研究生: |
鍾宇凡 Yu-Fan Chang |
---|---|
論文名稱: |
PEDOT:PSS導電高分子/α相二氧化錳之複合觸媒用於鋅空氣電池陰極之研究 Study of Poly(3,4-ethylenedioxythiophene) Polystyrene Sulfonate/α-MnO2 as Composite Cathode for Zinc-Air Battery |
指導教授: |
郭俞麟
Yu-Lin Kuo 周宏隆 Hung-Lung Chou |
口試委員: |
郭俞麟
Yu-Lin Kuo 周宏隆 Hung-Lung Chou 蘇昱銘 Yu-Ming Su |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 機械工程系 Department of Mechanical Engineering |
論文出版年: | 2017 |
畢業學年度: | 105 |
語文別: | 中文 |
論文頁數: | 94 |
中文關鍵詞: | 鋅空氣電池 、二氧化錳 、導電高分子 |
外文關鍵詞: | Zinc air battery, Manganese dioxide, Conducting polymer |
相關次數: | 點閱:338 下載:0 |
分享至: |
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
本研究利用簡單操作方法將陰極催化觸媒α相二氧化錳以不同比例之微量導電高分子PEDOT:PSS做表面改質,藉由PEDOT:PSS提供導電路徑給導電度不佳之α相二氧化錳,提升觸媒之導電性,加速電子傳導,進而使空氣電池之電性提升。
實驗以過錳酸鉀及醋酸錳作為前驅物,透過固態法製備α相二氧化錳觸媒,並透過溶膠凝膠法使製備之α相二氧化錳表面有不同比例之微量PEDOT:PSS塗層。在催化觸媒材料之鑑定方面,利用X光繞射儀、傅立葉轉換紅外光譜儀、場發掃描式電子顯微鏡以及場發穿透式電子顯微鏡等分析工具鑑定材料,觀察到由固態法製備之α相二氧化錳為細短棒狀(rod-like)之型態,材料表面有微量PEDOT:PSS之分布。
將不同PEDOT:PSS比例之α相二氧化錳催化觸媒搭配碳材塗佈於碳紙上,製備成空氣陰極進行電化學活性分析,分別測試半電池極化曲線、全電池充放電、交流阻抗分析及鋅空氣全電池放電方析。透過線性掃描伏安法測試結果得到,比例為1 %
PEDOT:PSS之α相二氧化錳在-0.6 V(vs. SCE)下有較高之電流密度-297.67 mA/cm2,以全電池充放電測試其穩定性,發現不論添加多少PEDOT:PSS之α相二氧化錳之庫倫效率皆於90 %左右,透過交流阻抗分析之等效電路可發現比例為1 %PEDOT:PSS之α相二氧化錳不論充放電循環前還是後皆有最小之電荷轉移電阻(Rct),證明添加1 %PEDOT:PSS之α相二氧化錳有較好之電性表現,以鋅金屬作為陽極測試全電池放電結果,證明PEDOT:PSS塗層不影響電池壽命但使放電電壓提升。
This study use the simple experimental to make α-MnO2 have different ratio of a little bit of PEDOT:PSS coating. PEDOT:PSS provide electronic transmission path to α-MnO2, because α-MnO2 have poor conductivity and promote battery performance.
In this study, α-MnO2 powders were prepared by solvent-free solid state method. Different ratio of PEDOT:PSS/α-MnO2 were prepared by sol-gel method. The materials had been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM) and field emission transmission electron microscopy (FE-TEM). It was observed that the α-MnO2 prepared by solvent-free solid state method was a rod-like type with a little bit of PEDOT: PSS distribution on the surface of the material.
Different PEDOT: PSS ratio of α-MnO2 catalyst with carbon coated on carbon paper. Preparation of air cathode were used for studying the electrochemical properties by half-cell polarization curve, full-cell charge/discharge test, EIS analysis and zinc air battery discharge test. Linear Sweep Voltammetry (LSV) measurement exhibited the current density of 1 %PEDOT: PSS/α-MnO2 further reached -297.67 mA/cm2 at -0.6 V(vs. SCE). Cycle stability test demonstrated the Coulombic efficiency of any ratio of PEDOT :PSS/
α-MnO2 close to 90 %. EIS analysis revealed 1 %PEDOT: PSS/α-MnO2 has lower Rct. It was demonstrated that 1 %PEDOT: PSS/α-MnO2 was evidently provided with excellent electrochemical activity.
