燃料电池金属双极板表面改性技术综述

文章从耐腐蚀性、导电性的角度,概述了燃料电池金属双极板的性能要求、表面改性涂层材料和改性加工方式,重点介绍了不同涂层材料表面改性的特点,及对金属双极板性能的影响,为燃料电池双极板的后续发展提供参考。     

钛双极板表面碳掺杂氮化钛耐腐蚀涂层制备

为改善钛双极板在质子交换膜(PEM)水电解槽环境中的耐腐蚀性能和导电性能，采用电泳沉积-热处理两步法在钛基底表面制备碳掺杂氮化钛(C-TiN)复合保护涂层，并在0.5 mol/L的H₂SO₄和5 mg/L的F^-溶液中模拟PEM水电解槽阳极环境测试其电化学腐蚀性。结果表明，电泳沉积及热处理改善了氮化钛纳米颗粒的连通性，增强了涂层与衬底的粘附力，实现了电子在电活性材料中快速传递。400℃下制备的碳掺杂氮化钛涂层(C-TiN-400℃),其导电性与耐蚀性均得到明显提升；相比于未处理的样品，镀有C-TiN-400℃涂层的样品在146.3 N/cm²压力下的接触电阻可达到2.25 mΩ·cm²。     

氢燃料电池中钛双极板研究进展

钛及钛合金密度低、比强度高且在酸性环境中耐蚀性优异,在氢燃料电池双极板中具有较高的应用价值。回顾了近年来氢燃料电池用钛双极板的研究进展,详述了钛双极板表面改性技术的研究成果,包括掺杂合金元素、钛表面涂覆金属基涂层(贵金属、金属碳/氮化物等)和碳基涂层(石墨、无定型碳等)。涂层结构组织的复合化和纳米化,有利于提升钛双极板的耐蚀性、导电性和疏水性,其对于提升氢燃料电池的性能及保证其运行的稳定性和耐久性具有重要作用。     

纯钛TA2激光气体氮化涂层的组织与性能

使用快速横流的CO2连续激光器在工业纯钛TA2表面进行激光气体氮化改性处理,制备形成致密、无裂纹缺陷的改性层。用扫描电镜和能谱分析仪对激光气体氮化改性层的色泽、宏观形貌和微观组织进行分析;利用显微硬度计对氮化区域的显微硬度进行测试。研究结果表明:经过激光表面氮化处理后,在基体纯钛TA2表面发生了化合反应,生成以TiN为增强相的金黄色耐磨涂层。氮化改性层的组织主要是由细小的、枝晶状的TiN构成。随着激光输出功率的增加,TiN涂层的色泽特征由浅变深,表面形态由平整变为皱状。工业纯钛TA2显微硬度提高,表面强化明显。     

TiO_2纳米颗粒自清洁航空涂料的性能研究

以有机硅改性聚氨酯树脂为主要成膜物质,经氟硅烷进行表面改性后的TiO2纳米颗粒作为无机填料,制备具有自清洁功能的航空涂料。利用透射电镜(TEM)、X射线光电子能谱仪(XPS)、扫描电镜(SEM)及接触角分析仪对氟硅烷的改性机制进行了分析,讨论了改性TiO2纳米颗粒的用量对涂层疏水性及其力学性能的影响,探讨了表面微观结构和涂层疏水性能之间的关系,并分析了有效改善涂层力学性能的技术途径。结果表明,氟硅烷分子水解后相互联结,在TiO2纳米颗粒表面形成一层氟硅烷分子包覆层,提高了TiO2纳米颗粒的分散性及疏水性。随着氟硅烷改性后的TiO2纳米颗粒添加量逐渐增多,制备的有机涂层表面粗糙度逐渐增大,疏水效果越来越明显。当改性TiO2纳米颗粒的用量为24%时,涂层具有超疏水性,水接触角为151.40°,涂层表面为微纳米双重粗糙结构。通过在基底表面刷涂一层质量分数为5%~15%的硅烷偶联剂(KH-550)乙醇溶液,可以提高涂层的力学性能,达到航空涂料的基本使用要求。     

