本研究分為兩部分來分析，第一部分是利用羧甲基纖維素(CMC)與甲基丙烯酸磺基甜菜鹼(SBMA)，透過oxa Michael addition反應合成出雙離子型高分子黏著劑，以克服低溫下離子移動的障礙。從SEM可以觀察到CMC-SBMA之粒徑尺寸為1-3 μm，小於PVDF與CMC作為碳電極黏著劑之5-10 μm，因此能提供較好的離子和電子傳導性來幫助超電容充放電。在電化學方面，當溫度從25 ℃降至-20 ℃時，PVDF、CMC和CMC-SBMA之電容保存率分別為65 %、50 %和80 %。透過DSC分析，CMC在-10.7 ℃和-19.8 ℃分別出現兩個結晶峰，而CMC-SBMA僅在-23 ℃有一個結晶峰，意味著CMC-SBMA黏著劑能有效增強離子的解離度且避免離子在低溫析出。
此外，在零下-20 ℃以12 A/g進行充放電測試，PVDF、CMC和CMC-SBMA超電容的能量密度分別為38Wh/kg、22 Wh/kg和49 Wh/kg，以CMC-SBMA表現最為優異。本研究證實，雙離子型黏著劑能有效提升碳電極顆粒之分散性，並在低溫下幫助離子解離，提供較佳的電化學表現。
本研究第二部分以擴充比電容值為首要目標，在CMC-SBMA黏著劑系統中，加入不同比例之甜菜鹼 (betaine)，尋找最適化條件作為電極添加劑。主要機制是利用固定化的SBMA與小分子betaine之間的庫倫吸引力，幫助水合離子脫水 (dehydration)，以增加比電容值。結果顯示，添加7.5 wt.% betaine到CMC-SBMA黏著劑中，可有效減少自由水的比例，促進離子的傳遞能力。在儲能表現，CMC-SBMA W/ 7.5% BET超電容在功率密度為1907 W/kg時，能量密度高達76.3 Wh/kg，且在1.5 A/g的充放電速率下，比電容值可達339.7 F/g。此篇研究提出一種利用低成本的製程提高提高離子導電度且增加元件的比電容值，可作為高效的儲能裝置。

This research was divided into two parts, the first part was Carboxymethyl cellulose (CMC) subjected to oxa-Michael addition with sulfobetaine methacrylate (SBMA) to produce CMC-SBMA as a novel binder. When the temperature decreased to -20 ℃, the capacitance retention calculated from GCD curves of PVDF, CMC, and CMC-SBMA based supercapacitor was 65 %, 50 % and 80 % respectively in comparison with 25 ℃. The results demonstrate that CMC-SBMA as binder acted as dissociation enhancer and provided anti-freezing property for the superior performance energy storage devices at low temperature.
In second part, glycine betaine (BET) added in CMC-SBMA binder was studied for the effectiveness in carbon electrode. Electrochemical impedance spectroscopy, dielectric constant, and loss tangent evidenced the addition of BET (7.5 wt.%) had the strong ion-dipole interaction with water molecule, exhibiting the highest specific capacitance of 340 F/g at current density of 1.5 A/g and possessed the highest energy density of 76.3 Wh/kg.

[1] M. F. El-Kady, V. Strong, S. Dubin, and R. B. Kaner, "Laser scribing of high-performance and flexible graphene-based electrochemical capacitors," Science, vol. 335, no. 6074, pp. 1326-1330, 2012.
[2] M. D. Stoller and R. S. Ruoff, "Best practice methods for determining an electrode material's performance for ultracapacitors," Energy & Environmental Science, vol. 3, no. 9, pp. 1294-1301, 2010.
[3] H.-C. Huang, C.-W. Huang, C.-T. Hsieh, P.-L. Kuo, J.-M. Ting, and H. Teng, "Photocatalytically reduced graphite oxide electrode for electrochemical capacitors," The Journal of Physical Chemistry C, vol. 115, no. 42, pp. 20689-20695, 2011.
