Development of advanced anion exchange membrane from the view of the performance of water electrolysis cell

Green hydrogen produced by water electrolysis combined with renewable energy is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.Among water electrolysis technologies,the anion exchange membrane(AEM) water electrolysis has gained intensive attention and is considered as the next-generation emerging technology due to its potential advantages,such as the use of low-cost non-noble metal catalysts,the relatively mature stack assembly process,etc.However,the AEM water electrolyzer is still in the early development stage of the kW-level stack,which is mainly attributed to severe performance decay caused by the core component,i.e.,AEM.Here,the review comprehensively presents the recent progress of advanced AEM from the view of the performance of water electrolysis cells.Herein,fundamental principles and critical components of AEM water electrolyzers are introduced,and work conditions of AEM water electrolyzers and AEM performance improvement strategies are discussed.The challenges and perspectives are also analyzed.

Electrochemical reconstruction of non-noble metal-based heterostructure nanorod arrays electrodes for highly stable anion exchange membrane seawater electrolysis

Direct seawater electrolysis for hydrogen production has been regarded as a viable route to utilize surplus renewable energy and address the climate crisis.However,the harsh electrochemical environment of seawater,particularly the presence of aggressive Cl^(-),has been proven to be prone to parasitic chloride ion oxidation and corrosion reactions,thus restricting seawater electrolyzer lifetime.Herein,hierarchical structure(Ni,Fe)O(OH)@NiCoS nanorod arrays(NAs)catalysts with heterointerfaces and localized oxygen vacancies were synthesized at nickel foam substrates via the combination of hydrothermal and annealing methods to boost seawater dissociation.The hiera rchical nanostructure of NiCoS NAs enhanced electrode charge transfer rate and active surface area to accelerate oxygen evolution reaction(OER)and generated sulfate gradient layers to repulsive aggressive Cl^(-).The fabricated heterostructure and vacancies of(Ni,Fe)O(OH)tuned catalyst electronic structure into an electrophilic state to enhance the binding affinity of hydroxyl intermediates and facilitate the structural transformation into amorphousγ-NiFeOOH for promoting OER.Furthermore,through operando electrochemistry techniques,we found that theγ-NiFeOOH possessing an unsaturated coordination environment and lattice-oxygen-participated OER mechanism can minimize electrode Cl^(-)corrosion enabled by stabilizing the adsorption of OH*intermediates,making it one of the best OER catalysts in the seawater medium reported to date.Consequently,these catalysts can deliver current densities of 100 and 500 mA cm-2for boosting OER at minimal overpotentials of 245and 316 mV,respectively,and thus prevent chloride ion oxidation simultaneously.Impressively,a highly stable anion exchange membrane(AEM)seawater electrolyzer based on the non-noble metal heterostructure electrodes reached a record low degradation rate under 100μV h-1at constant industrial current densities of 400 and 600 mA cm-2over 300 h,which exhibits a promising future for the nonprecious and stable AEMWE in the direct seawater electrolysis industry.

Towards high-performance and robust anion exchange membranes(AEMs)for water electrolysis:Super-acid-catalyzed synthesis of AEMs

The increasing demand for hydrogen energy to address environmental issues and achieve carbon neutrality has elevated interest in green hydrogen production,which does not rely on fossil fuels.Among various hydrogen production technologies,anion exchange membrane water electrolyzer(AEMWE)has emerged as a next-generation technology known for its high hydrogen production efficiency and its ability to use non-metal catalysts.However,this technology faces significant challenges,particularly in terms of the membrane durability and low ionic conductivity.To address these challenges,research efforts have focused on developing membranes with a new backbone structure and anion exchange groups to enhance durability and ionic conductivity.Notably,the super-acid-catalyzed condensation(SACC)synthesis method stands out due to its user convenience,the ability to create high molecular weight(MW)polymers,and the use of oxygen-tolerant organic catalysts.Although the synthesis of anion exchange membranes(AEMs)using the SACC method began in 2015,and despite growing interest in this synthesis approach,there remains a scarcity of review papers focusing on AEMs synthesized using the SACC method.The review covers the basics of SACC synthesis,presents various polymers synthesized using this method,and summarizes the development of these polymers,particularly their building blocks including aryl,ketone,and anion exchange groups.We systematically describe the effects of changes in the molecular structure of each polymer component,conducted by various research groups,on the mechanical properties,conductivity,and operational stability of the membrane.This review will provide insights into the development of AEMs with superior performance and operational stability suitable for water electrolysis applications.

