some electrochemical parameters involved in the redox reaction of lincomycin, such as parameter of kinetic ha, standard rate constant ks and the number of H^＋, were also calculated.

Hydrogen Separation Using Pt-Alumina Impregnated Membrane

A tubular commercial mesoporous support was used to prepare a Pt impregnated membrane using the reservoir method and tested for moderate temperature (300°C) gas transport of hydrogen (H2), helium (He) and nitrogen (N2) gas molecules. H2 and N2 gas permeation of 6.1 and 4.5 l/min at 1.0 barg feed pressure and 25°C respectively was obtained from the support. On the other hand, H2 and N2 gas permeation of 4.6 and 1.7 l/min at 1.0 barg feed pressure and 25&deg;C respectively was also obtained from the Pt membrane. Selectivity of H2 over He of 1.96 at 300°C and 1.6 barg for the Pt membrane was obtained and found to be higher than that of the theoretical Knudsen selectivity. Also, a selectivity of H2 over N2 of 2.72 at 25°C and 1.0 barg was obtained and found to be close to that of the theoretical Knudsen selectivity. The gas permeation and the selectivity performance of the membrane were evaluated.

Formation of Platinum (Pt) Nanocluster Coatings on K-OMS-2 Manganese Oxide Membranes by Reactive Spray Deposition Technique (RSDT) for Extended Stability during CO Oxidation

Nanocluster formation of a metallic platinum (Pt) coating, on manganese oxide inorganic membranes impregnated with multiwall carbon nanotubes (K-OMS-2/MWCNTs), applied by reactive spray deposition technology (RSDT) is discussed. RSDT applies thin films of Pt nanoclusters on the substrate;the thickness of the film can be easily controlled. The K-OMS-2/MWCNTs fibers were enclosed by the thin film of Pt. X-ray diffraction (XRD), scanning electron microscopy/X-ray energy dispersive spectroscopy (SEM/XEDS), focus ion beam/scanning electron microscopy (FIB/SEM), transmission electron microscopy (TEM), and X-ray 3D micro-tomography (MicroXCT) which have been used to characterize the resultant Pt/K-OMS-2/MWCNTs membrane. The non-destructive characterization technique (MicroXCT) resolves the Pt layer on the upper layer of the composite membrane and also shows that the membrane is composed of sheets superimposed into stacks. The nanostructured coating on the composite membrane material has been evaluated for carbon monoxide (CO) oxidation. The functionalized Pt/K-OMS-2/MWCNTs membranes show excellent conversion (100%) of CO to CO2 at a lower temperature 200℃ compared to the uncoated K-OMS-2/MWCNTs. Moreover, the Pt/K-OMS-2/MWCNTs membranes show outstanding stability, of more than 4 days, for CO oxidation at 200℃.

Recent advances in Pt catalysts and membrane electrode assemblies fabrication for proton exchange membrane fuel cells

Proton exchange membrane fuel cells(PEMFCs)have been identified as a highly promising means of achieving sustainable energy conversion.A crucial factor in enhancing the performance of PEMFCs for further potential energy applications is the advancement in the field of catalyst engineering that has led to remarkable performance enhancement in facilitating the oxygen reduction reaction(ORR).Subsequently,it is important to acknowledge that the techniques used in preparation of membrane electrode assemblies(MEAs),the vital constituents of PEMFCs,also possess direct and critical influence on exhibiting the full catalytic activity of meticulously crafted catalysts.Here,a succinct summary of the most recent advancements in Pt catalysts for ORR was offered and their underly catalytic mechanism were discussed.Then,both laboratory-scale and industrial-scale MEA fabrication techniques of Pt catalysts were summarized.Furthermore,a detailed analysis of the connections between materials,process,and performance in MEA fabrication was presented in order to facilitate the development of optimal catalyst layers.

