DOI QR코드

DOI QR Code

Electrochemical Characteristics of PFO pitch Anode prepared by Chemical Activation for Lithium Ion Battery

리튬이온전지용 화학적 활성화로 제조된 석유계 피치 음극소재의 전기화학적 특성

  • Hwang, Jin Ung (Department of Chemical Engineering, Chungbuk National University) ;
  • Lee, Jong Dae (Department of Chemical Engineering, Chungbuk National University)
  • Received : 2017.01.25
  • Accepted : 2017.02.13
  • Published : 2017.06.01

Abstract

In this study, the electrochemical performance of surface modified carbon using the PFO (pyrolyzed fuel oil) was investigated by chemical activation with KOH and $K_2CO_3$. PFO was heat treated at $390{\sim}400^{\circ}C$ for 1~3h to prepared the pitch. Three carbon precursors (pitch) prepared by the thermal reaction were 3903 (at $390^{\circ}C$ for 3h), 4001(at $400^{\circ}C$ for 1h) and 4002 (at $400^{\circ}C$ for 2h). Also, the effect of chemical activation catalysts and mixing time on the development of porosity during carbonization was investigated. The prepared carbon was analyzed by BET and FE-SEM. It was shown that chemical activation with KOH could be successfully used to develop carbon with specific surface area ($3.12m^2/g$) and mean pore size (22 nm). The electrochemical characteristics of modified carbon as the anode were investigated by constant current charge/discharge, cyclic voltammetry and electrochemical impedance tests. The coin cell using pitch (4002) modified by KOH has better initial capacity (318 mAh/g) than that of other pitch coin cells. Also, this prepared carbon anode appeared a high initial efficiency of 80% and the retention rate capability of 2C/0.1 C was 92%. It is found that modified carbon anode showed improved cycling and rate capacity performance.

본 연구에서는 PFO (pyrolyzed fuel oil)를 이용해 탄소 전구체(피치)를 얻은 후 KOH와 $K_2CO_3$를 이용한 화학적 활성화를 통해 표면 개질한 카본의 전기화학적 특성을 분석하였다. 탄소 전구체는 3903, 4001, 4002의 세 종류를 사용하였으며, 각 각 PFO를 $390^{\circ}C$ 3 시간, $400^{\circ}C$ 1시간, $400^{\circ}C$ 2 시간 열처리 하여 제조하였다. 또한 화학적 활성화 실험은 활성 촉매의 종류, 교반시간 등을 변화시키면서 비표면적 및 기공크기 등의 물성이 전기화학적 특성에 미치는 효과를 조사 하였다. 제조된 표면개질 PFO 피치의 물리적 특성은 BET, FE-SEM 등을 통해 분석되었으며, 음극 소재로서의 전기 화학적 성능은 충 방전, 순환전압전류, 임피던스, 속도 테스트를 통해 조사되었다. 화학적 활성화법을 이용해 제조한 카본의 평균 기공크기는 22 nm, 비표면적은 $3.12m^2/g$의 결과를 얻었다. 세 가지 개질된 석유계 피치를 음극소재로 사용하여 조사된 전기화학적 특성은 4001 피치가 가장 우수한 것으로 나타났으며, 이 때 표면개질 조건은 KOH를 사용하여 2시간 교반 후 화학적 활성화법에 의하여 열처리 하였다. KOH를 이용한 표면개질 PFO 피치를 사용해 제조한 전지의 초기 용량은 318 mAh/g, 초기효율은 80%로 우수한 결과를 보였으며, 2C/0.1C 속도 테스트 특성은 92%로 높은 특성을 보였다.

