Ti/(Ti,Cr)N/CrN multilayer coated 316L stainless steel by arc ion plating as bipolar plates for proton exchange membrane fuel cells

Arc ion plating (AIP) is applied to form Ti/(Ti,Cr)N/CrN multilayer coating on the surface of 316L stainless steel (SS316L) as bipolar plates for proton exchange membrane fuel cells (PEMFCs). The characterizations of the coating are analyzed by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Interfacial contact resistance (ICR) between the coated sample and carbon paper is 4.9 m Omega cm(2) under 150 N/cm(2), which is much lower than that of the SS316L substrate. Potentiodynamic and potentiostatic tests are performed in the simulated PEMFC working conditions to investigate the corrosion behaviors of the coated sample. Superior anticorrosion performance is observed for the coated sample, whose corrosion current density is 0.12 mu A/cm(2). Surface morphology results after corrosion tests indicate that the substrate is well protected by the multilayer coating. Performances of the single cell with the multilayer coated SS316L bipolar plate are improved significantly compared with that of the cell with the uncoated SS316L bipolar plate, presenting a great potential for PEMFC application. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Preparation of CS-CMC Bipolar Membrane and its Application in Electro-generated FeO_4^(2-)

CS-CMC bipolar membrane was prepared and the cross-section photograph of CS-CMC BM was observed by SEM. FT-IR spectrum indicated that CS-CMC BM contained -N=CRH2^＋ and -COO^- functional groups. The charge density of -N--CRH2^＋ in CS membrane was about 14.13 mmol/g and the charge density of -COO in CMC membrane was about 9.01 mmol/g. The electrochemistry properties of CS-CMC BM were also studied. CS-CMC BM not only can effectively stop FeO4^2- from diffusing into the cathode chamber, but also plays an important role in the supply of OH＂ consumed during the electro-generated FeO4^2- process.

Process and challenges of stainless steel based bipolar plates for proton exchange membrane fuel cells

Proton exchange membrane fuel cell(PEMFC)powered automobiles have been recognized to be the ultimate solution to replace traditional fuel automobiles because of their advantages of PEMFCs such as no pollution,low temperature start-up,high energy density,and low noise.As one of the core components,the bipolar plates(BPs)play an important role in the PEMFC stack.Traditional graphite BPs and composite BPs have been criticized for their shortcomings such as low strength,high brittleness,and high processing cost.In contrast,stainless steel BPs(SSBPs)have recently attracted much attention of domestic and foreign researchers because of their excellent comprehensive performance,low cost,and diverse options for automobile applications.However,the SSBPs are prone to corrosion and passivation in the PEMFC working environment,which lead to reduced output power or premature failure.This review is aimed to summarize the corrosion and passivation mechanisms,characterizations and evaluation,and the surface modification technologies in the current SSBPs research.The non-coating and coating technical routes of SSBPs are demonstrated,such as substrate component regulation,thermal nitriding,electroplating,ion plating,chemical vapor deposition,and physical vapor deposition,etc.Alternative coating materials for SSBPs are metal coatings,metal nitride coatings,conductive polymer coatings,and polymer/carbon coatings,etc.Both the surface modification technologies can solve the corrosion resistance problem of stainless steel without affecting the contact resistance,however still facing restraints such as long-time stability,feasibility of low-cost,and mass production process.This paper is believed to enrich the knowledge of high-performance and long-life BPs applied for PEMFC automobiles.

Using bipolar membrane electrodialysis to synthesize di-quaternary ammonium hydroxide and optimization design by response surface methodology

