PECVD法原位滲氮表面改性鈦雙極板的性能

馮利利; 侯玉星; 湯思遙; 李栓; 鄭捷; 李星國

doi:10.13374/j.issn2095-9389.2022.05.25.002

PECVD法原位滲氮表面改性鈦雙極板的性能

doi: 10.13374/j.issn2095-9389.2022.05.25.002

馮利利¹,
侯玉星^{1, 2},
湯思遙¹,
李栓^2, ,,
鄭捷²,
李星國^2, ,

1.
中國礦業大學（北京）化學與環境工程學院，北京 100083
2.
北京大學化學與分子工程學院，稀土材料化學及應用國家重點實驗室，北京分子科學國家實驗室，北京 100871

基金項目: 國家重點研發計劃資助項目（2018YFB1502104，2021YFE0107200）；越崎學者專項資金資助項目（2020QN11)；中央高校基本科研業務費資助項目(2022YJSHH20）

詳細信息

通訊作者:
李栓, E-mail: 15652783232@163.com

李星國, E-mail: xgli@pku.edu.cn

中圖分類號: TM911.4
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- 文章訪問數: 418
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- PDF下載量: 42
- 被引次數: 0
出版歷程
- 收稿日期: 2022-05-25
- 網絡出版日期: 2022-08-17
- 刊出日期: 2023-04-01

Evaluating the performances of surface-modified titanium bipolar plates using in situ nitriding by plasma-enhanced chemical vapor deposition

FENG Li-li¹,
HOU Yu-xing^{1, 2},
TANG Si-yao¹,
LI Shuan^{2
, ,},
ZHENG Jie²,
LI Xing-guo^{2
, ,}

1.
School of Chemical and Environmental Engineering, China University of Mining and Technology, Beijing 100083, China
2.
Beijing National Laboratory of Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

More Information

Corresponding author: LI Shuan, E-mail: 15652783232@163.com; LI Xing-guo, E-mail: xgli@pku.edu.cn

摘要

摘要: 為了提升鈦雙極板的導電性和耐腐蝕性，利用氮氣等離子體原位滲氮法對鈦片（TA2）進行表面改性，制備了系列氮化鈦涂層，系統研究了反應溫度和滲氮時間對涂層表面形貌、疏水性、界面導電性和耐腐蝕性的影響。結果表明，溫度過高會導致氮化鈦生長過快，顆粒尺寸較大；溫度較低不利于表面反應，涂層不能完全覆蓋鈦基底；滲氮時間較短，表面生成不規則的納米生長核，致使涂層不平整、鈦基底裸露；滲氮時間過長，涂層呈階梯堆垛狀，平整度降低。650 °C下滲氮90 min制備的氮化鈦涂層（TiN-650-90）均勻平整，組成為TiN_0.26；TiN-650-90的水接觸角提升至105.4°，表面疏水性有利于改善燃料電池的水管理性能；界面接觸電阻（ICR）隨加載壓力增大而降低，2.75 MPa時TiN-650-90的ICR穩定至6.5 mΩ·cm²，滿足美國能源部（DOE）要求（≤10 mΩ·cm²）；TiN-650-90的腐蝕電流密度為0.56 μA·cm^–2，–0.1 V恒電位下的電流密度為0.67 μA·cm^–2，耐腐性和穩定性較鈦的明顯提升。該方法制備氮化鈦涂層表面改性鈦雙極板，具有沉積溫度低、速度快，疏水性、導電性和耐腐蝕性優良等優點，可為金屬雙極板表面改性提供方法借鑒和工藝參考。
- 鈦雙極板 /
- 表面改性 /
- 等離子體增強化學氣相沉積 /
- 原位滲氮 /
- 氮化鈦涂層
Abstract: In this study, the surface modification of titanium plates was performed using in situ nitriding via plasma-enhanced chemical vapor deposition to improve the conductivity and corrosion resistance of the plates. A series of titanium nitride (TiN) coatings were synthesized at different nitriding temperatures and durations. The influence of nitriding temperatures and durations on the surface morphology, hydrophobicity, interfacial conductivity, and corrosion resistance of the as-prepared coatings was investigated. The results indicated that faster growth and larger particle size of TiN are observed at higher temperatures. However, lower temperatures are unfavorable for surface reactions; thus, the coating cannot entirely cover the titanium substrate. Moreover, a shorter nitriding time results in irregular nanogrowth nuclei on the surface, leading to an uneven coating and bare titanium substrate. Conversely, longer nitriding time encourages the continuous accumulation of TiN nanoparticles and forms a uniform coating of the titanium substrate but decreases the flatness because of the stacking of the coatings due to the long nitriding time (120 min). The TiN coating prepared by nitriding at 650 °C for 90 min (TiN-650-90) is relatively compact and smooth with the composition of TiN_0.26 and has an increased water contact angle of 105.4°. The change from hydrophilicity to hydrophobicity in TiN is beneficial to fuel cell water resistance. At a loading pressure of 1.5 MPa, the contact resistances of the coatings prepared at a nitriding time of 60 min can satisfy the U.S. Department of Energy requirement of less than 10 mΩ·cm². Despite a contact resistance of 13.2 mΩ·cm² for the TiN-650-90 coating, the contact resistance decreases with increasing loading pressure and is stable at 6.5 mΩ·cm² under a loading pressure of 2.75 MPa. The corrosion current density of the TiN-650-90 coating is 0.56 μA·cm^?2, and the corrosion potential positively shifts from ?0.37 to ?0.05 V at room temperature. The corrosion current density tested in the simulated operating environment of fuel cells is higher than that at room temperature but much lower than that of titanium (4.2 μA·cm^?2). Furthermore, the current density is stable at 0.67 μA·cm^?2 and at a ?0.1 V constant potential, indicating superior corrosion resistance and stability than titanium. The titanium bipolar plates modified by this method exhibit the advantages of relatively low deposition temperature, quick deposition speed, and good hydrophobicity, conductivity, and corrosion resistance. This work can pave the way for efficient surface modification of metal bipolar plates.
- titanium bipolar plates /
- surface modification /
- plasma-enhanced chemical vapor deposition /
- in situ nitriding /
- titanium nitride coatings

