目的 利用黏结剂喷射增材制造技术制备掺杂不同比例铌的钛基双极板材料,探索材料成分和烧结温度对其微观结构、电化学性能和导电性的影响。目标是通过优化工艺和成分,提高水电解槽钛基双极板的导电性、耐腐蚀性和性能稳定性,为现有贵金属涂层双极板的性能提升和降本提供新思路。方法 采用黏结剂喷射增材制造技术,制备了不同成分和不同烧结温度下的钛铌合金样品。分析样品的微观结构、相组成,并通过电化学测试评估材料的耐腐蚀性能。此外,测量界面接触电阻（ICR）以评价不同样品的导电性。结果 钛铌合金的致密性随烧结温度的升高显著提升,钛-10铌致密度在1 250 ℃温度下达到77.3%;由于热膨胀系数差异,添加20%（质量分数）铌粉的样品界面存在微裂纹,因此其孔隙率高于钛-10铌样品的孔隙率。在1 250 ℃烧结后,钛-10铌合金在2 V（vs.SHE,相对于标准氢电极SHE）高电位下的腐蚀电流密度为1.72×10-4 A/cm2,明显低于纯钛样品的。20 h恒电位极化后,界面接触电阻仅为4.54 mΩ·cm2,与纯钛样品相比降低了64.5%,表面极板具有更优的导电性能和耐久性。最终实现了复合钛极板的试制。结论 相比于传统钛极板,通过增材制造的钛铌合金电解槽双极板的导电性和耐腐蚀性显著提升。
Abstract
The work aims to fabricate titanium-based bipolar plate materials doped with varying proportions of niobium with binder jetting additive manufacturing technology and investigate the effects of material composition and sintering temperature on their microstructure, electrochemical performance, and electrical conductivity, so as to optimize the process and composition to enhance the electrical conductivity, corrosion resistance, and performance stability of titanium-based bipolar plate in water electrolyzer, providing a new idea for improving the performance and reducing the cost of existing precious metal coated bipolar plate. Titanium-niobium alloy samples with different compositions were prepared at different sintering temperatures through binder jetting additive manufacturing. The microstructure and phase composition of the samples were analyzed, and the corrosion resistance of the materials was evaluated through electrochemical testing. In addition, the interfacial contact resistance (ICR) was measured to evaluate the conductivity of different samples. The densification of titanium-niobium alloy significantly improved with the increase in sintering temperature. The density of Ti-10Nb reached 77.3% at 1 250 ℃. However, due to the difference in thermal expansion coefficients, microcracks formed at the interfaces in the sample with 20wt.% niobium powder, resulting in a higher porosity compared to the Ti-10Nb sample. The corrosion current density of the Ti-10Nb alloy sintered at 1 250 ℃ under a high potential of 2 V (vs. SHE) was 1.72×10-4 A/cm2, significantly lower than that of the pure titanium sample. After 20 h of constant potential polarization, the interfacial contact resistance was only 4.54 mΩ·cm2, a 64.5% reduction compared to the pure titanium sample, indicating superior conductivity and durability of the surface plate. Ultimately, the composite titanium plate was successfully prototyped. This study demonstrates that titanium-niobium alloy composite bipolar plates for PEM water electrolyzers, fabricated via additive manufacturing, exhibit significantly improved conductivity and corrosion resistance compared to traditional titanium plates.
关键词
水电解制氢 /
增材制造 /
黏结剂喷射 /
双极板 /
界面接触电阻
Key words
hydrogen production by water electrolysis /
additive manufacturing /
binder jetting /
bipolar plate /
interfacial contact resistance
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参考文献
[1] AJANOVIC A, SAYER M, HAAS R.The Economics and the Environmental Benignity of Different Colors of Hydrogen[J]. International Journal of Hydrogen Energy, 2022, 47(57): 24136-24154.
[2] DUNN S.Hydrogen Futures: Toward a Sustainable Energy System[J]. International Journal of Hydrogen Energy, 2002, 27(3): 235-264.
