전기이중층 커패시터용 내재적 미세 다공성 고분자 기반 3차원 다공성 탄소 전극

한재희; 서동학; 김태호; Jae Hee Han; Dong Hack Suh; Tae-Ho Kim

Applied Chemistry for Engineering, Vol.29, No.6, 759-764, December, 2018

DOI10.14478/ace.2018.1096 Export Citation

전기이중층 커패시터용 내재적 미세 다공성 고분자 기반 3차원 다공성 탄소 전극

Intrinsic Porous Polymer-derived 3D Porous Carbon Electrodes for Electrical Double Layer Capacitor Applications

한재희^{1, 2}, 서동학², 김태호^{1, †}

¹한국화학연구원 분리막연구센터
²한양대학교 화학공학과

Jae Hee Han^{1, 2}, Dong Hack Suh², and Tae-Ho Kim^{1, †}

¹Membrane Research Center, Korea Research Institute of Chemical Technology, 141 Gajeong-ro, Yuseong-gu, Daejeon 34114, Republic of Korea
²Department of Chemical Engineering, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 04763, Republic of Korea

E-mail:

초록

내재적 미세 다공성 고분자(polymer of intrinsic microporosity, PIM-1)를 사용하여 빈용매 유도 상전이법으로부터 3차원 다공성 구조를 가지는 필름을 형성하고, 이를 탄화하여 3차원 다공성 탄소(cNPIM)를 제조하였다. 전자주사현미경 분석을 통해 상전이 공정을 적용한 탄소소재가 마이크로, 메조, 매크로 기공을 모두 가지면서 서로 연결된 계층적 3차원 다공구조를 나타냄을 확인하였다. 특히 상전이 공정의 용매의 함량비를 조절함으로써 기공구조를 제어할 수 있었으며, 결과적으로 평균 0.75 nm의 기공 크기와 2101.1 m2/g의 높은 비표면적을 가지면서 약 30%의 메조, 마크로 기공구조를 겸비한 최적화된 다공성 탄소 전극을 제조할 수 있었다. 제조된 3차원 다공성 탄소소재를 전기이중층 캐퍼시터용 전극 물질로 사용하여 수계전해질에서 측정한 결과, 높은 비표면적을 가지는 탄소 소재 내의 비약적 이온 이동속도 향상 효과로 높은 비축전용량(304.8 F/g@10 mV/s)과 우수한 충.방전 속도(77% 용량유지율@100 mV/s)를 나타내었다.

3D porous carbon electrodes (cNPIM), prepared by solution casting of a polymer of intrinsic microporosity (PIM-1) followed by nonsolvent-induced phase separation (NIPS) and carbonization are presented. In order to effectively control the pore size of 3D porous carbon structures, cNPIM was prepared by varying the THF ratio of mixed solvents. The SEM analysis revealed that cNPIMs have a unique 3D macroporous structure having a gradient pore structure, which is expected to grant a smooth and easy ion transfer capability as an electrode material. In addition, the cNPIMs presented a very large specific surface area (2,101.1 m2/g) with a narrow micropore size distribution (0.75 nm). Consequently, the cNPIM exhibits a high specific capacitance (304.8 F/g) and superior rate capability of 77% in an aqueous electrolyte. We believe that our approach can provide a variety of new 3D porous carbon materials for the application to an electrochemical energy storage.

Keywords:porous polymer;porous carbons;nonsolvent-induced phase separation;carbonization;supercapacitor

[References]

