研究生: |
李怡親 Yi-Chin Li |
---|---|
論文名稱: |
承載鈷鎳氧化物碳微管指叉電極的平面超高電容器 Planar ultracapacitor of interdigital electrodes loaded with (CoNi)Ox and carbon nanotubes |
指導教授: |
蔡大翔
Dah-Shyang Tsai |
口試委員: |
戴 龑
Yian Tai 傅彥培 Yen-Pei Fu |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2010 |
畢業學年度: | 98 |
語文別: | 中文 |
論文頁數: | 135 |
中文關鍵詞: | 平面超高電容器 、鈷鎳氧化物 、碳微管 、指叉式電極 、對稱式電極 、非對稱式電 |
外文關鍵詞: | Ultracapacitor, Cobalt-nickel oxides, Carbon nanotubes, Interdigitated electrode, Symmetric electrode, Asymmetric electrode |
相關次數: | 點閱:257 下載:2 |
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摘要
本期研究以發展微型化之平面超高電容器為主軸,黃光微影技術製作圖案化指叉式電極,並以化學氣相沉積法(CVD)成長碳微管(CNT)及電化學電鍍擬電容材料NiCo2O4。利用循環伏安法(CV),交流阻抗,及充/放電分析平面超高電容器的性能,影響電容器性能表現最重要的因素為鑑別電極配置上是否為對稱式或非對稱式,次要因素為底電極之阻抗,我們利用添加金薄膜層於成長碳微管之鋁-鐵觸媒層下做改善。
在研究圖案化指叉式電極前,我們先成長碳微管於無圖案化平板式電極,再電鍍鈷鎳氧化物,之後鑑定其為微晶NiCo2O4。選擇電解液0.1 M KOH + 0.09 M Na2SO4,因其具有高導電度及適合的pH值,由於擬電容材料NiCo2O4於酸性溶液下會慢慢剝蝕,故使用之電解質必須為鹼性。
添加金於鋁-鐵觸媒層後,成長之碳微管結構會受到損壞,因為濺鍍的金會干擾微粒子影響碳微管的成長方向。在底電極無金電容器(Fe-Al/SiO2/Si)能得到垂直陣列碳微管,有好的高度20~30 μm,與高的密度>109 cm2,底電極添加金後,電極阻抗有所改善,卻也使碳微管隨機成長,高度只有1~2 μm,且降低密度。因此,循環伏安10 mVs-1掃描下,底層無金對稱式CNT + NiCo2O4電容器的比電容值得到199 mFcm-2,底層有金對稱式CNT + NiCo2O4電容器的比電容值為109 mFcm-2。但隨著增加掃描速率,無金電極比有金電極所得之電容值損失更為快速,快速下降的趨勢,是歸因於較大的電極阻抗所造成。由交流阻抗分析中,底電極無金對稱式電容器得到電阻值4167 Ω,比有金的電容器333 Ω來的高。
以儲存能量對輸出功率做Ragone圖,可見對稱式與非對稱式電極皆有彎勾型的曲線。無論底電極有、無金,皆以非對稱式電容器擁有較高之儲存能量及輸出功率。底電極無金非對稱式 CNT + NiCo2O4電容器有能量密度9170 μJ與輸出功率119 μW,底電極有金非對稱式 CNT + NiCo2O4電容器得到的儲存能量為756 μJ與輸出功率94 μW。
關鍵字:平面超高電容器、鈷鎳氧化物、碳微管、指叉式電極、對稱式電極、非對稱式電極。
ABSTRACT
In the present study, we develop the ultracapacitor cells of miniature size, which are prepared with photolithography, chemical vapor deposition of carbon nanotubes (CNT), and electrochemical deposition of pseudocapacitive NiCo2O4. The performance of the ultracapacitors is analyzed by cyclic voltammetry (CV), impedance, and charge-discharge experiments. The most important factor of capacitor performance is identified as whether the electrode configuration is symmetric or asymmetric. The second important factor is the resistance of bottom electrode, manipulated with the addition of gold in the Al-Fe seed layer for CNT growth.
Before the investigation of patterned cell of interdigital electrodes, we synthesize CNT forest with blanket growth and electrodeposit the oxide of nickel and cobalt oxide, which is later identified as microcrystalline NiCo2O4. The electrolyte of 0.1 M KOH and 0.09 M Na2SO4 is chosen for its high conductivity and pH value. The alkaline electrolyte is necessary for pseudocapacitive NiCo2O4, which slowly degrades in acidic solution.
