對於水系電解液的超級電容器而言，在實際應用上面臨的困境，主要
來自於和使用有機系電解液的超級電容器相比而言，相對較低的工作電壓
窗口，因而導致的低能量密度儲存量。本研究為改善此一問題，利用電極
表面修飾以提升正極的工作電壓窗口，並且透過後續組裝非對稱電容器，
以達到進一步拓寬使用電壓區間的效果。
研究內容透過利用水熱法以及熱處理，來進行氧化鋅以及四氧化三錳
的共沉積。均勻生長在四氧化三錳周圍的氧化鋅，不僅可以藉由提升導電
度，以增進四氧化三錳的電荷轉移能力； 同時利用氧化鋅在中性電解液環
境中，不進行電化學反應的特性，氧化鋅可以作為物理支撐，防止四氧化
三錳在充放電的過程中，發生顆粒團聚的現象。
將此氧化鋅/四氧化三錳正極和活性碳負極進行配比，組裝而成的非對
稱電容器可以在 1.0 M 的硫酸鈉電解液中，擁有高達 2.4 V 的工作電壓口，
並且在功率密度為 1051 W/kg 的情形下，輸出最高 54 Wh/kg 的能量密度。

The critical restriction of aqueous supercapacitors (SCs) lies in their low operating
potential comparing to those organic SCs, which severely limits the energy density and
further potential of practical applications. In this study, we used electrode surface
modification to broaden the operating voltage for cathodes and further extend the
potential window by assembling asymmetric supercapacitors (ASCs).
Herein, a well-distributed co-metal oxides system which combing Mn3O4 along
with ZnO via hydrothermal treatment followed by post-annealing treatment was
introduced. The well-distributed ZnO grown adjacent to Mn3O4 endows faster charge
transfer kinetics for Mn3O4. Besides, the inactive electrochemical property of ZnO in
neutral electrolyte also lets it become physical stabilizer for Mn3O4 preventing it from
aggregating during charge/discharge process.
By paring with commercial activated carbon anode, a wide operating voltage (2.4
V) asymmetric supercapacitors in 1.0 M Na2SO4 aqueous electrolyte was assembled.
Especially, the 2.4 V ZnO/Mn3O4//AC ASCs could deliver a maximum energy density
of up to 54 Wh kg-1 at a power density of 1051 W kg-1.

摘要………………………………………………………………….…………………I
Abstracrt ………………………………………………………………………… …. II
表目錄…………………………………………………………………………….….VI
圖目錄……………………………………………………...………………………. VII
第 1 章 緒論 ...............................................................................................................1
1.1 前言.................................................................................................................. 1
1.2 研究動機.......................................................................................................... 2
第 2 章 文獻回顧 .......................................................................................................4
2.1 超级電容器储能原理...................................................................................... 6
2.1.1 電雙層電容器 ............................................................................................. 7
2.1.2 擬電容器 ..................................................................................................... 9
2.2 雙電層電容器理論與模型演進.................................................................... 10
2.3 電解液............................................................................................................ 12
2.3.1 水系電解液 ............................................................................................... 12
2.3.2 有機系電解液 ........................................................................................... 13
2.3.3 離子液體 ................................................................................................... 13
2.4 水系電解液之工作電壓窗口研究................................................................ 14
2.4.1 非對稱超級電容器 ................................................................................... 15
2.4.2 氧化還原活性添加劑 ............................................................................... 16IV
2.4.3 電極表面設計與修飾 ............................................................................... 17
2.5 電極材料評估………………………………………………………………….18
第 3 章 實驗方法與分析 .........................................................................................28
3.1 實驗藥品........................................................................................................ 28
3.2 實驗步驟........................................................................................................ 28
3.2.1 高溫碳化蠶絲碳布製備 ........................................................................... 28
3.2.2 共沉積 ZnO/Mn3O4 正極製備.................................................................. 29
3.2.3 活性碳負極製備 ....................................................................................... 29
3.2.4 非對稱電容器鈕扣電池組裝 ................................................................... 30
3.3 實驗分析方法及使用儀器............................................................................ 30
3.4 電化學測試技術............................................................................................ 33
第 4 章 結果與討論 .................................................................................................37
4.1 雙相金屬氧化物 ZnO/Mn3O4 之分析........................................................... 37
4.1.1 X 光繞射光譜之晶體結構分析 .............................................................. 38
4.1.2 表面元素分析与化学组成 ....................................................................... 39
4.1.3 掃描式電子顯微鏡之形貌分析 ............................................................... 40
4.1.4 穿透式電子顯微鏡之形貌分析 ............................................................... 41
4.2 ZnO/Mn3O4 正極之電化學特性分析............................................................ 42
4.3 非對稱電容器之電化學特性分析................................................................ 45V
第 5 章 結論 .............................................................................................................67
参考文献 .....................................................................................................................68

[1] W. Zuo, C. Xie, P. Xu, Y. Li, J. Liu, A Novel Phase-Transformation Activation Process
toward Ni-Mn-O Nanoprism Arrays for 2.4 V Ultrahigh-Voltage Aqueous Supercapacitors,
Advanced Materials 29(36) (2017).