[4] J. Chmiola, G. Yushin, R. Dash, and Y. Gogotsi, "Effect of pore size and surface area of carbide derived carbons on specific capacitance," Journal of Power Sources, vol. 158, no. 1, pp. 765-772, 2006.
[5] K. Jost, G. Dion, and Y. Gogotsi, "Textile energy storage in perspective," Journal of Materials Chemistry A, vol. 2, no. 28, pp. 10776-10787, 2014.
[6] Z. Yu, L. Tetard, L. Zhai, and J. Thomas, "Supercapacitor electrode materials: nanostructures from 0 to 3 dimensions," Energy & Environmental Science, vol. 8, no. 3, pp. 702-730, 2015.
[7] L. Zhao et al., "An environment-friendly crosslinked binder endowing LiFePO 4 electrode with structural integrity and long cycle life performance," RSC Advances, vol. 10, no. 49, pp. 29362-29372, 2020.
[8] T. L. Makarova et al., "Electrical properties of two-dimensional fullerene matrices," Carbon, vol. 39, no. 14, pp. 2203-2209, 2001.
[9] M. J. Allen, V. C. Tung, and R. B. Kaner, "Honeycomb carbon: a review of graphene," Chemical reviews, vol. 110, no. 1, pp. 132-145, 2010.
[10] 王柏欣, "光固化高分子離子液體/離子液體作為固態電解質應用於超級電容器," 2017.
[11] W. Xing et al., "Superior electric double layer capacitors using ordered mesoporous carbons," Carbon, vol. 44, no. 2, pp. 216-224, 2006.
[12] C. Zhong, Y. Deng, W. Hu, J. Qiao, L. Zhang, and J. Zhang, "A review of electrolyte materials and compositions for electrochemical supercapacitors," Chemical Society Reviews, vol. 44, no. 21, pp. 7484-7539, 2015.
[13] Z. Bo, Z. Wen, H. Kim, G. Lu, K. Yu, and J. Chen, "One-step fabrication and capacitive behavior of electrochemical double layer capacitor electrodes using vertically-oriented graphene directly grown on metal," Carbon, vol. 50, no. 12, pp. 4379-4387, 2012.
[14] J. Hu, Z. Kang, F. Li, and X. Huang, "Graphene with three-dimensional architecture for high performance supercapacitor," Carbon, vol. 67, pp. 221-229, 2014.
[15] M.-F. Hsueh, C.-W. Huang, C.-A. Wu, P.-L. Kuo, and H. Teng, "The synergistic effect of nitrile and ether functionalities for gel electrolytes used in supercapacitors," The Journal of Physical Chemistry C, vol. 117, no. 33, pp. 16751-16758, 2013.
[16] H.-C. Huang et al., "An ether bridge between cations to extend the applicability of ionic liquids in electric double layer capacitors," Journal of Materials Chemistry A, vol. 4, no. 48, pp. 19160-19169, 2016.
[17] W. Raza et al., "Recent advancements in supercapacitor technology," Nano Energy, vol. 52, pp. 441-473, 2018.
[18] H. Du, X. Lin, Z. Xu, and D. Chu, "Electric double-layer transistors: a review of recent progress," Journal of Materials Science, vol. 50, no. 17, pp. 5641-5673, 2015.
[19] L. L. Zhang and X. Zhao, "Carbon-based materials as supercapacitor electrodes," Chemical Society Reviews, vol. 38, no. 9, pp. 2520-2531, 2009.
[20] J. S. Mattson and H. B. Mark, Activated carbon: surface chemistry and adsorption from solution. M. Dekker, 1971.
[21] H. D. Young, R. A. Freedman, and L. Ford, "University Physics Vol. 2 (Chapters 21–37), vol. 2," ed: Pearson education, 2007.
[22] M. K. Khawaja, M. F. Khanfar, T. Oghlenian, and W. Alnahar, "Fabrication and Electrochemical Characterization of Carbon Based Supercapacitor Electrodes," in 2019 10th International Renewable Energy Congress (IREC), 2019: IEEE, pp. 1-4.
