可逆高熵氧化物陽極應用於 鋰離子全電池之研究

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姓名

黃力朋(Li-Peng Huang) 查詢紙本館藏

畢業系所

材料科學與工程研究所

論文名稱

可逆高熵氧化物陽極應用於鋰離子全電池之研究
(Study on Reversible High Entropy Oxides as Anode in Lithium-Ion Batteries)

相關論文

★ Development of periodic nanostructure substrates for the applications of SERS and water-splitting	★ 高熵氧化物(Co0.2Cu0.2Mg0.2Ni0.2Zn0.2O)應用於鋰離子電池負極材料之研究
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★ 高熵硒化物觸媒應用於電芬頓反應降解有機污染物之研究

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至系統瀏覽論文 (2026-6-30以後開放)

摘要(中)

高熵氧化物 (HEO) 由於其出色的性能，如高溫熱穩定性和高離子導電性，對於鋰離子電池 (LIBs) 中的應用具有潛在的前景。本研究成功利用溶膠凝膠法合成一種新型的高熵氧化物 (Co0.2Ni0.2Cu0.2Mg0.2Zn0.2)O，該氧化物具有岩鹽結構，並將其作為LIBs的陽極活性材料。在50mA g-１ (0.1C)定電流充放電率 (C-rate) 條件下，可達到了450mAh g-1的比容量。為了解決高熵氧化物陽極反應初期不可逆容量損失的問題，會在與鎳鈷錳氧化物 (NCM811) 陰極組裝成全電池之前，通過預鋰化處理對高熵氧化物陽極表面進行改質。透過預鋰化改質成功將不可逆容量比從 50％降至 15％；在反應過程中，陽極/電解液界面也會形成磷酸鋰 (Li3PO4) 薄膜，可增強導電性並抑制鋰枝晶的生長。全電池的電化學測試結果顯示，高熵氧化物陽極在20mA g-1(0.1C)的C-rate條件下，實現了121mAh g-1的比容量，其工作電壓約2.4V，全電池的能量密度可達到292Wh kg-1。此外，為了探討高熵氧化物陽極的老化機制，透過拆解不同循環次數的HEO/Li袋裝型半電池及分析陽極表面形貌和元素價態的改變。以下提出了兩點造成老化的原因：1) HEO 材料結構中的鎂離子 (Mg2+) 還原為金屬鎂 (Mg) ，產生了氧(O) 造成電池膨脹；2) 鋰離子 (Li+) 與氧 (O) 結合形成氧化鋰 (Li2O) ，然後與電解液中的六氟磷酸鋰 (LiPF6) 反應，最終導致陽極表面上的 (Li3PO4)不斷增厚，造成界面阻抗增加。本研究通過對高熵氧化物陽極的效能測試及反應過程形貌與價態的變化深入研究，致力於推動高熵材料作為輕量、安全的活性材料應用在未來的儲能系統。

摘要(英)

High entropy oxides (HEOs) have great potential for lithium-ion batteries (LIBs) applications due to the exceptional properties, such as high-temperature stability and high ionic conductivity. This study successfully synthesized a novel HEO (Co0.2Ni0.2Cu0.2Mg0.2Zn0.2) O with a rock-salt structure with the sol-gel method and utilized it as the anode in LIBs. The HEO anode achieved a specific capacity of 450mAh g-1 at a constant current charging-discharging rate (C-rate) of 50mA g-1 (0.1C). To solve the issue of irreversible capacity loss during the initial stage of the electrocatalysis reaction, the HEO anode surface was optimized through the pre-lithiation modification before assembling with the high-nickel cobalt manganese oxide (NCM811) cathode to form full cells. This process successfully reduced the irreversible capacity ratio from 50% to 15% and formed a lithium phosphate (Li3PO4) thin film at the anode/ electrolyte interface, enhancing conductivity and inhibiting the growth of the lithium dendrites. Electrochemical measurements of the full cells showed that the HEO anode achieved a specific capacity of 121mAh g-1 at 20mA g-1 (0.1C) with a working voltage of around 2.4V. The energy density can reach 292Wh kg-1. Furthermore, in order to investigate the aging mechanism of the HEO anodes, this study also analyzed the morphology and elemental valence changes of the HEO anode. Two degradation mechanisms were proposed: 1) Reduction of magnesium ions (Mg2+) in the HEO material system to metallic magnesium (Mg), resulting in the generation of oxygen (O) and cell expansion; 2) Migration of lithium ions (Li+) combined with O to form lithium oxide (Li2O), which then reacted with the lithium hexafluorophosphate (LiPF6) in the electrolyte, eventually leading to the continuous thickening of Li3PO4 deposits on the anode surface and increased interface impedance. Through in-depth research and analysis of the HEO anode′s performance, morphology changes, and valence states, this study aims to promote the application of HEO as a lightweight and safe active material in future energy storage systems.