[2] D. Zhou, H. Lin, F. Zhang, H. Niu, L. Cui, Q. Wang, F. Qu, Freestanding MnO 2
nanoflakes/porous carbon nanofibers for high-performance flexible supercapacitor electrodes,
Electrochimica Acta 161 (2015) 427-435.
[3] J. Yan, Z. Fan, T. Wei, W. Qian, M. Zhang, F. Wei, Fast and reversible surface redox
reaction of graphene–MnO2 composites as supercapacitor electrodes, Carbon 48(13) (2010)
3825-3833.
[4] M. Tian, M. Du, L. Qu, K. Zhang, H. Li, S. Zhu, D. Liu, Conductive reduced graphene
oxide/MnO2 carbonized cotton fabrics with enhanced electrochemical, -heating, and -
mechanical properties, Journal of Power Sources 326 (2016) 428-437.
[5] G. Wang, X. Sun, F. Lu, H. Sun, M. Yu, W. Jiang, C. Liu, J. Lian, Flexible pillared
graphene-paper electrodes for high-performance electrochemical supercapacitors, Small 8(3)
(2012) 452-459.
[6] F. Liu, S. Song, D. Xue, H. Zhang, Folded structured graphene paper for high performance
electrode materials, Advanced Materials 24(8) (2012) 1089-1094.
[7] C.-L. Liu, K.-H. Chang, C.-C. Hu, W.-C. Wen, Microwave-assisted hydrothermal
synthesis of Mn3O4/reduced graphene oxide composites for high power supercapacitors,
Journal of Power Sources 217 (2012) 184-192.
[8] G.C. Li, P.F. Liu, R. Liu, M. Liu, K. Tao, S.R. Zhu, M.K. Wu, F.Y. Yi, L. Han, MOF -
derived hierarchical double-shelled NiO/ZnO hollow spheres for high-performance
supercapacitors, Dalton Trans 45(34) (2016) 13311-13316.
[9] G. Xin, Y. Wang, X. Liu, J. Zhang, Y. Wang, J. Huang, J. Zang, Preparation of self -
supporting graphene on flexible graphite sheet and electrodeposition of polyaniline for
supercapacitor, Electrochimica Acta 167 (2015) 254-261.
[10] L. Ma, R. Liu, L. Liu, F. Wang, H. Niu, Y. Huang, Facile synthesis of
Ni(OH)2/graphene/bacterial cellulose paper for large areal mass, mechanically tough and
flexible supercapacitor electrodes, Journal of Power Sources 335 (2 016) 76-83.
[11] D. Sheberla, J.C. Bachman, J.S. Elias, C.J. Sun, Y. Shao-Horn, M. Dinca, Conductive
MOF electrodes for stable supercapacitors with high areal capacitance, Nat ure Material 16(2)
(2017) 220-224.
[12] W. Cai, T. Lai, W. Dai, J. Ye, A facile approach to fabricate flexible all-solid-state
supercapacitors based on MnFe2O4/graphene hybrids, Journal of Power Sources 255 (2014)
170-178.
[13] Z. Tang, C.-h. Tang, H. Gong, A High Energy Density Asymmetric Supercapacitor from
Nano-architectured Ni(OH)2/Carbon Nanotube Electrodes, Advanced Functional Materials
22(6) (2012) 1272-1278.
[14] K.V. Sankar, R.K. Selvan, The ternary MnFe 2O4/graphene/polyaniline hybrid composite
as negative electrode for supercapacitors, Journal of Power Sources 275 (2015) 399 -407.
[15] Y. Wang, H. Wei, J. Wang, J. Liu, J. Guo, X. Zhang, B.L. Weeks, T.D. Shen, S. Wei, Z.
Guo, Electropolymerized polyaniline/manganese iron oxide hybrids with an enhanced color
switching response and electrochemical energy storage, Journal of Material Chemistry A 3(41)
(2015) 20778-20790.