[23] C. M. Brett and A. M. Oliveira, "Brett. Electrochemistry: Principles, Methods, and Applications," ed: Oxford University Press, New York, 1993.
[24] K.-C. Tsay, L. Zhang, and J. Zhang, "Effects of electrode layer composition/thickness and electrolyte concentration on both specific capacitance and energy density of supercapacitor," Electrochimica Acta, vol. 60, pp. 428-436, 2012.
[25] A. Daraghmeh, S. Hussain, L. Servera, E. Xuriguera, A. Cornet, and A. Cirera, "Impact of binder concentration and pressure on performance of symmetric CNFs based supercapacitors," Electrochimica Acta, vol. 245, pp. 531-538, 2017.
[26] S. Xun, X. Song, V. Battaglia, and G. Liu, "Conductive polymer binder-enabled cycling of pure tin nanoparticle composite anode electrodes for a lithium-ion battery," Journal of the Electrochemical Society, vol. 160, no. 6, p. A849, 2013.
[27] X. Sun, X. Zhang, H. Zhang, B. Huang, and Y. Ma, "Application of a novel binder for activated carbon-based electrical double layer capacitors with nonaqueous electrolytes," Journal of Solid State Electrochemistry, vol. 17, no. 7, pp. 2035-2042, 2013.
[28] A. Varzi, R. Raccichini, M. Marinaro, M. Wohlfahrt-Mehrens, and S. Passerini, "Probing the characteristics of casein as green binder for non-aqueous electrochemical double layer capacitors' electrodes," Journal of Power Sources, vol. 326, pp. 672-679, 2016.
[29] H. Buqa, M. Holzapfel, F. Krumeich, C. Veit, and P. Novák, "Study of styrene butadiene rubber and sodium methyl cellulose as binder for negative electrodes in lithium-ion batteries," Journal of Power Sources, vol. 161, no. 1, pp. 617-622, 2006.
[30] B. Song, F. Wu, Y. Zhu, Z. Hou, K.-s. Moon, and C.-P. Wong, "Effect of polymer binders on graphene-based free-standing electrodes for supercapacitors," Electrochimica Acta, vol. 267, pp. 213-221, 2018.
[31] M. Aslan, D. Weingarth, P. Herbeck-Engel, I. Grobelsek, and V. Presser, "Polyvinylpyrrolidone/polyvinyl butyral composite as a stable binder for castable supercapacitor electrodes in aqueous electrolytes," Journal of Power Sources, vol. 279, pp. 323-333, 2015.
[32] F. Sebesta, J. John, A. Motl, and K. Stamberg, "Evaluation of polyacrylonitrile (PAN) as a binding polymer for absorbers used to treat liquid radioactive wastes," Sandia National Labs., 1995.
[33] G. Wu et al., "Novel porous polymer electrolyte based on polyacrylonitrile," Materials chemistry and physics, vol. 104, no. 2-3, pp. 284-287, 2007.
[34] X. He, N. Zhang, X. Shao, M. Wu, M. Yu, and J. Qiu, "A layered-template-nanospace-confinement strategy for production of corrugated graphene nanosheets from petroleum pitch for supercapacitors," Chemical Engineering Journal, vol. 297, pp. 121-127, 2016.
[35] H. Ohno, M. Yoshizawa-Fujita, and Y. Kohno, "Design and properties of functional zwitterions derived from ionic liquids," Physical Chemistry Chemical Physics, vol. 20, no. 16, pp. 10978-10991, 2018.
[36] J. Ladd, Z. Zhang, S. Chen, J. C. Hower, and S. Jiang, "Zwitterionic polymers exhibiting high resistance to nonspecific protein adsorption from human serum and plasma," Biomacromolecules, vol. 9, no. 5, pp. 1357-1361, 2008.
[37] M.-C. Sin, S.-H. Chen, and Y. Chang, "Hemocompatibility of zwitterionic interfaces and membranes," Polymer journal, vol. 46, no. 8, pp. 436-443, 2014.
