共摻雜鐵、鋅來改善磷酸鋰鈷作為鋰離子電池陰極材料的電化學表現

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研究生：	李輝林 Li, Hui-Lin.
論文名稱：	共摻雜鐵、鋅來改善磷酸鋰鈷作為鋰離子電池陰極材料的電化學表現 Improved Electrochemical Performance of Fe-Zn co-doped LiCoPO4 as Cathode Material for Lithium Ion Battery
指導教授：	蔡哲正 Tsai, Cho-Jen.
口試委員:	陳翰儀 Chen, Han-Yi. 林居南 Lin, Ju-Nan.
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2021
畢業學年度：	109
語文別：	中文
論文頁數：	58
中文關鍵詞：	鋰離子電池、陰極材料、磷酸鋰鈷、摻雜
外文關鍵詞：	Lithium Ion Battery, Cathode Material, LiCoPO4, Co-Doping
相關次數：	點閱：2 下載：0
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LiCoPO4正極材料實際應用的主要問題是受限於相對較差的電子和離子傳導性，而離子摻雜被認為是改善固有電子和離子傳導性的重要策略。在本實驗中，通過溶膠-凝膠法合成的鐵鋅共摻雜LiCoPO4材料。XRD和Rietveld精修結果表明，鐵和鋅成功取代了LiCoPO4的鈷，而橄欖石結構卻沒有變。SEM結果可知，鐵和鋅摻雜不會導致材料的基本形貌發生變化，該材料由團聚的納米顆粒組成。EDX結果證實鐵和鋅是均勻分佈的。此外，相比未摻雜的LiCoPO4材料，鐵鋅共摻雜有效減輕了材料的極化現象，顯著提高了循環穩定性和變速率性能。
其中在1 C下，導電碳包覆的LiCo0.85Fe0.1Zn0.05PO4，初始電容量達到118.1 mAh/g ,100次循環容量保持率93.4 %,300圈後電容量仍有79 mAh/g。Randles – Sevcik方程式也表明在摻雜鐵的基礎上，少量鋅摻雜有效提高鋰離子的擴散速率。另外電化學阻抗譜(EIS)分析也可知，鋅的增加，內阻抗減小且在循環過程中內阻變化較小，這對電性穩定來說是有利的。但鋅的過量也會導致實際活物的減少，初始電容量有所下降，可能影響到鋰離子正常脫嵌。因此本實驗中得到鋅的摻雜應控制在5 %左右對電性改善最為有利。

Poor electronic and ionic conductivity are two main factors that limit the practical application of LiCoPO4 cathode materials. Ion doping is considered as an important strategy to improve the intrinsic electron and ion conductivity of LiCoPO4. In this word, a Fe-Zn co-doped LiCoPO4 cathode materials is synthesized using the sol-gel method. The results of X-ray powder diffraction (XRD) and Rietveld reﬁnement indicate that the dopants were successfully introduced to the olivine lattice, while the olivine structure was not changed. Scanning electron microscope (SEM) images indicated that Fe and Zn doping do not cause changes in the basic morphology of the material and Energy dispersive spectroscopy (EDS) images confirmed that Fe and Zn are evenly distributed. In addition, compared with undoped LiCoPO4, the Fe-Zn co-doped LiCoPO4 reduces polarization, improves cycle stability and rate performance.
Notably, the carbon coated LiCo0.85Fe0.1Zn0.05PO4 delivers an initial discharge capacity of 118.1 mAh/g, shows a capacity retention of 93.4 % after 100 cycles and remained 79 mAh/g after 300 cycles at 1 C. The Randles-Sevcik equation also shows that a small amount of Zn doping improves the diffusivity of lithium ions on the basis of Fe doping. With the increase of Zn, the internal resistance decreases during the cycle, which is beneficial to electrical stability. However, the excessive amount of Zn would not only lead to the reduction of actual active material but also adversely affect the electrochemical performance of the electrode. Therefore, it is known that the substitution of Zn should be controlled at about 5 % in this experiment.

Abstract    1
摘要    2
致謝    3
目錄    4
第1章    緒論    7
1 鋰電池的發展與應用    7
2 磷酸鋰鈷電池的運作原理及優缺點    10
第2章    文獻回顧    14
1 磷酸鋰鈷材料的合成方法    14
2 電性改良方法    14
2.1 顆粒尺寸控制    14
2.1.1 減小顆粒尺寸    14
2.1.2 控制顆粒形貌    15
2.2 表面包覆改質    17
2.2.1 碳包覆    17
2.2.2 穩定化合物包覆    19
2.3 離子摻雜    21
第3章    實驗動機與步驟    27
1 研究動機    27
2 實驗藥品    27
3 材料製備    28
3.1 溶膠凝膠法合成LiCoPO4、LiCo0.9-xFe0.1ZnxPO4 (x = 0, 0.05, 0.10, 0.15)    28
3.2 導電碳包覆    29
4 電極製備    29
5 鈕扣電池組裝    30
6 材料與電化學分析    31
6.1 X光粉末繞射儀    31
6.2 場發式掃描電子顯微鏡    31
6.3 電池循環壽命測試    31
6.4 循環伏安法    31
6.5 電池循環壽命測試    32
6.6 TGA熱重分析儀    32
第4章    結果與討論    33
1 LiCoPO4/C與LiCo0.9-xFe0.1ZnxPO4/C（x = 0，0.05，0.1和0.15）之材料分析    33
1.1 LiCoPO4/C與LiCo0.9-xFe0.1ZnxPO4/C（x = 0，0.05，0.1和0.15）之相分析    33
1.2 碳包覆分析    36
1.3 形貌與元素分析    37
2 電性表現    39
2.1 循環壽命    39
2.2 變速率充放電表現    42
3 電化學分析    43
3.1 工作電壓平台    43
3.2 循環伏安法    45
3.3 利用循環伏安法討論擴散速率    48
3.4 交流阻抗分析    51
第5章    結論    54
第6章    參考文獻    55


                                

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