[16] P. Xiong, C. Hu, Y. Fan, W. Zhang, J. Zhu, X. Wang, Ternary manganese
ferrite/graphene/polyaniline nanostructure with enhanced electrochemical capacitance
performance, Journal of Power Sources 266 (2014) 384-392.
[17] Y. Liu, N. Zhang, C. Yu, L. Jiao, J. Chen, MnFe 2O4@C Nanofibers as High-Performance
Anode for Sodium-Ion Batteries, Nano Letter 16(5) (2016) 3321-3328.
[18] P.J. Derbyshire, H. Barr, F. Davis, S.P. Higson, Lactate in human sweat: a critical review
of research to the present day, Journal Physiological Sciences 62(6) (2012) 429-440.
[19] S.-L. Kuo, N.-L. Wu, Electrochemical characterization on MnFe 2O4/carbon black
composite aqueous supercapacitors, Journal of Power Sources 162(2) (2006) 1437 -1443.
[20] X. Cheng, X. Gui, Z. Lin, Y. Zheng, M. Liu, R. Zhan, Y. Zhu, Z. Tang, Three -dimensional
α-Fe2O3/carbon nanotube sponges as flexible supercapacitor electrodes, Journal of Material69
Chemistry A 3(42) (2015) 20927-20934.
[21] B.E. Conway, Transition from “supercapacitor” to “battery” behavior in electrochemical
energy storage, Journal of the Electrochemical Society 138(6) (1991) 1539 -1548.
[22] B.K. Kim, S. Sy, A. Yu, J. Zhang, Electrochemical supercapacitors for energy storage
and conversion, Handbook of Clean Energy Systems (2015).
[23] V. Aravindan, J. Gnanaraj, Y.S. Lee, S. Madhavi, Insertion-Type Electrodes for
Nonaqueous Li-Ion Capacitors, Chemical Reviews 114(23) (2014) 11619-11635.
[24] S.-Y. Yang, K.-H. Chang, H.-W. Tien, Y.-F. Lee, S.-M. Li, Y.-S. Wang, J.-Y. Wang, C.-
C.M. Ma, C.-C. Hu, Design and tailoring of a hierarchical graphene -carbon nanotube
architecture for supercapacitors, Joural of Material Chemistry 21(7) (2011) 2374-2380.
[25] Y. Shao, M.F. El-Kady, L.J. Wang, Q. Zhang, Y. Li, H. Wang, M.F. Mousavi, R.B. Kaner,
Graphene-based materials for flexible supercapacitors, Chemical Society Reviews 44(11)
(2015) 3639-3665.
[26] B.K. Kim, S. Sy, A. Yu, J. Zhang, Electrochemical Supercapacitors for Energy Storage
and Conversion, Handbook of Clean Energy Systems. (2015) 1-25.
[27] E. Frackowiak, Carbon materials for supercapacitor application, Physical Chemistry
Chemical Physics 9(15) (2007) 1774-1785.
[28] B. Hsia, J. Marschewski, S. Wang, J.B. In, C. Carraro, D. Poulikakos, C.P. Grigoropoulos,
R. Maboudian, Highly flexible, all solid-state micro-supercapacitors from vertically aligned
carbon nanotubes, Nanotechnology 25(5) (2014) 055401.
[29] C. Liu, Z. Yu, D. Neff, A. Zhamu, B.Z. Jang, Graphene-based supercapacitor with an
ultrahigh energy density, Nano Letters 10(12) (2010) 4863-4868.
[30] C.C. Hu, K.H. Chang, A. Mingchamp Lin, Y.T. Wu, Design and Tailoring of the
Nanotubular Arrayed Architecture of Hydrous RuO 2 for Next Generation Supercapacitors,
Nano Letters 6(12) (2006) 2690-2695.
[31] X. Pan, G. Ren, M.N.F. Hoque, S. Bayne, K. Zhu, Z. Fan, Fast Supercapacitors Based
on Graphene-Bridged V2O3/VOxCore-Shell Nanostructure Electrodes with a Power Density
of 1 MW kg−1, Advanced Materials Interfaces 1(9) (2014) 1400398.
[32] S. Nagamuthu, S. Vijayakumar, K.-S. Ryu, Synthesis of Ag Anchored Ag 3VO4Stacked
Nanosheets: Toward a Negative Electrode Material for High-Performance Asymmetric
Supercapacitor Devices, The Journal of Physical Chemistry C 120(34) (2016) 18963 -18970.