Chen H, Cong TN, Yang W, Tan C, Li Y, Ding Y, Prog. Nat. Sci., 19, 291 (2009)
Aktas A, Erhan K, Ozdemir S, Ozdemir E, Electric Power Syst. Res., 144, 185 (2017)
Gonzalez A, Goikolea E, Barrena JA, Mysyk R, Renew. Sust. Energ. Rev., 58, 1189 (2016)
Wang G, Zhang L, Zhang J, Chem. Soc. Rev., 41, 797 (2012)
Pandolfo AG, Hollenkamp AF, J. Power Sources, 157(1), 11 (2006)
Liu RL, Wan L, Liu SQ, Pan LX, Wu DQ, Zhao DY, Adv. Funct. Mater., 25(4), 526 (2015)
Sheng K, Sun Y, Li C, Yuan W, Shi F, Sci. Rep., 2, 247 (2012)
Chmiola J, Yuschin G, Gotosi Y, Portet C, Simon P, Taberna PL, Science, 313, 1760 (2006)
Yoo BM, Park HB, Membr. J., 27, 216 (2017)
Shin JE, Park HB, Membr. J., 28, 221 (2018)
Budd PM, Elabas ES, Ghanem BS, Makhseed S, McKeown NB, Msayib KJ, Tattershall CE, Wang D, Adv. Mater., 16(5), 456 (2004)
Bonso JS, Kalaw GD, Ferraris JP, J. Mater. Chem. A, 2, 418 (2014)
Jeon JW, Han JH, Kim SK, Kim DG, Kim YS, Suh DS, Hong YT, Kim TH, Kim BG, J. Mater. Chem. A, 6, 8909 (2018)
Venault A, Chang Y, Wang DM, Bouyer D, Polym. Rev., 53, 568 (2013)
Park SJ, Jin SY, Kawasaki J, J. Korean Ind. Eng. Chem., 14(8), 1111 (2003)
Choi BG, Huh YS, Hong WH, Korean Chem. Eng. Res., 50(4), 754 (2012)
Chen PC, Shen G, Shi Y, Chen H, Zhou C, ACS Nano, 4, 4403 (2010)
Li Z, Mi Y, Liu X, Liu S, Yang S, Wang J, J. Mater. Chem., 21, 14706 (2011)
Xu J, Gao Q, Zhang Y, Tan Y, Tian W, Zhu L, Jiang L, Sci. Rep., 4, 5545 (2014)
Li Z, Xu Z, Wang H, Ding J, Zahiri B, Holt CMB, Tan X, Mitlin D, Energy Environ. Sci., 7, 1708 (2014)
Li F, Morris M, Chan KY, J. Mater. Chem., 21, 8880 (2011)
Wei L, Yushin G, Carbon, 49, 4830 (2011)
Cho KT, Lee SB, Lee HW, J. Phys. Chem. C, 118, 9357 (2014)
Portet C, Taberna PL, Simon P, Laberty-Robert C, Electrochim. Acta, 49(6), 905 (2004)

[1] Chen H, Cong TN, Yang W, Tan C, Li Y, Ding Y, Prog. Nat. Sci., 19, 291 (2009)

[2] Aktas A, Erhan K, Ozdemir S, Ozdemir E, Electric Power Syst. Res., 144, 185 (2017)

[3] Gonzalez A, Goikolea E, Barrena JA, Mysyk R, Renew. Sust. Energ. Rev., 58, 1189 (2016)

[4] Wang G, Zhang L, Zhang J, Chem. Soc. Rev., 41, 797 (2012)

[5] Pandolfo AG, Hollenkamp AF, J. Power Sources, 157(1), 11 (2006)

[6] Liu RL, Wan L, Liu SQ, Pan LX, Wu DQ, Zhao DY, Adv. Funct. Mater., 25(4), 526 (2015)

[7] Sheng K, Sun Y, Li C, Yuan W, Shi F, Sci. Rep., 2, 247 (2012)

[8] Chmiola J, Yuschin G, Gotosi Y, Portet C, Simon P, Taberna PL, Science, 313, 1760 (2006)

[9] Yoo BM, Park HB, Membr. J., 27, 216 (2017)

[10] Shin JE, Park HB, Membr. J., 28, 221 (2018)

[11] Budd PM, Elabas ES, Ghanem BS, Makhseed S, McKeown NB, Msayib KJ, Tattershall CE, Wang D, Adv. Mater., 16(5), 456 (2004)

[12] Bonso JS, Kalaw GD, Ferraris JP, J. Mater. Chem. A, 2, 418 (2014)

[13] Jeon JW, Han JH, Kim SK, Kim DG, Kim YS, Suh DS, Hong YT, Kim TH, Kim BG, J. Mater. Chem. A, 6, 8909 (2018)

[14] Venault A, Chang Y, Wang DM, Bouyer D, Polym. Rev., 53, 568 (2013)

[15] Park SJ, Jin SY, Kawasaki J, J. Korean Ind. Eng. Chem., 14(8), 1111 (2003)

[16] Choi BG, Huh YS, Hong WH, Korean Chem. Eng. Res., 50(4), 754 (2012)

[17] Chen PC, Shen G, Shi Y, Chen H, Zhou C, ACS Nano, 4, 4403 (2010)

[18] Li Z, Mi Y, Liu X, Liu S, Yang S, Wang J, J. Mater. Chem., 21, 14706 (2011)

[19] Xu J, Gao Q, Zhang Y, Tan Y, Tian W, Zhu L, Jiang L, Sci. Rep., 4, 5545 (2014)

[20] Li Z, Xu Z, Wang H, Ding J, Zahiri B, Holt CMB, Tan X, Mitlin D, Energy Environ. Sci., 7, 1708 (2014)

[21] Li F, Morris M, Chan KY, J. Mater. Chem., 21, 8880 (2011)

[22] Wei L, Yushin G, Carbon, 49, 4830 (2011)

[23] Cho KT, Lee SB, Lee HW, J. Phys. Chem. C, 118, 9357 (2014)

[24] Portet C, Taberna PL, Simon P, Laberty-Robert C, Electrochim. Acta, 49(6), 905 (2004)