The structure of CNT is damaged with the addition of gold in the Al-Fe seed layer, since the sputtered gold interferes with the guided growth of CNT. Without gold, the CNT demonstrates vertical aligned growth with an impressive height of 20-30 m, along with a high population density > 109 cm-2. With the addition of gold, the improvement on electrode resistance is accompanied with a small CNT height 1-2 m, randomly orientation, and a low population density. Thus, the electrode capacitance of symmetric CNT + NiCo2O4 cell on the Al-Fe layer, measured by CV, is 199 mFcm-2, while that of symmetric CNT + NiCo2O4 cell on the Al-Fe-Au layer 109 mFcm-2 at 10 mVs-1. But the capacitance of the electrode without Au decreases more rapidly with increasing sweep rate, compared with the electrode with Au. The more rapid decreasing trend is attributed to the larger electrode resistance, for the electrode without Au, the resistance is measured 4167 by impedance spectroscopy, higher than that of the electrode with Au 333 .
Ragone plots of power versus energy for the symmetric and asymmetric cells show the typical hooked-shape curve. Built on either Al-Fe or Al-Fe-Au bottom electrodes, the asymmetric cell exhibits the highest energy and power capability. On the Al-Fe bottom electrode, the asymmetric electrode of CNT + NiCo2O4 cell displays an energy capacity of 9170 J and a power level of 119 W. On the Al-Fe-Au bottom electrode, the asymmetric electrode of CNT + NiCo2O4 cell exhibits an energy capacity of 756 J, and a power level of 94 W.
Keywords:Ultracapacitor; Cobalt-nickel oxides; Carbon nanotubes; Interdigitated electrode; Symmetric electrode; Asymmetric electrode.
1. Kotz, R. and M. Carlen, Principles and applications of electrochemical capacitors. Electrochimica Acta, 2000. 45(15-16): p. 2483-2498.
2. Pillay, B. and J. Newman, The Influence of Side Reactions on the Performance of Electrochemical Double-Layer Capacitors. Journal of The Electrochemical Society, 1996. 143(6): p. 1806-1814.
3. Zheng, J.P., P.J. Cygan, and T.R. Jow, Hydrous Ruthenium Oxide as an Electrode Material for Electrochemical Capacitors. Journal of The Electrochemical Society, 1995. 142(8): p. 2699-2703.
4. Zheng, J.P. and T.R. Jow, A New Charge Storage Mechanism for Electrochemical Capacitors. Journal of The Electrochemical Society, 1995. 142(1): p. L6-L8.
5. Zheng, J.P. and T.R. Jow, High energy and high power density electrochemical capacitors. Journal of Power Sources, 1996. 62(2): p. 155-159.
6. Kim, I.-H. and K.-B. Kim, Ruthenium Oxide Thin Film Electrodes for Supercapacitors. Electrochemical and Solid-State Letters, 2001. 4(5): p. A62-A64.
7. Tsai, W.-T., M.-T. Lee, and J.-K. Chang, Effect of Iron Doping on the Pseudo-Capacitive Characteristics of Manganese Oxide. ECS Meeting Abstracts, 2006. 501(3): p. 122-122.
8. Chang, J.K., et al., Physicochemical properties and electrochemical behavior of binary manganese-cobalt oxide electrodes for supercapacitor applications. Materials Chemistry and Physics, 2008. 108(1): p. 124-131.
9. Rajendra Prasad, K. and N. Miura, Electrochemically synthesized MnO2-based mixed oxides for high performance redox supercapacitors. Electrochemistry Communications, 2004. 6(10): p. 1004-1008.
10. Burke, A., Ultracapacitors: why, how, and where is the technology. Journal of Power Sources, 2000. 91(1): p. 37-50.
11. Conway, B.E., Transition from ``Supercapacitor'' to ``Battery'' Behavior in Electrochemical Energy Storage. Journal of The Electrochemical Society, 1991. 138(6): p. 1539-1548.
12. 劉俊興, 氧化錳系超電容之研究. 大同大學碩士論文, 2006.
13. Mastragostino, M., C. Arbizzani, and F. Soavi, Polymer-based supercapacitors. Journal of Power Sources, 2001. 97-98: p. 812-815.
14. 王世育, 四氧化三鐵/碳材超高電容器之特性與機制探討. 國立台灣大學化學工程學研究所博士論文, 2004.
15. 陳怡倫, 以陽極沉積法製備之氧化錳電極的材料特性與擬電容性質. 國立成功大學材料科學及工程學系碩士論文, 2004.
16. Conway, B.E., Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications. Kluwer Academic,New York, 1999.
17. I. Tanahashi, A.Y., A. Nishino, Preparation and Characterization of Activated Carbon Tablets for Electric Double Layer Capacitors. Chem. Soc. Jpn., 1990. 63: p. 2755-2758.
18. Weng, T.C. and H.S. Teng, Characterization of high porosity carbon electrodes derived from mesophase pitch for electric double-layer capacitors. Journal of The Electrochemical Society, 2001. 148(4): p. A368-A373.
