质子交换膜燃料电池金属双极板表面改性研究进展

双极板是质子交换膜燃料电池（Proton exchange membrane fuel cell,PEMFC）的关键部件,对燃料电池的寿命、成本及性能具有重要影响。相比于石墨双极板和碳基复合材料双极板,金属双极板体积小、强度高、导电性能优异,已成为PEMFC双极板的主流材料。然而金属双极板易在PEFMC两极环境中产生腐蚀,且极板表面生成的氧化膜会降低其导电性,严重阻碍了金属双极板的进一步应用。从金属双极板基材选材、涂层结构设计及其性能等方面综述了金属双极板表面改性研究进展,特别探讨了金属双极板金属基涂层（贵金属、金属碳/氮化物、合金等）和碳基涂层（石墨、导电聚合物、无定型碳等）的最新研究成果,从涂层的膜基结合强度、耐蚀性、导电性和疏水性等方面探讨了现有涂层的优劣,涂层结构复合和纳米化有助于提升涂层的致密性,同时可进一步提升涂层导电性和耐蚀性。如何降低金属双极板材料和表面改性成本,提高极板耐蚀性、导电性和可靠性成为双极板研究的趋势,其对PEFMC性能提升和产业化推进具有重大意义。     

质子交换膜燃料电池不锈钢双极板的腐蚀行为及其表面防护的研究进展

质子交换膜燃料电池(PEMFCs)作为一种环境友好型电池装置,在倡导人与自然和谐相处的现代社会日渐受到重视.双极板是PEMFCs的重要组成之一,其性能的好坏与PEMFCs的发展密切相关.不锈钢双极板虽具有优异的导电性和强度,但在PEMFCs的严苛工作环境下,仍面临着腐蚀与钝化等问题.近年来,国内外的研究者为解决不锈钢双极板的表面防护问题展开了广泛的探索,深入研究发现,解决这一问题的有效途径是在其表面制备高导电性、高耐蚀性的防护涂层.简述了PEMFCs的工作原理以及对双极板的性能要求,从不锈钢双极板的运行环境和工作要求出发,提出其自身存在的问题和所面临的改性难题.另外,对近年来不锈钢双极板的表面防护涂层进行了分类,分别阐述了碳基涂层、金属及其化合物涂层和疏水涂层在不锈钢双极板防护上的研究进展,分析对比了不同方法制备涂层的优缺点,在此基础上,明确了不锈钢双极板表面防护的发展方向和未来表面改性技术的研究热点.     

质子交换膜燃料电池双极板防护涂层研究进展

质子交换膜燃料电池(PEMFC)作为第4代发电技术,具有结构紧凑、体积小、能量密度高、效率高、启动快、低温运行以及零排放的绝对优势,被认为是现阶段理想的清洁能源之一,是未来新能源汽车理想的供能部件,受到各国学者的广泛关注。双极板作为PEMFC重要的组成部件之一,不仅能够将单电池串联、并联或是混合联结形成电池堆,起到支撑作用,还能够隔绝阴极、阳极的反应气体,排出电池堆反应产生的热量和水,对PEMFC电池堆的性能至关重要。合适的双极板材料要具有优异的导电性和耐腐蚀性,已成为PEMFC研究领域的一个热点。简述了PEMFC的工作原理以及近年来石墨双极板、金属双极板以及复合双极板的研究情况,指出了PEMFC在工作条件下对金属双极板的性能要求及改性难题。着重对不锈钢双极板的表面涂层改性进行了研究,列举了碳基涂层、金属及其化合物涂层、导电高分子聚合物涂层、疏水涂层等一系列涂层的研究进展和性能,分析对比了它们在PEMFC双极板表面改性中的优缺点。分析结果表明,过渡金属碳、氮化物以及碳/陶瓷复合涂层具有良好的导电性和耐蚀性且成本较低,是当前以及未来的研究热点,同时如何增强涂层与基体的结合力,也是今后双极...     

质子交换膜燃料电池极板及其表面改性研究进展

在质子交换膜燃料电池（Proton exchange membrane fuel cells,PEMFCs）的部件中,双极板是重要组成部分。双极板约占燃料电池成本、质量、体积的40 %、80 %、50 %。传统的PEMFC因为石墨双极板的材料、工艺等问题,造成其体积和质量较大,这增加了汽车的重量,缩小了汽车底盘地可用空间,影响了质子交换膜燃料电池汽车的性能。因此开发体积小、成本低、制备工艺简单的双极板对推进质子交换膜燃料电池的商业化应用具有重要意义。金属双极板因其成本低、力学性能好、导电性、导热性、体积相对易控等特点,在PEMFC领域备受关注。但金属双极板在PEMFC环境中易生成钝化膜,导致其接触电阻增加。因此,如何在提高金属双极板耐蚀性的同时,保持良好的导电性,是当前对PEMFC研究的重点。本文综述了石墨、复合材料和金属双极板制备工艺及表面改性方法。讨论了双极板及其表面碳化物涂层、金属涂层和氮化物涂层的优缺点,并比较了这些涂层在PEMFC环境下的耐腐蚀性和界面接触电阻性能。     

