Recent advances in design of hydrogen evolution reaction electrocatalysts at high current density:A review

The electrolysis of water powered by renewable energy sources offers a promising method of"green hydrogen"production,which is considered to be at the heart of future carbon-neutral energy systems.In the past decades,researchers have reported a number of hydrogen evolution reaction(HER)electrocatalysts with activity comparable to that of commercial Pt/C,but most of them are tested within a small current density range,typically no more than 500 mA cm^(-2).To realize the industrial application of hydrogen production from water electrolysis,it is essential to develop high-efficiency HER electrocatalysts at high current density(HCD≥500 mA cm^(-2)).Nevertheless,it remains challenging and significant to rational design HCD electrocatalysts for HER.In this paper,the design strategy of HCD electrocatalysts is discussed,and some HCD electrocatalysts for HER are reviewed in seven categories(alloy,metal oxide,metal hydroxide,metal sulfide/selenide,metal nitride,metal phosphide and other derived electrocatalysts).At the end of this article,we also pro-pose some viewpoints and prospects for the future development and research directions of HCD electrocatalysts for HER.

A Hydrogen Iron Flow Battery with High Current Density and Long Cyclability Enabled Through Circular Water Management

The hydrogen-iron(HyFe)flow cell has great potential for long-duration energy storage by capitalizing on the advantages of both electrolyzers and flow batteries.However,its operation at high current density(high power)and over continuous cycling testing has yet to be demonstrated.In this paper,we discuss our design and demonstration of a water management strategy that supports high current and long cycling performance of a HyFe flow cell.Water molecules associated with the movement of protons from the iron electrode to the hydrogen electrode are sufficient to hydrate the membrane and electrode at a low current density of 100 mA cm^(-2)during the charge process.At higher charge current density,more aggressive measures must be taken to counter back-diffusion driven by the acid concentration gradient between the iron and hydrogen electrodes.Our water management approach is based on water vapor feeding in the hydrogen electrode,and water evaporation in the iron electrode,thus enabling the high current density operation of 300 mA cm^(-2).

Strong electronic coupling of CoNi and N-doped-carbon for efficient urea-assisted H2 production at a large current density

Exploiting efficient urea oxidation reaction(UOR)and hydrogen evolution reaction(HER)catalysts are significant for energy-saving H2 production through urea-assisted water electrolysis,but it is still challenging.Herein,carbon-encapsulated CoNi coupled with CoNiMoO(CoNi@CN-CoNiMoO)is prepared by solvothermal method and calcination to enhance the activity/stability of urea-assisted water electrolysis at large current density.It exhibits good activity for UOR(E10/1,000=1.29/1.40 V)and HER(E-10/-1000=-45/-245 mV)in 1.0 M KOH+0.5 M urea solution.For the UOR||HER system,CoNi@CN-CoNiMoO only needs 1.58 V at 500 mA cm-2 and shows good stability.Density functional theory calculation suggests that the strong electronic interaction at the interface between NiCo alloy and N-doping-carbon layers can optimize the adsorption/desorption energy of UOR/HER intermediates and accelerate the water dissociation,which can expedite urea decomposition and Volmer step,thus increasing the UOR and HER activity,respectively.This work provides a new solution to design UOR/HER catalysts for H2 production through urea-assisted water electrolysis.

Influence of the electrolyte conductivity on the critical current density and the breakdown voltage

The work investigates influence of the electrolyte conductivity on the onset of partial contact glow discharge electrolysis(CGDE)in a water electrolysis.Critical current density(CCD)and breakdown voltage were measured together with in situ observation of hydrogen bubble behavior,whose influence has not been focused on.For a fixed current during normal electrolysis,hydrogen coalescence adjacent to cathode surface was invigorated at a lower conductivity.Photographic analyses elucidated the hydrogen coalescence characteristics by quantifying size and population of detached hydrogen bubbles.The CCD increased about 104% within given range of conductivity(11.50-127.48 mS·cm^(-1))due to impaired bubble coalescence,which delays hydrogen film formation on the cathode.Meanwhile,decreasing trend of breakdown voltage was measured with increased conductivity showing maximum drop of 74%.It is concluded that onset of partial CGDE is directly affected by hydrodynamic bubble behaviors,whereas the electrolyte conductivity affects the bubble formation characteristics adjacent to cathode electrode.