Graphene/carbon structured catalyst layer to enhance the performance and durability of the high-temperature proton exchange membrane fuel cells

In this study,nitrogen doped electrochemically exfoliated reduced graphene oxide and carbon black supported platinum(Pt/Nr EGO_(2)-CB_(3))has been prepared to enhance the performance and durability of hightemperature PEMFCs with lower Pt loading.On the one hand,Pt/Nr EGO_(2)-CB_(3)with the strong interaction between the Pt and nitrogen(N)prevent agglomeration of Pt particles and Pt particles is 5.46±1.46 nm,which is smaller than that of 6.78±1.34 nm in Pt/C.Meanwhile,ECSA of Pt/Nr EGO_(2)-CB_(3)decrease 13.65%after AST,which is much lower than that of 97.99%in Pt/C.On the other hand,the Nr EGO flakes in MEAac act as a barrier to mitigate phosphoric acid redistribution,which improves the formation of triple-phase boundaries(TPBs)and gives stable operation of the MEAacwith a lower decay rate of 0.02 mV h^(-1)within100 h.After steady-state operation,the maximum power density of Pt/Nr EGO_(2)-CB_(3)(0.411 W cm^(-2))is three times higher than that of conventional Pt/C(0.134 W cm^(-2))in high-temperature PEMFCs.After AST,the mass transfer resistance of Pt/Nr EGO_(2)-CB_(3)electrode(0.560Ωcm^(2))is lower than that in Pt/C(0.728Ωcm^(2)).

高精度无损质子交换膜燃料电池膜电极Pt载量与分布测试方法

随着质子交换膜燃料电池商业化的推进,为提高膜电极制造的可重现性,保障膜电极制造工艺的产品控制,需要Pt载量和分布无损高精度在线检测提供技术支撑。根据欧姆定律与焦耳定律,利用质子交换膜燃料电池膜电极在直流激励电压下产生的电流密度和热分布信号可以对膜电极电阻进行分析,通过膜电极Pt载量与其电阻的关系就可以实现膜电极Pt载量和空间分布分析。通过不同直流激励电压下电流测试,证明了膜电极电阻与Pt载量反相关,Pt载量定量表征精度为0.0008~0.0025 mg/cm2;利用红外热成像法对直流激励电压下膜电极热分布信息的采集成功实现了Pt载量分布的定性分析;最后,通过直流激励前后膜电极性能的对比证明了该方法对膜电极性能是无损的。高精度无损的直流激励测试方法可以实现膜电极Pt载量的高效在线测试,提高膜电极质量和制造效率,降低膜电极制造成本,对于质子交换膜燃料电池大规模商用具有重要意义。

质子交换膜燃料电池Pt/C催化剂材料制备研究

质子交换膜燃料电池主要成本集中在贵金属Pt催化剂,而Pt/C催化剂是目前质子交换膜燃料电池的关键材料之一。为此,对机械化学法、乙醇机械化学法、乙醇浸渍搅拌法等工艺方法制备Pt/C催化剂进行研究,并对退火、铂金属用量等条件进行探索。结果表明:高温退火会降低Pt/C催化剂的催化性能,故退火温度要适当,不能超过900℃;3种方法制备Pt/C电催化性能进行对比,乙醇机械法和乙醇浸渍搅拌法性能相当,机械化学法优于前两者,并对其进行平行试验验证,重复性较好,测试性能稳定,具有可操作性;对其机械化学法Pt负载量(20%~40%)电催化性能对比发现,Pt负载量增加,电催化性能增加;对比扩大球磨和玛瑙研磨发现,扩大球磨的电催化性能好,说明该方法可实现扩大实施,对质子交换膜燃料电池工业化应用具有重要的指导意义。

PEMFC催化剂的研究:自制Pt/C电催化剂的性质

研究了一种用于质子交换膜燃料电池(PEMFC)的自制Pt/C电催化剂(标记为THYT-1)的物理化学和电化学性质.将THYT-1电催化剂与E-TEK公司的同类电催化剂的组成、形态及电催化性能进行了比较.单电池测试结果显示,THYT-1的电催化性能优于E-TEK电催化剂.CV测试结果表明CO在这两种电催化剂上的电氧化性能相近;TEM分析表明两种催化剂上Pt晶粒在炭载体上呈均匀分布,平均粒径均为2～3nm;XPS和XRD测试结果表明两种催化剂中Pt主要以金属态存在.这些数据表明THYT-1催化剂的物理化学性质与E-TEK公司的相类似.