GO-PTFE-C涂层改性Ti金属板的防腐性能研究

目的提高钛金属板的抗腐蚀性能。方法采用水热浸渍两道工序在Ti双极板上制备GO-PTFE-C复合改性涂层。使用0.1 mol/L葡萄糖溶液作为碳源,在170℃+10 h条件下,于反应釜中完成碳涂层制备。对获得的涂层进行热处理,浸渍5%(质量分数)的聚四氟乙烯(PTFE)溶液和不同浓度氧化石墨烯(GO)的混合悬浮液后,在350℃热处理得到涂层。采用傅氏转换红外线光谱分析仪(FTIR)、扫描电子显微镜(SEM)和能谱仪(EDS)分析表面形貌和成分,选取三电极体系并利用电化学工作站(CHI 660e)表征改性前后双极板电化学性能,在模拟质子交换膜燃料电池(PEMFC)环境中测试其抗腐蚀性能。结果与单一的碳涂层相比,GO-PTFE表面具有更多的C=O官能团,同时由于聚四氟乙烯表面的F与含氧官能团的氧原子电子云的诱导效应,涂层附着力明显提高。其中,采用5%PTFE+3 g/L GO浸渍的涂层的腐蚀电流密度和接触角分别为0.008μA/cm~2和103.6°,恒电位极化测试(0.6 V和-0.1 V)显示,涂层的腐蚀电流密度均低于1μA/cm~2。结论以碳涂层为基体,浸渍GO和PTFE的混合液后,制备所得的钛基双极板在PEMFC的双极板中显示出巨大的应用前景。     

硅烷流量对钛合金双极板表面改性碳膜性能的影响

目的通过对钛合金基底进行表面改性,提高其作为质子交换膜燃料电池(PEMFC)金属双极板的耐蚀导电性能。方法通过等离子体增强化学气相沉积法(PECVD),调控不同的Si H4流量(0～10 mL/min),在钛基底表面制备了含硅非晶碳膜。利用电化学工作站、界面接触电阻测量仪、水接触角测量仪、纳米压痕仪,分别测试了薄膜的耐蚀性、导电性、疏水性和力学性能。通过拉曼光谱分析了腐蚀前后薄膜内部杂化比变化,并结合扫描电子显微镜和高分辨透射电子显微镜研究了薄膜厚度、腐蚀形貌和内部结构。结果 SiH4流量为8m L/min时,制备的含硅非晶碳膜具有最佳耐蚀性和导电性,该含硅非晶碳膜水接触角为102.91°,硬度为9.28 GPa,弹性模量为60.34 GPa,厚度为2.822μm。其动电位腐蚀电流密度为0.017μA/cm2,相比钛基底提升3个数量级(80.51μA/cm~2),在1.4 MPa压力下,其界面接触电阻为47.06 mΩ·cm~2。结论硅的引入诱导非晶碳膜生成类石墨烯结构,提高了非晶碳膜的导电性能和耐蚀性能,提升了薄膜的力学性能及疏水性。用含硅非晶碳膜对钛双极板进行表面改性,有望显著提高极板的燃料电池性能。     

空间燃料电池金属钛表面复合涂层制备与性能研究

金属 Ti 因其密度小（仅为不锈钢的 0.6 倍）和比强度高等特点,是轻量化空间燃料电池金属板材料的首要选择,但其在弱酸性环境中长时间工作容易被腐蚀。为了改善金属 Ti 双极板耐蚀性,采用多弧离子镀技术在金属 Ti 表面制备了由 Ti 过渡层及 TiN 表层构成的 Ti / TiN 复合涂层,研究制备工艺参数对 Ti / TiN 复合涂层微观结构及力学、电化学性能的影响规律。利用场发射扫描电子显微镜（SEM）分析涂层的微观形貌,利用 X 射线衍射仪分析涂层的相组成,利用纳米压痕仪评价涂层的力学性能,利用电化学工作站评价涂层在模拟质子交换膜燃料电池（PEMFC）阴极工作环境下的耐蚀性。结果表明：制备工艺参数优化后的 Ti / TiN 复合涂层具有优异的表面质量和良好的耐蚀性,腐蚀电流密度为 6.383 μA / cm² ,是金属 Ti 腐蚀电流密度的 0.6 倍,Ti / TiN 复合涂层显著提高了金属 Ti 的耐蚀性,可为空间燃料电池金属双极板表面改性提供技术支持。     

硼化钛涂层阴极碳块性能的初步研究

测量了硼化钛涂层(基体为普通底碳块)的导电性、耐蚀性以及与熔融铝的润湿性.结果表明,涂层的导电性优于普通底碳块;涂层碳块比未加涂层的碳块电解时的膨胀率约减小40％;在电解质、铝和电极三相体系中,铝在石墨和碳板上的润湿角均为179～180°,铝在硼化钛涂层上的润湿角小于80°.     

