研究生: |
鄭銘堯 Ming-Yao Cheng |
---|---|
論文名稱: |
新穎介孔尺度限制空間內奈米/奈米複合材料之合成與其電化學特性 Novel Synthesis of Nano-/Nano-composite Materials in Confined Space of Mesoporous Materials and Their Electrochemical Properties |
指導教授: |
黃炳照
Bing-Joe Hwang |
口試委員: |
萬其超
none 周澤川 none 何國川 none 杜景順 none 楊明長 none 蔡大翔 none 李嘉平 none |
學位類別: |
博士 Doctor |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2007 |
畢業學年度: | 95 |
語文別: | 英文 |
論文頁數: | 163 |
中文關鍵詞: | 規則介孔材料 、限制空間 、疏水性膠囊化 、鋰離子電池 、陽極 、奈米複合材料 、奈米 、氧化鎳 |
外文關鍵詞: | ordered mesoporous material, hydrophobic encapsulation route |
相關次數: | 點閱:665 下載:6 |
分享至: |
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本研究成功地建立ㄧ名為疏水性膠囊化(hydrophobic encapsulation)的合成方法,可完全將無機材料合成於多孔擔體之限制空間內,可藉由此概念將NiO奈米粒子合成於規則介孔SBA-15材料之限制空間。首先,以此法合成之NiO/ SBA-15奈米複合材料具有新穎的奈米孔洞結構,且孔道中的NiO奈米粒子尺寸十分均ㄧ,並均勻的分散於限制空間內且無阻塞的問題。此新穎的奈米結構具有相當的潛力應用於新型非均相催化觸媒上。除了解決一般常見的介孔材料阻塞問題,此複合材料更具有高度的熱穩定性,造成高度熱穩定性的原因可能為NiO奈米粒子與氧化矽結構表面的強作用力所導致(NiO 平均晶粒大小由2.83 nm (400℃熱處理) 些微增加至3.69 nm (900℃熱處理) )。
將SBA-15從NiO/SBA-15 奈米複合材料移除所得到之NiO奈米粒子應用於鋰離子電池陽極材料,發現其具備極佳的電化學性質。其於高速充放電50圈後,仍可維持相當之電容量,此特性與一般的NiO材料完全不同,一般NiO材料在長時間充放電後會導致電容量大幅下降。此優異的電化學特性可能來自於較穩定的奈米結構。另外,其充放電平台電位之差異較小,代表其電極之內部阻抗較小。
另外,一種新穎三維奈米電流收集器/奈米電解質之奈米電極結構概念亦可藉由所建立的疏水性膠囊化合成法來實現。此新穎的奈米電極結構可應用於多種的電化學系統之電極上,在本研究中以鋰離子電池陽極來闡述此奈米結構的優點。本研究利用規則介孔CMK-3扮演奈米電流收集器的角色,而其介孔孔道可作為此奈米電極結構中之奈米電解質,而NiO活性材料則可合成於介孔孔道中,且不會阻塞電解質進出的通道。此NiO/CMK-3奈米複合材料具備十分優異的充放電特性,在快速充放電下仍能為維持高電容量,且於長期操作下幾乎沒有衰退,充分展現此新穎三維奈米電極結構之優勢。
In this study, a general route, named as a hydrophobic encapsulation route, has been successfully developed for the exclusive formation of inorganic materials in the confined spaces of porous hosts. The concept was first demonstrated by the formation of NiO nanoparticles in the pore channels of mesoporous SBA-15. The synthesized NiO/ SBA-15 nanocomposites shows superior nano-architecture in the pore channels of SBA-15 that the formed NiO nanoparticles are highly uniform and well-distributed in the confined space without blocking the pore channels. The novel nano-architecture of the synthesized NiO/ SBA-15 is of great potential for advanced heterogeneous catalyst applications. The blockage problem usually encountered in mesoporous materials can be avoided by the developed route. Furthermore, the high thermal stability of the synthesized NiO/ SBA-15 was revealed by XRD and TPR analyses, indicating strong interaction of NiO nanoparticles with silica framework (average grain size of NiO only slightly increases from 2.83 (heated at 400 oC) to 3.69 nm (heated at 900 oC)).
The ultra fine NiO nanoparticles extracted from the synthesized NiO/ SBA-15 shows excellent electrochemical properties as Li-ion battery anodes. The excellent capacity retention behavior for the ultra fine NiO nanoparticles is displayed for the first time even cycling at higher C rate. It may be contributed by the outstanding stability of the electrode made of the ultra fine NiO nanoparticles whose grain size are too small to be pulverized electrochemically (3.11 nm). The smaller hysteresis loop between the charge and discharge plateau indicates the less internal resistance of the electrode made of the synthesized ultra fine NiO nanoparticles compared to the commercial NiO nanoparticles.
In addition, a novel concept for 3-D nano-current collector/ nano-electrolyte architecture as an anode material of Li-ion battery is introduced and demonstrated. The nano-architecture can be constructed by taking mesoporous CMK-3 as 3-D nano-current collector and the pore channels of the CMK-3 as the said nano-electrolyte after impregnating with liquid electrolyte. The NiO nanoparticles can be synthesized in the confined space of CMK-3 by the developed hydrophobic encapsulation route together with the nature of spontaneous oxidation of metal nanoparticles. The capacity retention and rate capability of the NiO/CMK-3 nanostructured materials applied in a lithium battery are excellent, indicating the effectiveness of the novel electrode nano-architectured by the developed concept. The concept can be applied to other materials for advanced electrochemical devices with proper modification of the process.
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