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研究生：	藍三 Nasara, Ralph Nicolai
論文名稱：	以熱還原法合成快速充放電鈦酸鋰缺陷尖晶石 Synthesis of lithium titanate defect spinel with enhanced rate capability utilizing thermal reduction
指導教授：	林士剛 Lin, Shih-kang
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2016
畢業學年度：	104
語文別：	英文
論文頁數：	68
中文關鍵詞：	鋰鈦氧材料、熱還原法、電容率、鋰離子電池、缺陷
外文關鍵詞：	lithium titanate, thermal reduction, rate capability, lithium ion batteries, defects
相關次數：	點閱：131 下載：10
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由於鋰鈦氧尖晶石材料(Li4Ti5O12)在充放電中鋰離子遷入遷出的程序裡，擁有穩定的電壓及可忽略的體積變化的優勢，使其成為極具潛力的鋰電池負極材料。然而，先天高阻值的特性(10-13 S cm-1)阻礙鋰鈦氧尖晶石材料在高功率產品應用上的發展，為能改善這項缺點，複合化與奈米化係為兩項常用且發展成熟的技術，前者協助改善鋰鈦氧材料的電性，後者則縮短鋰離子遷入與遷出的擴散路徑。儘管如此，電極材料中的氧缺陷效應對於改善鋰鈦氧電性性質的影響仍不比前兩者方法來的直觀，甚者，技術上也非常難以直接控制氧缺陷之分布。這本次研究中，我們使用熱還原法製程來製備鋰鈦氧材料，藉由添加乙醇的熱還原法以達複合效應中高程度的還原方式，系統性的控制鋰鈦氧材料中氧缺陷的濃度。對比於傳統合成的白色鋰鈦氧材料，本次研究中可成功合成出藍色的鋰鈦氧材料，缺陷工程技術可望拓展鋰鈦氧材料更多的優化技術與發展空間。本期研究中亦詳細探討其微結構與電性性質之量測，例如循環次數表現、電容率。此外，我們也使用了基於密度泛函理論的第一原理計算來確認缺陷改質後鋰鈦氧材料的電化性質。本篇論文中，缺陷改質鋰鈦氧材料的生成機制以及優異的電化性質原因將被詳細探討

Lithium titanate (Li4Ti5O12) has been one of the most promising anode materials for lithium ion batteries because of its negligible volume change and stable operating voltage (1.55 V) during intercalation-deintercalation. However, the intrinsic insulating property (10-13 S cm-1) of Li4Ti5O12 hinders its high power applications. Compositing and nanonization are two well-understood approaches to overcome this drawback. The former enhances the external electrical conductivity of Li4Ti5O12, while the latter shortens the length of diffusion during the intercalation-deintercalation process. Nevertheless, the effects of presence of defects, e.g. oxygen vacancies, in electrode materials are not as straightforward as compared to the former approaches. Moreover, it is technically difficult to control the concentration and distribution of intentionally introduced defects, namely to engineer these oxygen vacancies. In this work, Li4Ti5O12 anode were synthesized via a thermal reduction process. Systematic introduction of oxygen vacancies was facilitated under the thermal reduction of ethanol, where a higher degree of reduction was achieved from a compounding effect. Unlike the conventional (white) Li4Ti5O12 material, (blue) Li4Ti5O12 material were synthesized. Defect engineering presents further opportunities for exploration and optimization. The microstructures and electrochemical properties, i.e., cycle performance and rate capability of the defect engineered Li4Ti5O12 were examined. In addition, ab initio calculations based on density functional theory (DFT) were performed to clarify the enhanced electrochemical properties of the defect engineered Li4Ti5O12. The formation mechanism of the defect engineered Li4Ti5O12, as well as the origin of superior electrochemical properties, is elaborated in this paper.

Table of Contents

摘要	ii
Abstract	iii
Acknowledgements	iv
List of Figures	viii
List of Tables	x
Chapter I	1
1.1	Introduction	1
1.2	Batteries and their principle	3
1.3	The increasing demand for lithium ion batteries	9
1.4 	Motivation and Challenge	11
1.6 	The role of Defect Engineering	14
1.7 	General Organization	20
Chapter II Experimental Method	21
2.1 	Computational method	21
2.2 	Materials	21
2.3 	Synthesis of Li4Ti5O12	22
2.4 	General Characterization	23
2.5 	Electrochemical Characterization	23
Chapter III Results and Discussions	25
3.1 	XRD Analysis	25
3.2 	XPS Analysis	30
3.3 	Particle morphology (SEM/TEM/BET)	32
3.4 	First principles calculations	36
3.5 	Cyclic Voltammetry	38
3.6 	Electrochemical Impedance Spectroscopy	40
3.7 	Cycling performance	45
3.8 	Thermal reduction formation mechanism	50
3.8.1 	Oxygen vacancy formation driving force	53
3.8.2 	Intentionally introduced oxygen defects	53
Chapter IV Conclusions	55
4.1 	Conclusions	55
Chapter V Outlook	57
5.1 	Future Work	57
References	59