Bipolar membrane electrodialysis(BMED) has already been described for the preparation of quaternary ammonium hydroxide. However, compared to quaternary ammonium hydroxide, di-quaternary ammonium hydroxide has raised great interest due to its high thermal stability and good oriented performance.In order to synthesize N,N-hexamethylenebis(trimethyl ammonium hydroxide)(HM(OH)_2) by EDBM,experiments designed by response surface methodology were carried out on the basis of single-factor experiments. The factors include current density, feed concentration and flow ratio of each compartment(feed compartment: base compartment: acid compartment: buffer compartment). The relationship between current efficiency and the above-mentioned three factors was quantitatively described by a multivariate regression model. According to the results, the feed concentration was the most significant factor and the optimum conditions were as follows: the current efficiency was up to 76.2%(the hydroxide conversion was over 98.6%), with a current density of 13.15 m A·cm^(-2), a feed concentration of 0.27 mol·L^(-1) and a flow ratio of 20 L·h^(-1):26 L·h^(-1):20 L·h^(-1):20 L·h^(-1) for feed compartment, base compartment, acid compartment, and intermediate compartment, respectively. This study demonstrates the optimized parameters of manufacturing HM(OH)_2 by direct splitting its halide for industrial application.

Electro-generation of TGA by Ni-mSA-mCS bipolar membrane

Ni-mSA-mCS bipolar membrane （BM） was prepared by sodium alginate （SA） and chitosan （CS）, which were modified by Ca^2＋ and glutaraldehyde as linking reagents, respectively, mSA-mCS membrane was characterized by FTIR, SEM, TG and used as a separator in the electrolysis cell to produce thioglycolic acid （TGA）. The experiment results show that TGAwas prepared effectively by electro-reduction of dithiodiglycolic acid （DTDGA） with the mixture of TGA and DTDGA in the cathodic chamber. The current efficiency was up to 66.7% at the room temperature （25 ℃） during the current density of 10 mA/cm^2. Compared with the traditional metal reduction method, the electro-reduction technology saves the zinc powder and eliminates the pollution to environment.

Water Dissociation Phenomena on a Bipolar Membrane──Current-voltage Curve in Relation with IonicTransport and Limiting Current Density

The water dissociation mechanism on a bipolar membrane under the electrical field was investigated and characterized in terms of ionic transport and limiting current density. It is considered that the depletion layer exists at the junction of a bipolar membrane, which is coincided with the viewpoint of the most literatures, but we also consider that the thickness and conductivity of this layer is not only related with the increase of the applied voltage but also with the limiting current density. Below the limiting current density, the thickness of the depletion layer keeps a constant and the conductivity decreases with the increase of the applied voltage; while above the limiting current density, the depletion thickness will increase with the increase of the applied voltage and the conductivity keeps a very low constant. Based on the data reported in the literatures and independent determinations, the limiting current density was calculated and the experimental curves Ⅰ-Ⅴ in the two directions were com

Stable overall water splitting in an asymmetric acid/ alkaline electrolyzer comprising a bipolar membrane sandwiched by bifunctional cobalt-nickel phosphide nanowire electrodes

Water splitting has been proposed to be a promising approach to producing clean hydrogen fuel.The two half-reactions of water splitting,that is,the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),take place kinetically fast in solutions with completely different pH values.Enabling HER and OER to simultaneously occur under kinetically favorable conditions while using exclusively low-cost,earth-abundant electrocatalysts is highly desirable but remains a challenge.Herein,we demonstrate that using a bipolar membrane(BPM)we can accomplish HER in a strongly acidic solution and OER in a strongly basic solution,with bifunctional self-supported cobaltnickel phosphide nanowire electrodes to catalyze both reactions.Such asymmetric acid/alkaline water electrolysis can be achieved at 1.567 V to deliver a current density of 10 mA/cm2 with ca.100%Faradaic efficiency.Moreover,using an“irregular”BPM with unintentional crossover the voltage needed to afford 10 mA/cm2 can be reduced to 0.847 V,due to the assistance of electrochemical neutralization between acid and alkaline.Furthermore,we show that BPM-based asymmetric water electrolysis can be accomplished in a circulated single-cell electrolyzer delivering 10 mA/cm2 at 1.550 V and splitting water very stably for at least 25 hours,and that water electrolysis is enabled by a solar panel operating at 0.908 V(@13 mA/cm2),using an“irregular”BPM.BPMbased asymmetric water electrolysis is a promising alternative to conventional proton and anion exchange membrane water electrolysis.