质子交换膜燃料电池金属双极板材料研究进展

双极板在质子交换膜燃料电池(PEMFC)中具有隔离反应介质、收集电流、提供气体通道的作用，金属材料用于双极板面临腐蚀及表面层钝化影响电池性能等问题．在介绍了研究金属双极板性能的方法，包括接触电阻测试、电池极化性能测试、模拟电化学方法等测试方法的同时，着重介绍了在双极板中应用的不同种类铁基金属材料、轻金属材料的性能及各种表面涂层技术的研究进展．简单介绍了PEMFC中，金属双极板材料研究所应重点解决的技术问题．     

在纯钛表面制备疏水和抗腐蚀性碳-PTFE复合涂层的性能（英文）

采用水热法和浸渍法两步工艺在钛板上制备由碳和聚四氟乙烯(PTFE)组成的复合涂层。采用扫描电子显微镜(SEM)、傅里叶变换红外光谱(FTIR)、水接触角计、X射线光电子能谱(XPS)和电化学技术对复合涂层的形貌、组分、疏水和腐蚀性能进行表征,研究不同聚四氟乙烯浓度的浸渍液对复合涂层腐蚀性能的影响。结果表明,当以0.1 mol/L的葡萄糖溶液为碳源、20 wt.%PTFE悬浮液为浸渍液时,聚四氟乙烯均匀分布于所获得的碳复合涂层表面。20 wt.%PTFE浸制的碳涂层与钛板具有良好的结合强度和疏水性,此时润湿角为142.3°,且涂层耐腐蚀性能良好,腐蚀电流密度低至0.0045μA/cm~2。因此,钛基体上制备的碳-PTFE复合涂层具有良好的疏水性和耐腐蚀性,在汽车和金属防腐工业中具有较好的应用前景。     

质子交换膜燃料电池金属双极板改性碳基涂层技术研究进展

对比了碳基涂层改性金属极板、未涂覆的金属极板和传统石墨极板性能的优劣,阐述了碳基涂层在优化金属极板导电耐蚀性能方面取得的最新成果,以及在质子交换膜燃料电池(Proton exchange membrane fuel cells, PEMFCs)环境长期运行后,碳基涂层出现性能失效及寿命受限等问题。通过分析影响碳基涂层性能的因素,指出由于非晶碳材料设计、微观结构等对其性能影响规律的系统化研究不足,导致非晶碳涂层/金属极板损伤及退化机理不明确。重点阐述了国内外关于PEMFCs金属极板改性碳基涂层材料技术的研究进展,包括调控本征碳基涂层(a-C)微观形貌优化涂层性能;采用理论计算与实验相结合的方法制备金属掺杂碳基涂层(a-C:Me),解决涂层与特定金属基体间粘附性差、压应力高等问题;设计多层结构碳基涂层以减少贯穿性缺陷。探讨了几类涂层失效机制,并对金属极板改性用碳基涂层技术进行了展望。     

Surface modification by carbon ion implantation for the application of ni-based amorphous alloys as bipolar plate in proton exchange membrane fuel cells

Ni-based amorphous alloys with surface modification by carbon ion implantation are proposed as an alternative bipolar plate material for polymer electrolyte membrane fuel cells (PEMFCs). Both Ni₆₀Nb₂₀Ti₁₀Zr₁₀ alloys with and without carbon ion implantation have corrosion resistance as good as graphite as well as much lower contact resistance than 316L stainless steel in the PEMFC environment. The formation of conductive surface carbide due to carbon ion implantation results in a decrease in the contact resistance to a level comparable to that of graphite. This combination of excellent properties indicates that carbon ion implanted Ni-based amorphous alloys can be potential candidate materials for bipolar plates in PEMFCs.     

Corrosion behavior of coated steels and Mn‐ and Co‐alloyed steels for separator materials on the cathode side in molten carbonate fuel cells

The corrosion behavior and the electrical resistivity of the oxide scale that forms on alternative materials for bipolar plates in molten carbonate fuel cells (MCFCs) were investigated. Commercial stainless steels (SS) containing cobalt (Haynes 556) and manganese (Nitronic 30, Nitronic 50, and Nitronic 60) were tested under cathodic MCFC conditions Additionally, 316L SS coated with cobalt by thermal spraying was studied. Oxide‐scale resistivity measurements were coupled with observations of microstructural/compositional changes over time. All tested materials formed multilayered oxide scales. The composition of these phases was the key factor in determining the interfacial electrical resistivity. The high cobalt content of Haynes 556 (18 wt%) did not decrease its electrical resistivity or improve its corrosion resistance. Thus, Co‐containing stainless steels, such as Haynes 556, do not appear to be candidate bipolar plate materials for MCFCs. In contrast, the cobalt coating on 316L SS did lead to improved corrosion resistance. The Nitronic alloys formed Mn‐containing oxide scales, which appear to have a beneficial effect on lowering the resistivity of the oxide scale. The corrosion resistance of these Mn‐containing stainless steels was greater than that of 316L SS, the present bipolar plate material.     