19. Portet, C., et al., Influence of carbon nanotubes addition on carbon-carbon supercapacitor performances in organic electrolyte. Journal of Power Sources, 2005. 139(1-2): p. 371-378.
20. 張仍奎, 超高電容器錳氧化物電極之電化學製備法、材料特性及擬電容行為. 國立成功大學博士論文, 2005.
21. Arbizzani, C., M. Mastragostino, and F. Soavi, New trends in electrochemical supercapacitors. Journal of Power Sources, 2001. 100(1-2): p. 164-170.
22. Gamby, J., et al., Studies and characterisations of various activated carbons used for carbon/carbon supercapacitors. Journal of Power Sources, 2001. 101(1): p. 109-116.
23. Kim, C., Electrochemical characterization of electrospun activated carbon nanofibres as an electrode in supercapacitors. Journal of Power Sources, 2005. 142(1-2): p. 382-388.
24. 高維欣, 電化學方法製備釕氧化物電極與其特性之探討. 國立高雄應用科技大學化學工程系, 2004.
25. Mayer, S.T., R.W. Pekala, and J.L. Kaschmitter, The Aerocapacitor: An Electrochemical Double-Layer Energy-Storage Device. Journal of The Electrochemical Society, 1993. 140(2): p. 446-451.
26. Niu, C., et al., High power electrochemical capacitors based on carbon nanotube electrodes. Applied Physics Letters, 1997. 70(11): p. 1480-1482.
27. Lin, C., J.A. Ritter, and B.N. Popov, Characterization of Sol-Gel-Derived Cobalt Oxide Xerogels as Electrochemical Capacitors. Journal of The Electrochemical Society, 1998. 145(12): p. 4097-4103.
28. Lee, H.Y. and J.B. Goodenough, Supercapacitor behavior with KCl electrolyte. Journal of Solid State Chemistry, 1999. 144(1): p. 220-223.
29. 陳奕勳,胡啟章, 循環伏安法製備錳-鎳氧化物於電化學電容器的應用. 2002年材料年會論文, 2002.
30. Pang, S.C., M.A. Anderson, and T.W. Chapman, Novel electrode materials for thin-film ultracapacitors: Comparison of electrochemical properties of sol-gel-derived and electrodeposited manganese dioxide. Journal of The Electrochemical Society, 2000. 147(2): p. 444-450.
31. 張仍奎,蔡文達, 含水氧化錳電極之製備與擬電容特性之研究. 2002年材料年會論文, 2002.
32. Jeong, Y.U. and A. Manthiram, Amorphous ruthenium-chromium oxides for electrochemical capacitors. Electrochemical and Solid State Letters, 2000. 3(5): p. 205-208.
33. Wilde, P.M., et al., Strontium ruthenate perovskite as the active material for supercapacitors. Journal of Electroanalytical Chemistry, 1999. 461(1-2): p. 154-160.
34. 胡啟章,江鴻儒, 循環伏安法及電鍍法製備釕電極在電化學電容器的應用. 國立中正大學化學工程學系碩士論文, 2000.
35. Liu, K.-C. and M.A. Anderson, Porous Nickel Oxide/Nickel Films for Electrochemical Capacitors. Journal of The Electrochemical Society, 1996. 143(1): p. 124-130.
36. Lee, H.Y. and J.B. Goodenough, Ideal supercapacitor behavior of amorphous V2O5 center dot nH(2)O in potassium chloride (KCl) aqueous solution. Journal of Solid State Chemistry, 1999. 148(1): p. 81-84.
37. Takasu, Y., et al., Dip-Coated Ru-V Oxide Electrodes for Electrochemical Capacitors. Journal of The Electrochemical Society, 1997. 144(8): p. 2601-2606.
38. Pang, S.-C., M.A. Anderson, and T.W. Chapman, Novel Electrode Materials for Thin-Film Ultracapacitors: Comparison of Electrochemical Properties of Sol-Gel-Derived and Electrodeposited Manganese Dioxide. Journal of The Electrochemical Society, 2000. 147(2): p. 444-450.
39. Srinivasan, V. and J.W. Weidner, Capacitance studies of cobalt oxide films formed via electrochemical precipitation. Journal of Power Sources, 2002. 108(1-2): p. 15-20.
40. Wohlfahrt-Mehrens, M., et al., New materials for supercapacitors. Journal of Power Sources, 2002. 105(2): p. 182-188.
41. Cao, L., M. Lu, and H.-L. Li, Preparation of Mesoporous Nanocrystalline Co[sub 3]O[sub 4] and Its Applicability of Porosity to the Formation of Electrochemical Capacitance. Journal of The Electrochemical Society, 2005. 152(5): p. A871-A875.
42. Simpraga, R.P., Reversibility and irreversibility in the formation and reduction of oxide film states on Co at ambient and low temperatures. Journal of Electroanalytical Chemistry, 1993. 355(1-2): p. 79-96.