關鍵字(中)

★ 高熵氧化物
★ 溶膠凝膠法
★ 鋰離子電池
★ 陽極材料
★ 失效機制

關鍵字(英)

★ High entropy oxide
★ sol-gel method
★ lithium-ion batteries
★ anode materials
★ failure mechanism

論文目次

中文摘要 I
Abstract II
致謝 III
目錄 IV
圖目錄 VI
表目錄 VII
第一章緒論 1
1-1　前言 1
1-2 研究背景 1
第二章基礎理論及文獻回顧 4
2-1 二次電池系統介紹及ESG指標 4
2-2 鋰離子電池 7
2-2-1　鋰離子電池的原理及電池結構 7
2-2-2　影響鋰離子電池性能的因素 11
2-2-3　正負極活性材料介紹及正極/負極電容比（A/ C比） 13
2-3　全電池不可逆電容及負極預鋰化處理比較 15
2-4 高熵材料介紹及儲能領域的相關應用 18
2-4-1　高熵材料的定義特性及對ESG影響 18
2-4-2　高熵材料在儲能領域相關應用 21
2-5 高熵氧化物（高熵陶瓷）製備方法比較 25
2-5-1　固態機械球磨法 (Mechanical ball milling method) 25
2-5-2　氣相沉積法 (Vapor deposition Method) 26
2-5-3　液態反應法 26
2-5-3-1　共沉法 (Co-precipitation method) 26
2-5-3-2　噴霧裂解法 (Spray pyrolysis method) 27
2-5-3-3　溶膠凝膠法 (Sol-gel method) 29
第三章實驗步驟 31
3-1 化學藥品 31
3-2　高熵氧化物電極製備及鋰離子電池封裝流程 32
3-2-1　高熵氧化物電極製備 32
3-2-1-1　高熵氧化物 (HEO) 粉末製備 32
3-2-1-2　高熵陽極電極片製備 33
3-2-2　鋰離子半電池 (HEO/ Li) 封裝流程 33
3-2-2-1　鈕扣型電池封裝 33
3-2-2-2　袋裝型（軟包裝）電池封裝 34
3-2-3　高熵陽極預鋰化處理及全電池 (NCM811/ HEO) 封裝 34
3-2-3-1　高熵陽極預鋰化處理 34
3-2-3-2　全電池封裝流程 35
3-3 分析儀器 35
3-3-1　材料特徵分析 35
3-3-2　電化學量測系統 36
3-3-2-1　循環伏安法 (Cyclic Voltammetry, CV) 36
3-3-2-2　電化學阻抗圖譜 (Electrochemical Impedance Spectroscopy, EIS) 37
3-3-2-3　定電流長時間循環充放電測試 (Galvanostatic charge-discharge testing, GCD) 37
3-3-2-4　充放電率測試 (C-rate) 38
第四章結果與討論 39
4-1 高熵氧化物之粉末材料特徵分析與討論 39
4-1-1　高熵氧化物粉末之X-ray 繞射分析 (XRD) 39
4-1-2　高熵氧化物粉末之掃描式電子顯微鏡形貌分析 (SEM) 40
4-1-3　高熵氧化物粉末之粒徑分析 (PSD) 41
4-1-4　高熵氧化物粉末之穿透式電子顯微鏡分析 (TEM) 42
4-1-4　X-ray光電子光譜分析 (XPS) 42
4-2　高熵陽極半電池 (HEO/ Li) 性能測試分析與討論 45
4-2-1　循環伏安圖分析 (CV) 45
4-2-3　電化學阻抗圖譜 (EIS) 46
4-2-2　充放電率測試 (C-rate) 47
4-2-3　長時間穩定性測試 (Long cycle stability testing) 49
4-3 全電池 (NCM811/ HEO) 性能測試分析與討論 50
4-3-1　電化學阻抗圖譜 (EIS) 52
4-3-2　充放電率測試 (C-rate) 53
4-3-3　長時間穩定性測試 (Long cycle stability testing) 54
4-4　高熵陽極之老化/ 失效機制分析探討 55
第五章結論與未來工作 61
5-1 結論 61
5-2 未來工作 62
參考文獻 63

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指導教授

洪緯璿(Wei-Hsuan Hung)

審核日期

2023-8-15

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