Pt/Nafion复合膜的研制

Ｐｔ／Ｎａｆｉｏｎ复合膜的研制段天平夏代宽刘期崇王建华（四川联合大学化工系，成都６１００６５）关键词Ｐｔ／Ｎａｆｉｏｎ膜内沉积浸渍－还原１前言固体聚合物电解质技术（ＳＰＥ）将反应与分离相结合，在能量高效转换领域具有重要应用背景。铂附着于Ｎａｆｉｏｎ...

PEMFC催化剂的研究:自制抗CO中毒Pt-Ru/C电催化剂的性质

用胶体法制备了抗CO中毒PEMFC阳极Pt Ru/C电催化剂 (标记为THYT 2 ) ,对比研究了THYT 2与JohnsonMatthey(JM)公司同类品牌Pt Ru/C催化剂的电化学及其它物理化学性能 .结果表明 ,THYT 2电催化剂在甲醇燃料电池和CO/H2(ΦCO=1× 10 -4)的氢氧燃料电池中的电催化行为与JM催化剂相当 ,但THYT 2在低浓度CO氢气燃料中的电池性能更好 .两种催化剂的其它物理化学性质具有类似性 :XPS分析结果表明THYT 2和JM催化剂中都有三种不同价态的Pt存在 :即金属态Pt(0 )、氧化态Pt(II)和Pt(IV) .HRTEM测试结果表明两种催化剂的粒径处在 2～ 3nm左右 ,这可能是它们拥有良好电化学性能的主要原因之一 .本文还对催化剂中Pt与Ru组分的分布和相互作用进行了讨论 ,提出了改进Pt

碳载Pt-P催化剂对氧还原的电催化性能

用NaH2PO2液相还原方法制得碳载Pt-P(Pt-P/C)催化剂(m(Pt):m(P)=5:1)。X射线衍射谱测量表明,Pt-P/C催化剂的Pt衍射峰的2θ值稍大于Pt/C催化剂的相应值,表明P进入了Pt晶格,形成了Pt-P合金。电化学测试表明,Pt-P/C催化剂对氧还原的电催化性能要比商品化的E-TEKPt/C催化剂好,其还原电位正移了40mV。由于Pt-P/C催化剂中Pt-P粒子的平均粒径和相对结晶度与Pt/C催化剂相似,推测Pt-P/C催化剂对氧还原的电催化性能好于Pt/C催化剂的原因可能为P的作用。

PEMFC用Pt-Co/C催化剂的制备及性能

用液相沉积-高温合金化法制备了铂基合金催化剂,EDS、XRD的研究结果表明催化剂具有面心立方的结构,粒度小、分散性好,同时元素Co的加入使催化剂的Pt-Pt间距缩小。该催化剂的质子交换膜燃料电池伏安曲线表明,Pt-Co/C催化剂的性能优越,具有比纯铂更强的电催化能力,文中讨论了Co对催化剂活性的强化作用。

Pt/Nafion膜制备的研究

采用还原剂渗透还原法制备了不同Pt载量的Pt/Nafion膜,并利用扫描电镜(SEM),X射线衍射分析(XRD)对反应不同时间制得的Pt/Nafion膜中的Pt在膜内及膜表面的生长情况进行了研究.实验发现:Pt在膜内及膜表面均能发生生长,且主要沉积在膜内靠近膜表面处的一段区间.采用KBH_4还原H_2PtCl_6有利于Pt(111)晶面的生长.分析不同反应时间的横截面及正面照片,提出了Pt生长的可能机理.