參考文獻
1. 歷年發電量占比,台灣電力公司,2016。
2. A policy framework for climate and energy in the period from 2020 to 2030, European commission, 2014.
3. Erneuerbaren Energien weltweit zum Durchbruch verhelfen, Agentur fürErneuerbare Energien.
4. M. Steigenberger, E. Bayer, M. M. Kleiner, Report on the German power system Version 1.01, 2015.
5. 張雲朋,燃料電池:由空氣產生電能的新能源-鋅空氣燃料電池,科學發展,2003/7月,367 期,12~15頁。
6. L. Mao, T. Sotomura, K. Nakatsu, N. Koshiba, D. Zhang, T. Ohsaka, J.Electrochem. Soc., 2002, 149, 4.
7. L. Mao, D. Zhang, T. Sotomura, K. Nakatsu, N. Koshiba, T. Ohsaka, Electrochim. Acta, 2003, 48, 1015.
8. 漢聲精選目擊者叢書,化學,漢聲雜誌社,1996。
9. 李世興,電池活用手冊,全華,1999。
10. M. Winter, R. J. Brodd, What Are Batteries, Fuel Cells, and Supercapacitors, Chem. Rev., 2004, 104, 4245.
11. 李文雄,鋰電池 E世代的能源,科學發展,2003/2月,362期,32~35頁。
12. W. R. Grove, On Voltaic Series and the Combination of Gases by Platinum, Philosophical Magazine and Journal of Science vol. XIV, 1839, 127-130.
13. W. R. Grove, On a Gaseous Voltaic Battery, Philosophical Magazine and Journal of Science vol. XXI, 1842, 417-420.
14. 楊志忠、林頌恩、韋文誠,燃料電池的發展現況,科學發展,2003/7月,367期,30~33頁。
15. 金屬空氣電池-高安全、低成本的再生能源儲能技術,經濟部能源局,2015/9月。
16. J. Goldstein, I. Brown, B. Koretz, New developments in the Electric Fuel Ltd. zinc/air system, Journal of Power Sources, 1999, 171-179.
17. 郭炳焜、李新海,楊松青化學電源:電池原理及製造技術,中南大學出版,2009。
18. B. W. Jensen, M. Forsyth, D. R. MacFarlane, High Rates of Oxygen Reduction over a Vapor Phase Polymerized PEDOT Electrode, Science, 2008.
19. C. Chang, Zinc-Air Batteries, Technol. Rev, 2001, 86-87.
20. D. Linden, Handbook of Batteries, McGraw-Hill Publishing company, 2nd ed, 1994.
21. J. S. Spendelow, A. Wieckowshi, Electrocatalysis of Oxygen Reduction and Small Alcohol Oxidation in Alkaline Media, Phys. Chem. Chem. Phys. 2007, 9, 2654.
22. P. A. Christensen, A. Hamnett, D. Linares-Moya,Oxygen Reduction and Fuel Oxidation in Alkaline Solution, Phys. Chem. Chem. Phys. 2011, 13, 5206.
23. W. Vielstich, A. Lamm, H. A. Gasteiger, Handbook of Fuel Cells– Fundamentals, Technology and Applications, Wiley, Chichester, 2003.
24. L. Jörisen, Bifunctional Oxygen/Air Electrode, J. Power Sources, 2006, 155, 23.
25. F. Cheng, J. Chen, Metal-Air Batteries: from Oxygen Reduction Electrochemistry to Cathode Catalysts, Chem. Soc. Rev., 2012, 41, 2172.
26. V. Neburchilov, H. Wang, J. J. Martin, W. Qu, A Review on Air Cathodes for Zinc– Air Fuel Cells, J. Power Sources, 2010, 195, 1271.
27. J. S. Lee, S. T. Kim, R. Cao, N. S. Choi, M. Liu, K. T. Lee and J. Cho, Metal–air batteries with high energy density: Li–air versus Zn–air Energy, Advanced Energy Materials, 2011, 1, 34.
