臺灣博碩士論文加值系統

本研究以噴霧熱解法在400、500 ℃(SP400、SP500)熱解溫度下製備具中空球形的錳氧化物粉體作為超級電容器之電極活性材料，並以靜電沉積方式收集粉體，再藉由電泳沉積法將粉末沉積於石墨基材上，來探討其電容特性。除了製備純錳氧化物粉體外，也於先驅物中添加少量的醋酸鉻或醋酸鋅(0、1、2、5、10 at.%)形成錳/鉻或錳/鋅複合氧化物，探討添加這兩個元素對於錳氧化物薄膜電極對於電容性質的影響。
經由XRD比對的結果發現噴霧熱解所製備的粉體為奈米晶Mn3O4相，其中添加鉻或鋅的錳氧化物同樣具有Mn3O4相，由晶格體積的計算發現在SP400與SP500試樣中隨著鉻添加量的增加晶格有增大的趨勢，而隨添加鋅含量的增加其晶胞體積則有減小的現象；在這兩個溫度下隨著鉻或鋅含量的增加其晶粒皆有變小的趨勢，顯示添加鉻或鋅都會抑制晶粒的成長。從SEM的觀察發現所製備的粉體皆呈現中空球狀且表面有凹陷、皺摺與顆粒破碎的情形，其平均顆粒大小分布在420~690 nm之間；藉由電泳沉積後其表面仍有顆粒堆疊的多孔結構。
經由電泳沉積後的薄膜，經過循環伏安測試電化學性質，在25 mVs-1的掃描速率下，在SP400時錳氧化物隨著鉻含量的增加其電容值有增加的趨勢，其中以添加10 at.% Cr時電容值最高(246 F/g)，在SP500也有相同趨勢，但以添加1 at.% Cr的電容值較高(257 F/g)，添加鉻有助於錳氧化物晶胞體積的增加，使其有較佳的電容值；同樣的掃描速率在SP400不同鋅添加量的錳氧化物，其電容值也隨著鋅含量的增加而有所提升，其中又以添加10 at.% Zn時最高達298 F/g，雖然添加鋅時其晶胞體積會縮小，但由於氧化鋅有好的電子學性質與擬電容特性有助於錳氧化物電容性質的提升。

In the present research, Mn-oxide powders with a hollow spherical structure were prepared by spray pyrolysis (SP) at temperatures of 400 and 500 ?aC (SP400, SP500) for the applications of supercapacitor electrode. The resulting powders were collected by electrostatic deposition technique, and subsequently deposited onto graphite substrates by electrophoresis deposition (EPD) method for the investigations of pseudocapacitive properties. Furthermore, small amounts of chromium acetate or zinc acetate (0, 1, 2, 5, 10 at.%) were respectively added into the precursor solution for the Mn/Cr oxide or Mn/Zn oxide composite syntheses. The influences of the additions on the supercapacitive properties of the manganese oxide film electrode were thus investigated.
According to XRD analyses, the resulting powder was identified as a nanocrystalline Mn3O4 phase after SP. From the calculation of the XRD data, the lattice volume of SP400 and SP500 was found to increase with the increase of chromium content; whereas, decrease with the increase of zinc content. The grain sizes of both the SP400 and SP500 exhibited a decline trend when chromium or zinc was added, showing that the additives can inhibit the grain growth of the SP Mn-oxide powders. The SEM observation showed that the resulting particles were spherical in shape with a hollow structure and wrinkle surfaces. Moreover, some of SP particles even exhibited fracture surfaces. The average particle size ranged between 420-690 nm. After EPD, the particles were observed to stack to be a porous structure showing a high specific surface area.
After EPD, electrochemical properties of the SP powders were examined by cyclic voltammetry at a scan rate of 25 mVs-1. The specific capacitance of SP400 increased with increasing the chromium content, attaining its highest value (246 F/g) when 10 at.% chromium was added. The SP500 also exhibited a similar trend, but reached its highest value (257 F/g) when 1 at.% chromium was added. Chromium addition might increase the lattice volume of Mn-oxide to show a better capacitive performance of the EPD coating. The specific capacitance of zinc-added SP400 increased with increasing the amount of zinc at the same scan rate. The capacitance attained its highest value at 298 F/g when the 10 at.% zinc was added. Although the lattice volume of the zinc-added Mn-oxide was reduced, good electronics and pseudocapacitive natures of zinc oxide might improve the pseudocapacitive performances of SP Mn-oxide powder.

摘要 I
Abstract III
目錄 V
表目錄 VIII
第一章、前言 1
第二章、 文獻回顧 3
2.1電化學電容介紹 3
2.2 電化學電容器 4
2.2.1 電化學電容器之分類 7
2.2.1.1 電雙層電容器(electrical double-layer capacitors, EDLCs) 7
2.2.1.2 擬電容電容器(Pseudocapacitnce) 9
2.2.1.3 混和電化學電容器(Hybrid electrochemical capacitors, HECs) 12
2.3 金屬氧化物電極的種類、製備與應用 12
2.3.1 錳氧化物電極製備法 14
2.3.2 電化學電容器電解液的種類 20
2.3.3 金屬氧化物電極的製備方法 24
2.4 噴霧熱解法 28
2.4.1 噴霧熱解法簡介 28
2.4.2 噴霧熱解製程 29
2.4.2.1 先驅物溶液 29
2.4.2.2 先驅物霧化 29
2.4.2.3 溶劑之蒸發 30
2.4.2.4 乾燥 31
2.5 電化學反應系統 33
第三章、實驗目的與方法 35
3.1 實驗設計與目的 35
3.2 錳氧化物粉體之製備與收集 36
3.3 電極製備 37
3.3.1 電極基材前處理 37
3.3.2 電泳披覆錳氧化物與添加鐵或鎳之錳氧化物薄膜 37
3.4 氧化錳之粉體與電極材料分析 38
3.4.1 熱重分析 38
3.4.2 傅立葉轉換紅外線光譜分析 39
3.4.3 X光繞射分析 39
3.4.4 高解析穿透式電子顯微鏡粉體結構分析 40
3.4.5 冷場發射掃描式電子顯微鏡表面型態分析 40
3.5 氧化錳電極之電容特性分析 41
3.5.1 循環伏安分析 42
3.5.2 計時電位充放電測試 42
第四章、結果與討論 43
4.1 錳/鉻、錳/鋅複合氧化物薄膜 43
4.1.1 先驅物粉體之特性分析 43
4.1.2 錳/鉻複合氧化物噴霧熱解粉體之特性分析 44
4.1.2.1 XRD結晶結構分析 44
4.1.2.2 錳/鉻複合氧化物粉體之TEM微結構觀察 48
4.1.2.3 錳/鉻複合氧化物之FESEM表面型態分析 50
4.1.3 錳/鉻複合氧化物薄膜之電性分析 56
4.1.3.1 CV測試 56
4.1.3.2 充放電分析 65
4.1.4 錳/鋅複合氧化物噴霧熱解粉體之特性分析 67
4.1.4.1 XRD結晶結構分析 67
4.1.4.2 錳/鋅複合氧化物粉體之TEM微結構觀察 70
4.1.4.3 錳/鋅複合氧化物之FESEM表面型態分析 73
4.1.5 錳/鋅複合氧化物薄膜之電性分析 78
4.1.5.1 CV測試 78
4.1.5.2 充放電分析 86
第五章、結論 88
第六章、未來工作 90
參考文獻 91

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