氧化錳/碳黑複合材料之製備應用於超級電容器

The preparation of manganese oxide/carbon black composites application for supercapacitors

10.6845/NCHU.2015.00253

游智堯

超級電容 ； 錳系氧化物 ； 表面改質碳黑 ； 比電容 ； supercapacitors (SCs) ； manganese oxide (MO) ； surface modified carbon black (SMCB) ； specific capacitance.

中興大學材料科學與工程學系所學位論文

2015年

碩士

顏秀崗

英文

超級電容是一種利用高比表面積快速將電力儲存的裝置,應用於車用電子、大型儲能建物以及太空設備上,而錳氧化物-碳材(MO-C)二元複材系為目前常被用來作為超級電容電極的研究。但由於錳系金屬氧化物具有較差的電子導電度與低比表面積, 因此在本研究企圖將碳黑(CB)置於富氧環境中使表面改質(SM)而富含OH- 官能基, 再將錳系金屬氧化物直接沉積析出於碳黑(CB), 企圖上強化錳系金屬氧化物與碳黑之間的鍵結並增加其導電度與或比表面積。 配製三種不同錳離子莫爾濃度再混入固定重量表面改質碳黑(SMCB)形成代號為MO/SMCB 0.01:1、0.03:1、0.05:1三種複合材料,部分複材並經250-4000C-2小時熱處理,透過X-ray繞射(XRD)、場發射掃描式電子顯微鏡(FE-SEM)、高解析度穿透式電子顯微鏡即時傅立葉轉換 (HR-TEM Live-FFT)、X-ray 光電子能譜 (XPS)、感應耦合電漿質譜儀 (ICP-MS)、傅立葉轉換紅外線光譜儀 (FTIR) 進行材料分析, 並以循環伏安法 (CV)、充放電法 (GCD)與電化學阻抗頻譜 (EIS)分析測試電化學性能。XRD顯示剛製備之MO/SMCB 0.01:1與0.03:1之複材係MnO2之結構, 經4000C退火2小時候轉換成Mn2O3晶體結構, 但FTIR 顯示前後兩者均富含OH基, 而且XPS之化學狀態分析也顯示O 1s 可分為Mn-O-Mn及Mn-O-H兩種化學鍵結狀態,經最後TGA之分析推論應修正為非化學計量之MnxO2-x(OH)2x與Mn2O3-x(OH)2x, HRTEM微結構之觀察顯示片狀MnO2均勻混入SMCB中,退火後則將SMCB包覆形成核殼 (core-shell) 結構, 其薄膜厚約15~30 nm, 使其比電容由純SMCB之52 F/g 提升至MO/SMCB 0.03:1之200 F/g (未退火)與400 F/g (退火後)。相較下, 0.05:1則無論退火前後均為方形Mn3O4之晶體結構, 也能均勻散佈於SMCB中, 比電容有218 F/g, 但退火後降至178 F/g。此創新MO/SMCB 複材之製備己展現極優之比電容,將有利於未來超級電容之發展。

The supercapacitor is a device used to store the charge fast by high specific surface area, applied to the electricity of vehicle, great energy-stored building and facilities in space. The manganese oxide-carbon (MO-C) binary composites are currently investigated as electrodes of supercapacitors. However, manganese oxides have poor electric conductivity and low specific surface area. Therefore in this study, we attempted to modify the surface of carbon black (CB) to generate more OH- radicals for the precipitation of manganese oxide directly on it to strengthen the bonding between them and improve the conductivity and/or the specific area. Three kinds of molar Mn2+ concentrated solutions were mixed with the surface modified carbon black (SMCB) of a fixed weight to form MO/SMCB 0.01:1, 0.03:1 and 0.05:1 composites, respectively. Some composites were finally annealed at 2500C~4000C for 2 h. The features of these composites were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy-live fast Fourier transform (HR TEM-Live FFT), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-mass spectrometry (ICP-MS), and Fourier transform infrared (FTIR), while the electrochemical performance by cyclic voltammetry (CV), Galvanostat charge-discharge (GCD) and Electrochemical impedance spectroscopy (EIS) tests. XRD patterns indicate that the as-prepared MO/SMCB 0.01:1 and 0.03:1 composites are MnO2 and transformed into Mn2O3 after annealed at 4000C for 2 hr. However, FTIR results indicate that they both are full of OH bonds. Also, the analyses of XPS indicate that the chemical states of O 1s are composed of Mn-O-Mn and Mn-O-H chemical bonds. Finally, through the analysis of TGA, non-stoichiometric MnxO2-x(OH)2x, Mn2O3-x(OH)2x and Mn3O4-x(OH)2x are speculated. HRTEM observations show that MnO2 flakes are mixed in the SMCB matrix uniformly, MnO2 films after annealed cover SMCB to form the core-shell structure with the film thickness about 15~30 nm. The specific capacitance increases from 52 F/g for pure SMCB to 200 F/g for un-annealed MO/SMCB 0.03:1 and 400 F/g after annealed. For MO/SMCB 0.05:1, no phase transformation occurs and Mn3O4 cubes are uniformly dispersed in SMCB, revealing the specific capacitance of 218 before and 178 F/g after annealed. These creative MO/SMCB composites have revealed the outstanding specific capacitance, which is helpful for developing supercapacitors in the future.

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