[3] CARMO M, FRITZ D L, MERGEL J, et al.A Comprehensive Review on PEM Water Electrolysis[J]. International Journal of Hydrogen Energy, 2013, 38(12): 4901-4934.
[4] ZHANG K X, LIANG X, WANG L N, et al.Status and Perspectives of Key Materials for PEM Electrolyzer[J]. Nano Research Energy, 2022, 1: e9120032.
[5] SALEHMIN M N I, HUSAINI T, GOH J, et al. High-Pressure PEM Water Electrolyser: A Review on Challenges and Mitigation Strategies towards Green and Low-Cost Hydrogen Production[J]. Energy Conversion and Management, 2022, 268: 115985.
[6] AYERS K E, ANDERSON E B, CAPUANO C, et al.Research Advances towards Low Cost, High Efficiency PEM Electrolysis[J]. ECS Transactions, 2010, 33(1): 3-15.
[7] HERMANN A, CHAUDHURI T, SPAGNOL P.Bipolar Plates for PEM Fuel Cells: A Review[J]. International Journal of Hydrogen Energy, 2005, 30(12): 1297-1302.
[8] 唐普洪, 张晓飞, 张嘉波, 等. 燃料电池电极板材料工艺发展趋势[J]. 精密成形工程, 2024, 16(2): 165-173.
TANG P H, ZHANG X F, ZHANG J B, et al.Development Trend of Fuel Cell Electrode Plate Material Process[J]. Journal of Netshape Forming Engineering, 2024, 16(2): 165-173.
[9] WANG H, TURNER J A.Reviewing Metallic PEMFC Bipolar Plates[J]. Fuel Cells, 2010, 10(4): 510-519.
[10] 何壮, 戚明睿. PEM水电解制氢研究现状与展望[J]. 化工设计通讯, 2024, 50(11): 129-133.
HE Z, QI M R.Current Status and Prospects of Hydrogen Production by PEM Electrolysis[J]. Chemical Engineering Design Communications, 2024, 50(11): 129-133.
[11] 张正, 宋凌珺. 电解水制氢技术: 进展、挑战与未来展望[J]. 工程科学学报, 2025, 47(2): 282-295.
ZHANG Z, SONG L J.Hydrogen Production by Water Electrolysis: Advances, Challenges and Future Prospects[J]. Chinese Journal of Engineering, 2025, 47(2): 282-295.
[12] FENG Q, YUAN X Z, LIU G Y, et al.A Review of Proton Exchange Membrane Water Electrolysis on Degradation Mechanisms and Mitigation Strategies[J]. Journal of Power Sources, 2017, 366: 33-55.
[13] PRESTAT M.Corrosion of Structural Components of Proton Exchange Membrane Water Electrolyzer Anodes: A Review[J]. Journal of Power Sources, 2023, 556: 232469.
[14] WU J F, YUAN X Z, MARTIN J J, et al.A Review of PEM Fuel Cell Durability: Degradation Mechanisms and Mitigation Strategies[J]. Journal of Power Sources, 2008, 184(1): 104-119.
[15] DE LAS HERAS N, ROBERTS E P L, LANGTON R, et al. A Review of Metal Separator Plate Materials Suitable for Automotive PEMfuel Cells[J]. Energy & Environmental Science, 2009, 2(2): 206-214.
[16] YASIN M C, JOHAR M, GUPTA A, et al.A Comprehensive Review of the Material Innovations and Corrosion Mitigation Strategies for PEMWE Bipolar Plates[J]. International Journal of Hydrogen Energy, 2024, 88: 726-747.
[17] LOW H C, LIM B H, MASDAR M S, et al.Understanding the Factors Influencing the Corrosion of Bipolar Plate to the Performance and Durability of Unitized Regenerative Proton Exchange Membrane Fuel Cell: A Review[J]. International Journal of Hydrogen Energy, 2024, 57: 420-430.
[18] DING R Q, LI Y M, LIU J N, et al.Recent Progress in the Preparation and Performance of Protective Coatings on Metal Bipolar Plates of Proton Exchange Membrane Fuel Cells-a Review[J]. Applied Materials Today, 2025, 42: 102556.