43. Tseung, A.C.C. and S. Jasem, Oxygen evolution on semiconducting oxides. Electrochimica Acta, 1977. 22(1): p. 31-34.
44. Gupta, V., S. Gupta, and N. Miura, Potentiostatically deposited nanostructured CoxNi1-x layered double hydroxides as electrode materials for redox-supercapacitors. Journal of Power Sources, 2008. 175(1): p. 680-685.
45. Gupta, V., S. Gupta, and N. Miura, Electrochemically synthesized nanocrystalline spinel thin film for high performance supercapacitor. Journal of Power Sources, 2010. 195(11): p. 3757-3760.
46. Y-Y Liang, S.-J.B., H-L Li Nanocrystalline nickel cobalt hydroxides/ultrastable Y zeolite composite for electrochemical capacitors Journal of Solid State Electrochemistry, 2007: p. 571-576.
47. Kuan-Xin, H., et al., Electrodeposition of Nickel and Cobalt Mixed Oxide/Carbon Nanotube Thin Films and Their Charge Storage Properties. Journal of The Electrochemical Society, 2006. 153(8): p. A1568-A1574.
48. Zheng, Z., et al., Large-scale synthesis of mesoporous CoO-doped NiO hexagonal nanoplatelets with improved electrochemical performance. Solid State Sciences, 2009. 11(8): p. 1439-1443.
49. Hu, C.-C. and C.-Y. Cheng, Ideally Pseudocapacitive Behavior of Amorphous Hydrous Cobalt-Nickel Oxide Prepared by Anodic Deposition. Electrochemical and Solid-State Letters, 2002. 5(3): p. A43-A46.
50. Fan, Z., et al., Preparation and capacitive properties of cobalt-nickel oxides/carbon nanotube composites. Electrochimica Acta, 2007. 52(9): p. 2959-2965.
51. Hu, Z.-A., et al., Synthesis and electrochemical characterization of mesoporous CoxNi1-x layered double hydroxides as electrode materials for supercapacitors. Electrochimica Acta, 2009. 54(10): p. 2737-2741.
52. Zhou, W.J., et al., Electrodeposition and characterization of ordered mesoporous cobalt hydroxide films on different substrates for supercapacitors. Microporous and Mesoporous Materials, 2009. 117(1-2): p. 55-60.
53. Gupta, V., et al., Potentiostatically deposited nanostructured [alpha]-Co(OH)2: A high performance electrode material for redox-capacitors. Electrochemistry Communications, 2007. 9(9): p. 2315-2319.
54. Chuang, P.-Y. and C.-C. Hu, The electrochemical characteristics of binary manganese-cobalt oxides prepared by anodic deposition. Materials Chemistry and Physics, 2005. 92(1): p. 138-145.
55. Nam, K.W. and K.B. Kim, A study of the preparation of NiOx electrode via electrochemical route for supercapacitor applications and their charge storage mechanism. Journal of The Electrochemical Society, 2002. 149(3): p. A346-A354.
56. Serebrennikova, I. and V.I. Birss, Mass changes accompanying the electrochemical reaction of sol-gel formed 50 : 50 Ni-Co oxide films. Journal of Electroanalytical Chemistry, 2000. 493(1-2): p. 108-116.
57. Lin, C., J.A. Ritter, and B.N. Popov, Development of Carbon-Metal Oxide Supercapacitors from Sol-Gel Derived Carbon-Ruthenium Xerogels. Journal of The Electrochemical Society, 1999. 146(9): p. 3155-3160.
58. J. C. F. Boodts, S.T., Hydrogen evolution on iridium oxide cathodes. Journal of Applied Electrochemistry 1988. 19: p. 255-262.
59. Jiang, Y.Q., Q. Zhou, and L. Lin. Planar MEMS Supercapacitor using Carbon Nanotube Forests. in Micro Electro Mechanical Systems, 2009. MEMS 2009. IEEE 22nd International Conference on. 2009.
60. Iijima, S., Helical microtubules of graphitic carbon. Nature, 1991. 354(6348): p. 56-58.
61. Chen, M., et al., Catalyzed growth model of carbon nanotubes by microwave plasma chemical vapor deposition using CH4 and CO2 gas mixtures. Diamond and Related Materials. 12(10-11): p. 1829-1835.
62. Bard, A.J.F., L.R., Electrochemical principles, methods, and applications. 1996.
63. Komukai, T., et al., Density control of carbon nanotubes through the thickness of Fe/Al multilayer catalyst. Japanese Journal of Applied Physics Part 1-Regular Papers Brief Communications & Review Papers, 2006. 45(7): p. 6043-6045.
64. 袁國輝, 電化學電容器. 化學電源技術叢書 2006.