耐腐蚀涂层Cr_2N在质子交换膜燃料电池中的应用性能研究

采用固体粉末包埋工艺在316L不锈钢双极板上沉积Cr_2N涂层,通过动电位和恒电位极化测试研究了Cr_2N涂层的耐腐蚀性,并测量了界面接触电阻(ICR)和接触角。结果表明,与316L不锈钢相比,在1 100℃下沉积的Cr_2N涂层表现出较好的物相形貌、耐腐蚀性和较低的ICR值;Cr_2N涂层的腐蚀电流密度在0.84 V(vs.SHE)下约5.01×10~(-8) A/cm~2,比316L不锈钢低了三个数量级;Cr_2N涂层的ICR值在150 N/cm~2时为8.7 mΩ·cm~2,约为316L不锈钢的1/8;Cr_2N涂层致密、平滑、连续,其阻抗和相位角在电解质溶液中变化较小,能够阻止SO■、F~-向基底渗透,起到有效的防腐作用。此外,Cr_2N涂层还可以改善双极板的疏水性,在沉积Cr_2N涂层后,不锈钢双极板的接触角从79.7°提升到105.7°。Cr_2N涂层是用于质子交换膜燃料电池的316L不锈钢双极板的理想保护层。     

质子交换膜燃料电池双极板用不锈钢的聚苯胺涂层改性

将苯胺单体滴加到硫酸溶液中配制成电解液,采用恒电流法在304不锈钢板表面沉积聚苯胺涂层,通过动电位极化和恒电位极化分析不锈钢板的防腐性能,利用自制的导电性能测试设备分析涂层与不锈钢板的界面接触电阻,探讨聚苯胺涂层用于质子交换膜燃料电池双极板改性的可能性。结果表明,在优化工艺条件下制备的聚苯胺涂层的腐蚀电位和腐蚀电流密度分别为369 mV和0.479μA/cm2,与裸钢相比,腐蚀电位升高536 mV,腐蚀电流密度降低4个数量级。模拟质子交换膜燃料电池的实际工作环境进行恒电位极化曲线测试,分析测试后的溶液离子含量。结果表明,涂层改性不锈钢板的腐蚀电流密度比裸钢低2个数量级,具有很好的耐久性;阳极环境比阴极环境具有更强的腐蚀性。恒电位极化测试前,压力为1.4 MPa时,裸钢和涂层试样的界面接触电阻分别为97和145 mΩ·cm2,腐蚀后涂层试样的界面接触电阻比裸钢的低更多。用聚苯胺改性的不锈钢的防腐和导电性能在一定程度上都能达到目标值,在质子交换膜燃料电池双极板中具有很大的应用潜力。     

TiO_2纳米管的制备及其性能研究

为使钛基金属适宜人体的植入环境,提高润湿性及耐腐蚀性。以NH4F和乙二醇溶液为电解液,在25 V直流电压下,采用阳极氧化法在钛片表面制备Ti O2纳米管,系统研究阳极氧化时间对Ti O2纳米管形貌、物相组成、润湿性及耐腐蚀性的影响。利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)表征Ti O2纳米管的形貌和物相组成。利用接触角测量仪测试试样的水接触角。利用动电位极化曲线研究试样的耐腐蚀性。结果表明:当氧化时间为2h时,钛表面出现高度有序的Ti O2纳米管,孔径范围大约在30~40 nm,孔壁厚约为20 nm;钛片与水的接触角较小约为28.8°,润湿性较好;自腐蚀电压为0.145 V,比纯钛提高约34%,自腐蚀电流约为0.468μA/cm2,腐蚀电阻Rp约为1.023×105Ω/cm2,显著提高了耐腐蚀性。     

取向硅钢绝缘涂层绝缘性能影响因素分析

绝缘性能是取向硅钢的一个重要指标,本文研究了涂层烧结温度、涂液中硅溶胶含量、绝缘涂层涂敷量对取向硅钢绝缘性能的影响。研究发现:烧结温度升高,涂层表面逐渐出现微观裂纹,钢板表面在850℃下烧结时出现裂纹,退火温度达到900℃后,涂层表面裂纹会急剧增加,导致涂层绝缘性降低。在相同烧结温度下,提高涂液中SiO2含量,将导致涂层表面出现微观裂纹,不利于涂层的绝缘性能。在相同烧结温度下,提高绝缘涂层的涂敷量,有利于提高钢板的层间电阻。在烧结温度为850℃,涂敷量为6 g/m2时,钢板层间电阻可达到82.6Ω·cm2。     