28. F. Cheng, J. Chen, Metal-Air Batteries: from Oxygen Reduction Electrochemistry to Cathode Catalysts, Chem. Soc. Rev., 2012, 41, 2172.
29. Y. Li,H. Dai, Recent advances in zinc-air batteries, Chem. Soc. Rev., 2014.
30. T. P. Dirkse, The Behavior of the Zinc Electrode in Alkaline Solutions, J. Electrochem. Soc. 1981, 128, 1412.
31. W. G. Sunu, D. N. Bennion, Transient and Failure Analysis of the Porous Zinc Electrode I. Theoretical, J. Electrochem. Soc., 1980, 127, 2007.
32. W. G. Sunu, D. N. Bennion, Transient and Failure Analysis of the Porous Zinc Electrode I. Theoretical, J. Electrochem. Soc., 1980, 127, 2007-2016.
33. 曹玉佳,鋅-空氣燃料電池陰極之奈米化結構研發,國立中正大學碩士論文,2007。
34. P. Pei, K. Wang, Z. Ma, Technologies for extending zinc–air battery’s cyclelife: A review, Applied Energy, 2014 ,315–324.
35. R. E. Durkot, L. Lin and P. B. Harris, US Pat., 6284410, 2001.
36. H. Ma, C. S. Li, Y. Su, J. Chen, J. Mater, Studies on the vapour-transport synthesis and electrochemical properties of zinc micro-, meso- and nanoscale structures, Journal of Materials Chemistry, 2007.
37. J. F. Drillet, M. Adam, S. Barg, A. Herter, D. Koch, V. M. Schmidt and M. Wilhelm, Development and Characterization of an Electrically Rechargeable Zinc-Air Battery Stack, ECS Trans., 2010, 28, 13.
38. S. J. Banik and R. Akolkar, J. Electrochem. Soc., 2013, 160, 519.
39. S. M. Lee, Y. J. Kim, S. W. Eom, N. S. Choi, K. W. Kim, S. B. Cho, J. Power Sources, 2013, 227, 177.
40. D. P. Bhatt and R. Udhayan, J. Power Sources, 1994, 47, 177.
41. A. R. S. Kannan, S. Muralidharan, K. B. Sarangapani, V. Balaramachandran and V. Kapali, J. Power Sources,1995, 57, 93.
42. Y. D. Cho, G. T. K. Fey, J. Power Sources, 2008, 184, 610.
43. Y. Sato, M. Takahashi, H. Asakura, T. Yoshida, K. Tada, K. Kobayakawa, N. Chiba, K. Yoshida, J. Power Sources,1992, 38, 317.
44. J. Y. Huot, J. Appl. Electrochem., 1992, 22, 443.
45. J. McBreen and E. Gannon, J. Power Sources, 1985, 15, 169.
46. J. McBreen and E. Gannon, J. Electrochem. Soc., 1983, 130, 1980.
47. S. J. Banik and R. Akolkar, J. Electrochem. Soc., 2013, 160, 519.
48. J. M. Wang, L. Zhang, C. Zhang, J. Q. Zhang, Effects of bismuth ion and tetrabutylammonium bromide on the dendritic growth of zinc in alkaline zincate solutions Original Research, J. Power Sources, 2001, 102, 139.
49. C. Iwakura, S. Nohara, N. Furukawa, H. Inoue, The Possible Use of Polymer Gel Electrolytes in Nickel/Metal Hydride Battery, Solid State Ionics, 2002, 148, 487.
50. C. A. Vincent, B. Scrosati, M. Lazzari, F. Bonino,“Modern Battery”, Thomso Litho Ltd, East Kilbrid, Scotland, 1984
51. G. Q. Zhang, X. G. Zhang, MnO2/MCMB Electrocatalyst for All Solid-State Alkaline Zinc-Air Cells, Electrochim. Acta, 2004, 49, 873.
52. M. Maja, C. Orecchia, M. Strano, P. Tosco, M. Vanni,Electrochim. Acta, 2000, 46, 423.
53. F. Zhang, T. Saito, S. Cheng, M. A. Hickner, B. E. Logan, Microbial Fuel Cell Cathodes with Poly(dimethylsiloxane) Diffusion Layers Constructed around Stainless Steel Mesh Current Collectors, Environ. Sci. Technol., 2010, 44, 1490.