List of Figures


Figure 1.1 Schematic diagrams showing the discharge and charge mechanisms for Primary batteries and Rechargeable batteries	3
Figure 1.2 Schematic diagram of a lead acid battery	4
Figure 1.3 Energy storage capability of commercial rechargeable batteries	5
Figure 1.4 The components of a typical lithium-ion battery	6
Figure 1.5 The graphic profiles, summarizes the characteristics and possible applications of different electrodes 	8
Figure 1.6 Increasing revenues of the Global lithium-based battery Market	9
Figure 1.7 Li-ion Battery Demand projections on a Capacity Basis 	10
Figure 1.8 Web of Science results showing Li4Ti5O12-related published items 	11
Figure 1.9 Unit cells of (a) Li4Ti5O12 and (b) Li7Ti5O12 phases	13
Figure 2.1 Home-made Swagelok reactor vessel	22
Figure 3.1 XRD pattern of the material with various heating temperatures of 600, 700 and 800°C	25
Figure 3.2 XRD pattern of the material with various annealing times of 0, 1, 2, 4 and 8 hours	26
Figure 3.3 Magnified peak of reduced-Li4Ti5O12 at various annealing time of 0, 1, 2, 4, and 8 hours	27
Figure 3.4 XRD Patterns of the pristine and reduced-Li4Ti5O12	28
Figure 3.5 Magnified peaks of: (i) pristine-Li4Ti5O12 (ii) reduced-Li4Ti5O12	29
Figure 3.6 Ti2p XPS Spectra of pristine and reduced-Li4Ti5O12; and (b) Normalized difference (pristine minus reduced- Li4Ti5O12)	31
Figure 3.7 Peak fitted Ti 2p characteristic peaks the pritine and reduced-Li4Ti5O12	32
Figure 3.8 O 1s XPS spectra for the pritine and reduced-Li4Ti5O12	33
Figure 3.9 SEM (a) reduced-Li4Ti5O12 and (b) pristine-Li4Ti5O12; TEM images of (a) reduced-Li4Ti5O12 (b) pristine-Li4Ti5O12	34
Figure 3.10 Schematic diagram for adsorption of a cold gas	35
Figure 3.11 BET Surface area plot	37
Figure 3.12 Supercell models corresponding to (a) Li32Ti40O96 (b) Li32Ti40O95	39
Figure 3.13 Total density of states (DOS) of (a) the pristine-Li4Ti5O12 and; (b) the reduced Li4Ti5O11.875.	39
Figure 3.14 Cyclic voltammogram at a scan rate of 0.1 mV s-1 of the pristine and reduced-Li4Ti5O12	40
Figure 3.15 Nyquist plots of the pristine and reduced-Li4Ti5O12	42
Figure 3.16 Schematic diagram of the equivalent circuit used for fitting both Li4Ti5O12 electrodes	43
Figure 3.17 Plots of the real part of the impedance as a function of the inverse square root of angular frequency in the Warburg region	44
Figure 3.18 Capacity voltage profiles at different current rates of 0.1 C, 1 C, 2C and 5 C for pristine and reduced-Li4Ti5O12	47
Figure 3.19 Cycling performance of pristine and reduced LTO at (a) C/10 rate (17 mA/g); (b) multiple C-rate (1.0C, 2.0C, 5.0C and 10.0C)	48
Figure 3.20 Collected residual carbon	54
Figure 3.21 XRD Patterns comparing the incorporation of Ethanol	54
Figure 5.1 Poor reusability for Swagelok SS316 unions and caps	58
Figure 5.2 Inconel 625 High-temperature and High-pressure custom reactor vessel	58





List of Tables

Table 1 Reported Electronic conductivity values for lithium titanate spinel	15
Table 2 Lattice parameters of the pristine and reduced-Li4Ti5O12 samples	29
Table 3 Summary of parameters	35
Table 4 Kinetic parameters from the cyclic voltammograms	39
Table 5 EIS parameters for pristine and reduced-Li4Ti5O12	44
                                    

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