钼镧合金表面FeCrAl涂层耐腐蚀性能

采用非平衡磁控溅射工艺在Mo–La合金表面沉积FeCrAl涂层,研究所制备涂层的耐腐蚀性及涂层的腐蚀机理。结果表明：FeCrAl涂层样品在360℃、18.6 MPa、纯水的高压釜中腐蚀72 h,平均腐蚀速率为3.8 mg·dm_?²,低于同条件下锆合金以及未沉积涂层的钼镧合金的腐蚀速率,且涂层中的Al与外界环境介质中的氧发生反应,在涂层表面形成致密的Al₂O₃薄膜,在一定程度上减缓了涂层的腐蚀速度,有效保护了基体材料。FeCrAl涂层样品在1200℃、0.1 MPa的高温水蒸气环境下腐蚀8 h,Al₂O₃氧化膜厚度在4.0μm左右,涂层维持保护效果,钼镧合金基体未暴露在腐蚀环境中;经淬火后,Al₂O₃氧化膜厚度减小至2.5μm左右,涂层依旧维持结构完整性,没有出现贯穿性脱落,满足Mo–La合金表面耐腐蚀性的使用要求。     

织构对纳米晶纯镍镀层耐蚀性能的影响

采用脉冲电镀法在黄铜表面制备出具有(111)、(200)和(220)晶面择优生长织构的纳米晶纯镍镀层.采用扫描电镜对镀层的显微形貌进行观察,采用X射线衍射对不同晶面织构的择优性进行表征,并对镀层在3.5%NaCl溶液中的动电位极化曲线和交流阻抗谱进行了测试,研究不同织构镀层的耐蚀性能.不同织构镀层的耐蚀性能存在显著差异:具有(220)强织构的镀层耐蚀性最差,其自腐蚀电流密度最大,为1.23μA·cm-2,镀层的电荷转移电阻为2.09kΩ·cm2;具有(200)强织构的镀层耐蚀性能最佳,镀层的电荷转移电阻为27.32kΩ·cm2,自腐蚀电流密度为0.15μA·cm-2;具有(111)织构镀层的耐蚀性居中.认为织构引起的表面胞状物的差别是造成纯镍镀层耐蚀性能不同的原因.      

钛合金表面硬化与固体润滑处理层的电化学腐蚀行为研究

分别利用等离子氮化技术和离子束增强沉积(IBED)技术使钛合金表面获得硬质抗磨层和MoS2，MoS2-Ti固体润滑膜层。通过电化学测试技术研究了膜层和钛合金基材在含Cl^-介质中的抗蚀性能和接触腐蚀敏感性：研究结果表明：Ti与MoS2的复合改善了MoS2膜的环境适应性，MoS2—17Ti复合膜层与钛合会接触相容；IBED TiN较钛合金电化学活性低，阳极极化行为与Ti6Al4V合金相近，与钛合金基体间电偶腐蚀敏感性低；钛合金等离子氮化处理层在NaCl水溶液中无论处于自然腐蚀电位还上弱阳极极化状态，均较钛合金电化学活性低，且与钛合金基体间电偶腐蚀敏感性低。     

Effects of Nitrogen Flow Rate on the Performances of Cathodic Arc Deposited TiN Films on 316L Stainless Steels as Bipolar Plates for the Proton-Exchange Membrane Fuel Cell

