鋅空氣電池之空氣陰極研究－新電極結構與新碳材料

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研究生：	紀元發 Yuan-Fa Chi
論文名稱：	鋅空氣電池之空氣陰極研究－新電極結構與新碳材料 Air Cathode in Zinc-Air Battery－New Electrode Structure and Novel Carbon Support/Catalyst
指導教授：	金重勳 Tsung-Shune Chin
口試委員:
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：	2005
畢業學年度：	93
語文別：	中文
論文頁數：	94
中文關鍵詞：	鋅空氣、電池、碳材、金屬空氣、空氣極
外文關鍵詞：	zinc-air, battery, carbon, metal-air, air electrode
相關次數：	點閱：2 下載：0
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　　在金屬-空氣電池中，空氣陰極的效能、製作成本以及耐用性為一重大課題。在本實驗中嘗試突破創新，有兩大不同之處：一、實驗所用電極網，利用良好催化性之發泡鎳，搭配良好支撐性之不繡鋼網，提升催化以及支撐兩要素。二、導入新碳材料，利用近年來受注目的產品－竹炭，將竹炭引進催化層材料，探討與過去文獻中，所利用的碳黑、石墨、活性碳等不同處。實驗量測以電位極化掃描法探究電化學性質，並輔以SEM對於電極表面進行觀察；XRD對於電極材料結構進行觀察，求得最佳化空氣極。
　　結果顯示，新電極結構對於催化性上，與純發泡鎳電極，在電壓-0.4 VHg/HgO時電流相差不到10 %，但卻比純不繡鋼網電極好75 %；而電極結構強度上，與不繡鋼網相同，卻比純發泡鎳好甚多，促使大面積使用上，可有良好支撐及催化性。
　　對於竹炭引入空氣極的使用，電性表現上，在電壓-0.4 VHg/HgO時電流可達161.4 mA，相較於過去習用碳材至少可提升25%以上的效能，可說是相當成功的一個創舉。
　　對於催化劑MnO2或LiCoO2兩者，及其合成之尖晶石型氧化物之催化性，在多孔性碳材的催化上，無明顯成效，在催化劑使用方面還有待繼續努力研究。

The performance, manufacture cost and durability of air cathodes are key issues in metal-air battery. Two major innovations were proposed in this research. The combination of Ni foam and stainless steel as current collectror is the first one. It results in both high electrochemical performance and good mechanical strength. The second one is the adoption of bamboo carbon into catalyst layer as a novel carbon support/ catalyst. In order to optimize the air cathode, linear sweep voltametry (LSV), scanning electron microscope (SEM) and X-ray diffraction (XRD) were conducted to examine the electrochemical performance, surface morphology and lattice structure, respectively. According to cathodic polarization results, under -0.4 VHg/HgO, the combination of Ni foam and stainless steel revealed 75 % higher and 10 % lower in current density compared to stainless steel and Ni foam alone, respectively. In addition, the new electrode structure performed much better mechanical strength than does Ni foam alone. The new electrode structure could provide both the high electrochemical performance and good mechanical strength demanded by large area/current applications.
The usage of bamboo carbon into activation layer as novel carbon support/catalyst was supposed to be a good innovation. Under -0.4 VHg/HgO, the current density was about 161.4 mA/cm2, at least 25 % enhancement was achieved compared to the conventional others.
On the other hand, the use of MnO2, LiCoO2 and spinel-type oxides as catalyst was considered to be of little help for cathodes composed of porous carbon. It requires to further studies.

摘要                                     I
Abstract                                 II
目錄                                     III
圖目錄                                   VI
表目錄                                   VIII
第一章　序論                             1
第二章　文獻回顧                         3
1 電池簡介                             3
1.1一次電池                            4
1.2二次電池                            6
1.3電池原理                            7
2 金屬空氣電池                         9
2.1金屬空氣電池發展史                  9
2.2金屬空氣電池種類                    12
3 鋅空氣電池                           13
3.1鋅空氣電池簡介                      13
3.2鋅空氣電池優缺點                    13
4 鋅空氣電池之構成                     15
4.1全反應                              15
4.2鋅電極                              16
4.2.1鋅電極之構成                      16
4.2.2鋅電極之氧化還原                  17
4.3空氣電極                            18
4.3.1空氣極之構成                      18
4.3.2空氣極之氧化還原                  19
4.3.2.1氧還原機制                      19
4.3.2.2氧氣生成機制                    20
4.3.3碳材                              21
4.3.4催化劑                            22
4.3.5聚四氟乙烯（PTFE）                25
4.3.6集電網                            25
4.4電解液                              26
5 鋅空氣電池外在影響因素               28
5.1濕度影響                            28
5.2溫度影響                            29
6 各款式鋅空氣電池                     30
6.1一次鋅空氣電池                      30
6.1.1鋅板式鋅空氣電池                  30
6.1.2鈕扣式鋅空氣電池                  30
6.1.3電解液循環式鋅空氣電池            31
6.2二次鋅空氣電池                      33
6.2.1循環式鋅空氣電池                  33
6.2.2電解液固定式鋅空氣電池            34
6.2.3三極式電解液固定式之鋅空氣電池    35
第三章　實驗                             36
1 試藥                                 36
2 實驗儀器                             37
2.1 X光繞射分析儀（XRD分析）           37
2.2掃描式電子顯微鏡（SEM分析）         37
2.3熱重/熱差分析（TGA/DTA）            37
2.4電化學分析                          38
3 實驗流程                             39
3.1催化劑製作                          39
3.1.1尖晶石型氧化物                    39
3.1.2催化劑之前處理                    40
3.2空氣極製備                          41
3.2.1集電網                            41
3.2.2催化層                            42
3.2.3擴散層                            42
3.2.4空氣極製作                        42
4 鋅空氣電池實驗設備                   47
4.1實驗設備                            47
4.2實驗測試條件                        48
5 空氣極研究                           49
5.1碳材研究                            49
5.2催化劑研究                          49
5.3空氣極支撐結構研究                  50
5.4催化層之碳粉比例研究                50
第四章　結果與討論                       51
1 碳材特性分析                         51
1.1基本特性                            51
1.2碳材之XRD分析                       51
1.3碳材之表面形貌                      54
2 催化劑之特性分析                     58
2.1合成催化劑尖晶石型氧化物            58
2.1.1 DTA                              58
2.1.2 XRD                              59
2.1.3 SEM                              62
2.2碳粉與催化劑之再處理                62
2.2.1 XRD                              64
2.2.2 SEM                              67
3 空氣陰極之性能分析                   68
3.1單一碳材製作成空氣極                68
3.1.1空氣陰極之極化曲線                69
3.1.2空氣陰極之SEM圖                   72
3.2兩種碳材料混合製作成空氣極          75
3.2.1空氣陰極之極化曲線                76
3.2.2催化層之SEM圖                     78
3.3添加不同催化劑之空氣極              80
3.3.1不同催化劑之空氣極                80
3.3.1.1極化曲線分析                    81
3.3.2具前處理催化劑之空氣極            81
3.3.2.1極化曲線分析                    83
3.4不同支撐結構之空氣極                85
3.4.1極化曲線分析                      86
3.5活性碳與竹炭之比例                  88
3.5.1極化曲線分析                      88
第五章    結論                           91
參考文獻                                 93

                                

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