電場誘導聚乙烯醇改質雙馬來醯亞胺複合薄膜於鹼性直接乙醇燃料電池之應用

簡易檢索 / 詳目顯示

回結果列表

研究生：	黃奕雲 Yi-Yun Huang
論文名稱：	電場誘導聚乙烯醇改質雙馬來醯亞胺複合薄膜於鹼性直接乙醇燃料電池之應用
指導教授：	諸柏仁
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
論文出版年：	2018
畢業學年度：	106
語文別：	中文
論文頁數：	137
中文關鍵詞：	燃料電池
相關次數：	點閱：10 下載：0
分享至:	分享至facebook 分享至twitter

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

鹼性燃料電池因其可使用非白金觸媒，有望降低價格，為近年來再生能源研究發展的一大趨勢；然薄膜研究上仍欠缺足夠條件使其商業化，其中最需克服的為同時擁有良好的離子導電度以及較低的燃料竄透。
本研究係利用分歧狀雙馬來醯亞胺聚合物（mBMI）和聚乙烯醇（PVA）之間形成semi-IPN（半互穿網絡）結構所製備的薄膜以降低乙醇的竄透率。同時，由於PVA及mBMI本身帶有親水官能基且相鄰醯亞胺基之間有利於氫氧根離子的傳遞，使此薄膜在鹼性溶液（KOH）下的離子導電度能隨添加mBMI的含量增加而有所提升，達到良好的離子導電度；另外，隨著添加mBMI含量增加，半互穿網絡交聯程度上升亦能使薄膜膨潤程度下降。
此外，本研究另一重點為以外加電場極化的狀態下製備成膜，可以將薄膜內部電負度較大的原子(如：O、N等)暴露以增加親水官能基，同時形成有序的親水離子傳導通道使非結晶區更為緻密。相較於無電場極化下的複合薄膜，在外加電場極化下的mBMI/PVA複合薄膜顯示出更優異的OH- 離子導電率（1.20*10 -2 S / cm 至3.82*10 -2 S / cm）、更低的乙醇竄透性（3.61*10 -7 cm 2 / s至7.77*10 -8 cm2 / s），以及極高的選擇率 (將近4*105)；此外，電場極化產生更緻密膜材結構，亦提高了薄膜的化學穩定性以及機械強度。
本研究顯示以外加電場的方式製備成膜可以提升離子導電度、降低燃料竄透以提升薄膜的選擇率，並同時提升薄膜的機械強度以及化學穩定性等物性，在最後ADEFC單電池測試中，薄膜亦相較於文獻中PVA薄膜有更卓越的表現，其電流密度達225 mA/cm2、功率密度達48 mA/cm2，顯示此類型薄膜可有效應用於鹼性燃料電池中。

A new category of hydroxide ion exchange membrane bearing ordered interpenetrating network (semi-IPN) structure established by electric field poling during membrane formation, lead to balanced property where high ion conductivity and low alcohol (methanol and ethanol) permeability co-existed. Success of this membrane preparation scheme is illustrated with the semi-IPN membrane formed by dendritic modified bismaleimide (mBMI) and polyvinyl alcohol (PVA) hydrogel casted together under applied electric field (E-field> 2000V/cm, Ac=1-20Hz,). Detailed morphology and water diffusion studies shows electric field poling establishes higher ordered amorphous domains that induces preferentially oriented conducting path that raised ion conductivity. On the other hand, semi-IPN network effectively reduces methanol and ethanol permeation and improves membrane toughness. When PVA:mBMI equals 2 to 3 weight ratio, the membrane delivered impressive room temperature OH ion conductivity of 38.2 mS/cm and a substantially reduced ethanol permeation of 7.7x10-8 cm2/s; giving exceedingly high ethanol selectivity ratio (>105) with electric field poling preparation. Ordering in the semi-IPN structure by electric field poling also causses densification of the amorphous domain that leads to improved chemical stability (99wt% mass retention in 6M KOH for nearly a month) and mechanical toughness (Tensile strength increased from 3.5 MPa to 7.0 MPa, and elongation at break raised from 60% to 92%). The study concludes the application of an external electric field initiated reorganization of membrane morphology where high performance fuel cell membrane bearing high ion conductivity; low fuel permeation; high membrane strength; and high chemical stability can be established, simultaneously.