A MOF derived hierarchically porous 3D N‐CoP_(x)/Ni_(2)P electrode for accelerating hydrogen evolution at high current densities

Hydrogen evolution reaction is a critical reaction in water splitting for hydrogen production.However,developing effective and stable non‐noble‐metal electrocatalysts which work well at high current densities demanded by industry still remain great challenge.Herein,taking advantage of the highly tunable metal‐organic framework(MOF)templates,nitrogen doped binary transition metal phosphides electrocatalysts(N‐CoP_(x)/Ni_(2)P)with three‐dimensional(3D)conductive network structure were successfully synthesized.The 3D open porous channels could expose more catalytically active sites;nitrogen doping and the synergistic effect between CoP and Ni_(2)P can increase the electron density of Co atoms at active sites,further optimizing the Gibbs free energy of hydrogen(ΔGH*)and water(ΔG_(H_(2)O*)).As a result,the obtained N‐CoP_(x)/Ni_(2)P catalyst exhibits extraordinary electrocatalytic activity in a wide pH range.Especially,it requires an extremely low overpotential of 152 mV to deliver a high current density of 650 mA cm^(–2) in alkaline media.This work may shed some light on the rational design of cheap electrocatalysts and electrode materials that work well at high current densities.

Hydrogen spillover bridged dual nano-islands triggered by built-in electric field for efficient and robust alkaline hydrogen evolution at ampere-level current density

Employing the alkaline water electrolysis system to generate hydrogen holds great prospects but still poses significant challenges,particularly for the construction of hydrogen evolution reaction(HER)catalysts operating at ampere-level current density.Herein,the unique Ru and RuP_(2)dual nano-islands are deliberately implanted on N-doped carbon substrate(denoted as Ru-RuP_(2)/NC),in which a built-in electric field(BEF)is spontaneously generated between Ru-RuP_(2)dual nano-islands driven by their work function difference.Experimental and theoretical results unveil that such constructed BEF could serve as the driving force for triggering fast hydrogen spillover process on bridged Ru-RuP_(2)dual nano-islands,which could invalidate the inhibitory effect of high hydrogen coverage at ampere-level current density,and synchronously speed up the water dissociation on Ru nano-islands and hydrogen adsorption/desorption on RuP_(2)nano-islands through hydrogen spillover process.As a result,the Ru-RuP_(2)/NC affords an ultra-low overpotential of 218 mV to achieve 1.0 A·cm^(−2)along with the superior stability over 1000 h,holding the great promising prospect in practical applications at ampere-level current density.More importantly,this work is the first to advance the scientific understanding of the relationship between the constructed BEF and hydrogen spillover process,which could be enlightening for the rational design of the cost-effective alkaline HER catalysts at ampere-level current density.

大电流密度下高性能析氢电催化剂研究进展

H_(2)作为一种清洁能源,被认为是缓解能源危机和减少环境污染最有前景的替代能源之一。利用可再生能源电解水制氢是生产绿氢的重要方法,但是工业电解水制氢大多存在运行电流密度低、能耗高等难题。提高电流密度是提高产氢速率最直接的方式,但是在未对电催化剂进行优化的情况下,提高电流密度会造成电耗的增加,因此亟需开发出在大电流密度下低过电位的高性能析氢反应(以下简称“HER”)电催化剂。首先介绍了在酸性和碱性介质中的HER反应机理:Volmer-Heyrovsky和Volmer-Tafel,提出了在大电流密度下高性能HER电催化剂需满足的要求;然后从单原子催化剂、合金催化剂和异质结构催化剂等角度出发,阐述了近年来国内外贵金属、非贵金属HER电催化剂的研究进展;最后对HER电催化剂未来发展所面临的挑战和机遇进行了分析。