Atmospheric Plasma Surface Modification on Stainless Steel Bipolar Plate in PEMFC

In this research,stainless steel bipolar plates for proton exchange membrane fuel cell(PEMFC)have been treated by an atmospheric plasma surface modification technology.The chemical composition and thickness of the oxide film formed by plasma are conducted to verify by Auger electron spectroscopy(AES).Pitting resistance,potentiodynamic polarization curves and electrochemical impedance spectroscopy(EIS)are measured to evaluate the corrosion mechanism and electrochemical properties.The results show that the treated plates have a much thicker oxide film which leads to higher pitting potential,improved corrosion rate,less and smaller pitting holes than those without treatment.The stable chemical and electrochemical properties of the treated stainless steel bipolar plate indicate the stabilization of cell performance and longer service life.     

Characterization of electroless Ni-based alloys for use in bipolar plates of direct methanol fuel cells

In this study, an electroless Ni-P deposit is employed as an anodic coating layer to protect the metallic bipolar plate of a direct methanol fuel cell (DMFC). An inductively coupled plasma-mass spectrometer, grazing incidence X-ray diffractometer, and potentiodynamic polarization measurements were used to study changes in the composition, crystalline structures and corrosion resistance of the Ni-P deposits at various bath pHs and temperatures. The crystalline structure of the Ni-P deposits was observed to change from crystal to amorphous as the P content increased, thus enhancing the corrosion resistance of the plate. The optimal conditions for obtaining the highest P content were found to be at pH 4.3 and 70 °C. Furthermore, the potentiostatic test for the Ni-P deposits prepared under the optimal condition was performed in a simulated anode working environment (0.5 M H₂SO₄ + 10 vol.% methanol), with the test showing that a negative corrosion current was observed at all times, therefore indicating that cathodic protection was employed throughout. Even after 10 h of potentiostatic treatment, no metal ions were found in a test solution. In addition, the result of a DMFC performance test demonstrated that bipolar plates using an anticorrosion coating of Ni-P deposits obtained a lower bulk resistance and an enhanced cell performance when compared to commercially available plates. Hence, the low-cost electroless Ni-P deposit demonstrates high potential for use as a corrosion protection layer in a DMFC bipolar plate with a Cu interlayer.     

Plain carbon steel bipolar plates for PEMFC

Bipolar plates are a multifunctional component of PEMFC. Comparing with the machined graphite and stainless steels, the plain carbon steel is a very cheap commercial metal material. In this paper, the possibility of applying the plain carbon steels in the bipolar plate for PEMFC was exploited. In order to improve the corrosion resistance of the low carbon steel in the PEMFCs' environments,two surface modification processes was developed and then the electrochemical performances and interfacial contact resistance (ICR) of the surface modified plate of plain carbon steel were investigated. The results show that the surface modified steel plates have good corrosion resistance and relatively low contact resistance, and it may be a candidate material as bipolar plate of PEMFC.     

Electrochemical Behavior of Biomedical Titanium Alloys Coated with Diamond Carbon in Hanks’ Solution

Biomedical implants in the knee and hip are frequent failures because of corrosion and stress on the joints. To solve this important problem, metal implants can be coated with diamond carbon, and this coating plays a critical role in providing an increased resistance to implants toward corrosion. In this study, we have employed diamond carbon coating over Ti-6Al-4V and Ti-13Nb-13Zr alloys using hot filament chemical vapor deposition method which is well-established coating process that significantly improves the resistance toward corrosion, wears and hardness. The diamond carbon-coated Ti-13Nb-13Zr alloy showed an increased microhardness in the range of 850 HV. Electrochemical impedance spectroscopy and polarization studies in SBF solution (simulated body fluid solution) were carried out to understand the in vitro behavior of uncoated as well as coated titanium alloys. The experimental results showed that the corrosion resistance of Ti-13Nb-13Zr alloy is relatively higher when compared with diamond carbon-coated Ti-6Al-4V alloys due to the presence of β phase in the Ti-13Nb-13Zr alloy. Electrochemical impedance results showed that the diamond carbon-coated alloys behave as an ideal capacitor in the body fluid solution. Moreover, the stability in mechanical properties during the corrosion process was maintained for diamond carbon-coated titanium alloys.