中文摘要    ii
Abstract    iv
目錄    vi
圖目錄    xi
表目錄    xvi
第一章    緒論    1
1-1 前言    1
1-2 燃料電池簡介及原理    3
第二章    文獻回顧    8
2-1 鹼性燃料電池介紹    8
2-1-1 鹼性燃料電池的優缺點    8
2-1-2 鹼性直接乙醇燃料電池    9
2-2 鹼性燃料電池離子交換膜種類與介紹    11
2-2-1 離子交換膜傳遞機制    12
2-2-2 陰離子交換膜    17
2-2-3 鹼摻雜高分子薄膜    20
2-2-4 有機/無機複合高分子薄膜    23
2-3 聚乙烯醇(PVA)/改質雙馬來醯亞胺(mBMI)薄膜    25
2-4 電場誘導高分子與奈米無機物的性質與探討    32
2-4-1 電場裝置的設計與應用原理    32
2-4-2 外加電場誘導奈米無機物與高分子之性質探討    34
2-4-3 外加電場於離子交換膜上的應用    37
2-5 研究動機    44
第三章 實驗方法與原理    47
3-1 實驗儀器及技術原理    47
3-1-1 掃描式電子顯微鏡(Scanning Electron Microscopy, SEM)    47
3-1-2 示差掃描熱卡計(Differential Scanning Calorimeter, DSC)    48
3-1-3 熱重分析儀(Thermal Gravimetric Analysis, TGA)    48
3-1-4 小角度X光散射(Small angle X-ray scattering, SAXS)    49
3-1-5 X光散射光譜儀(X-Ray Diffraction, XRD)    50
3-1-6 薄膜吸水量(Water Uptake)及膨潤率(Swelling)    51
3-1-7 離子交換容量(Ion Exchange Capacity, IEC)    51
3-1-8 複合薄膜機械強度測試    52
3-1-9 化學穩定性測試(Chemical stability)    54
3-1-10 乙醇竄透率    54
3-1-11 離子導電度測量    55
3-1-12 ADEFC單電池效能測試    57
3-2 物質合成及薄膜製備    59
3-2-1 高分岐鏈鍵結雙馬來醯亞胺合成步驟    59
3-2-2 交聯型固態高分子電解質薄之製備    60
3-2-3 外加電場裝置設計    60
3-3 實驗藥品    62
3-4 樣品命名規則    63
第四章    結果與討論    64
4-1    添加不同分岐長度的雙馬來醯亞胺高分子(mBMI)複合薄膜性質探討    ……………………………………………………………………..66
4-1-1 NMR聚合程度分析    66
4-1-2 不同分歧長度mBMI之SAXS小角度散射為結構    68
4-1-3 不同分歧長度mBMI之DSC薄膜保水性質分析    70
4-1-4 不同分歧長度mBMI複合薄膜之吸水性、膨潤率與離子導電度之比較    71
4-1-5 不同分歧長度mBMI複合薄膜離子導電度與乙醇竄透比較    73
4-1-7 不同分歧長度mBMI複合薄膜之選擇性(Selectivity)    75
4-2 取較佳分歧長度的雙馬來醯亞胺高分子(mBMI)，以添加不同含量對複合薄膜的性質探討    76
4-2-1 相同分歧長度mBMI複合薄膜之DSC薄膜保水性質分析    76
4-2-2 相同分歧長度mBMI複合薄膜之吸水性、膨潤率與離子導電度之比較    77
4-2-3 相同分歧長度mBMI複合薄膜之熱穩定性分析    79
4-2-4 相同分歧長度mBMI複合薄膜之機械效能測試    81
4-2-5 相同分歧長度mBMI複合薄膜離子導電度與乙醇竄透比較    82
4-2-6 相同分歧長度mBMI複合薄膜之選擇性(Selectivity)    84
4-3 外加電場誘導高分子複合薄膜探討及性質分析    85
4-3-1 SEM薄膜微結構影像    86
4-3-2 DSC薄膜保水性質分析    87
4-3-3 SAXS小角度散射微結構    89
4-3-4 XRD薄膜結晶度分析    91
4-3-5 複合薄膜之熱穩定性測試    93
4-3-6 IEC離子交換容量    94
4-3-7 吸水性、膨潤率及離子導電度比較    95
4-3-8 複合薄膜機械效能測試    97
4-3-9 化學穩定性測試    98
4-3-10 變溫及變濕離子導電度測試    100
4-3-11 離子導電度與乙醇燃料竄透率比較    102
4-3-12 複合薄膜選擇性(Selectivity)    103
4-3-13 ADEFC單電池效能測試    104
第五章    結論與未來展望    106
5-1    結論    106
5-2    未來展望與研究建議    108
參考文獻    110
 