[38] J. Wu, W. Lin, Z. Wang, S. Chen, and Y. Chang, "Investigation of the hydration of nonfouling material poly (sulfobetaine methacrylate) by low-field nuclear magnetic resonance," Langmuir, vol. 28, no. 19, pp. 7436-7441, 2012.
[39] C. Tiyapiboonchaiya et al., "The zwitterion effect in high-conductivity polyelectrolyte materials," Nature materials, vol. 3, no. 1, pp. 29-32, 2004.
[40] Y. Chang, W.-J. Chang, Y.-J. Shih, T.-C. Wei, and G.-H. Hsiue, "Zwitterionic sulfobetaine-grafted poly (vinylidene fluoride) membrane with highly effective blood compatibility via atmospheric plasma-induced surface copolymerization," ACS applied materials & interfaces, vol. 3, no. 4, pp. 1228-1237, 2011.
[41] X. Peng et al., "A zwitterionic gel electrolyte for efficient solid-state supercapacitors," Nature communications, vol. 7, no. 1, pp. 1-8, 2016.
[42] K. Ge and G. Liu, "Suppression of self-discharge in solid-state supercapacitors using a zwitterionic gel electrolyte," Chemical Communications, vol. 55, no. 50, pp. 7167-7170, 2019.
[43] C. Yang et al., "Flexible aqueous Li‐ion battery with high energy and power densities," Advanced materials, vol. 29, no. 44, p. 1701972, 2017.
[44] Y. Tamai, H. Tanaka, and K. Nakanishi, "Molecular dynamics study of polymer− water interaction in hydrogels. 1. Hydrogen-bond structure," Macromolecules, vol. 29, no. 21, pp. 6750-6760, 1996.
[45] D. Capitani, V. Crescenzi, A. De Angelis, and A. Segre, "Water in hydrogels. An NMR study of water/polymer interactions in weakly cross-linked chitosan networks," Macromolecules, vol. 34, no. 12, pp. 4136-4144, 2001.
[46] M. A. Bag and L. M. Valenzuela, "Impact of the hydration states of polymers on their hemocompatibility for medical applications: A review," International Journal of Molecular Sciences, vol. 18, no. 8, p. 1422, 2017.
[47] E. Brini, C. J. Fennell, M. Fernandez-Serra, B. Hribar-Lee, M. Luksic, and K. A. Dill, "How water’s properties are encoded in its molecular structure and energies," Chemical reviews, vol. 117, no. 19, pp. 12385-12414, 2017.
[48] G. A. Mabbott, "An introduction to cyclic voltammetry," Journal of Chemical education, vol. 60, no. 9, p. 697, 1983.
[49] L. NadjO, J. Savéant, and D. Tessier, "Convolution potential sweep voltammetry: III. Effect of sweep rate cyclic voltammetry," Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, vol. 52, no. 3, pp. 403-412, 1974.
[50] Y. Zhou et al., "Phosphorus/sulfur Co-doped porous carbon with enhanced specific capacitance for supercapacitor and improved catalytic activity for oxygen reduction reaction," Journal of Power Sources, vol. 314, pp. 39-48, 2016.
[51] G. Instruments, "Basics of electrochemical impedance spectroscopy," G. Instruments, Complex impedance in Corrosion, pp. 1-30, 2007.
[52] A. Lasia, "Electrochemical impedance spectroscopy and its applications," in Modern aspects of electrochemistry: Springer, 2002, pp. 143-248.
[53] J. Huang, "Diffusion impedance of electroactive materials, electrolytic solutions and porous electrodes: Warburg impedance and beyond," Electrochimica Acta, vol. 281, pp. 170-188, 2018.
[54] S. Tairov and L. C. Stevanatto, "The novel method for estimating VRLA battery state of charge," in 2011 IEEE Electronics, Robotics and Automotive Mechanics Conference, 2011: IEEE, pp. 211-215.