54. D. Chartouni, N. Kuriyama, T. Kiyobayashi, J. Chen, Air–Metal Hydride Secondary Battery with Long Cycle Life, J. Alloys Compd, 2002, 330, 766.
55. 劉霖錡,鋅空氣電池空氣極的製備與性能,逢甲大學碩士論文,2003。
56. K. Kinoshita, Carbon: electrochemical and physicochemical properties, Wiley- Interscience, 1988.
57. Y. Y. Shao, J. Liu, Y. Wang, Y. H. Lin, Novel Catalyst Support Material for PEM Fuel Cell: Current Status and Future Prospects, J. Mater. Chem., 2009, 19, 46.
58. M. Pirjamali, Y. Kiros, Effects of carbon pretreatment for oxygen reduction in alkaline electrolyte, J. Power Sources, 2002, 109, 446-451.
59. M. E. Lai, A. Bergel, Electrochemical reduction of oxygen on glassy carbon: catalysis by catalase, J. Electroanal. Chem., 2000, 494, 1, 30-40.
60. M. Maja, C. Orecchia, M. Strano, P. Tosco, M. Vanni, Effect of structure of the electrical performance of gas diffusion electrodes for metal air batteries, Electrochim. Acta, 2000, 46, 2-3, 423-432.
61. H. Meng and P. K. Shen, Electrochem. Commun., 2006, 8, 588.
62. Y. Li and H. Dai, Recent advances in zinc–air batteries, hem. Soc. Rev., 2014, 43, 5257.
63. T. Wang, M. Kaempgen, P. Nopphawan, G. Wee, S. Mhaisalkar, M. Srinivasan, Silver Nanoparticle-Decorated Carbon Nanotubes as Bifunctional Gas- Diffusion Electrodes for Zinc–Air Batteries, J. Power Sources, 2010, 195, 4350.
64. Y. Li, M. Gong, Y. Liang, J. Feng, J. E. Kim, H. Wang, G. Hong, B. Zhang, H. Dai, Advanced Zinc-Air Batteries Based on High-Performance Hybrid Electrocatalysts, Nat. Commun., 2013.
65. J. Yang, J. J. Xu, Nanostructured Amorphous Manganese Oxide Cryogel as a High-Rate Lithium Intercalation Host, Electrochem. Commun., 2003, 5, 306.
66. Y. Yang, Q. Sun, Y. S. Li, H. Li, Z. W. Fu, A CoOx/Carbon Double-Layer Thin Film Air Eectrode for Nonaqueous Li-Air Batteries, J. Power Sources, 2013, 223, 312.
67. Z. Chen, A. Yu, R. Ahmed, H. Wang, H. Li, Z. Chen, Manganese Dioxide Nanotube and Nitrogen-Doped Carbon Nanotube Based Composite Bifunctional Catalyst for Rechargeable Zinc-Air Battery, Electrochim. Acta, 2012, 69, 295.
68. Y. S. Ding, X. F. Shen, S. Sithambaram, S. Gomez, R. Kumar, V. M. B. Crisostomo, S. L. Suib, M. Aindow, Synthesis and Catalytic Activity of Cryptomelane-Type Manganese Dioxide Nanomaterials Produced by a Novel Solvent-Free Method, Chem. Mater., 2005, 17, 5382.
69. F. Cheng, Y. Su, J. Liang, Z. Tao, J. Chen, MnO2-Based Nanostructures as Catalysts for Electrochemical Oxygen Reduction in Alkaline Media, Chem. Mater., 2010, 22, 898.
70. Y. Liang, Y. Li, H. Wang, J. Zhou, J. Wang, T. Regier, H. Dai, Co3O4 Nanocrystal on Graphene as a Synergistic Catalyst for Reduction Reaction, Nat. Mater., 2011, 10, 780.
71. M. Yuasa, M. Nishida, T. Kida, N. Yamazoe, K. Shimanoe, Bi-Functional Oxygen Electrodes Using LaMnO3/LaNiO3 for Rechargeable Metal-Air Batteries, J. Electrochem. Soc., 2011, 158.