                                

[1] https://outlook.stpi.narl.org.tw/index/focusnews/detail/432.
[2] http://www.tfci.org.tw/台灣燃料電池資訊網
[3]https://zh.wikipedia.org/wiki/%E7%87%83%E6%96%99%E7%94%B5%E6%B1%A0.
[4] http://www.pro.energy.dtu.dk/Research/Fuel-cells.
[5] http://www2.nsysu.edu.tw/physdemo/2012/E2/E2.php.
[6] https://panx.asia/archives/51225.
[7] 衣寶廉, 燃料電池-原理與應用, 2005, 五南圖書出版股份有限公司。
[8] G. McLean, T. Niet, S. Prince-Richard, N. Djilali, An assessment of alkaline fuel cell technology, International Journal of Hydrogen Energy 27(5) (2002) 507-526.
[9] N. Wagner, M. Schulze, E. Gülzow, Long term investigations of silver cathodes for alkaline fuel cells, Journal of Power Sources 127(1-2) (2004) 264-272.
[10] Shanfu Lu, Jing Pan, Aibin Huang, Lin Zhuang, Juntao Lu, Alkaline polymer electrolyte fuel cells completely free from noble metal catalysts, PNAS 105(52) (2008) 20611-20614.
[11] J.R. Varcoe, R.C. Slade, Prospects for alkaline anion‐exchange membranes in low temperature fuel cells, Fuel cells 5(2) (2005) 187-200.
[12] G. Merle, M. Wessling, K. Nijmeijer, Anion exchange membranes for alkaline fuel cells: A review, Journal of Membrane Science 377(1-2) (2011) 1-35.
[13] E. Gülzow, Alkaline fuel cells: a critical view, Journal of Power Sources 61(1-2) (1996) 99-104.
[14] E. Gülzow, M. Schulze, Long-term operation of AFC electrodes with CO2 containing gases, Journal of Power Sources 127(1-2) (2004) 243-251.
[15] G. Merle, M. Wessling, K. Nijmeijer, Anion exchange membranes for alkaline fuel cells: A review, Journal of Membrane Science 377(1-2) (2011) 1-35.
[16] Y. Li, T. Zhao, Z. Liang, Performance of alkaline electrolyte-membrane-based direct ethanol fuel cells, Journal of Power Sources 187(2) (2009) 387-392.
[17] T. Zhao, Y. Li, S. Shen, Anion-exchange membrane direct ethanol fuel cells: Status and perspective, Frontiers of Energy and Power Engineering in China 4(4) (2010) 443-458.
[18] Q. Xu, T. Zhao, W. Yang, R. Chen, A flow field enabling operating direct methanol fuel cells with highly concentrated methanol, international journal of hydrogen energy 36(1) (2011) 830-838.
[19] K.S. Roelofs, T. Hirth, T. Schiestel, Dihydrogenimidazole modified silica-sulfonated poly (ether ether ketone) hybrid materials as electrolyte membranes for direct ethanol fuel cells, Materials Science and Engineering: B 176(9) (2011) 727-735.
[20] M. Kamarudin, S.K. Kamarudin, M. Masdar, W.R.W. Daud, Direct ethanol fuel cells, International Journal of Hydrogen Energy 38(22) (2013) 9438-9453.
[21] J.R. Varcoe, R.C. Slade, E.L.H. Yee, S.D. Poynton, D.J. Driscoll, Investigations into the ex situ methanol, ethanol and ethylene glycol permeabilities of alkaline polymer electrolyte membranes, Journal of Power Sources 173(1) (2007) 194-199.
[22] C.-C. Yang, S.-J. Chiu, K.-T. Lee, W.-C. Chien, C.-T. Lin, C.-A. Huang, Study of poly (vinyl alcohol)/titanium oxide composite polymer membranes and their application on alkaline direct alcohol fuel cell, Journal of Power Sources 184(1) (2008) 44-51.
[23] S. Song, W. Zhou, Z. Zhou, L. Jiang, G. Sun, Q. Xin, V. Leontidis, S. Kontou, P. Tsiakaras, Direct ethanol PEM fuel cells: the case of platinum based anodes, International Journal of Hydrogen Energy 30(9) (2005) 995-1001.