Electrochemical hydrogen storage properties of non-equilibrium Ti_(2-x)Mg_xNi alloys

Amorphous Ti2?xMgxNi (x=0?0.3) alloys were prepared by mechanical milling of elemental powders. Charge and discharge test, linear polarization (LP) and potential-step measurement were carried out to investigate the electrochemical hydrogen storage properties of the alloys before and after heat treatment. The results show that the maximum discharge capacity of heat-treated Ti2?xMgxNi alloy can reach 275.3 mA·h/g, which is 100 mA·h/g higher than that of the amorphous Ti2?xMgxNi alloy. The heat-treated Ti1.9Mg0.1Ni alloy presents the best cycling stability with a high discharge capacity of 210 mA·h/g after 30 cycles. The results of LP and potential-step measurement of the Ti1.9Mg0.1Ni alloy show that the exchange current density increases from 101.1 to 203.3 mA/g and the hydrogen diffusion coefficient increases from 3.20×10?11 to 2.70×10?10 cm2/s after the heat treatment, indicating that the heat treatment facilitates both the charge-transfer and hydrogen diffusion processes, resulting in an improvement in electrochemical hydrogen storage properties of Ti2?xMgxNi (x=0?0.3) alloys.

脉冲电流对电化学除氯的影响

目的探究不同电流密度下,直流和脉冲2种电流模式对钢筋混凝土电化学除氯的影响,降低钢筋渗氢量,减小通电后阴极产生的氢气使钢筋发生氢脆的风险,提高除氯效率,改善电化学除氯效率的均匀性。方法通过在电流密度为2、3、4A/m2的条件下,对混凝土进行直流和脉冲电流电化学修复,测定处理后的钢筋的释氢电流,计算释氢总电量,来表示钢筋渗氢量,对比处理后强电流区和弱电流区混凝土的氯离子含量,分析2种方式除氯效率的均匀性,同时用扫描电子显微镜观察电化学除氯前后混凝土的微观结构。结果计算得到不同通电电流密度下钢筋的释氢总电量和除氯效率,脉冲电流的释氢总电量比直流电流低约20%,而除氯效率提高了约10%。结论增加电流密度可以提高除氯效率,但是会增加钢筋发生氢脆的风险。相较于直流电流,脉冲电流电化学修复可以降低钢筋渗氢量,显著提高弱电流区的除氯效率,从而改善除氯效率的均匀性。

Aligned porous carbon film with ultralow loadings of Pt single atoms and clusters for high-current-density hydrogen generation

The development of electrocatalysts toward the hydrogen evolution reaction(HER)with high-current-density capability is critical for the practical application of water splitting for hydrogen production.While Pt-based materials are regarded as the most efficient HER catalysts,they suffer from scarcity and high price.Thus,it is of vital importance to lower the loading of Pt while maintaining high activity.Here,we report the fabrication of a monolithic aligned porous carbon film electrode co-modified with Pt single atoms and Pt nanoclusters(Pt SA/NC-AF)containing ultralow Pt content(0.038 wt.%)via a facile electrochemical deposition process.Benefiting from the aligned porous structure of the carbon film and the high exposure of the Pt species,the optimized Pt SA/NCAF electrode exhibits outstanding HER performance in 0.5 M H_(2)SO_(4)with exceptional intrinsic activity(turnover frequency(TOF)=904.9 s^(−1)atη=100 mV)and ultrahigh mass activity(888.6 A·mg_(Pt)^(−1)atη=100 mV).Further,it can deliver an industrially relevant current density of 1,000 mA·cm−2 at an overpotential as low as 139 mV.This work provides a feasible avenue for the rational design of metal single-atom and nanocluster catalysts and additionally promotes the application of ultralow-loading noble metal-based catalysts in high-rate hydrogen production.

