臺灣博碩士論文加值系統

本研究第一部分為利用奈米碳球（CNC）與中孔性碳材（MPC）兩種碳材作為碳晶種，經由多元醇法與低溫回流的方式合成出晶種為碳材之二氧化錳奈米線（CNC/MnO2 N.W.與MPC/MnO2 N.W.）。經由XRD與XPS分析得知合成材料為Cryptomelane型態的二氧化錳。利用旋轉電極測試CNC/MnO2 N.W.添加導電碳材CNT後，其有最大電子轉移數為3.94。接著進行全電池測試，固定電流密度50 mA/cm2，放電電壓為1.1 V，比電容值為819 mAh/g。由極化曲線結果，可得知最大功率密度為131 mW/cm2。在循環充放電300圈後，CNC/MnO2 N.W.+CNT擁有89.2 %的電壓保留率，相較於市售白金觸媒78.8 %高。
第二部分為利用靜電紡絲法製備載體為碳纖維之金屬觸媒，以自行合成之PI系高分子與氯化鈷、鈷乙醯丙酯進行靜電紡絲。由EDS得知纖維由C、O、Co元素所組成，經XRD分析結果，鈷為立方β相之結構的純鈷金屬態。且CoCl2/PI-CNF與Co(acac)2/PI-CNF，其電子轉移數為別為3.83、3.75。接著將CoCl2/PI-CNF進行全電池測試，固定電流密度50 mA/cm2，放電電壓約為1.1 V，比電容值分別為799 mAh/g。極化曲線結果得知CoCl2/PI-CNF擁有最大功率密度為112 mW/cm2。在循環充放電測試中，經300圈的測試後，得知CoCl2/PI-CNF擁有91.7 %的電壓保留率，相較於市售白金觸媒78.8 %高。
第三部分為利用不同材料集電網進行全電池測試，經由極化曲線測試，其碳紙與碳布之最大功率密度分別為57 mW/cm2、73 mW/cm2，相較於金屬集電網（如：鎳網122 mW/cm2）低。並使用鎳網、銅網、鈦網、不銹鋼網作為集電網使用，其最大功率密度大小為：鎳網（122 mW/cm2）> 銅網（120 mW/cm2）> 鈦網（119 mW/cm2）> 不鏽鋼網（85 mW/cm2）。同時探討不同大小之不銹鋼網，其最大功率密度大小為：500 mesh（119 mW/cm2）> 450 mesh（114 mW/cm2）> 10 mesh（109 mW/cm2）> 16 mesh（106 mW/cm2）> 200 mesh（96 mW/cm2），因500 mesh反應電荷傳輸阻抗較小，使得電池效能達到最佳化。



關鍵詞：二氧化錳、奈米、靜電紡絲、集電網

The first part of the study is to investigate the performance of the manganese dioxide nanowires used in the catalyst layer for zinc air battery. Carbon nanocapsule and mesoporous carbon were employed as the substrates for dioxide manganese nanowires. The properties of the CNC/MnO2 N.W. and MPC/MnO2 N.W. were analyzed with scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS). The results confirmed that the cryptomelane-type MnO2 was formed. The CNC/MnO2 N.W. had the highest number of electrons transferred which is calculated as 3.94 by rotating ring-disk electrode test (RRDE). The discharge voltage of 1.1 V and the specific capacity of 819 mA/g were achieved at 50 mA/cm2. The maximum power density is 131 mW/cm2 at 179 mA/cm2. The discharge potential retention is 89.2 % after 300 cycles test.
Polyimide carbon fibers containing metal catalyst were prepared by electrospinning technology. The materials properties of the CoCl2/PI-CNF and Co(acac)2/PI-CNF were analyzed with scanning electron microscope (SEM), X-ray diffraction (XRD). The results confirmed that cubic β-phase pure cobalt metal was formed. The CoCl2/PI-CNF had the highest number of electrons transferred which is calculated as 3.83 by rotating ring-disk electrode test (RRDE). During full battery test, the discharge voltage of CoCl2/PI-CNF is about 1.1 V and the specific capacity is 799 mA/g at 50 mA/cm2. The maximum power density is 112 mW/cm2 at 158 mA/cm2. The discharge potential retention of battery is 91 % after 300 cycling test.
Current collectors were studied using a rariety of metal materials with different mesh numbers. The battery performance was investigated as function of the different mesh size of the stainless steel mesh. According the results of full battery, the power density of 119 mW/cm2 at 169 mA/cm2, can be achieved by the stainless steel with mesh number of 500.