Pore-Scale Investigation of Coupled Two-Phase and Reactive Transport in the Cathode Electrode of Proton Exchange Membrane Fuel Cells

A three-dimensional multicomponent multiphase lattice Boltzmann model(LBM)is established to model the coupled two-phase and reactive transport phenomena in the cathode electrode of proton exchange membrane fuel cells.The gas diff usion layer(GDL)and microporous layer(MPL)are stochastically reconstructed with the inside dynamic distribution of oxygen and liquid water resolved,and the catalyst layer is simplifi ed as a superthin layer to address the electrochemical reaction,which provides a clear description of the fl ooding eff ect on mass transport and performance.Diff erent kinds of electrodes are reconstructed to determine the optimum porosity and structure design of the GDL and MPL by comparing the transport resistance and per-formance under the fl ooding condition.The simulation results show that gradient porosity GDL helps to increase the reactive area and average concentration under fl ooding.The presence of the MPL ensures the oxygen transport space and reaction area because liquid water cannot transport through micropores.Moreover,the MPL helps in the uniform distribution of oxygen for an effi cient in-plane transport capacity.Crack and perforation structures can accelerate the water transport in the assembly.The systematic perforation design yields the best performance under fl ooding by separating the transport of liquid water and oxygen.

Water Distribution and Removal along the Flow Channel in Proton Exchange Membrane Fuel Cells

Distribution expressions of total gas pressure and partial water vapor pressure along the channel direction were established based on lumped model by analyzing pressure loss in the channel and gas diffusion in the layer. The mechanism of droplet formation in the flow channel was also analyzed. Effects of the relative humidity, working temperature and stoichiometry on liquid water formation were discussed in detail. Moreover, the force equilibrium equation of the droplet in the flow channel was deduced, and the critical flow velocity for the water droplet removal was also addressed. The experimental results show that the threshold position of the liquid droplet is far from the inlet with the increase of temperature, and it decreases with the increase of the inlet total pressure. The critical flow velocity decreases with the increase of the radius and the working pressure.

Ternary layered double hydroxide oxygen evolution reaction electrocatalyst for anion exchange membrane alkaline seawater electrolysis

Anion exchange membrane(AEM)water electrolyzers are promising energy devices for the production of clean hydrogen from seawater.However,the lack of active and robust electrocatalysts for the oxygen evolution reaction(OER)severely impedes the development of this technology.In this study,a ternary layered double hydroxide(LDH)OER electrocatalyst(NiFeCo-LDH)is developed for high-performance AEM alkaline seawater electrolyzers.The AEM alkaline seawater electrolyzer catalyzed by the NiFeCo LDH shows high seawater electrolysis performance(0.84 A/cm^(2)at 1.7 Vcell)and high hydrogen production efficiency(77.6%at 0.5 A/cm^(2)),thus outperforming an electrolyzer catalyzed by a benchmark IrO_(2)electrocatalyst.The NiFeCo-LDH electrocatalyst greatly improves the kinetics of the AEM alkaline seawater electrolyzer,consequently reducing its activation loss and leading to high performance.Based on the results,this NiFeCo-LDH-catalyzed AEM alkaline seawater electrolyzer can likely surpass the energy conversion targets of the US Department of Energy.

Patterned catalyst layer boosts the performance of proton exchange membrane fuel cells by optimizing water management

Mass transport is crucial to the performance of proton exchange membrane fuel cells,especially at high current densities.Generally,the oxygen and the generated water share same transmission medium but move towards opposite direction,which leads to serious mass transfer problems.Herein,a series of patterned catalyst layer were prepared with a simple one-step impressing method using nylon sieves as templates.With grooves 100μm in width and 8μm in depth on the surface of cathode catalyst layer,the maximum power density of fuel cell increases by 10%without any additional durability loss while maintaining a similar electrochemical surface area.The concentration contours calculated by finite element analysis reveal that the grooves built on the surface of catalyst layer serve to accumulate the water nearby while oxygen tends to transfer through relatively convex region,which results from capillary pressure difference caused by the pore structure difference between the two regions.The separation of oxidant gas and generated water avoids mass confliction thus boosts mass transport efficiency.

Design and Performance Analysis of Micro Proton Exchange Membrane Fuel Cells

This study describes a novel micro proton exchange membrane fuel cell(PEMFC)(active area,2.5 cm2).The flow field plate is manufactured by applying micro-electromechanical systems(MEMS) technology to silicon substrates to etch flow channels without a gold-coating.Therefore,this investigation used MEMS technology for fabrication of a flow field plate and presents a novel fabrication procedure.Various operating parameters,such as fuel temperature and fuel stoichiometric flow rate,are tested to optimize micro PEMFC performance.A single micro PEMFC using MEMS technology reveals the ideal performance of the proposed fuel cell.The optimal power density approaches 232.75 mW·cm-1 when the fuel cell is operated at ambient condition with humidified,heated fuel.

