能源是世界範圍內的一個重大問題。 許多國家和科學家建議從不可再生能源轉向可再生能源。 氫氣是替代化石燃料的替代燃料。 全球約 96% 的氫氣生產基於不可再生和不可持續的技術，例如蒸汽甲烷重整、煤氣化和石油氧化，這些技術產生 CO2 產物並依賴化石燃料。 由於原料（水）豐富，水電解技術可以克服這些缺點，並且可以產生綠色氫氣。 由於鉑（Pt）和二氧化銥（IrO2）或二氧化釕（RuO2）分別作為氫和氧析出反應的基準，催化劑成本高，電解僅貢獻了全球氫氣生產的約4%。 這就是我們使用電解技術通過開發具有綠色合成、可擴展方法和良好操作耐久性的高性能地球豐富催化劑來產生氫氣的原因。
在這項工作中，我們通過濺射技術報告了一種新型鎳基雙金屬合金和雙層電催化劑。 通過 X 射線衍射 (XRD)、場發射掃描電子顯微鏡 (FE-SEM)、高解析度透射電子顯微鏡 (HR-TEM)、X 射線光電子能譜 (XPS) 和電化學分析對其結構進行了表徵，包括 過電位、動力學反應、電荷轉移電阻、表面活性面積和耐久性。 本論文共分為五個部分，包括用於制氫的雙金屬CoNix合金、用於制氫的雙層Ni/CoNi4、用於析氧的NiFe-LDH、用於全電池水電解的Ni/CoNi4||NiFe-180和Ni/CoNi4|。 |用於鹼性交換膜 (AEM) 水電解的 NiFe-180，如下所述：
I：採用射頻磁控濺射技術成功濺射出摩爾比 x = 1、2、4 和 8 的雙金屬 CoNix 合金催化劑。 通過在鹼性介質中的電化學分析測量催化活性。 作為最佳摩爾比，CoNi4 合金具有 53 和 175 mV 的低過電位，分別達到 10 和 100 mA/cm2，Tafel 斜率為 68.08 mV/dec。 CoNi4 合金具有最低的電荷轉移電阻 1.14 Ω 和最大的電化學活性表面積 485 cm2。 CoNi4合金的耐久性是在10和50 mA/cm2的恒定電流密度下連續運行20小時來檢驗的。
II：採用兩步濺射技術製備了一種具有顆粒結構的新型雙層Ni/CoNi-4薄膜電極，以提高鹼性溶液中高電流密度下的導電性和耐久性。 電化學分析表明，與單層相比，雙層 Ni/CoNi4 薄膜電極技術具有大大提高的催化活性。 實現 100、250、500 和 1000 mA/cm2 的電流密度分別只需要 108、182、260 和 343 mV 的過電勢。 雙層 Ni/CoNi-4 薄膜電極具有 37.3 mV/dec 的更快動力學反應和 1.27 Ω 的更低電子轉移電阻。 在塗覆 CoNi4 層後，Ni 層的活性表面積顯著增加。 雙層 Ni/CoNi-4 薄膜電極的優異耐久性在計時電位法中以 250、500 和 1000 mA/cm2 的連續恒定電流密度顯示 100 小時。 這種顯著的催化活性可歸因於鎳膜的協同作用，可提高導電性並降低膜應力。 這表明 Ni 層在提高 CoNi4 薄膜的催化活性方面起著至關重要的作用。
III：由於其高析氧反應性能，選擇NiFe-LDH作為陽極。 最佳沉積時間為 180 秒的電沉積 NiFe-LDH 顯示出 245、277 和 323 mV 的低過電勢，可實現 100、250 和 500 mA/cm2 的電流密度。 另一個電化學參數顯示NiFe-180具有最快的動力學反應、最低的電子轉移電阻和最高的活性表面積。
IV：我們將雙層 Ni/CoNi¬4 薄膜電極與 NiFe-180 分別作為陰極和陽極耦合，用於全電池水電解。 使用 Ni/CoNi4||NiFe-180 的水電解槽僅需要低至 1.61、1.71 和 1.83 V 的電池電壓即可分別在 100、250 和 500 mA/cm2 的電流密度下驅動水電解。 這些電勢明顯低於 40% Pt/C||RuO2 的 HER 和 OER 催化劑的基準。 計時電位測試表明Ni/CoNi4||NiFe-180的耐久性遠優於Pt/C||RuO2。
V：我們的催化劑在工業應用中的適用性是通過組裝一個放大 16 倍的 Ni/CoNi4||NiFe-180 的堆疊電池電解槽來評估的。 我們的 Ni/CoNi4||NiFe-180 電池需要潛力

Energy is a major issue worldwide. Many countries and scientists propose switching from nonrenewable to renewable energy sources. Hydrogen is an alternative fuel to replace fossil fuels. About 96% of global hydrogen production is based on unrenewable and unsustainable techniques, such as steam methane reforming, coal gasification, and oil oxidation, which have CO2 products and dependence on fossil fuels. Those disadvantages could be overcome with the water electrolysis technique due to the abundant feedstock (water) and could generate green hydrogen. The electrolysis only contributes about 4 % of global hydrogen production due to the high cost of the catalysts, such as platinum (Pt) and iridium dioxide (IrO2) or ruthenium dioxide (RuO2) as the benchmark of hydrogen and oxygen evolution reaction, respectively. This is the reason why we used the electrolysis technique to generate hydrogen by developing a high-performance earth-abundant catalyst with a green synthesis, scalable method, and good operational durability.