碱溶液中电积回收镓的工艺研究

针对碱性条件下,镓电积过程中不锈钢阴极易发生析氢反应,致使电流效率低这一难题,重点研究了电积镓过程电流密度、初始NaOH浓度、Ga^(3+)浓度、电积温度对电流效率的影响,优化了电积镓工艺条件。实验结果表明,采用镀镓不锈钢作为阴极,较优的电积工艺参数为温度45℃、电流密度500 A/m^(2)、初始NaOH浓度140 g/L、初始Ga^(3+)浓度150 g/L;在优化工艺参数下,可以有效地减少镓电积过程中氢气的析出,电流效率稳定在75%以上,产品纯度达99.995%。

大电流密度过渡金属硫族化合物析氢催化剂界面工程展望

氢能是未来可持续社会中理想的能量载体,利用可再生能源电解水制取绿氢的技术受到研究人员的广泛关注.电解水制绿氢技术由实验室向工业应用跨越的前提是发展大电流密度下性能优异且稳定的电催化剂.析氢反应(HER)是一种非均相反应,涉及催化剂-基底、催化剂-电解液、催化剂-气体三个界面.界面性质会影响电化学传质行为、电荷传输行为和催化剂的力学性质,从而影响大电流密度下制氢性能.因此,优化界面结构和性质是提升大电流密度下电解水催化剂性能并解决电解水技术工业应用挑战的关键.二维过渡金属硫族化合物(TMDCs)具有电子结构可调、活性位点丰富、合成方法多样等优势,自1976年首次应用于光电催化水分解反应、加氢脱硫反应以来,已有大量工作报道了TMDCs催化剂应用于HER.本文以TMDCs催化剂为例研究界面工程对大电流密度下HER的提升作用及机制.探讨了电化学反应中上述三个界面上发生的物理化学过程,系统分析了大电流密度下质量传输、电荷传输速率受限和力学强度不足三方面挑战,并总结了适用于大电流密度的催化剂性能描述符.分别归纳了针对以上三个界面的界面工程策略及相应作用,简要概括为:(1)催化剂-基底界面结合力增强、界面电阻降低、界面电子结构调控等策略;(2)催化剂-电解液界面形貌调控、表面化学、电解液环境调控等策略;(3)催化剂-气体界面疏气性调控、外场作用等策略.从反应机理研究、膜电极界面设计及电解槽界面性质调控三个角度对电解水反应界面工程未来的发展与应用提出了建议及展望.在反应机理方面,大电流条件下的界面性质如界面电阻、传质行为等仍需更深入的认识.在膜电极中,催化剂、离子交换膜、离子型聚合物、气体扩散层所形成的多元界面,尤其是催化剂-膜界面、催化剂-气体扩散层界面的结构仍需进一步优化以提升膜电极的活性及稳定性.在电解槽界面性质调控方面,催化剂-基底界面结合力等参数与催化剂寿命间的关系,电解过程中界面处的温度场及流场分布,适配于实际生产系统的电流密度等仍需深入研究.综上,本文从基本物理化学过程、策略及作用、挑战与展望等多个方面介绍了界面工程.本文有助于研究人员理解非均相电化学反应过程中界面的重要作用,提出催化剂、膜电极、电解槽界面设计新策略,并开发新型表征方法以深入对界面性质的认识,推动高效电解水技术的开发及应用.

质子交换膜电解水制氢技术发展现状及展望

电解水制氢技术已成为绿氢制取的重要方法,其中最具发展潜力的是质子交换膜(PEM)电解水制氢技术。其结构紧凑,占地面积小,电解效率高,能在高压条件下获得高纯度氢气,更为重要的是,质子交换膜电解槽与间歇性的风光可再生波动电源具有良好的适配性,因而成为行业关注的焦点。目前PEM电解水制氢已进入发展的快车道,国外PEM制氢技术市场应用占比超过50%,国内多项PEM制氢项目已开工投产。近年来我国在材料、组件、系统集成方面均取得了实质性进展,但在关键性技术、效率寿命提升、经济性方面与国际先进水平仍存在一定差距。能耗较高、寿命不足、成本居高不下仍是大规模商业化应用的主要制约因素。大规模、大功率、高压差是PEM制氢系统未来发展的方向,需要结合实际工况,在衰减机制、基础技术、创新性材料开发和低成本组件方面取得突破。提升电流密度,提升不同输入特性下PEM电解槽的寿命,减少贵金属用量、加快非贵金属替代技术研究以进一步降低成本。