[24] L. An, T. Zhao, R. Chen, Q. Wu, A novel direct ethanol fuel cell with high power density, Journal of power sources 196(15) (2011) 6219-6222.
[25] L. An, T. Zhao, S. Shen, Q. Wu, R. Chen, Alkaline direct oxidation fuel cell with non-platinum catalysts capable of converting glucose to electricity at high power output, Journal of power sources 196(1) (2011) 186-190.
[26] L. An, T. Zhao, Performance of an alkaline-acid direct ethanol fuel cell, international journal of hydrogen energy 36(16) (2011) 9994-9999.
[27] 吳千舜，「奈米複合離子交換膜的離子與分子多尺度的動態行為之研究」，國立中央大學，博士論文，民國99年。
[28] X. Duan, S. Scheiner, Analytic functions fit to proton transfer potentials, Journal of molecular structure 270 (1992) 173-185.
[29] N. Laurs, P. Bopp, Modelling the H3O+‐Ion: A Simulation Study of an Aqueous HCl Solution, Berichte der Bunsengesellschaft für physikalische Chemie 97(8) (1993) 982-995.
[30] 侯官廷，「磺酸化二氧化鈦奈米管 Nafion 複合質子交換膜及燃料電池應用」，國立中央大學，碩士論文，民國100 年。
[31] W. Lu, Z.-G. Shao, G. Zhang, Y. Zhao, J. Li, B. Yi, Preparation and characterization of imidazolium-functionalized poly (ether sulfone) as anion exchange membrane and ionomer for fuel cell application, international journal of hydrogen energy 38(22) (2013) 9285-9296.
[32] H. Sun, G. Zhang, Z. Liu, N. Zhang, L. Zhang, W. Ma, C. Zhao, D. Qi, G. Li, H. Na, Self-crosslinked alkaline electrolyte membranes based on quaternary ammonium poly (ether sulfone) for high-performance alkaline fuel cells, international journal of hydrogen energy 37(12) (2012) 9873-9881.
[33] Y. Xiong, Q.L. Liu, Q.H. Zeng, Quaternized cardo polyetherketone anion exchange membrane for direct methanol alkaline fuel cells, Journal of Power Sources 193(2) (2009) 541-546.
[34] J. Fang, P.K. Shen, Quaternized poly (phthalazinon ether sulfone ketone) membrane for anion exchange membrane fuel cells, Journal of Membrane Science 285(1-2) (2006) 317-322.
[35] L. Wu, Q. Pan, J.R. Varcoe, D. Zhou, J. Ran, Z. Yang, T. Xu, Thermal crosslinking of an alkaline anion exchange membrane bearing unsaturated side chains, Journal of Membrane Science 490 (2015) 1-8.
[36] J. Ran, L. Wu, Y. Ru, M. Hu, L. Din, T. Xu, Anion exchange membranes (AEMs) based on poly (2, 6-dimethyl-1, 4-phenylene oxide)(PPO) and its derivatives, Polymer Chemistry 6(32) (2015) 5809-5826.
[37] T.A. Sherazi, S. Zahoor, R. Raza, A.J. Shaikh, S.A.R. Naqvi, G. Abbas, Y. Khan, S. Li, Guanidine functionalized radiation induced grafted anion-exchange membranes for solid alkaline fuel cells, international journal of hydrogen energy 40(1) (2015) 786-796.
[38] Q.H. Zeng, Q.L. Liu, I. Broadwell, A.M. Zhu, Y. Xiong, X.P. Tu, Anion exchange membranes based on quaternized polystyrene-block-poly (ethylene-ran-butylene)-block-polystyrene for direct methanol alkaline fuel cells, Journal of Membrane Science 349(1-2) (2010) 237-243.
[39] H. Hou, G. Sun, R. He, Z. Wu, B. Sun, Alkali doped polybenzimidazole membrane for high performance alkaline direct ethanol fuel cell, Journal of Power Sources 182(1) (2008) 95-99.
[40] B. Xing, O. Savadogo, Hydrogen/oxygen polymer electrolyte membrane fuel cells (PEMFCs) based on alkaline-doped polybenzimidazole (PBI), Electrochemistry communications 2(10) (2000) 697-702.