The corrosion resistance, interfacial contact resistance (ICR), and hydrophobicity of cathodic arc deposited TiN films on 316L stainless steels at different nitrogen flow rates as bipolar plates (BPs) for the proton-exchange membrane fuel cell (PEMFC) are investigated. It is shown in the results that the TiN-coated 316L stainless steel prepared at a moderate nitrogen flow rate (250 sccm) exhibits a low stable corrosion current density of 6.5 × 10⁻⁸ A cm⁻² in the simulated corrosive cathode environment of PEMFC, and a low ICR of 8.94 mΩ cm⁻² at a pressure of 1.38 MPa after corrosion, meanwhile presents a good hydrophobicity before and after corrosion. These results are discussed by considering the probable effects of the nitrogen flow rate on the substrate/coating system based on the microstructural characterization of the substrate/coating interface and the coating, which shows that the interdiffusion will be started in the deposition process and a moderate nitrogen flow rate during the coating process will promote to the broadening of interface region and lead to the formation of a robust and high-quality coating with fewer defects that can effectively improve the performances of the 316L stainless steel substrate as the BP for PEMFC.     

Properties of nanolayer erosion-resistant coatings based on metal carbides and nitrides

Vacuum-arc ion-assisted deposition is used to form nanolayer protective 2D coatings based on the nitrides or carbides of titanium and chromium, vanadium carbide, and aluminum nitride with a layer thickness of 5–80 nm and a total thickness up to 25 μm. The phase composition of the coatings is studied after deposition and tests. Titanium alloy VT1-0 (EP866 steel)-nanolayer coating compositions are subjected to hot-strength and rapid cyclic corrosion tests, and the erosion resistance of the 2D nanolayer coatings in a dust-air flux (the average fraction of quartz sand is 300–350 μm) is studied. Among the 2D nanolayer coatings on titanium and steel substrates, a composition of VT1-0 alloy with a TiN/CrN coating at a nanolayer thickness of 60–70 nm and a total thickness of 19 μm has the maximum erosion resistance. The erosion resistance of the TiN/CrN coating is shown to decrease with decreasing nanolayer thickness, and it has a high thermal stability after holding at 700°C for 100 h.     

Effect of novel surface treatment on corrosion behavior and mechanical properties of a titanium alloy

A new surface treatment process is presented that improves the properties of Ti-6 Al-4 V alloy.This process is based on thermal oxidation, in which the surface properties of the titanium alloy are improved via simultaneous nitriding and oxidation.The test results indicate that the resulting surface layer consists of TiO_2 and TiN.The sample with the best mechanical properties and corrosion resistance was sintered at a temperature of 800 ℃.     

反应等离子喷涂TiN复相涂层的组织与性能研究

采用工业纯钛粉,利用反应等离子喷涂技术,在45钢表面原位合成TiN复相涂层。利用X射线衍射仪分析了涂层的物相组成,采用扫描电镜观察涂层的组织结构、显微压痕、断口和磨损形貌,采用能谱仪分析压痕微区成分,测试了涂层的显微硬度和耐磨性能。结果表明:复相涂层由TiN、TiN0.3、Ti3O组成;涂层具有典型的层状组织结构,且层与层之间、层与基体之间结合较好;涂层的显微硬度为983~1 254 HV0.1;显微压痕形状清晰、规则,且压痕周围无翘边现象;断口形貌说明涂层具有一定的韧性,为介于陶瓷材料与韧性材料之间的混合断裂机制;涂层在低载荷时耐磨性能最佳。     

Effect of vacuum ion-plasma treatment on the electrochemical corrosion characteristics of titanium-alloy implants

The effect of mechanical polishing and various types of vacuum ion-plasma treatment of model implants made of VT1-0, VT20, and VT6 titanium alloys on their electrochemical corrosion characteristics in a 0.9% NaCl solution (Ringer’s solution) is studied. Ion nitriding and the evaporation of a titanium nitride coating are shown to form a surface structure that provides an increase in the hardness, wear resistance, and corrosion resistance of these implants.     

Wear resistance in ceramic silicon nitride cutting tools bearing continuous or discrete titanium nitride coatings

Measurements have been made on the wear resistance of ceramic cutters based on silicon nitride and bearing titanium nitride coating during the continuous machining of ShKh15 steel. The coatings were deposited by cathode sputtering. Use was made of continuous coatings and discrete ones in the form of ordered fragments. The continuous TiN coatings raise the wear resistance by a factor of 1.7, while the factor is 2.2 for the discrete TiN coatings. The performance of the tool is also improved in the case of the discrete coatings as the cutting speed and feed can be raised by comparison with tools with continuous coating.