A Simple Model to Determine the Trends of Electric Field Enhanced Water Dissociation in a Bipolar Membrane

This work is concentrated on elucidating the mechanism of the electric field enhanced water dissociation. A simple model was established for the theoretical current-voltage characteristics in water dissociation process on a bipolar membrane based on the existence of a depletion layer and Onsager's theory. Particular attention was given to the influence of applied voltage on depletion thickness and the dissociation constant. The factors on the water splitting process, such as water diffusivity, water content, ion exchange capacity, temperature, relative permittivity, etc. Were adequately analysed based on the derived model equations and several suggestions were proposed for decreasing the applied voltage in practical operation. The water dissociation tests were conducted and compared with both the theoretical calculation and the measured current-voltage curves reported in the literature, which showed a very good prediction to practical current-voltage behavior of a bipolar membrane at high current densities when the splitting of water actually commenced.

Research on Bipolar Membrane Electrodialysis for Ion Exchange of Molecular Sieves

In view of the problems associated with large amount of discharged wastewater and serious pollution in the existing technology for removing sodium species from molecular sieves,this research work introduces the bipolar membrane electrodialysis into the process of removing sodium species from molecular sieves,and proposes a novel method of cleanly removing sodium from molecular sieves.The results show that the technology for removing sodium ions from the molecular sieves with an indirect electrodialysis process is feasible,and can recover Na OH solution.The bipolar membrane electrodialysis is especially suitable for treating the USY,ZSM-5 and Beta molecular sieves with high acid-resistance,and the physicochemical properties and catalytic performance of the prepared molecular sieves are roughly equivalent to those of the ammonium ion-exchange method.In comparison with the ammonium ion-exchange method,the process is clean and environmentally friendly,which consumes less water,and does not discharge wastewater to exhibit a rosy prospect of industrial application.

Waste Water Treatment in Direct Borohydride Fuel Cell with Bipolar Membrane

It was established that application of bipolar membrane in a direct borohydride fuel cell (DBFC) with H2O2 co-generation enabled to keep constant pH in catholyte within 2.5 - 3.2 limits, which allowed us to carry out treatment of water polluted by organic compounds in fuel cell catholyte. Treatment of water was carried out by electro-Fenton and photo-electro-Fenton methods. With the view of efficiency, photo-electro-Fenton method of treatment was the most efficient, which enabled to decrease COD of catholytes containing (in each case) phenol, valsaren, 400 g/L dymethoate (BI-58) and valsaciper from 500 ppm to 30, 11, 9 and 3 ppm, respectively after 180 min treatment. By increasing the catholyte temperature from 20℃?to 40℃?in the same period, phenol COD fell to 5 ppm.

Bipolar ionomer electrolytes with desirable self-discharge suppression for supercapacitors

Supercapacitors based on electric double layers are prone to serious self-discharge due to electrolyte ion desorption and the resulting energy loss severely limits the application range of supercapacitors.Rational design of polymer electrolyte systems to address this problem shows considerable generality and high feasibility.Herein,we reported a quasi-solid-state bipolar ionomer electrolyte prepared by an in-situ layer-by-layer ultraviolet-curing method,which has an integrated Janus structure with an intermediate binding layer.Based on the synergistic effect of confining impurity ions by ionizable groups and electrostatic repulsion to stabilize the electric double layers and superimposing synergies on both sides,the assembled device not only possesses ideal supercapacitor characteristics,but also exhibits an ultrahigh voltage retention of 71% after being left to stand for 100 h after being fully charged.Furthermore,through the quasi-in-situ energy dispersive X-ray spectroscopy linear scanning,the characteristics of ion diffusion in this ionomer electrolyte are revealed,suggesting its correlation with self-discharge behavior.

双极膜水解离性能改进研究进展

双极膜因其独特的水解离性能、易与其他电化学技术集成等优势,在碳捕获、节能减排和资源综合利用等领域具有重要的应用。现有双极膜存在水解离效率低、选择渗透性和稳定性差等问题,严重制约其广泛应用,因此近年来,大量研究工作致力于提升双极膜水解离性能。本文从离子交换层性能优化、中间层催化剂及几何结构调控三方面,梳理了国内外双极膜水解离性能改进及优化策略,重点评述了水解离催化剂、膜结构调控规律等方面的研究进展,并对该领域面临的主要挑战和未来发展方向进行展望,以期为高水解离性能双极膜的开发提供借鉴,从而促进其在能源转化和资源再利用等领域的应用。

