||The Investigation of TMOs/rGO Nanocomposite as an Anode for Lithium Ion Batteries
||Department of Materials Science and Engineering
self-assemble hollow sphere structure
本研究之第一部分實驗為結合氧化鋅(理論電容量：978 mAh g-1)與氧化石墨烯(graphene oxide)，形成ZnO/rGO自組裝中空球 (self-assembled hollow-sphere) 奈米複合(nanocomposite)材料。藉由電化學測試後，由實驗結果顯示，無論是電容量、循環穩定性以及材料內部阻抗等電池性質，複合材料顯現之性質皆優於氧化石墨烯，且經過20圈充放電測試後，ZnO/rGO奈米複合材料仍維持605.36 mAh g-1的電容量，為氧化石墨烯第20圈電容量133.82 mAh g-1的4倍。從結果得知當過渡金屬化物與氧化石墨烯結合，的確可以提升電池表現。
因此，第二部分實驗則將過渡金屬氧化物改為理論電容量更高的二氧化錳(理論電容量：1232 mAh g-1)，並合成二氧化錳(MnO2)奈米針(nanoneedle)、MnO2/rGO奈米複合材料，再將MnO2/rGO奈米複合材料經過還原處理得到四氧化三錳/還原氧化石墨烯(Mn3O4/rGO)六角片狀奈米複合材料(hexagonal-flat structure nanocomposite)。由於三種材料之結構皆具有奈米尺度，因此，提供更多有利於鋰離子擴散的途徑，使鋰離子與材料有更多反應位置，進而提供更高的電容量，又因複合材料之協同效應(synergistic effect)，使得複合材料維持了較穩定的循環壽命及高電容量維持率(retention)。
本研究結合氧化鋅/氧化錳與還原氧化石墨烯，製備具奈米結構之複合材料並應用於鋰離子電池負極。由於當過渡金屬氧化物與還原氧化石墨烯結合之後，還原氧化石墨烯扮演緩衝層以及導電層的角色，減緩過渡金屬氧化物在鋰化/去鋰化(lithiation/de-lithiation)過程中過渡金屬氧化物的體積變化，並提升材料導電性；而過渡金屬氧化物則能夠提高整體電容量，並且減緩還原氧化石墨烯重複再堆疊(re-stacking)的現象發生。兩者結合所產生的協同效應(Synergistic effect)，使二氧化錳/還原氧化石墨烯(MnO2/rGO)奈米複合材料以及四氧化三錳/還原氧化石墨烯(Mn3O4/rGO)奈米複合材料經過250圈充放電測試後，仍維持高循環穩定性以及高達387.15 mAh g-1以及631.49 mAh g-1之電容量；在快速(2C, 2464 mAg-1)充放電的過程中，兩材料分別維持443.05 mAh g-1和549.35 mAh g-1的高電容量，具有應用在鋰離子電池負極材料中的潛能。
We investigate the lithium storage properties of two kinds of materials as anode for LIB: graphene oxide (GO) and self-assembled hollow-sphere zinc oxide/reduced graphene oxide (ZnO/rGO) nanocomposite. GO is obtained by Hummers method controlled by the various process parameters. The ZnO/rGO hollow sphere nanocomposite is synthesized by a low temperature (95 °C) chemical solution reaction. For ZnO/rGO composite, the capacity is increased remarkably as compared to GO sheets, and this is due to the synergistic effects of both the components in the composite. The GO acts as a conductive buffer layer that promotes the conductivity, and suppresses the volume expansion of ZnO during the charge/discharge process. ZnO/rGO hollow sphere structure nanocomposite has higher capacity 605.36 mAh g-1, which is 4.5 times higher than GO (133.82 mAh g-1), after 20 cycles. The capacity variation with the charge-discharge rate of ZnO/rGO nanocomposite showed a higher capacity (299.95 mAhg-1 at 1700 mAg-1) than GO (20.09 mAhg-1 at 1488 mAg-1) after 32 cycles.
In the second part of the study, we synthesized the high performance of the MnO2/rGO nad Mn3O4/rGO nanocomposite as an anode electrode of a lithium-ion battery. The composite is synthesized by a low temperature (83 °C) chemical solution reaction, and shows relatively high specific capacities (660 mAh g-1) after 50 cycles. For MnOx/rGO composites, the cycling stability is increased remarkably as compared to that seen with individual MnOx, and this is due to the synergistic effects of both the components in the composite. The rGO acts as a conductive buffer layer that suppresses the volume change of MnOx, and simultaneously promotes the conductivity of MnOx. The functional groups of graphene oxide facilitate the formation of MnOx at low temperature and connecting with MnOx, thus improving the capacity and cyclic stability.
