具高能量密度與成本低廉的可充電鋅-空氣電池(Rechargeable Zn-air battery)是近期極具潛力取代鋰離子電池的儲能系統；然而，在實現商品化之前仍有許多嚴峻的挑戰需要解決，其中一項最具挑戰性的課題是如何設計具有雙功能特性的電催化觸媒於電池空氣端，在充放電操作下能分別有效催化氧氣析出反應 (oxygen evolution reaction, OER)與氧氣還原反應 (oxygen reduction reaction, ORR)。為了要實現兼具OER與ORR雙功能特性，一般所使用的方法是將分別具有ORR良好特性的Pt/C與具有OER良好特性的RuOx以物理混合方式將其塗佈在工作電極表面。然而，成本高昂的貴金屬以及長期穩定性不佳等問題皆讓Pt/C+RuOx雙功能觸媒限制了可充電鋅-空氣電池的發展，造成實際應用上的瓶頸。
有鑑於此，本研究開發以類沸石咪唑框架(Zeolitic imidazolate frameworks, ZIF)材料ZIF-67作為雙功能電催化觸媒的反應前驅物，並首度提出雙功能可調性的概念來有效控制單一粒子上ORR與OER活性面積比例，藉由ZIF-67衍生成具有雙功能特性的電催化觸媒，並進一步應用在可充電鋅-空氣電池的空氣電極端。在第四章中，以ZIF-67作為反應前驅物，將其轉換成NiCo層狀氫氧化物(Layered double hydroxide, LDH)與Co(OH)2的特性，透過轉化順序與反應時間來有效控制其部分轉換比例，來實現雙功能電催化能力進而最適化其OER以及ORR性能。從實驗結果得知ZIF-67衍生的Co(OH)2，因其導電性不足進而影響到ORR的性能，因此本研究導入奈米碳管於ZIF-67結構中來提高其衍生物導電性。本研究透過控制轉化順序以及轉化時間來控制ZIF-67內外層的NiCo LDH與Co(OH)2比例，進而最適化其OER以及ORR性能。為了進一步證明此NiCo LDH/Co(OH)2/CNT雙功能電催化觸媒的實用性，將其實際應用在可充電鋅空氣電池的空氣電極上來進行電池輸出分析。從結果可以發現NiCo LDH/Co(OH)2/CNT在各方面仍然展現了優異的性能，除了具有587 mAh g-1的比電容量之外，功率密度也達到了44 mW cm-2，展現了接近於利用物理混合Pt/C+RuOx商業化觸媒的電池效能並且可以穩定的連續充放電55個小時。
然而，從第四章結果可歸納出NiCo LDH/Co(OH)2/CNT的ORR效能仍然遜色於Pt/C一大截進而造成整體電池性能不足；因此，如何增加雙功能電催化觸媒的ORR活性來進一步提升電池效能為本研究下一個目標。根據第四章的研究經驗，ZIF-67衍生物必須導入CNT增加其整體導電性才能有效提升ORR能力，因此第五章將以同時具有良好ORR特性與優異導電性的氮摻雜奈米碳管 (N-doped carbon nanotube, NCNT)作為電催化觸媒主體並透過ZIF-67衍生物修飾來實現雙功能電催化特性。導入N原子摻雜於CNT表面所形成的NCNT能有效提供更多電催化活性位點來提升ORR效能，使其ORR起始電位能提升至0.85 V (vs. RHE)。為了更進一步提升NCNT的ORR活性以及實現其雙功能電催化特性，本研究以NCNT作為擔體並進一步合成出ZIF-67/NCNT，作為反應前驅物來合成NiCo LDH/Co3O4/NCNT。透過具雙功能可調性的ZIF-67衍生物所製備而成的NiCo LDH/Co3O4/NCNT，除了可以藉由部分ZIF-67衍生NiCo LDH來做為OER活性材料，也可透過部分ZIF-67衍生Co3O4來進一步提升其原有ORR效能，使其電催化能力接近Pt/C商業觸媒。本研究透過ZIF-67/NCNT比例與轉化時間來最適化ORR以及OER性能。最後將其實際應用在可充電鋅空氣電池的空氣電極上來進行電池輸出分析。從結果可以發現NiCo LDH/Co3O4/NCNT在各方面仍然展現了優異的性能，除了具有617 mAh g-1的比電容量之外，功率密度也達到了46 mW cm-2，展現了接近於利用物理混合Pt/C+RuOx商業化觸媒的電池效能並且可以穩定的連續充放電55個小時。

Rechargeable Zn-air battery with high energy density and low cost is an energy storage system that has the potential to replace lithium-ion batteries in the future. One of the most challenging topics is how to design an bifunctional electrocatalyst on the air electrode of the battery, which can effectively catalyze the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) under charge and discharge. In order to achieve the bifunction, the generally used method is to physically mix Pt/C with good ORR performance and RuOx with good OER performance to coat on the surface of the working electrode. However, high cost precious metals and poor long-term stability have caused Pt/C+RuOx bifunctional electrocatalyst to limit the development of rechargeable zinc-air batteries, causing bottlenecks in practical applications.