[41] A.Y. Leykin, O.A. Shkrebko, M.R. Tarasevich, Ethanol crossover through alkali-doped polybenzimidazole membrane, Journal of Membrane Science 328(1-2) (2009) 86-89.
[42] J. Fu, J. Qiao, H. Lv, J. Ma, X.-Z. Yuan, H. Wang, Alkali doped poly (vinyl alcohol)(PVA) for anion-exchange membrane fuel cells: Ionic conductivity, chemical stability and FT-IR characterizations, ECS Transactions 25(13) (2010) 15-23.
[43] R. Nagarale, W. Shin, P.K. Singh, Progress in ionic organic-inorganic composite membranes for fuel cell applications, Polymer Chemistry 1(4) (2010) 388-408.
[44] C.-C. Yang, Y.J. Li, T.-H. Liou, Preparation of novel poly (vinyl alcohol)/SiO2 nanocomposite membranes by a sol–gel process and their application on alkaline DMFCs, Desalination 276(1-3) (2011) 366-372.
[45] C. DeMerlis, D. Schoneker, Review of the oral toxicity of polyvinyl alcohol (PVA), Food and Chemical Toxicology 41(3) (2003) 319-326.
[46] M.I. Baker, S.P. Walsh, Z. Schwartz, B.D. Boyan, A review of polyvinyl alcohol and its uses in cartilage and orthopedic applications, Journal of Biomedical Materials Research Part B: Applied Biomaterials 100(5) (2012) 1451-1457.
[47] J.M. Yang, W.Y. Su, M.C. Yang, Evaluation of chitosan/PVA blended hydrogel membranes, journal of Membrane Science 236(1-2) (2004) 39-51.
[48] D.S. Muggli, A.K. Burkoth, K.S. Anseth, Crosslinked polyanhydrides for use in orthopedic applications: degradation behavior and mechanics, Journal of Biomedical Materials Research Part A 46(2) (1999) 271-278.
[49] S. Kaity, J. Isaac, A. Ghosh, Interpenetrating polymer network of locust bean gum-poly (vinyl alcohol) for controlled release drug delivery, Carbohydrate polymers 94(1) (2013) 456-467.
[50] C.-C. Yang, S. Lin, Preparation of alkaline PVA-based polymer electrolytes for Ni–MH and Zn–air batteries, Journal of applied electrochemistry 33(9) (2003) 777-784.
[51] Y. Wu, C. Wu, Y. Li, T. Xu, Y. Fu, PVA–silica anion-exchange hybrid membranes prepared through a copolymer crosslinking agent, Journal of Membrane Science 350(1-2) (2010) 322-332.
[52] J. Qiao, J. Fu, R. Lin, J. Ma, J. Liu, Alkaline solid polymer electrolyte membranes based on structurally modified PVA/PVP with improved alkali stability, Polymer 51(21) (2010) 4850-4859.
[53] Y. Lu, A.A. Armentrout, J. Li, H.L. Tekinalp, J. Nanda, S. Ozcan, A cellulose nanocrystal-based composite electrolyte with superior dimensional stability for alkaline fuel cell membranes, Journal of Materials Chemistry A 3(25) (2015) 13350-13356.
[54] P.P. Chu, C.-S. Wu, P.-C. Liu, T.-H. Wang, J.-P. Pan, Proton exchange membrane bearing entangled structure: Sulfonated poly (ether ether ketone)/bismaleimide hyperbranch, Polymer 51(6) (2010) 1386-1394.
[55] 陳品豪，「雙馬來醯亞胺與磺酸化苯基馬來醯亞胺共聚物改質之質子交換膜」，國立中央大學，碩士論文，民國100年。
[56] http://www.pjtime.com/2009/10/21543387.shtml.
[57] W. Eerenstein, N. Mathur, J.F. Scott, Multiferroic and magnetoelectric materials, nature 442(7104) (2006) 759.
[58] C. Martin, J. Sandler, A. Windle, M.-K. Schwarz, W. Bauhofer, K. Schulte, M. Shaffer, Electric field-induced aligned multi-wall carbon nanotube networks in epoxy composites, Polymer 46(3) (2005) 877-886.