Internal Polarization Field Induced Hydroxyl Spillover Effect for Industrial Water Splitting Electrolyzers

The formation of multiple oxygen intermediates supporting efficient oxygen evolution reaction(OER)are affinitive with hydroxyl adsorption.However,ability of the catalyst to capture hydroxyl and maintain the continuous supply at active sits remains a tremendous challenge.Herein,an affordable Ni2P/FeP2 heterostructure is presented to form the internal polarization field(IPF),arising hydroxyl spillover(HOSo)during OER.Facilitated by IPF,the oriented HOSo from FeP2 to Ni2P can activate the Ni site with a new hydroxyl transmission channel and build the optimized reaction path of oxygen intermediates for lower adsorption energy,boosting the OER activity(242 mV vs.RHE at 100 mA cm-2)for least 100 h.More interestingly,for the anion exchange membrane water electrolyzer(AEMWE)with low concentration electrolyte,the advantage of HOSo effect is significantly amplified,delivering 1 A cm^(-2)at a low cell voltage of 1.88 V with excellent stability for over 50 h.

Interfacial engineering of atomic platinum-doped molybdenum carbide quantum dots for high-rate and stable hydrogen evolution reaction in proton exchange membrane water electrolysis

Platinum(Pt)-based electrocatalysts remain the only practical cathode catalysts for proton exchange membrane water electrolysis(PEMWE),due to their excellent catalytic activity for acidic hydrogen evolution reaction(HER),but are greatly limited by their low reserves and high cost.Here,we report an interfacial engineering strategy to obtain a promising low-Pt loading catalyst with atomically Pt-doped molybdenum carbide quantum dots decorated on conductive porous carbon(Pt-MoCx@C)for high-rate and stable HER in PEMWE.Benefiting from the strong interfacial interaction between Pt atoms and the ultra-small MoCx quantum dots substrate,the Pt-MoCx catalyst exhibits a high mass activity of 8.00 A·mgPt−1,5.6 times higher than that of commercial 20 wt.%Pt/C catalyst.Moreover,the strong interfacial coupling of Pt and MoCx substrate greatly improves the HER stability of the Pt-MoCx catalyst.Density functional theory studies further confirm the strong metal-support interaction on Pt-MoCx,the critical role of MoCx substrate in the stabilization of surface Pt atoms,as well as activation of MoCx substrate by Pt atoms for improving HER durability and activity.The optimized Pt-MoCx@C catalyst demonstrates>2000 h stability under a water-splitting current of 1000 mA·cm^(−2)when applied to the cathode of a PEM water electrolyzer,suggesting the potential for practical applications.

Numerical Investigation on the Effects of Design Parameters and Operating Conditions on the Electrochemical Performance of Proton Exchange Membrane Water Electrolysis

Proton exchange membrane electrolysis cell(PEMEC)is one of the most promising methods to produce hydrogen at high purity and low power consumption.In this study,a three-dimensional non-isothermal model is used to simulate the cell performance of a typical PEMEC based on computational fluid dynamics(CFD)with the finite element method.Then,the model is used to investigate the distributions of current density,species concentration,and temperature at the membrane/catalyst(MEM/CL)interface.Also,the effects of operating conditions and design parameters on the polarization curve,specific electrical energy demand,and electrical cell efficiency are studied.The results show that the maximum distribution of current density,hydrogen concentration,oxygen concentration,and temperature occur beneath the core ribs and increase towards the channel outlet,while the maximum water concentration distribution happens under the channel and decreases towards the channel exit direction.The increase in gas diffusion layer(GDL)thickness reduces the uneven distribution of the contour at the MEM/CL interface.It is also found that increasing the operating temperature from 323 K to 363 K reduces the cell voltage and specific energy demand.The hydrogen ion diffusion degrades with increasing the cathode pressure,which increases the specific energy demand and reduces the electrical cell efficiency.Furthermore,increasing the thickness of the GDL and membrane rises the specific energy demand and lowers the electrical efficiency,but increasing GDL porosity reduces the specific electrical energy demand and improves the electrical cell efficiency;thus using a thin membrane and GDL is recommended.