HYDROGEN DAMAGE IN HIGH PURITY IRON

Hydrogen damage in iron or 99.99% purity has been investigated by Doppler broadening measurement.Experimental results show that when the iron is charged with hydrogen in 0.5mol/L H_2SO_4 solution,the critical current density to cause hydrogen damage is 20mA/cm^2.While a little As_2O_3,saying 250mg/L,added to H_2SO_4 solution,even rather small current density.≤0.2mA/cm^2,would cause hydrogen damage.With the help ofi slow tensile test,it revealed that the hydrogen damage occurred in the specimen may be influential to the subsequent process of deformation and fracture.

电解水制氢技术及大电流析氧反应研究与展望

当今时代对可持续能源的迫切需求推动了可再生能源技术的不断改进,其中氢能因其清洁环保且能量密度高而受到了科研人员广泛关注.电解水制氢作为一种绿色环保的制氢方式,其阳极析氧反应(OER)的高能耗限制了电解水制氢技术的广泛应用.近年来,高性能的OER催化剂的研究得到了长足发展,但催化剂的测试范围小,且很少能够连续工作数百小时,远远不能满足实际应用的需求.为了更好的适用于工业应用,OER催化剂需要满足更苛刻的测试环境,如在低过电位下提供大电流密度、在强气体排放过程中维持稳定性和耐久性,因此开发在大电流密度下的高活性OER催化剂是当前工作的重中之重.结合大电流OER催化剂的研究进展,本文首先提出氢能是目前最有前途的能源之一,并调研了大电流密度下电催化剂的研究现状.其次通过对OER机理进行分析,发现采取元素掺杂、界面工程、缺陷工程和形貌工程等措施可以提升催化剂在大电流密度下的活性.最后,对大电流析氧领域在工业发展中现阶段存在的挑战及未来发展方向进行了展望.

Fabrication of Large Scale Self-supported WC/Ni(OH)_(2) Electrode for High-current-density Hydrogen Evolution

In the industry, cheap and stable electrocatalysts are eagerly expected for hydrogen evolution reaction(HER) at a high current density. Two-component electrochemical catalysts with integrated multiple interfaces seem to be an expedient strategy to enhance the inherent electronic structure of hybrid electrocatalysts and optimize the catalytic ability. In this work, we report an active tungsten carbide and nickel hydroxide(WC/Ni(OH)_(2)) electrocatalyst seamlessly synthesized on the substrate of W foil. Ni(OH)_(2) trends to adsorb OH_(ad) and WC can effectively adsorb H_(ad). Prompted by the synergistic effect, the ability of the catalyst manifests an effective HER kinetics with an overpotential of 475 m V(vs. RHE) at a high current density of 1000 m A/cm^(2) in 1 M KOH. Moreover, due to its self-supported construction, the catalyst presents reliable long-term stability with no obvious active property loss after 8000 cycles and 50 hours of operation in an alkaline solution.

脱合金效应提升NiRu@C催化剂的析氢性能

电催化析氢反应(HER)是获得可再生氢能的有效策略,但电催化析氢催化剂活性和稳定性仍有待提高。基于此,通过热解镍盐、钌盐、柠檬酸的络合物制备了碳包覆镍钌催化剂,为了克服该催化剂中Ru原子利用率低的缺点,采用乙酸对碳包覆镍钌催化剂进行刻蚀制备脱合金NiRu@C催化剂。通过XRD、BET、ICP等手段对脱合金NiRu@C催化剂进行表征,在摩尔浓度1.0 mol/L KOH电解质中测定脱合金NiRu@C催化剂的电催化析氢性能。结果表明:脱合金处理后,Ni从NiRu晶格中溶解出来,形成富Ru的多孔结构,Ni的溶出造成催化剂结构及晶格参数的改变,多孔结构的形成使催化剂比表面积大幅度增加,增加了Ru活性位点的暴露;脱合金NiRu@C催化剂具有优异的HER活性,在电流密度10 mA/cm^(2)下过电位仅为36 mV,与未脱合金的NiRu@C催化剂相比,HER性能提升4倍,优于商业Pt/C催化剂(40 mV)。脱合金策略为优化HER活性提供一种新的思路。