BPM2型双极膜装置硫酸钠制碱的工业化应用研究

针对原有的双极膜装置制碱的电流效率过低、碱浓度低、能耗过高等缺点,采用自主研制的BPM2型双极膜装置进行硫酸钠制碱的研究。所用的工业化双极膜装置采用的膜尺寸为400 mm×800 mm,共60组,3隔室,有效膜面积为15 m2,产碱能力为100 t/a。双极膜采用国产膜,单极膜采用专用阻酸阻碱膜,电流密度为600 A/m2(150 A)。对电流效率、转化率、能耗、酸碱浓度、制酸碱成本进行了研究与讨论。结果表明,由于膜性能的提高与双极膜装置的改进,电流效率提高至70%以上,碱浓度提高至70 g/L、制碱能耗大幅降低至1 800 kWh/t以下,为进一步硫酸钠制碱的大型工业化生产打下基础。

双极膜研究进展及应用展望

双极膜是一类具有特殊“三明治”结构的离子交换膜。在反向偏压下,双极膜界面层独特的水解离行为使其具有在线生成H+和OH-能力,因而在酸碱生产、资源分离回收等领域发挥着越来越重要的作用。双极膜界面层催化剂的引入可以有效降低水解离反应电阻。然而,大部分双极膜由于界面层构筑不当使其存在水解离电压过高、膜层结合力差、催化剂泄漏以及第一极限电流密度大等问题,无法实现大规模的工业化制备及应用。因此,本文立足于双极膜及技术近期研究进展,从双极膜的水解离机理出发,综述了界面层催化剂的种类、界面构筑方式及膜层的复合工艺三个方面的研究进展,深度分析了浸蘸法、涂覆法、静电组装、原位生长、层层堆叠等界面催化剂固定方式的优缺点,力求为双极膜的规模化制备提供相应的理论支撑。文中也指出了双极膜在工业化酸碱生产过程中的瓶颈问题,提出了不对称双极膜电渗析在工业化酸碱生产应用中的关键作用。最后对双极膜的电化学应用前景进行了展望,即应该努力探索双极膜在电解水制氢、二氧化碳还原、电化学合成氨、燃料电池、液流电池等能源领域的应用前景,以此来推动双极膜的发展。

双极膜电渗析资源化硝酸钠制酸碱

工业生产中产生的含有NaNO_(3)的高盐废水是一种可回收再利用的资源,通过双极膜电渗析(BMED)技术可制备出相应的酸和碱,对高盐废水的资源化利用具有重要的意义。采用三隔室双极膜电渗析膜堆,以NaNO_(3)溶液模拟高盐废水制备HNO_(3)和NaOH。选取能耗、电流效率、转化率作为评价指标,探究电流密度、原料液浓度、极液种类及浓度、酸碱室初始浓度对BMED制酸碱过程的影响。结果表明:随着电流密度的增大,盐转化率提高,能耗增加;随着原料液浓度的增大,电流效率增加,能耗降低,原料液浓度过高会导致电流效率明显降低;极液以3%(质量分数)的NaOH最宜;酸碱室初始浓度的增加可提高盐转化率,降低能耗。综合各因素最优参数进行实验,在电压为35 V、电流密度为700 A/m^(2)、酸碱室初始浓度为0.05 mol/L、原料液为12%(质量分数)的硝酸钠、极液为3%(质量分数)的NaOH的条件下,制得的碱浓度为2.227 mol/L,盐转化率可达93.42%,电流效率为60.83%,能耗为3.23 kW·h/kg。研究结果可为工业生产中NaNO_(3)高盐废水的资源化利用提供参考。