[55] Q. Zhang, X. Tang, T. Wang, F. Yu, W. Guo, and M. Pei, "Thermo-sensitive zwitterionic block copolymers via ATRP," RSC Advances, vol. 4, no. 46, pp. 24240-24247, 2014.
[56] C. Leng et al., "Probing the surface hydration of nonfouling zwitterionic and PEG materials in contact with proteins," ACS applied materials & interfaces, vol. 7, no. 30, pp. 16881-16888, 2015.
[57] Y. Nayatani, "Simple estimation methods for the Helmholtz—Kohlrausch effect," Color Research & Application: Endorsed by Inter‐Society Color Council, The Colour Group (Great Britain), Canadian Society for Color, Color Science Association of Japan, Dutch Society for the Study of Color, The Swedish Colour Centre Foundation, Colour Society of Australia, Centre Français de la Couleur, vol. 22, no. 6, pp. 385-401, 1997.
[58] H. Hanibah, N. N. Hashim, and I. Shamsudin, "Molar conductivity behavior of ionic liquid compare to inorganic salt in electrolyte solution at ambien temperature," in AIP Conference Proceedings, 2017, vol. 1877, no. 1: AIP Publishing LLC, p. 050003.
[59] A. Jarosik, S. R. Krajewski, A. Lewandowski, and P. Radzimski, "Conductivity of ionic liquids in mixtures," Journal of Molecular Liquids, vol. 123, no. 1, pp. 43-50, 2006.
[60] Z. Li, M. Li, Q. Fan, X. Qi, L. Qu, and M. Tian, "Smart-fabric-based supercapacitor with long-term durability and waterproof properties toward wearable applications," ACS Applied Materials & Interfaces, vol. 13, no. 12, pp. 14778-14785, 2021.
[61] A. Eisenberg and M. Hara, "A review of miscibility enhancement via ion‐dipole interactions," Polymer Engineering & Science, vol. 24, no. 17, pp. 1306-1311, 1984.
[62] L. Liu, S. Gou, H. Zhang, L. Zhou, L. Tang, and L. Liu, "A zwitterionic polymer containing a hydrophobic group: enhanced rheological properties," New Journal of Chemistry, vol. 44, no. 23, pp. 9703-9711, 2020.
[63] M. Saadiah, D. Zhang, Y. Nagao, S. Muzakir, and A. Samsudin, "Reducing crystallinity on thin film based CMC/PVA hybrid polymer for application as a host in polymer electrolytes," Journal of Non-Crystalline Solids, vol. 511, pp. 201-211, 2019.
[64] A. J. Roberts, A. F. D. De Namor, and R. C. Slade, "Low temperature water based electrolytes for MnO 2/carbon supercapacitors," Physical Chemistry Chemical Physics, vol. 15, no. 10, pp. 3518-3526, 2013.
[65] S. Prabaharan, R. Vimala, and Z. Zainal, "Nanostructured mesoporous carbon as electrodes for supercapacitors," Journal of Power Sources, vol. 161, no. 1, pp. 730-736, 2006.
[66] A. Tanimura, A. Kovalenko, and F. Hirata, "Molecular theory of an electrochemical double layer in a nanoporous carbon supercapacitor," Chemical physics letters, vol. 378, no. 5-6, pp. 638-646, 2003.
[67] H. Y. Lee and J. B. Goodenough, "Supercapacitor behavior with KCl electrolyte," Journal of Solid State Chemistry, vol. 144, no. 1, pp. 220-223, 1999.
[68] G. Barbero and I. Lelidis, "Analysis of Warburg's impedance and its equivalent electric circuits," Physical Chemistry Chemical Physics, vol. 19, no. 36, pp. 24934-24944, 2017.
[69] L.-H. Tseng, P.-H. Wang, W.-C. Li, C.-H. Lin, and T.-C. Wen, "Enhancing the ionic conductivity and mechanical properties of zwitterionic polymer electrolytes by betaine-functionalized graphene oxide for high-performance and flexible supercapacitors," Journal of Power Sources, vol. 516, p. 230624, 2021.