72. N. A. Merino, B. P. Barbero, P. Grange, L. E. Cadus, La1−xCaxCoO3 Perovskite-Type Oxides: Preparation, Characterisation, Stability, and Catalytic Potentiality for the Total Oxidation of Propane, J. Catal., 2005, 231, 232.
73. S. Pathaka, J. Kuebler, A. Payzantc, N. Orlovskaya, Mechanical Behavior and Electrical Conductivity of La1−xCaxCoO3 (x = 0, 0.2, 0.4, 0.55) Perovskites, J. Power Sources, 2010, 195, 3612.
74. M. Maja, C. Orecchia, M. Strano, P. Tosco, M. Vanni, Effect of Structure of the Electrical Performance of Gas Diffusion Electrodes for Metal Air Batteries, Electrochim. Acta, 2000, 46, 423.
75. J. E. Post, Maganese Oxide Minerals: Crystal Structure and Economic and Environmental Significance, Proc. Natl. Acad. Sci. U. S. A., 1999, 96, 3447.
76. J. P. Bernet, Electrochemical Behaviour of Metallic Oxides, J. Power Sources, 1979, 4, 183.
77. L. Mao, T. Sotomura, K. Nakatsu, K. Nobuharu, D. Zhang, T. Ohsaka, Electrochemical Characterization of Catalytic Activities ofManganese to Oxygen Reduction in Alkaline Aqueous Solution, J. Electrochem. Soc., 2002, 149, A504.
78. M. Toupin, T. Brousse, D. Be´langer, Charge Storage Mechanism of MnO2 Electrode Used in Aqueous Electrochemical Capacitor, Chem. Mater., 2004, 16, 3184.
79. S. Devaraj, N. Munichandraiah, Effect of Crystallographic Structure of MnO2 on Its Electrochemical Capacitance Properties, J. Phys. Chem. C, 2008, 112, 4406.
80. 李柏潔,奈米結構之Au/MnO2複合陰極觸媒材料對於高效能金屬空氣電池之研究,國立中央大學碩士論文,2013。
81. N. Wang, X. Cao, G. Lin, Y. Shihe, MnO2 Nanodisks and Their Magnetic Properties, Nanotechnology, 2007, 18, 475605.
82. F. Cheng, Y. Su, J. Liang, Z. Tao, J. Chen, MnO2-Based Nanostructures as Catalysts for Electrochemical Oxygen Reduction in Alkaline Media, Chem. Mater., 2010, 22, 898.
83. S. Liang, F. Teng, G. Bulgan, R. Zong, Y. Zhu, Effect of Phase Structure of MnO2 Nanorod Catalyst on the Activity for CO Oxidation, J. Phys. Chem. C, 2008, 112, 5307.
84. X. Wang, Y. Li, Selected-Control Hydrothermal Synthesis of MnO2 Single Crystal Nanowires, J. Am. Chem. Soc., 2002, 124, 2880.
85. Y. Yang, L. Xiao, Y. Zhao, F. Wang, Hydrothermal Synthesis and Electrochemical Characterizationo-MnO2 Nanorods as Cathode Material for Lithium Batteries, Int. J. Electrochem. Sc., 2008, 3, 67.
86. M. Lua, S. Kharkwala, H. Y. Ng, S. Y. Li, Carbon Nanotube Supported MnO2 Catalysts for Oxygen Reduction Reaction and Their Applications in Microbial Fuel Cells, Biosens. Bioelectron, 2011, 26, 4728.
87. S. B. Ma, K. W. Nam, W. S. Yoon, X. Q. Yang, Y. Ahn, K. B. Kim, Electrochemical Properties of Manganese Oxide Coated onto Carbon Nanotubes for Energy Storage Applications, J. Power Sources, 2008, 178, 483.
88. A. Zolfagharia, F. Ataherian, M. Ghaemi, A. Gholami, Capacitive Behavior of Nanostructured MnO2 prepared by Sonochemistry Method, Electrochim. Acta, 2007, 52, 2806.