[59] H. Wang, H. Zhang, W. Zhao, W. Zhang, G. Chen, Preparation of polymer/oriented graphite nanosheet composite by electric field-inducement, Composites science and technology 68(1) (2008) 238-243.
[60] H.L. Ricks-Laskoski, A.W. Snow, Synthesis and electric field actuation of an ionic liquid polymer, Journal of the American Chemical Society 128(38) (2006) 12402-12403.
[61] W. Li, Q. Meng, Y. Zheng, Z. Zhang, W. Xia, Z. Xu, Electric energy storage properties of poly (vinylidene fluoride), Applied Physics Letters 96(19) (2010) 192905.
[62] M. Y. Chung and D. C. Lee, Electrical Properties of Polyvinylidene Fluoride Films Prepared by the High Electric Field Applying Method, Journal of the Korean Physical Society 38 (2001) 117-122.
[63] M. Wegener, Polarization-electric field hysteresis of ferroelectric PVDF films: Comparison of different measurement regimes, Review of Scientific Instruments 79(10) (2008) 106103.
[64] H.-L. Lin, T.L. Yu, F.-H. Han, A method for improving ionic conductivity of Nafion membranes and its application to PEMFC, Journal of Polymer Research 13(5) (2006) 379-385.
[65] X. Wei, M. Yates, Nafion®/polystyrene-b-poly (ethylene-ran-butylene)-b-polystyrene composite membranes with electric field-aligned domains for improved direct methanol fuel cell performance, Journal of Power Sources 195(3) (2010) 736-743.
[66] 曾御程，「電場誘導一維奈米金屬氧化物複合薄膜之研究」，國立中央大學，碩士論文，民國103年。
[67] D. Liu, M. Yates, Tailoring the structure of S-PEEK/PDMS proton conductive membranes through applied electric fields, Journal of Membrane Science 322(1) (2008) 256-264.
[68] S.B. Boob, Field-structured proton exchange membranes for fuel cells, (2007).
[69] S. Zhao, J. Ren, Y. Wang, J. Zhang, Electric field processing to control the structure of titanium oxide/sulfonated poly (ether ether ketone) hybrid proton exchange membranes, Journal of membrane science 437 (2013) 65-71.
[70] M.D. Stamate, On the dielectric properties of dc magnetron TiO2 thin films, Applied Surface Science 218(1-4) (2003) 318-323.
[71] 方煜馨，「電場誘導聚苯醚碸摻雜複合薄膜之研究」，國立中央大學，碩士論文，民國105年。
[72] 陳正平，「結構用鋼材基本特性介紹」，技師報，764期，100年7月。
[73] 李亮儀，「奈米管複合高分子中高溫質子交換膜」，國立中央大學，碩士論文，民國97年。
[74] C.-C. Yang, Synthesis and characterization of the cross-linked PVA/TiO2 composite polymer membrane for alkaline DMFC, Journal of Membrane Science 288(1-2) (2007) 51-60.
[75] C.-Y. Huang, J.-S. Lin, W.-H. Pan, C.-M. Shih, Y.-L. Liu, S.J. Lue, Alkaline direct ethanol fuel cell performance using alkali-impregnated polyvinyl alcohol/functionalized carbon nano-tube solid electrolytes, Journal of Power Sources 303 (2016) 267-277.
[76] M. Sairam, M.B. Patil, R.S. Veerapur, S.A. Patil, T.M. Aminabhavi, Novel dense poly (vinyl alcohol)–TiO2 mixed matrix membranes for pervaporation separation of water–isopropanol mixtures at 30° C, Journal of membrane science 281(1-2) (2006) 95-102.
[77] G. Wu, S. Lin, C. Yang, Preparation and characterization of PVA/PAA membranes for solid polymer electrolytes, Journal of Membrane Science 275(1-2) (2006) 127-133.
[78] G. Nasar, M.S. Khan, U. Khalil, Structural study of PVA composites with inorganic salts by X-ray diffraction, J. Pak. Mater. Soc 3 (2009) 67-70.

簡易檢索 / 詳目顯示

相關論文