[70] A. Allagui et al., "Review of fractional-order electrical characterization of supercapacitors," Journal of Power Sources, vol. 400, pp. 457-467, 2018.
[71] L. Liu, H. Zhao, Y. Wang, Y. Fang, J. Xie, and Y. Lei, "Evaluating the role of nanostructured current collectors in energy storage capability of supercapacitor electrodes with thick electroactive materials layers," Advanced Functional Materials, vol. 28, no. 6, p. 1705107, 2018.
[72] E. P. Gilshteyn, D. Amanbayev, A. S. Anisimov, T. Kallio, and A. G. Nasibulin, "All-nanotube stretchable supercapacitor with low equivalent series resistance," Scientific Reports, vol. 7, no. 1, pp. 1-9, 2017.
[73] M. Hahn, O. Barbieri, R. Gallay, and R. Kötz, "A dilatometric study of the voltage limitation of carbonaceous electrodes in aprotic EDLC type electrolytes by charge-induced strain," Carbon, vol. 44, no. 12, pp. 2523-2533, 2006.
[74] Y. Sun, Q. Wu, and G. Shi, "Supercapacitors based on self-assembled graphene organogel," Physical Chemistry Chemical Physics, vol. 13, no. 38, pp. 17249-17254, 2011.
[75] F. Kolpak and J. Blackwell, "Determination of the structure of cellulose II," Macromolecules, vol. 9, no. 2, pp. 273-278, 1976.
[76] L. Cao, Z. Zhao, J. Li, Y. Yi, and Y. Wei, "Gelatin-Reinforced Zwitterionic Organohydrogel with Tough, Self-Adhesive, Long-Term Moisturizing and Antifreezing Properties for Wearable Electronics," Biomacromolecules, vol. 23, no. 3, pp. 1278-1290, 2022.
[77] D. Schymanski, C. Goldbeck, H.-U. Humpf, and P. Fürst, "Analysis of microplastics in water by micro-Raman spectroscopy: release of plastic particles from different packaging into mineral water," Water research, vol. 129, pp. 154-162, 2018.
[78] A. Raudino and D. Mauzerall, "Dielectric properties of the polar head group region of zwitterionic lipid bilayers," Biophysical journal, vol. 50, no. 3, pp. 441-449, 1986.
[79] P. Taberna, P. Simon, and J.-F. Fauvarque, "Electrochemical characteristics and impedance spectroscopy studies of carbon-carbon supercapacitors," Journal of the Electrochemical Society, vol. 150, no. 3, p. A292, 2003.
[80] S. Das and A. Ghosh, "Ionic conductivity and dielectric permittivity of PEO-LiClO4 solid polymer electrolyte plasticized with propylene carbonate," AIP Advances, vol. 5, no. 2, p. 027125, 2015.
[81] Y.-H. Su et al., "Postinjection gelation of an electrolyte with high storage permittivity and low loss permittivity for electrochemical capacitors," Journal of Power Sources, vol. 481, p. 228869, 2021.
[82] X. C. Chen et al., "Study of segmental dynamics and ion transport in polymer–ceramic composite electrolytes by quasi-elastic neutron scattering," Molecular Systems Design & Engineering, vol. 4, no. 2, pp. 379-385, 2019.
[83] C. H. Chan and H.-W. Kammer, "Low frequency dielectric relaxation and conductance of solid polymer electrolytes with PEO and blends of PEO and PMMA," Polymers, vol. 12, no. 5, p. 1009, 2020.
[84] Y. Kubota, A. Yoshimori, N. Matubayasi, M. Suzuki, and R. Akiyama, "Molecular dynamics study of fast dielectric relaxation of water around a molecular-sized ion," The Journal of Chemical Physics, vol. 137, no. 22, p. 224502, 2012.
[85] S. Liu, L. Wei, and H. Wang, "Review on reliability of supercapacitors in energy storage applications," Applied Energy, vol. 278, p. 115436, 2020.