89. H. Adelkhania, M. Ghaemi, Characterization of Manganese Dioxide Electrodeposited by Pulse and Direct Current for Electrochemical Capacitor, J. Alloys Compd, 2010, 493, 175.
90. S. Chen, J. Zhu, Q. Han, Z. Zheng, Y. Yang, X. Wang, Shape-Controlled Synthesis of One-Dimensional MnO2 via a Facile Quick-Precipitation Procedure and its Electrochemical Properties, Cryst. Growth Des., 2009, 9, 4356.
91. M. Xu, L. Kong, W. Zhou, H. Li, Hydrothermal Synthesis and Pseudocapacitance Properties of MnO2 Hollow Spheres and Hollow Urchins, J. Phys. Chem. C, 2007, 111, 19141.
92. J. Luo, H. T. Zhu, H. M. Fan, J. K. Liang, H. L. Shi, G. H. Rao, J. B. Li, Z. M. Du, Z. X. Shen, Synthesis of Single-Crystal Tetragonal MnO2 Nanotubes, J. Phys. Chem. C, 2008, 112, 12594.
93. W. Li, Q. Liu, Y. Sun, J. Sun, R. Zou, G. Li, X. Hu, G. Song, G. Ma, J. Yang, Z. Chen J. Hu, MnO2 Ultralong Nanowires with Better Electrical Conductivity and Enhanced Supercapacitor Performances, J. Mater. Chem., 2012, 22, 14864.
94. I. Roche, E. Chaînet, M. Chatenet, J. Vondrák, Carbon-Supported Manganese Oxide Nanoparticles as Electrocatalysts for the Oxygen Reduction Reaction (ORR) in Alkaline Medium: Physical Characterizations and ORR Mechanism, J. Phys. Chem. C, 2007, 111, 1434.
95. P. Zoltowski, D. M. Drazic, L. Vorkapic, The Mechanism of Oxygen Reduction on MnO2-Catalyzed Air Cathode in Alkaline Solution, J. Appl. Electrochem., 1973,3, 271.
96. J. P. Brebet, Electrochemical Behaviour of Metallic Oxides, J. Power Sources, 1979, 4, 183.
97. 白川英樹,從導電性高分子中看到什麼?,三田出版社,1990。
98. I. György, A New Era in Electrochemistry. Monographs in Electrochemistry. Springer. , 2008, 1–6. ISBN 978-3-540-75929-4.
99. Yu. L. Kuo, C. C. Wu, W. S. Chang, C. R. Yang, H. L. Chou, Electrochimica Acta, 2015, 176, 1324-1331.
100. T.T. Tung, T. Y. Kim, H. W. Lee, E. Kim, T. H. Lee, K. S. Suh, Journal of The Electrochemical Society, 2009, 156, 12, K218-K222.
101. Y. Xuan , M. Sandberg , M. Berggren, X. Crispin, Organic Electronics, 2012, 13, 632-637.
102. D. H. Yoon, S. H. Yoon, K. S. Ryu, Y. J. Park, Scientific Reports, 2016.
103. F. Wua, J. Liua, L. Lia, X. Zhanga, R. Luoa, Y. Yea, R. Chen, ACS Appl. Mater. Interfaces, 2016.
104. Z. Su, C. Yang, C. Xu, H. Wu, Z. Zhang, T. Liu, C. Zhang, Q. Yang, B. Li, F. Kang, Journal of Materials Chemistry A, 2013.
105. I. H. Ko, S. J. Kim, J. Lim, S. H. Yu, J. Ahn, J. K. Lee, Y. E. Sung, Electrochimica Acta, 2016, 187, 340-347.
106. 呂明修,α相二氧化錳觸媒於高充放電效率鋅空氣電池陰極之研究,國立臺灣科技大學碩士論文,2014。
107. 葉祐任,層狀過量鋰陰極材料之合成及其表面修飾對電池性能增進機制之研究,國立臺灣科技大學碩士論文,2016。
108. I. D. Raistrick, D. R. Franceschetti, J. R. Macdonald, The Electrical Analogs of Physical and Chemical Processes in Impedance Spectroscopy Theory, Experiment and Aplications, JohnWiley & Sons, New Jersey, 2005.