[19] LIU J S, ZHANG L J, YUAN B, et al.Design and Development of Coating for Metallic Bipolar Plates in Proton Exchange Membrane Fuel Cell (PEMFC): A Review[J]. Materials & Design, 2024, 246: 113338.
[20] BIAN H F, LI C C, PENG H, et al.Recent Advances in Conducting Polymer Coatings for Metal Bipolar Plates in PEMFC[J]. Progress in Organic Coatings, 2024, 192: 108502.
[21] MENG Q, YUE X Z, SHANG L L, et al.Corrosion Behavior of Metallic Coatings on Titanium Bipolar Plates of Proton Exchange Membrane Water Electrolysis[J]. International Journal of Hydrogen Energy, 2024, 63: 1105-1115.
[22] LETTENMEIER P, WANG R, ABOUATALLAH R, et al.Coated Stainless Steel Bipolar Plates for Proton Ex-
change Membrane Electrolyzers[J]. Journal of the Electrochemical Society, 2016, 163(11): F3119-F3124.
[23] LÆDRE S, KONGSTEIN O E, OEDEGAARD A, et al. Materials for Proton Exchange Membrane Water Electrolyzer Bipolar Plates[J]. International Journal of Hydrogen Energy, 2017, 42(5): 2713-2723.
[24] MENG W, FAN Y Z, WANG X P, et al.Nanoscale Niobium Coatings Including Superior Conducting and Corrosion Resistance on Titanium Foil Materials for PEMFC Bipolar Plates[J]. Surface and Coatings Technology, 2024, 494: 131366.
[25] PATEL S, LIU Y, SIDDIQUE Z, et al.Metal Additive Manufacturing: Principles and Applications[J]. Journal of Manufacturing Processes, 2024, 131: 1179-1201.
[26] BOURELL D L, LEU M C, CHAKRAVARTHY K, et al.Graphite-Based Indirect Laser Sintered Fuel Cell Bipolar Plates Containing Carbon Fiber Additions[J]. CIRP Annals, 2011, 60(1): 275-278.
[27] HUDKINS J R, WHEELER D G, PEÑA B, et al. Rapid Prototyping of Electrolyzer Flow Field Plates[J]. Energy & Environmental Science, 2016, 9(11): 3417-3423.
[28] YANG G Q, YU S L, MO J K, et al.Bipolar Plate Development with Additive Manufacturing and Protective Coating for Durable and High-Efficiency Hydrogen Production[J]. Journal of Power Sources, 2018, 396: 590-598.
[29] SÁNCHEZ-MOLINA M, AMORES E, ROJAS N, et al. Additive Manufacturing of Bipolar Plates for Hydrogen Production in Proton Exchange Membrane Water Electrolysis Cells[J]. International Journal of Hydrogen Energy, 2021, 46(79): 38983-38991.
[30] SUN H, XU Z T, ZHANG D.First-Principles Calculations to Investigate Doping Effects on Electrical Conductivity and Interfacial Contact Resistance of TiO2[J]. Applied Surface Science, 2023, 614: 156202.
[31] SUN H, XU Z T, ZHANG D, et al.Effects of Charge Rearrangement on Interfacial Contact Resistance of TiO2/Graphite from First-Principles Calculations[J]. Applied Surface Science, 2023, 635: 157640.
[32] SUN X, ZHANG H L, WANG D, et al.Large Recoverable Strain with Suitable Transition Temperature in TiNb-Based Multicomponent Shape Memory Alloys: First-Principles Calculations[J]. Acta Materialia, 2021, 221: 117366.
[33] ROJAS N, SÁNCHEZ-MOLINA M, SEVILLA G, et al. Coated Stainless Steels Evaluation for Bipolar Plates in PEM Water Electrolysis Conditions[J]. International Journal of Hydrogen Energy, 2021, 46(51): 25929-25943.
[34] AUKLAND N, BOUDINA A, EDDY D S, et al.Alloys that Form Conductive and Passivating Oxides for Proton Exchange Membrane Fuel Cell Bipolar Plates[J]. Journal of Materials Research, 2004, 19(6): 1723-1729.
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