In view of this, this research has developed the zeolitic imidazolate frameworks (ZIF) material ZIF-67 as the reaction precursor of the bifunction electrocatalyst and proposed for the concept of bifunctional tunability to effectively control the active area ratio of ORR to OER on the single particles. In Chapter 4, ZIF-67 is used as the reaction precursor, and it can be converted into NiCo layered double hydroxide (LDH) and Co(OH)2, through the conversion sequence and reaction time to effectively control its partial conversion ratio to achieve bifunction capability and optimize its OER and ORR performance. From the experimental results, it is known that the conductivity of Co(OH)2 derived from ZIF-67 is insufficient, which affects the performance of ORR. Therefore, this study introduced carbon nanotubes into the structure of ZIF-67 to improve the conductivity of its derivatives. In this study, the ratio of NiCo LDH to Co(OH)2 in the inner and outer layers of ZIF-67 was controlled by controlling the conversion sequence and conversion time to optimize its OER and ORR performance. In order to further prove the practicability of the NiCo LDH/Co(OH)2/CNT, it was applied to the air electrode of a rechargeable zinc-air battery for battery output analysis. From the results, it can be found that NiCo LDH/Co(OH)2/CNT still exhibits excellent performance in all aspects. In addition to the specific capacitance of 587 mAh g-1, the power density has also reached 44 mW cm-2, charged and discharged continuously for 55 hours.
However, from the results in Chapter 4, it can be concluded that the ORR performance of NiCo LDH/Co(OH)2/CNT is still inferior to that of Pt/C by a large amount, which causes the overall battery performance to be insufficient. Therefore, how to improve ORR activity of bifunctional electrocatalyst to further increase battery performance is the next goal of this research. Therefore, Chapter 5 will use nitrogen-doped carbon nanotubes (NCNT) that have both good ORR performance and excellent conductivity. NCNT as the main body of the electrocatalyst and modified by ZIF-67 derivatives to achieve bifunctional electrocatalytic properties. In order to further enhance the ORR activity of NCNT and realize its bifunctional electrocatalytic properties, this study uses NCNT as a support and further synthesizes ZIF-67/NCNTs as reaction precursors to synthesize NiCo LDH/Co3O4/NCNT. NiCo LDH/Co3O4/NCNT prepared by ZIF-67 derivatives with bifunction tunability can be used as OER active material by partially deriving NiCo LDH from ZIF-67, but also part of ZIF-67 derives Co3O4 to further enhance its original ORR performance, making its electrocatalytic capacity close to Pt/C commercial catalysts. In addition to the specific capacitance of 617 mAh g-1, the power density has also reached 46 mW cm-2, charged and discharged continuously for 55 hours.

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