HTML全文

圖 1 等離子體滲氮裝置示意圖

Figure 1. Schematic diagram of the plasma nitriding instrument

下載: 全尺寸圖片幻燈片

圖 2 鈦基底與不同溫度下滲氮90 min制備的氮化鈦涂層的XRD圖譜

Figure 2. XRD patterns of the titanium substrate and titanium nitride coatings prepared by nitriding at different temperatures for 90 min

下載: 全尺寸圖片幻燈片

圖 3 不同溫度和滲氮時間下制備的氮化鈦涂層的SEM圖像(a~h)和滲氮前后樣品的光學照片(i). (a) TiN-450；(b) TiN-550；(c) TiN-650；(d) TiN-750；(e) TiN-650-30；(f) TiN-650-60；(g) TiN-650-90；(h) TiN-650-120

Figure 3. SEM images (a–h) of titanium nitride coatings at different temperatures and nitriding time and optical photograph (i) of a prepared titanium nitride coating: (a) TiN-450; (b) TiN-550; (c) TiN-650; (d) TiN-750; (e) TiN-650-30; (f) TiN-650-60; (g) TiN-650-90; and (h) TiN-650-120.

下載: 全尺寸圖片幻燈片

圖 4 TiN-650-90涂層的面掃描能譜圖. (a) SEM; (b) Ti; (c) N; (d) O

Figure 4. SEM–EDS elemental mapping images of the TiN-650-90 coating: (a) SEM; (b) Ti; (c) N; (d) O

下載: 全尺寸圖片幻燈片

圖 5 鈦基底(a)和TiN-650-90涂層(b)的水接觸角

Figure 5. Water contact angles of the titanium substrate (a) and TiN-650-90 coating (b)

下載: 全尺寸圖片幻燈片

圖 6 鈦基底與650 °C、不同滲氮時間下制備的氮化鈦涂層的接觸電阻. (a)和(c)不同加載壓力下的表面接觸電阻；(b)和(d) 1.5 MPa加載壓力下的表面接觸電阻

Figure 6. The interface contact resistance (ICR) of the titanium substrate and titanium nitride coatings prepared at 650 °C for different nitriding time: (a) and (c) ICR under various loading pressure; (b) and (d) ICR under the loading pressure of 1.5 MPa

下載: 全尺寸圖片幻燈片

圖 7 鈦基底與不同溫度(a)和滲氮時間(b)下制備的氮化鈦涂層的Tafel曲線及模擬PEMFC工作環境下測試的Tafel曲線(c)

Figure 7. Tafel curves of the titanium substrate and titanium nitride coatings prepared at different temperatures (a) and nitriding time (b), and those tested under simulated PEMFC working environment (c)

下載: 全尺寸圖片幻燈片

圖 8 鈦基底與TiN-650-90樣品在0.6 V (a)和–0.1 V (b)下的恒電位極化曲線

Figure 8. Potentiostatic polarization curves of the titanium substrate and TiN-650-90 sample at 0.6 V (a) and ?0.1 V (b)

下載: 全尺寸圖片幻燈片

表 1 鈦基底與不同溫度和滲氮時間制備的氮化鈦涂層的腐蝕電位和腐蝕電流密度

Table 1. Corrosion potential and current density values of the titanium substrate and titanium nitride coatings prepared at various temperatures and nitriding times

Samples	E_corr/(V vs SCE)	I_corr/(μA·cm^–2)
Bare Ti	–0.37	4.2
TiN-450	–0.295	2.5
TiN-550	–0.25	1.2
TiN-650	–0.05	0.56
TiN-750	–0.15	0.78
TiN-650-30	–0.335	1.25
TiN-650-60	–0.295	0.86
TiN-650-90	–0.05	0.56
TiN-650-120	–0.225	0.8
TiN-650-90 (tested at 70 °C)	0.05	2.47

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