In this work, we report a novel Ni-based bimetal alloy and bilayer electrocatalyst by a sputtering technique. Their structures were characterized by X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), high-resolution transmission electron microscope (HR-TEM), X-ray photoelectron spectroscopy (XPS), and electrochemical analysis including the overpotential, kinetic reactions, charge transfer resistance, surface active area, and durability. There are five parts in this thesis including bimetallic CoNix alloy for hydrogen generation, bilayer Ni/CoNi4 for hydrogen generation, NiFe-LDH for oxygen evolution, Ni/CoNi4||NiFe-180 for full-cell water electrolysis, and Ni/CoNi4||NiFe-180 for alkaline exchange membrane (AEM) water electrolysis with stack-cell method, as discussed below:
I: Bimetallic CoNix alloy catalysts, with molar ratios x = 1, 2, 4, and 8, were successfully sputtered by the radio frequency magnetron sputtering technique. The catalytic activity was measured by the electrochemical analysis in an alkaline medium. As the most optimum molar ratio, CoNi4 alloy possessed low overpotentials of 53 and 175 mV to achieve 10 and 100 mA/cm2, respectively, with the Tafel slope value of 68.08 mV/dec. CoNi4 alloy had the lowest charge transfer resistance of 1.14 Ω and the largest electrochemical active surface area of 485 cm2. The durability of CoNi4 alloy was examined under the continuous operation of constant current densities of 10 and 50 mA/cm2 for 20 hours.
II: A novel bilayer Ni/CoNi¬4 film electrode with a granular structure was fabricated by a two-step sputtering technique to enhance electrical conductivity and durability at the high current density in alkaline solutions. The electrochemical analysis revealed that the bilayer Ni/CoNi4 film electrode technique had much improved catalytic activity as compared to the single layer. Achieving current densities of 100, 250, 500, and 1000 mA/cm2 only required overpotentials of 108, 182, 260, and 343 mV, respectively. Bilayer Ni/CoNi¬4 film electrode had a faster kinetic reaction of 37.3 mV/ dec and lower electron transfer resistance of 1.27 Ω. The active surface area of the Ni layer was significantly increased following coating with the CoNi4 layer. The superior durability of the bilayer Ni/CoNi¬4 film electrode was displayed in chronopotentiometry with continuous constant current densities of 250, 500, and 1000 mA/cm2 for 100 hours. This significant catalytic activity can be attributable to the synergistic action of Ni film, which could boost conductivity and reduce film stress. This demonstrates that the Ni layer serves a vital role in increasing the catalytic activity of CoNi4 films.
III: The NiFe-LDH was selected as the anode due to its high oxygen evolution reaction performance. The as-electrodeposited NiFe-LDH with the most optimum deposition time of 180 seconds builds exhibited low overpotentials of 245, 277, and 323 mV to achieve current densities of 100, 250, and 500 mA/cm2. The other electrochemical parameter displayed that NiFe-180 had the fastest kinetic reactions, the lowest electron transfer resistance, and the highest active surface area.
IV: We coupled the bilayer Ni/CoNi¬4 film electrode with that NiFe-180 as cathode and anode, respectively, for full-cell water electrolysis. The water electrolyzers using Ni/CoNi4||NiFe-180 only require cell voltages as low as 1.61, 1.71, and 1.83 V to drive water electrolysis at current densities of 100, 250, and 500 mA/cm2, respectively. These potentials are significantly lower than of that the benchmark of HER and OER catalysts of 40% Pt/C||RuO2. The chronopotentiometry test revealed that the durability of Ni/CoNi4||NiFe-180 is much better than that of Pt/C||RuO2.
V: The applicability of our catalysts for industrial application was evaluated by assembling a stacked cell electrolyzer with sixteen times scaled-up Ni/CoNi4||NiFe-180. Our Ni/CoNi4||NiFe-180 cells need potentials of 1.62 and 1.75 V to reach 100 and 250 mA/cm2, respectively, in 1.0 M KOH. The stability test at 250 mA/cm2 for 25 hours showed a slight decline. Furthermore, the next 25 hours of the stability test in 6.9 M KOH require cell potentials of 1.57 and 1.71 V to achieve 100 and 250 mA/cm2, respectively. The chronopotentiometry shows a slight degradation due to powerful gas bombardment at a high current of 4500 mA. Our electrolyzer cell can produce 1820 and 890 mL/h of hydrogen and oxygen gasses, respectively, with the calculated stack cell efficiency of 70.9%.
Keywords: magnetron sputtering, bimetallic, cobalt-nickel alloy, bilayer film, electrocatalyst, hydrogen evolution reaction, stack-cell.

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