A systematic review of system modeling and control strategy of proton exchange membrane fuel cell

The proton exchange membrane fuel cell,as a novel energy device,exhibits a wide array of potential applications.This paper offers a comprehensive review and discussion of modeling and control strategies for fuel cell systems.It commences with a concise introduction to the structure and principles of fuel cells.Subsequently,it outlines modeling approaches for various fuel cell subsystems,encompassing the fuel cell stack,air supply system,hydrogen supply system,thermal management system,and water management system.Following this,it conducts a comparative analysis and discussion of prevalent control strategies for the aforementioned subsystems.Lastly,the paper outlines future research trends and directions in the modeling and control strategies of fuel cells.The aim of this paper is to provide ideas and inspirations for the design and management of membrane fuel cell systems from control aspects.

Modulating metal-organic frameworks for catalyzing acidic oxygen evolution for proton exchangemembrane water electrolysis

Proton exchangemembrane(PEM)water electrolysis represents one of the most promising technologies to achieve green hydrogen production,but currently its practical viability is largely affected by the slow reaction kinetics of the anodic oxygen evolution reaction(OER)in an acidic environment.While noble metal-based catalysts containing iridium or ruthenium are excellent catalysts for the acidic OER,their practical use in PEM electrolyzers is hindered due to their low abundance and high cost.Most recently,metal-organic frameworks(MOFs)have been demonstrated as a perfect platform to facilitate the design of acidic OER catalysts with both high efficiency and cost-effectiveness.Here,we pro-vide a timely and comprehensive overview of the recent progress on MOF-based acidic OER catalysts.The fundamental mechanisms of the acidic OER are first introduced,followed by a summary of the development of pristine MOFs and MOF derivatives as acidic OER catalysts.Importantly,a number of catalyst design strategies are discussed aiming at improving the acidic OER catalytic per-formance of MOF-based candidates.The integration of MOF-based catalysts into real PEM water electrolyzers is also included.Finally,future research directions are provided to achieve better MOF-based catalysts operational in acidic envi-ronments and PEM devices.

Numerical investigation of water and temperature distributions in a proton exchange membrane electrolysis cell

A three-dimensional, non-isothermal, two-phase model for a PEM water electrolysis cell(PEMEC) is established in this study.An effective connection between two-phase transport and performance in the PEMECs is built through coupling the liquid water saturation and temperature in the charge conservation equation. The distributions of liquid water and temperature with different operating(voltage, temperature, inlet velocity) and physical(contact angle, and porosity of anode gas diffusion layer) parameters are examined and discussed in detail. The results show that the water and temperature distributions, which are affected by the operating and physical parameters, have a combined effect on the cell performance. The effects of various parameters on the PEMEC are of interaction and restricted mutually. As the voltage increases, the priority factor caused by the change of inlet water velocity changes from the liquid water saturation increase to the temperature drop in the anode catalyst layer. While the priority influence factor caused by the contact angle and porosity of anode gas diffusion layer is the liquid water saturation. Decreasing the contact angle or/and increasing the porosity can improve the PEMEC performance especially at the high voltage. The results can provide a better understanding of the effect of heat and mass transfer and the foundation for optimization design.

高温质子交换膜水电解用Nafion/BN复合膜的制备与性能研究

在研究高温质子交换膜水电解系统时,膜脱水引致质子传导率降低的情况是造成电解性能较低的主要问题。针对该问题,引入了氮化硼(BN)作为一种无机吸湿改性剂。通过采用掺杂浇铸技术,成功制备了Nafion/BN复合膜。氮化硼的卓越吸湿能力,以及其表面碱性基团与Nafion分子链上磺酸基团之间的酸碱相互作用,共同形成了一个密集的氢键网络,从而推进质子的传递。扫描电子显微镜(SEM)和X射线能量散射光谱(EDS)的分析结果验证了氮化硼在复合膜中的均匀分布。吸水率的测试结果显示,BN的引入显著增强了复合膜的水吸附能力。通过质子电导率的测试,证实BN的掺杂显著提升了复合膜的质子电导率。在130℃的高温条件下,采用Nafion/BN复合膜构建的水电解装置表现出了卓越的电解效能,尤其是在2.0 V电压下,电流密度达到2.04 A/cm^(2),表明Nafion/BN复合膜在高温质子交换膜水电解领域内具有一定的发展潜力。

