Suppression of current-induced membrane discharge of bipolar membranes by regulating ion crossover transport

Bipolar membranes(BPMs)exhibit the unique capability to regulate the operating environment of electrochemical system through the water dissociation-combination processes.However,the industrial utilization of BPMs is limited by instability and serious energy consumption.The current-induced membrane discharge(CIMD)at high-current conditions has a negative influence on the performance of anion-exchange membranes,but the underlying ion transport mechanisms in the BPMs remain unclear.Here,the CIMD-coupled Poisson-Nernst-Planck(PNP)equations are used to explore the ion transport mechanisms in the BPMs for both reverse bias and forward bias at neutral and acid-base conditions.It is demonstrated that the CIMD effect in the reverse-bias mode can be suppressed by enhancing the diffusive transport of salt counter-ions(Na^(+)and Cl^(−))into the BPMs,and that in the forward-bias mode with acid-base electrolytes can be suppressed by matching the transport rate of water counter-ions(H_(3)O^(+)and OH^(−)).Suppressing the CIMD can promote the water dissociation in the reverse-bias mode,as well as overcome the plateau of limiting current density and reduce the interfacial blockage of salt co-ions(Cl^(−))in the anion-exchange layer in the forward-bias mode with acid-base electrolytes.Our work highlights the importance of regulating ion crossover transport on improving the performance of BPMs.

Review on high-performance polymeric bipolar membrane design and novel electrochemical applications

Electrochemical devices allow the conversion and storage of renewable energy into high-value chemicals to mitigate carbon emissions,such as hydrogen production by water electrolysis,carbon dioxide reduction,and the electrochemical synthesis of ammonia.Independent regulation of the electrode pH environment is essential for optimizing the electrode reaction kinetics and enriching the catalyst species.The in situ water dissociation(WD,H2O→H++OH-)in bipolar membranes(BPMs)offers the possibility of realizing this pH adjustment.Here,the design principles of high-performance polymeric BPMs in electrochemical device applications are presented by analyzing and connecting WD principles and current–voltage curves.The structure–transport property relationships and membrane durability,including the chemical and mechanical stability of the anion-and cation-exchange layers as well as the integrality of the interfacial junction,are systematically discussed.The advantages of BPMs in new electrochemical devices and major challenges to break through are also highlighted.The improved ion and water transport in the membrane layer and the minimized WD overpotential and ohmic loss at high current densi-ties are expected to facilitate the promotion of BPMs from conventional chemical production to novel electrochemical applications.

Comparative review of corrosion-resistant coatings on metal bipolar plates of proton exchange membrane fuel cells

In the realm of proton exchange membrane fuel cells(PEMFCs),the bipolar plates(BPs)are indispensable and serve pivotal roles in distributing reactant gases,collecting current,facilitating product water removal,and cooling the stack.Metal BPs,characterized by outstanding manufacturability,cost-effectiveness,higher power density,and mechanical strength,are emerging as viable alternatives to traditional graphite BPs.The foremost challenge for metal BPs lies in enhancing their corrosion resistance and conductivity under acidic conditions,necessitating the application of various coatings on their surfaces to ensure superior performance.This review summarizes and compares recent advancements in the research of eight distinct types of coatings for BPs in PEMFCs,including noble metal,carbide,ni-tride,and amorphous carbon(a-C)/metal compound composite coatings.The various challenges encountered in the manufacturing and fu-ture application of these coatings are also delineated.

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.

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.

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.

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.

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.

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.

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。

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。

基于双极膜电渗析的膜集成技术的高矿化度矿井水资源化处理

在当前煤矿矿井水“零排放”及煤炭与水资源逆向分布背景下,西部矿区的高矿化度矿井水如若不进行合理处置便直接排放,不仅对当地生态环境造成不可估量的破坏,而且造成严重的水资源浪费,最终将制约煤炭绿色开发与生态文明建设。传统的高盐废水零排放技术主要是利用蒸发结晶技术将无机盐由溶液态转变为结晶态进行回收。从经济性方面分析,该技术受投资高、运行成本高、无机盐附加值低等问题制约。基于此,以西部某矿井水为原水,以矿井水资源化零排放利用及脱盐低碳化为目标进行膜集成工艺设计,并在此基础上重点探讨电渗析和双极膜电渗析工序不同操作条件(操作电压、进料液浓度、温度、酸碱度、电流密度等)对电渗析脱盐性能及双极膜电渗析制酸碱性能的影响规律,之后以实验数据及经济评估模型,探究其经济可行性,旨在探索出适用于西部矿区高矿化度矿井水处理的膜集成技术,为高矿化度矿井水绿色资源化处理工艺的开发提供新的研究思路。通过对电渗析−双极膜电渗析实验过程探究,发现双极膜系统进料液质量浓度应不超过80 g/L、适宜的操作电压为18 V、适宜的进料液温度为25℃、进料液pH保持中性、更适合采用恒电压操作。此外,证实了以双极膜电渗析为核心的膜集成系统可实现高矿化度矿井水绿色资源化处理,以电渗析系统进料液总含盐量20 g/L为例,总的净收益为18604299元/a,且在耦合光伏电力供应系统时具有明显的二氧化碳减排效应,二氧化碳减排将超过3162 t/a,具有良好的经济效益和社会效益。

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。

焦化尾水资源化回用集成工艺中试

为实现焦化尾水的资源化回用,开发了以预处理、压力-电驱动膜组合及双极膜电渗析技术为核心的集成工艺,并进行了中试研究。集成工艺中,化学软化和臭氧-双氧水复合氧化工艺用于去除原水中的硬度和反渗透浓水中的难降解有机物,纳滤工艺完成了一价离子与高价离子的分离,电渗析和双极膜电渗析工艺实现了焦化尾水的近零排放和酸碱资源再生。化学软化工艺对原水的硬度去除率可达64.2%;臭氧-双氧水复合氧化工艺对反渗透浓水的COD去除率可达35.0%;纳滤工艺的脱盐率可达30.2%,对氯离子、硫酸根、硬度和TOC去除率分别可达-6.8%、97.3%、78.4%和87.4%;双极膜电渗析工艺可得浓度均为2 mol/L以上的酸和碱,能耗为4.0 kW·h/kg。该集成工艺的水回用率大于90%,酸碱可短程循环利用。

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。