Keywords

References

  1. Jung, M. J., Park, J. Y. and Lee, J. D., "Electrochemical Characteristics of Silicon/Carbon Composites with CNT for Anode Material," Korean Chem. Eng. Res., 54(1), 16-21(2016). https://doi.org/10.9713/kcer.2016.54.1.16
  2. Lv, Y., Zhang, F., Dou, Y., Zhai, Y., Wang, J., Liu, H., Xia, Y., Tu, B. and Zhao, D., "A Comprehensive Study on KOH Activation of Ordered Mesoporous Carbons and Their Supercapacitor Application," J. Mater. Chem., 22(1), 93-99(2012). https://doi.org/10.1039/C1JM12742J
  3. Jeong, J. H., Jung, D. W., Kong, B. S., Shin, C. M. and Oh, E. S., "The Effect of Graphene Nanosheets as an Additive for Anode Materials in Lithium Ion Batteries," Korean J. Chem. Eng., 28(11), 2202-2205(2011). https://doi.org/10.1007/s11814-011-0102-9
  4. Elmouwahidi, A., Zapata-Benabithe, Z., Carrasco-Marín, F. and Moreno-Castilla, C., "Activated Carbons from KOH-activation of Argan (Argania spinosa) Seed Shells as Supercapacitor Electrodes," Bioresour. Technol., 111, 185-190(2012). https://doi.org/10.1016/j.biortech.2012.02.010
  5. He, X., Zhao, N., Qiu, J., Xiao, N., Yu, M., Yu, C., Zhang, X. and Zheng, M., "Synthesis of Hierarchical Porous Carbons for Supercapacitors from Coal Tar Pitch with Nano-$Fe_2O_3$ as Template and Activation Agent Coupled with KOH Activation," J. Mater. Chem. A, 1(33), 9440-9448(2013). https://doi.org/10.1039/c3ta10501f
  6. Chen, Y., Liu, C., Sun, X., Ye, H., Cheung C. and Zhou, L., "Recycled Diesel Carbon Nanoparticles for Nanostructured Battery Anodes," J. Power Sources, 275, 26-31(2015). https://doi.org/10.1016/j.jpowsour.2014.10.200
  7. Qie, L., Chen, W., Xu, H., Xiong, X., Jiang, Y., Zou, F., Hu, X., Xin, Y., Zhang, Z. and Huang, Y., "Synthesis of Functionalized 3D Hierarchical Porous Carbon for High-performance Supercapacitors," Energy & Environmental Science, 6(8), 2497-2504(2013). https://doi.org/10.1039/c3ee41638k
  8. Zhu, Y., Xiang, X., Liu, E., Wu, Y., Xie, H., Wu, Z. and Tian, Y., "A Microporous Carbon Derived from Phenol-melamine-formaldehyde Resin by $K_2CO_3$ Activation for Lithium Ion Batteries," Ionics, 19(3), 409-414(2013). https://doi.org/10.1007/s11581-012-0776-y
  9. Hayashi, J. I., Uchibayashi, M., Horikawa, T., Muroyama, K., amd Gomes, V. G., "Synthesizing Activated Carbons from Resins by Chemical Activation with $K_2CO_3$," Carbon, 40(15), 2747-2752 (2002). https://doi.org/10.1016/S0008-6223(02)00151-3
  10. Moon, S. Y., Lee, B. H. and Lim, Y. S., "Characterization and Fabrication of Chemically Activated Carbon Fibers with Various Drying Temperatures Using OXI-PAN Fibers," Carbon letters, 8(1), 30-36(2007). https://doi.org/10.5714/CL.2007.8.1.030
  11. Hayashi, J. I., Kazehaya, A., Muroyama, K. and Watkinson, A. P., "Preparation of Activated Carbon from Lignin by Chemical Activation," Carbon, 38(13), 1873-1878(2000). https://doi.org/10.1016/S0008-6223(00)00027-0
  12. Cheng, Q., Yuge, R., Nakahara, K., Tamura, N. and Miyamoto, S., "KOH Etched Graphite for Fast Chargeable Lithium-ion Batteries," J. Power Sources, 284, 258-263(2015). https://doi.org/10.1016/j.jpowsour.2015.03.036
  13. Kim, J. G., Kim, J. H., Song, B. J., Lee, C. W. and Im, J. S., "Synthesis and Its Characterization of Pitch from Pyrolyzed Fuel Oil (PFO)," J. Industrial & Engineering Chemistry, 36, 293-297(2016). https://doi.org/10.1016/j.jiec.2016.02.014
  14. Lian, P., Zhu, X., Liang, S., Li, Z., Yang, W. and Wang, H., "Large Reversible Capacity of High Quality Graphene Sheets as An Anode Material for Lithium-ion Batteries," Electrochim. Acta, 55(12), 3909-3914(2010). https://doi.org/10.1016/j.electacta.2010.02.025
  15. Kim, K. H., Park, M. S., Jung, M. J. and Lee, Y. S., "Influence of Textural Structure by Heat-treatment on Electrochemical Properties of Pitch-based Activated Carbon Fiber," Appl Chem Eng., 26(5), 598-603(2015). https://doi.org/10.14478/ace.2015.1085
  16. Campbell, B., Ionescu, R., Favors, Z., Ozkan, C. S. and Ozkan, M., "Bio-Derived, Binderless, Hierarchically Porous Carbon Anodes for Li-ion Batteries," Sci. Rep., 5, 14575(2015). https://doi.org/10.1038/srep14575

Cited by

  1. SiOx 함량에 따른 CB/SiOx/C 음극재의 전기화학적 특성 vol.32, pp.1, 2017, https://doi.org/10.14478/ace.2020.1086