BPM2型双极膜电渗析装置的研制

目前国内能正式应用的双极膜电渗析装置比较缺乏,根据双极膜装置的特点与要求,参考国内外先进的电渗析装置的有关技术,研制出适合双极膜电渗析过程的装置。该装置具有耐腐蚀(耐强酸、强碱、有机溶剂)、膜堆体积小(隔板厚度为0.6mm)、有效膜面积比率大、密封效果好、防漏电、防内漏、阻力小、电流效率高、使用寿命长、可以多次反复拆装等特点。本文介绍了装置的主要构成、特性及测试情况,并对几种典型的双极膜过程进行性能测试,发现其各种性能比文献报道的装置均有所改进,从而为我国双极膜的推广应用提供成型的装置以及为理论研究提供研究平台。

质子交换膜燃料电池服役环境对TA1腐蚀行为的影响

选用纯钛(钛金属牌号TA1)为实验基材,通过动电位、恒电位、电化学阻抗谱(EIS)和模拟工况测试等方法研究了运行环境(温度、pH值、气体氛围)和运行工况(电位和模拟工况时长)对其腐蚀行为的影响,并利用光学显微镜(OM)、能量色散X射线能谱(EDX)、X射线光电子能谱(XPS)、界面接触电阻(ICR)、接触角和表面粗糙度等测试方法,对不同时长模拟工况测试后TA1基材的表面形貌和性能进行了分析.结果表明,运行环境和运行工况对TA1耐蚀性均有影响,在10 h模拟工况测试后,TA1基材表面氧化层的堆积提高了其耐蚀性,腐蚀电流密度从2.62μA/cm^(2)降至0.94μA/cm^(2);其导电性和疏水性显著降低,与商用碳纸之间的ICR值从31.75 mΩ·cm^(2)增加至333.17 mΩ·cm^(2),接触角从86.28°减小至68.04°.

质子交换膜燃料电池核心部件分析

对质子交换膜燃料电池工作原理、结构进行分析,重点对质子交换膜燃料电池的双极板、质子交换膜、电催化剂、膜电极关键部件进行分析研究,质子交换膜燃料电池生产成本高是影响商业化普及的重要原因,未来随着质子交换膜燃料电池技术的进步,生产成本将大幅度降低,有望在汽车产业得到广泛应用。

PEMFC金属双极板氮化物涂层的研究进展

质子交换膜燃料电池(PEMFC)金属双极板具有机械强度高、易加工、成本低等优势,但其在PEMFC的酸性环境中容易被腐蚀,从而会对其寿命及导电性产生不利的影响。通过采用氮化物涂层改性的双极板表面结构会变得更加致密,能够提高基体的耐腐蚀性能,从而提高燃料电池的工作寿命。本文从氮化物涂层的种类出发,回顾了近年来氮化物涂层的研究进展。然后介绍了涂层常见的制备方法,同时对其原理进行了分析,对不同的方法制备出的氮化物涂层进行了分析对比。随后总结了不同种类涂层的特点及存在的问题,对不同种类的涂层的耐腐蚀性能进行了比较。最后指出了氮化物涂层存在的问题,并对其未来的发展方向进行了展望。

双极膜/疏水透气膜-电化学体系高效去除废水中氨氮的研究

氨氮作为地表水和地下水中的主要污染物之一,其形态受水体pH影响。针对废水中氨氮处理过程的pH依赖性问题,利用双极膜在电化学反应过程中H~+/OH~-稳定生成的特性,构建了双极膜/疏水透气膜-电化学(BPM/GPM-EC)体系。该体系通过电化学分离(回收)和氧化(降解)两种工艺的结合,实现了高效的氨氮去除效率。当初始氨氮浓度为4 000 mg·L^(-1)时,在电流密度10 mA·cm^(-2)条件下,BPM/GPM-EC间歇式(以回收为目的)运行5 h后,废水中氨氮去除率达到99.3%,回收率为92.3%,比能耗为18.2 kW·h·kg^(-1) N。而BPM/GPM-EC采用连续式(氨氮回收/氧化协同进行)运行处理含4 000 mg·L^(-1)氨氮的模拟废水,在0.28 mL·min^(-1)流速条件下,可实现76.2%的氨氮回收率及废水中氨氮的全部去除,比能耗仅为14.9 kW·h·kg^(-1) N。研究结果表明,BPM/GPM-EC体系通过集成氨氮的分离与氧化,实现了废水中氨氮的低耗高效处理,为含氨废水的治理探索出了一条新途径。