[33] Y. Chen, K. Cai, C. Liu, H. Song, X. Yang, High‐Performance and Breathable Polypyrrole
Coated Air‐Laid Paper for Flexible All‐Solid‐State Supercapacitors, Advanced Energy
Materials 7(21) (2017).
[34] A. Yu, V. Chabot, Z. Chen, J. Zhang, Electrochemical Supercapacitors for Energy Sto rage
and Delivery, Crc Press (2013).
[35] D.C. Grahame, The electrical double layer and the theory of electrocapillarity, Chemical
Reviews 41(3) (1947) 441-501.
[36] M.A.V. Devanathan, B.V.K.S.R.A. Tilak, The Structure of the Electrical Double Layer
at the Metal-Solution Interface, Chemical Reviews 65(6) (1965) 635-684.
[37] B.E. Conway, Electrochemical Supercapacitors, Plenum Press1999.
[38] A. Burke, R&D considerations for the performance and application of electrochemical
capacitors, Electrochimica Acta 53(3) (2007) 1083-1091.
[39] H.A. Mosqueda, O. Crosnier, L. Athouël, Y. Dandeville, Y. Scudeller, P. Guillemet, D.M.
Schleich, T. Brousse, Electrolytes for hybrid carbon–MnO 2 electrochemical capacitors,
Electrochimica Acta 55(25) (2010) 7479-7483.
[40] M. Morita, M. Goto, Y. Matsuda, Ethylene carbonate-based organic electrolytes for
electric double layer capacitors, Journal of Applied Electrochemistry 22(10) (1992) 901 -908.
[41] T. Morimoto, K. Hiratsuka, Y. Sanada, K. Kurihara, Electric double -layer capacitor using
organic electrolyte, Mrs Proceedings 496(2) (1997) 239-247.
[42] Q. Zhu, Y. Song, X. Zhu, X. Wang, Ionic liquid -based electrolytes for capacitor
applications, Journal of Electroanalytical Chemistry 601(1) (2007) 229 -236.
[43] T.Y. Kim, H.W. Lee, M. Stoller, D.R. Dreyer, C.W. Bielawski, R.S. Ruoff, K.S. Suh,
High-Performance Supercapacitors Based on Poly(ionic liquid) -Modified Graphene
Electrodes, Acs Nano 5(1) (2011) 436-442.
[44] T. Zhai, X. Lu, Y. Ling, M. Yu, G. Wang, T. Liu, C. Liang, Y. Tong, Y. Li, A new
benchmark capacitance for supercapacitor anodes by mixed -valence sulfur-doped V6O(13-x),70
Advanced Materials 26(33) (2014) 5869-5875.
[45] C. Zhou, Y. Zhang, Y. Li, J. Liu, Construction of high-capacitance 3D CoO@polypyrrole
nanowire array electrode for aqueous asymmetric supercapacitor, Nano Letters 13(5) (2013)
2078-2085.
[46] Z. Gao, W. Yang, J. Wang, N. Song, X. Li, Flexible all -solid-state hierarchical NiCo2O
4 /porous graphene paper asymmetric supercapacitors with an exceptional combina tion of
electrochemical properties, Nano Energy 13 (2015) 306-317.
[47] J. Chang, M. Jin, F. Yao, T.H. Kim, V.T. Le, H. Yue, F. Gunes, B. Li, A. Ghosh, S. Xie,
Asymmetric Supercapacitors Based on Graphene/MnO 2 Nanospheres and Graphene/MoO3
Nanosheets with High Energy Density, Advanced Functional Materials 23(40) (2013) 5074 -
5083.
[48] M. Yu, Y. Lu, H. Zheng, X. Lu, New Insights into the Operating Voltage of Aqueous
Supercapacitors, Chemistry - A European Journal (2017).24(15)
[49] S.E. Chun, B. Evanko, X. Wang, D. Vonlanthen, X. Ji, G.D. Stucky, S.W. Boettcher,
Design of aqueous redox-enhanced electrochemical capacitors with high specific energies
and slow self-discharge, Nature Communications 6 (2015) 7818.
[50] J.Y. Hwang, M. Li, M.F. El-Kady, R.B. Kaner, Next‐Generation Activated Carbon
Supercapacitors: A Simple Step in Electrode Processing Leads to Remarkable Gains in Energy
Density, Advanced Functional Materials 27(15) (2017) 1605745.