In this study, zinc oxide/manganese oxide and reduced graphene oxide were combined to prepare composites with nanostructures and applied to lithium ion battery anodes. When the transition metal oxide is combined with the reduced graphene oxide, the reduced graphene oxide acts as a buffer layer and a conductive layer, supressing the volume change of the manganese oxide during the lithiation/delithiation process and improving the conductivity of the material. And the transition metal oxide can increase the overall capacity and supress the phenomenon of re-stacking situation of reduced graphene oxide. MnO2/rGO nanocomposite and Mn3O4/rGO nanocomposite can not only maintain the capacity of 387.15 mAh g-1 and 631.49 mAh g-1 after 250 cycles charge/discharge test, respectively, but also maintaining 443.05 mAh g-1 and 549.35 mAh g-1, respectively when charge/discharge with high charge current density 2464 mAg-1 due to the synergistic effect.
Extend abstract V
第一章 緒論 1
1.1 前言 1
1.2 研究動機 1
第二章 文獻回顧 3
2.1 鋰離子電池之發展與演進 3
2.2 鋰離子電池組成及工作原理 5
2.3 鋰離子電池負極材料簡介 10
2.3.1 碳材 11
2.3.2 過渡金屬氧化物/石墨烯奈米複合材料簡介 14
2.3.3 過渡金屬氧化物與(氧化)石墨烯奈米複合材料在鋰離子電池中的應用 18
184.108.40.206 氧化鋅/(氧化)石墨烯奈米複合材料在鋰離子電池負極材料之應用 18
220.127.116.11 氧化錳/(氧化)石墨烯奈米複合材料在鋰離子電池負極材料之應用 27
第三章 實驗方法與步驟 38
3.1 實驗材料 38
3.2 實驗設備 39
3.3 實驗設計 39
3.4 活性材的製備 40
3.4.1 氧化石墨烯(Graphene oxide)的製備 40
3.4.2 氧化鋅/還原氧化石墨烯自組裝中空球(ZnO/rGO self-assembled hollow sphere nanocomposites)奈米複合材料的製備 41
3.4.3 二氧化錳(MnO2)與MnO2/rGO奈米複合材料之製備 42
3.4.4 四氧化三錳/還原氧化石墨烯(Mn3O4/rGO)自組裝六角片狀(Self-assembled hexagonal plate shape)奈米複合材料之製備 42
3.5 材料鑑定及分析 43
3.5.1 X-ray繞射分析儀 (X-ray diffraction spectrometer: XRD) 43
3.5.2 電子能譜化學分析儀 (Electron Spectroscopy for Chemical Analysis: ESCA) 44
3.5.3 拉曼光譜分析儀 (Raman spectroscopy，Raman) 45
3.5.4 高解析場發射掃描式電子顯微鏡 (High resolution field emission scanning electron microscopy，FE-SEM) 47
3.5.5 高解析分析電子顯微鏡 (Ultrahigh Resolution Analytical Electron Spectroscopy，HR-AEM) 48
3.6 鈕扣型半電池組裝及測試 49
3.6.1 極片製備流程 49
3.6.2 鈕扣型半電池組裝 50
3.6.3 半電池充放電測試 51
3.5.4 交流阻抗分析 52
第四章 結果與討論 54
4.1 ZnO/rGO 自組裝中空球奈米複合材料 54
4.1.1 活性材料之形貌與結構分析 54
18.104.22.168 XRD 結構及定性分析 54
22.214.171.124 表面形貌及顯微結構之FESEM分析 56
126.96.36.199 表面形貌及顯微結構之TEM分析 58
188.8.131.52 碳原子結構之Raman圖譜分析 61
184.108.40.206 材料成分比例之TGA分析 64
4.1.2 半電池的組裝與測試 65
220.127.116.11 充放電測試 65
18.104.22.168 循環穩定性之充放電測試 67
22.214.171.124 不同充放電速率測試(C-rate test) 70
126.96.36.199 交流阻抗分析 72
4.2 MnO2、MnO2/rGO及Mn3O4/rGO奈米複合材料 74
4.2.1 活性材料之形貌與結構分析 74
188.8.131.52 XRD 結構及定性分析 74
184.108.40.206 鍵結能貢獻及變化之ESCA分析 77
220.127.116.11 表面形貌與顯微結構之SEM分析 83
18.104.22.168 表面形貌與顯微結構之TEM分析與電子繞射圖譜分析 86
22.214.171.124 材料成分比例之TGA分析 91
4.2.2 鈕扣型半電池之組裝及測試 93
126.96.36.199 充放電測試 93
188.8.131.52 循環伏安法分析(Cyclic voltammetry analysis) 98
184.108.40.206 循環壽命之充放電測試 104
220.127.116.11 不同充放電速率測試 108
18.104.22.168 交流阻抗(Electrochemistry Impedance Spectroscopy)分析測試 111
第五章 結論 117
Future work 120
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