2SO4+2 ppm HF 水溶液)下實(shí)現(xiàn)了0.0525 μA/cm2的超低腐蝕電流密度,在1.4 MPa的壓緊力下實(shí)現(xiàn)了1.49 mΩ/cm2的極低ICR值。結(jié)論 采用磁過濾真空陰極弧沉積法制備的nc-TiC/a-C:H涂層可以在寬的負(fù)偏壓范圍內(nèi)有效提高SS 304不銹鋼雙極板的耐腐蝕和導(dǎo)電性,滿足DOE 2025目標(biāo)對(duì)氫燃料電池雙極板的性能需求,該工作為大規(guī)模制備高性能金屬雙極板涂層開辟了一條新途徑。"/>

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氫燃料電池金屬雙極板表面TiC/a-C:H涂層的制備和表征
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1.北京師范大學(xué)核科學(xué)與技術(shù)學(xué)院射線束技術(shù)教育部重點(diǎn)實(shí)驗(yàn)室;2.北京師范大學(xué),北京市科學(xué)技術(shù)研究院輻射技術(shù)所;3.北京市科學(xué)技術(shù)研究院輻射技術(shù)所;4.北京億華通科技股份有限公司

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國家自然科學(xué)基金面上項(xiàng)目資助(項(xiàng)目號(hào)12275028);廣東省重點(diǎn)研發(fā)計(jì)劃資助(項(xiàng)目號(hào)2019B090909002);北京市科學(xué)與技術(shù)研究院2023年財(cái)政項(xiàng)目創(chuàng)新工程和2023年創(chuàng)新培育項(xiàng)目資助;北京億華通科技股份公司委托項(xiàng)目資助。


Preparation and characterization of TiC/a-C: H coating on the surface of metal bipolar plates in hydrogen fuel cells
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    摘要:

    目的 研究沉積離子能量對(duì)沉積在氫燃料電池金屬雙極板表面的TiC/a-C:H涂層導(dǎo)電性和耐腐蝕性能影響。方法 通過磁過濾真空陰極弧沉積技術(shù)以Ti靶為Ti源,通入乙炔氣體在-100~-500 V基體負(fù)偏壓下于SS 304不銹鋼和單晶硅表面沉積了厚度為0.52~1.05 μm的TiC/a-C:H復(fù)合涂層,研究分析了涂層的微觀結(jié)構(gòu)、涂層成分、相結(jié)構(gòu)、耐腐蝕性能和導(dǎo)電性能的變化規(guī)律。結(jié)果 在-100~-500 V基體負(fù)偏壓下沉積的TiC/a-C:H復(fù)合涂層均呈現(xiàn)致密的低缺陷特征,涂層為非晶碳包覆的nc-TiC納米晶所構(gòu)建的納米晶/非晶復(fù)合結(jié)構(gòu),隨著負(fù)偏壓增大,涂層中納米晶尺寸從3.3 nm增至7.9 nm。最優(yōu)的nc-TiC/a-C:H涂層(負(fù)偏壓-100 V)在模擬氫燃料電池腐蝕環(huán)境(80℃, 0.5 mol/L H2SO4+2 ppm HF 水溶液)下實(shí)現(xiàn)了0.0525 μA/cm2的超低腐蝕電流密度,在1.4 MPa的壓緊力下實(shí)現(xiàn)了1.49 mΩ/cm2的極低ICR值。結(jié)論 采用磁過濾真空陰極弧沉積法制備的nc-TiC/a-C:H涂層可以在寬的負(fù)偏壓范圍內(nèi)有效提高SS 304不銹鋼雙極板的耐腐蝕和導(dǎo)電性,滿足DOE 2025目標(biāo)對(duì)氫燃料電池雙極板的性能需求,該工作為大規(guī)模制備高性能金屬雙極板涂層開辟了一條新途徑。

    Abstract:

    Filtered cathodic vacuum arc deposition has an ultra-high ionization rate (nearly 100%), which can effectively suppress micro defects in the coatings optimize the microstructure of the coatings, and improve the performance of the coatings. In response to the poor corrosion resistance of metal bipolar plates in hydrogen fuel cells and their tendency to dissolve in acidic environments during long-term operation of proton exchange membrane fuel cells , we used a filtered cathodic vacuum arc deposition process to deposite a series of high conductivity and strong corrosion resistant nc-TiC/a-C: H coatings on the surface of metal bipolar plates in proton exchange membrane fuel cells In this paper, the effects of deposited ion energy on the conductivity and corrosion resistance of TiC/a-C: H coatings deposited on the surface of metal bipolar plates in hydrogen fuel cells were investigated. Nc-TiC/a-C: H nanocomposite coatings with a thickness of 0.52-1.05 μm were deposited on the surfaces of SS 304 stainless steel and monocrystalline silicon at negative substrate bias voltages of -100~-500 V with acetylene gas flow rate of 30 sccm by a dual bend filtered cathodic vacuum arc deposition process. The phase structure of the coatings were analyzed using X-ray diffraction (X pert pro MPD); The cross-section and surface microstructures of the coatings were characterized by field emission scanning electron microscopy (S-4800, Hitachi); Observation of high-resolution morphology of coatings using transmission electron microscopy (FEI CM200, Philips); The chemical element composition and chemical bond structure of the coating were analyzed by X-ray photoelectron spectroscopy (ESCALAB 250Xi, Thermofish); Raman spectroscopy (LavRAM Aramis, Horiba Jobin Yvon) characterizes the chemical structure distribution of carbon elements in the coating; The electrochemical workstation (IM6ex, Zahner elektrik) evaluated the corrosion resistance of coatings under simulated hydrogen fuel cell operating conditions. The surface contact resistance tester tested the contact resistance under different pressures; The study analyzed the changes in microstructure, coating composition, phase structure, corrosion resistance, and conductivity of TiC/a-C: H coatings under different negative bias voltages. The results show that the TiC/a-C: H composite coatings deposited under negative bias voltage of -100~-500 V exhibit dense low defect characteristics. The coatings are nanocrystalline/amorphous composite structure constructed by amorphous carbon coated nc-TiC nanocrystals. As the negative bias voltage increases, the size of nanocrystals in the coating increases from 3.3 nm to 7.9 nm. The optimal nc-TiC/a-C: H coating (coating deposited at negative bias -100 V) achieved an ultra-low corrosion current density of 0.0525 μA/cm2 in a simulated hydrogen fuel cell corrosion environment (80 ℃, 0.5 mol/L H2SO4+2 ppm HF aqueous solution), and achieved an extremely low ICR value of 1.49 mΩ/cm2 under a compression force of 1.4 MPa. Our results show that the nc-TiC/a-C:H coatings prepared by filtered cathodic vacuum arc deposition process can effectively improve the corrosion resistance and conductivity of SS 304 stainless steel bipolar plates within a wide negative bias range, meeting the performance requirements of DOE 2025 target for hydrogen fuel cell bipolar plates. This work open up a new avenue for the large-scale preparation of high-performance metal bipolar plate coatings.

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王浩琦,華青松,歐伊翔,付薇,鄭威龍,侯莉,王連才,曾心苗,李飛強(qiáng),徐云飛,曹季東,曲觀書.氫燃料電池金屬雙極板表面TiC/a-C:H涂層的制備和表征[J].稀有金屬材料與工程,2024,53(9):2580~2587.[Wang Haoqi, Hua Qingsong,歐伊翔,Fu Wei, Zheng Weilong, Hou Li, Wang Liancai, Zeng Xinmiao, Li Feiqiang, Xu Yunfei, Cao Jidong, Qu Guanshu. Preparation and characterization of TiC/a-C: H coating on the surface of metal bipolar plates in hydrogen fuel cells[J]. Rare Metal Materials and Engineering,2024,53(9):2580~2587.]
DOI:10.12442/j. issn.1002-185X.20230459

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  • 收稿日期:2023-07-24
  • 最后修改日期:2023-08-18
  • 錄用日期:2023-08-24
  • 在線發(fā)布日期: 2024-09-13
  • 出版日期: 2024-09-04