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研究生:黃郁銘
研究生(外文):HUANG,YU-MING
論文名稱:鋰離子電池正極鎳鈷錳三元材料的改質探討:以摻雜鈉離子與披覆TiO2為例
論文名稱(外文):Modification Study of LIBS Positive Electrode material (Ni-Co-Mn) Ternary Material by Dopping Sodium Atoms or Capping TiO2
指導教授:廖儒修
指導教授(外文):LIAO,JU-HSIOU
口試委員:楊鐘松李茂田
口試委員(外文):YANG,CHUNG-SUNGLEE,MAW-TIEN
口試日期:2021-07-07
學位類別:碩士
校院名稱:國立中正大學
系所名稱:化學暨生物化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2021
畢業學年度:109
語文別:中文
論文頁數:100
中文關鍵詞:三元材料溶膠-凝膠法二氧化鈦鈉摻雜
外文關鍵詞:Ternary materialsSol-gelSodium dopedTitanium dioxide
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近年來,鋰離子電池的需求增大,具高電容量、低成本、毒性較低的層狀結構鎳鈷錳三元材料為研究的重點之一,在LiNi1-x-yCoxMnyO2三元材料中,LiNi0.6Co0.2Mn0.2O2為較常使用的比例,但也因為鎳的比例佔高比例,在電池長期充放電高溫時鋰鎳會相轉變而導致電池壽命減短,因此鎳鈷錳三元材料修飾成為現在解決循環壽命的問題之一,本研究透過物理摻雜的方式將鈉摻雜到鎳鈷錳三元材料晶格中,與透過共沉澱法搭配溶膠-凝膠法將二氧化鈦披覆到材料表面,以二氧化鈦進行表面修飾之LiNi0.6Co0.2Mn0.2O2。在透過X光粉末繞射儀、穿透式電子顯微鏡鑑定樣品的結晶型態與形狀、大小,再以掃描式電子顯微鏡觀察修飾前後的差異,最後以穿透式電子顯微鏡與掃描式電子顯微鏡附掛的能量分散圖譜確認鎳鈷錳比例與鈉摻雜的含量、披覆的鈦含量,期許未來可以提升三元材料的循環穩定性以及提升電容量。
In recent years, the demand for lithium-ion batteries has been increased, and layered nickel-cobalt-manganese ternary materials with high capacity, low cost and low toxicity have been one of the focuses of research. In the LiNi1-x-yCoxMnyO2 ternary material, LiNi0.6Co0.2Mn0.2O2 is the most used compound, because of the high proportion of nickel accounts,the lithium nickel will phase transite during the long-term charging and discharging of the battery at working temperature.therefore,the lifespan is shortened.the modification of nickel-cobalt-manganese ternary material becomes one of the problems requiring to solve for the cycle life. This study uses stoichiometric technique to dope sodium atoms into the nickel-cobalt-manganese ternary material lattice by the co-precipitation method ,on the other hand,the sol-gel method is used to coat the titanium dioxide onto the surface of the ternary material,LiNi0.6Co0.2Mn0.2O2.The crystal form, shape, and size of the sample are identified via the X-ray powder diffraction and transmission electron microscope.The difference between before and after the modification is observed by the scanning electron microscope.Finally,the attached energy dispersion map is employed to confirm the ratio among nickel, cobalt and manganese, the content of doped sodium atoms and the capped titanium. The new prepared material is expected to have the higer cycle stability in comparison with the ternary material. Thus,the electric capacity is also expected to be improved.
總目錄 I
圖目錄 V
表目錄 IX
中文摘要 1
Abstract 2
第一章 緒論 4
第二章 文獻回顧 6
2-1二次鋰離子電池介紹 6
2-1-1二次鋰離子電池工作原理 9
2-2鋰離子電池的組成 10
2-3正極材料 11
2-3-1鋰鈷氧化物LiCoO2 12
2-3-2鋰鎳氧化物LiNiO2 13
2-3-3尖晶石型鋰錳氧化物LiMn2O4 14
2-3-4鈦酸鋰Li4Ti5O12 15
2-3-5磷酸鋰鐵LiFePO4 16
2-4 負極材料 17
2-4-1石墨 17
2-4-2鋰合金 18
2-5 電解質 18
2-6 隔離膜材料 19
2-7 不同鎳鈷錳比例的三元正極材料 (LiNixCoyMnzO2(x+y+z=1)) 20
2-7-1 NCM333 20
2-7-2 NCM523 21
2-7-3 NCM622 22
2-7-4 NCM7 1.5 1.5 23
2-7-5 NCM811 24
2-8 NCM三元材料的修飾 25
2-8-1以摻雜方式修飾NCM 26
2-8-2以包覆方式修飾NCM 27
2-9 TiO2特性 27
第三章 實驗藥品與方法 29
3-1實驗藥品 29
3-1-1 NCM製備藥品 29
3-1-2藥品結構 30
3-2實驗儀器 32
3-3 Na摻雜NCM622合成方法 33
3-3-1 Na-NCM622合成步驟 33
3-4 TiO2包覆NCM622合成方法 34
3-4-1 TiO2包覆NCM622合成步驟 34
第四章 鈉摻雜與TiO2披覆NCM622鑑定與分析 36
4-1 Pristine NCM622 36
4-1-1 P-XRD結果鑑定與分析 36
4-1-2 TEM結果鑑定與分析 38
4-1-3 SEM結果鑑定與分析 41
4-2鈉摻雜NCM622結果鑑定與分析 43
4-2-1 P-XRD鑑定與分析 43
4-2-2 TEM鑑定與分析 45
4-2-2-1 2% Na-NCM622 45
4-2-2-2 3% Na-NCM622 49
4-2-2-3 4% Na-NCM622 53
4-2-2-4 5% Na-NCM622 56
4-2-3 SEM鑑定與分析 58
4-2-3-1 2% Na-NCM622 58
4-2-3-2 3% Na-NCM622 62
4-2-3-3 4% Na-NCM622 65
4-2-3-4 5% Na-NCM622 68
4-3 TiO2^NCM622結果鑑定與分析 71
4-3-1 P-XRD結果鑑定與分析 71
4-3-2 TEM結果鑑定與分析 73
4-3-2-1 4hr TiO2^NCM622 73
4-3-2-2 8hr TiO2^NCM622 76
4-3-2-3 16hr TiO2^NCM622 79
4-3-2-4 24hr TiO2^NCM622 82
4-3-3 SEM結果鑑定與分析 85
4-3-3-1 4hr TiO2^NCM622 85
4-3-3-2 8hr TiO2^NCM622 90
4-3-3-3 16hr TiO2^NCM622 92
4-3-3-4 24hr TiO2^NCM622 94
第五章 結論 96
第六章 參考文獻 98


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