[51] L.Q. Mai, A. Minhaskhan, X. Tian, K.M. Hercule, Y.L. Zhao, X. Lin, X. Xu, Synergistic
interaction between redox-active electrolyte and binder-free functionalized carbon for
ultrahigh supercapacitor performance, Nature Communications 4(1) (2013) 2923.
[52] J. Deng, P. Ren, D. Deng, L. Yu, F. Yang, X. Bao, Highly active and durable nonprecious-metal catalysts encapsulated in carbon nanotubes for hydrogen evolution reaction,
Energy & Environmental Science 7(6) (2014) 1919-1923.
[53] Y. Zheng, Y. Jiao, M. Jaroniec, S.Z. Qiao, Advancing the electrochemist ry of the
hydrogen-evolution reaction through combining experiment and theory, Angewandte Chemie
International Edition 54(1) (2015) 52-65.
[54] N. Jabeen, A. Hussain, Q. Xia, S. Sun, J. Zhu, X. Hui, High‐Performance 2.6 V Aqueous
Asymmetric Supercapacitors based on In Situ Formed Na0.5MnO2 Nanosheet Assembled
Nanowall Arrays, Advanced Materials 29(32) (2017).
[55] H.J. Chu, C.Y. Lee, N.H. Tai, Green preparation using black soybeans extract for
graphene-based porous electrodes and their applications in supercapacitors, Journal of Power
Sources 322 (2016) 31-39.
[56] B.K. Kim, S. Sy, A. Yu, J. Zhang, Electrochemical Supercapacitors for Energy Storage
and Conversion, John Wiley & Sons, Ltd 2014:1-25.
[57] S. Ban, J. Zhang, L. Zhang, K. Tsay, D. Song, X. Zou, Charging and discharging
electrochemical supercapacitors in the presence of both parallel leakage process and
electrochemical decomposition of solvent, Electrochimica Acta 90(1) (2013) 542 -549.
[58] J.W. Lee, A.S. Hall, J.D. Kim, T.E. Mallouk, A Facile and Template-Free Hydrothermal
Synthesis of Mn3O4 Nanorods on Graphene Sheets for Supercapacitor Electrodes with Long
Cycle Stability, Cheminform 43(24) (2012) 1158-1164.
[59] T. Prasankumar, V.S.I. Aazem, P. Raghavan, K.P. Ananth, S. Biradar, R. Ilangovan, S.
Jose, Microwave assisted synthesis of 3D network of Mn/Zn bimetallic oxide -high
performance electrodes for supercapacitors, Journal of Alloys & Compounds 695 (2017)
2835-2843.
[60] C. Xiong, T. Li, A. Dang, T. Zhao, H. Li, H. Lv, Two -step approach of fabrication of
three-dimensional MnO2-graphene-carbon nanotube hybrid as a binder-free supercapacitor
electrode, Journal of Power Sources 306 (2016) 602-610.
[61] N. Yu, H. Yin, W. Zhang, Y. Liu, Z. Tang, M.-Q. Zhu, High-Performance Fiber-Shaped
All-Solid-State Asymmetric Supercapacitors Based on Ultrathin MnO 2 Nanosheet/Carbon
Fiber Cathodes for Wearable Electronics, Advanced Energy Materials 6(2) (2016) 1501458.
[62] H. Yi, H. Wang, Y. Jing, T. Peng, Y. Wang, J. Guo, Q. He, Z. Guo, X. Wang, Advanced
asymmetric supercapacitors based on CNT@Ni(OH) 2 core–shell composites and 3D graphene
networks, Journal of Materials Chemistry A 3(38) (2015) 19545-19555.
[63] B. Amutha, M. Sathish, A 2 V asymmetric supercapacitor based on reduced graphene
oxide-carbon nanofiber-manganese carbonate nanocomposite and reduced graphene oxide in71
aqueous solution, Journal of Solid State Electrochemistry 19(8) (2015) 2311 -2320.
[64] C.H. Wang, H.C. Hsu, J.H. Hu, High-energy asymmetric supercapacitor based on petalshaped MnO2 nanosheet and carbon nanotube-embedded polyacrylonitrile-based carbon
nanofiber working at 2V in aqueous neutral electrolyte, Journal of Power Sources 249(1)
(2014) 1-8.
[65] H. Xu, X. Hu, H. Yang, Y. Sun, C. Hu, Y. Huang, Flexible Asymmetric Micro -
Supercapacitors Based on Bi2O3 and MnO2 Nanoflowers: Larger Areal Mass Promises Higher
Energy Density, Advanced Energy Materials 5(6) (2015) 1401882.