Keywords：Manganese dioxide, Nano, Electrospinning, Current collector

誌謝 I
中文摘要 III
Abstract V
目錄 VII
表目錄 X
圖目錄 XI
第一章 緒論 1
1-1 前言 1
1-2 金屬空氣電池之簡介 3
1-2-1 鋅空氣電池之發展史 4
1-2-2 鋅空氣電池之電化學原理 7
1-2-2-1 鋅空氣電池放電反應 7
1-2-2-2 鋅空氣電池充電反應 11
1-2-2-3 鋅陽極反應 12
1-2-2-4 其他反應 14
1-2-3 鋅空氣電池之構造 15
1-2-3-1 鋅陽極 16
1-2-3-2 電解液 20
1-2-3-3 空氣陰極 22
1-3 靜電紡絲之簡介 25
1-3-1 靜電紡絲之發展史 25
1-3-2 靜電紡絲之原理 26
第二章 文獻回顧 28
2-1 鋅空氣電池之陰極觸媒 28
2-1-1 錳系氧化物材料 31
2-1-2 靜電紡絲PI系碳纖維 38
2-1-3 其他觸媒 44
2-1-4 鋅空氣電池陰極之相關文獻回顧整理 48
2-2 鋅空氣電池之集電網 63
2-2-1 金屬材料之集電網 63
2-2-2 碳材料之集電網 65
2-3 研究動機與目的 69
第三章 實驗步驟與研究方法 70
3-1 實驗架構 70
3-2 二氧化錳-奈米線材料之製備 72
3-2-1 實驗藥品與耗材 72
3-2-2 實驗裝置 73
3-2-3 實驗步驟 74
3-2-4 實驗檢測儀器 76
3-3 利用靜電紡絲法製備金屬觸媒碳纖維 77
3-3-1 實驗藥品與耗材 77
3-3-2 實驗裝置 78
3-3-3 實驗步驟 79
3-3-4 實驗檢測儀器 82
3-4 鋅空氣電池-電化學測試 83
3-4-1 實驗藥品與耗材 83
3-4-2 實驗裝置 84
3-4-3 實驗步驟 85
3-4-3-1 觸媒材料（CNCs@MnO2）之製備 85
3-4-3-2 旋轉電極漿料配製 87
3-4-3-3 空氣陰極製作 89
3-4-3-4 電化學測試 94
3-4-4 實驗檢測儀器 96
第四章 結果與討論 97
4-1 晶種為碳材之二氧化錳奈米線觸媒 98
4-1-1晶種為碳材之二氧化錳奈米線觸媒之特性分析 101
4-1-1-1 碳晶種之BET分析 101
4-1-1-2 晶種為碳材之二氧化錳奈米線觸媒之SE-mapping分析 103
4-1-1-3 晶種為碳材之二氧化錳奈米線觸媒之XRD分析 106
4-1-1-4 晶種為碳材之二氧化錳奈米線觸媒之XPS分析 109
4-1-1-5 實驗小節 113
4-1-2晶種為碳材之二氧化錳奈米線觸媒於鋅空氣電池上之應用 114
4-1-2-1 旋轉電極的測試 114
4-1-2-2 鋅空氣電池全電池測試 132
4-1-2-3 實驗小節 137
4-2 載體為碳纖維之金屬觸媒 138
4-2-1 不同鈷之前驅物 139
4-2-2 載體為碳纖維之金屬觸媒特性分析 142
4-2-2-1 載體為碳纖維之金屬觸媒之XRD分析 142
4-2-3 載體為碳纖維之金屬觸媒於鋅空氣電池上之應用 145
4-2-3-1 旋轉電極的測試 145
4-2-3-2 鋅空氣電池全電池測試 155
4-2-3-3 實驗小節 161
4-3 利用不同材料與網目大小之集電網應用於鋅空氣電池 162
4-3-1 碳材之集電網 163
4-3-2 碳材之集電網於鋅空氣電池上之應用 164
4-3-3 金屬材料之集電網 165
4-3-4 金屬材料之集電網於鋅空氣電池上之應用 176
4-3-5 實驗小節 179
第五章 總結與未來展望 180
5-1 總結 180
5-2 未來展望 183
參考文獻 184
附錄 195
附錄A 錳金屬與氧之相圖 195
附錄B CNC/MnO2 N.W. 與 MPC/MnO2 N.W. 之TGA結果 196
附錄C 無碳晶種之二氧化錳奈米線的SEM圖 197
附錄D ORR起始電位與半波電位值的判別方法 198
附錄E OER起始電位取得方式 199
附錄F EIS測量流程圖 200
附錄G 利用含浸法使CNC@MnO2觸媒附著於碳紙上之實驗流程圖 201

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