阴离子交换膜电解水制氢技术的研究进展

氢能是我国2060年“碳中和”的关键支撑,氢气制备又是氢能产业链“制、储、输、用”四大环节中的首要环节,绿色高效地制取氢气是氢能发展的基础。阴离子交换膜电解水(AEMWE)作为新兴的“绿氢”技术,充分结合了碱性水电解技术与质子交换膜电解技术的优势,有望成为最具发展潜力的可再生能源制氢技术。对AEMWE的原理与研究现状做了简要分析,详细论述阴离子交换膜(AEM)水电解槽关键部件的研究进展与发展方向,包括阴离子交换膜、阳极、阴极催化剂、双功能催化剂、离聚物、膜电极、多孔传输层、双极板及电解液。最后结合研究现状,展望了AEMWE制氢技术的研究方向。

质子交换膜燃料电池气体扩散层研究进展

质子交换膜燃料电池(PEMFC)可以提供较高的功率/能量密度,是未来空间探索最有前途的动力设备之一,其性能主要取决于内部反应物的传输和水管理。气体扩散层(GDL)作为燃料电池中的重要组成部件,与燃料电池的质量、水、热和电的多相传输紧密相关,是反应物和液态水的主要传输场所。因此,要提高燃料电池性能,合理的气体扩散层的设计至关重要。从提升空间燃料电池的使用寿命、稳定性及电化学性能的角度出发,综述了气体扩散层的物理化学特性,并介绍了多种改性方法,包括疏水性、结构和新型一体式GDL以及其对燃料电池性能的影响,为未来空间燃料电池高性能GDL设计提供了参考。

具有泡沫金属流场的燃料电池研究进展

泡沫金属是一种具有高孔隙率、高电导率、良好传热性和重量较轻等优点的新型多功能材料,在质子交换膜燃料电池(PEMFC)中嵌入泡沫金属作为流场的应用受到越来越多的关注。重点综述PEMFC流场的研究进展,探讨泡沫金属结构参数、流场设计和环境因素等对功率密度、气体分布、压降和水热管理等性能的影响。进一步讨论泡沫金属流场在PEMFC应用中所面临的腐蚀和水淹问题,以及具备耐腐蚀涂层泡沫金属的研究进展,为PEMFC泡沫金属流场的发展和优化提供有益的启示,以期推进泡沫金属在PEMFC中的应用。

高性能Ir基阳极双催化层阴离子交换膜电解水

设计高性能低Ir阳极催化层对阴离子交换膜电解水(AEMWE)商业化发展至关重要。本研究采用催化剂涂覆基底(CCS)方法,构建基于氧化铱(IrO_(2))和碳载铱(IrC)双催化层的阳极结构,提出了一种新型双Ir催化层并提高了AEMWE性能。研究表明,在IrC-IrO_(2)(先喷涂碳载铱,后喷涂氧化铱)催化层中,IrC高度分散特性有利于提高催化层中Ir的利用率,优化了催化层内电子、氢氧根离子的传输。采用商业Pt/C催化剂作为阴极,IrC-IrO_(2)阳极双催化层组装成碱性膜电极,在1 mol/L KOH电解质条件下,2.0 V时IrC-IrO_(2)电极达到了2.31 A/cm^(2)的高电流密度,而且在低浓度电解质以及纯水中依旧保持较高的性能。本研究为碱性膜电解水技术高效催化层的设计提供了参考。

基于阴离子交换膜电解水的离聚物研究进展

在能源日益匮乏的今天,氢能作为一种可再生、绿色环保的新型能源成为全球节能降碳的重要载体。传统的碱水电解(Alkaline water electrolysis,AWE)制氢要求较高pH的碱液作为电解液,而且只能在低电流密度下工作;质子交换膜电解水(Proton exchange membrane water electrolysis,PEMWE)制氢技术具有电流密度大、效率高的特点,被人们视为最有前景的电解水制氢技术,但是其昂贵的催化剂以及所需的高耐酸性部件成为制约PEMWE发展的重要因素。阴离子交换膜电解水(Anion exchange membrane water electrolysis,AEMWE)作为一种新兴的技术,可以实现低成本“绿氢”制备。相较于AWE,AEMWE避免了高浓度碱液的循环;相较于PEMWE,AEMWE则具有成本低、腐蚀性低等优势。离聚物作为关键部件膜电极(Membrane electrode assembly,MEA)中三相界面(Triple phase boundary,TPB)的重要组成部分,对AEMWE内部催化作用和水管理能力起着重要作用。本文首先围绕AEMWE技术原理和离聚物在AEMWE中的作用进行了概述,随后对常见的不同种类的阴离子离聚物结构及特点进行了总结,最后从结构、含量以及添加剂调控三种调控策略入手,针对如何调控离聚物以达到更加优异的电解性能进行了具体的分析总结。