高差压质子交换膜水电解制氢系统设计及性能实验

研制了制氢量为0.3 Nm^(3)/h,输出压力为3.0 MPa的差压PEM(质子交换膜)水电解制氢装备,并测试分析了装置的电化学、气体纯度和水电解过程中质子膜内水分迁移等方面的性能。结果表明:装置在压力3.0 MPa、温度45℃、电流密度1 A/cm^(2)工况下,小室平均电压为1.843 V,氧中氢体积分数浓度为14 500×10^(-6),排水与氢气物质的量之比为4左右。结论:电池堆电化学特性及氢气安全性均满足设计要求,提升电堆极板的表面状况和导电性能将提高电堆整体能效。阴极出水低压释氢以及原位催化除氢,是降低氧中氢浓度、保障安全的有效途径。差压下水分传输系数与电流密度成正比关系,而等压下成反比关系,且差压下的值小于等压的值。

Double active sites promoting hydrogen evolution activity and stability of CoRuOH/Co_(2)P by rapid hydrolysis

Cobalt-based phosphides show excellent hydrogen evolution reaction(HER)performance,however,improving the intrinsic activity and stability of it in alkaline electrolyte still remains a challenge.Herein,CoRuOH/Co_(2)P/CF with heterojunction structure was developed by means of molten salt and rapid hydrolysis(30 s).The OH-from rapid surface hydrolysis of Co_(2)P as a hydrogen adsorption site can facilitate the formation of thin CoRuOH layer as a water dissociation site,which may bring out better synergistic effect for alkaline HER.Moreover,the covering of CoRuOH can improve the stability of Co_(2)P for HER.When drives at 100 mA/cm^(2),it only requires overpotential of 81 mV in 1.0 mol/L KOH(25℃).Even at higher current density(1000 mA/cm^(2)),CoRuOH/Co_(2)P/CF can also operate stability for at least 100 h.When coupling with NiFe-LDH/IF in a two-electrode system,the voltage of NiFe-LDH/IF(+)||CoRuOH/Co_(2)P/CF(-)at 1000 mA/cm^(2)is merely 1.77 V with 100 h,demonstrating great potential for water splitting.The implementation of this work provides a new strategy and reference for the further improvement of transition metal phosphides as HER electrocatalysts.

阴极电流密度对超高强钢锌镍镀层腐蚀及氢脆性能的影响

碱性电镀锌镍因生产过程更环保、镀层耐蚀性好等优点,已成为代镉技术的首选。但是,由于氢脆等原因,暂未应用于超高强钢A100的表面防护。采用一种碱性镀液配方,在不同阴极电流密度下对超高强钢A100表面进行电镀及钝化,同时对钝化后的镀层进行了物相、微观形貌、电化学性能、盐雾、氢脆等组织及性能进行表征。结果表明:在阴极电流密度为2—4 A∙dm^(−2)范围内,可得到单一γ相镀层,并且镍含量在12%—13%左右;当阴极电流密度为2 A∙dm^(−2)时,析氢反应进行得比高电流密度时剧烈,电镀效率较低,需要更长的电镀时间才能得到与阴极电流密度为3—4 A∙dm^(−2)时耐蚀性相近的镀层。本镀液配方制备的镀层氢脆性能好,带有镀层的试棒均通过了200 h缺口拉伸测试,且在3—4 A∙dm^(−2)阴极电流密度电镀时渗氢电流也保持在了一个较低水平。