Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
권호 표지
DOI QR코드

DOI QR Code

Electrochemical Characteristics of Surface Modified CTP Anode by H3PO4 Treatment

인산 처리된 표면 개질 음극 석탄계 피치의 전기화학적 특성

  • Lee, Ho Yong (Department of Chemical Engineering, Chungbuk National University) ;
  • Lee, Jong Dae (Department of Chemical Engineering, Chungbuk National University)
  • Received : 2016.06.09
  • Accepted : 2016.07.04
  • Published : 2016.08.10
Download PDF
⟨ Previous Next ⟩

Abstract

To enhance electrochemical performances of anode materials, the surface of coal tar pitch (CTP) was modified by incorporating heteroatoms through chemical treatment with phosphoric acid ($H_3PO_4$). The prepared anode materials with modified CTP was analyzed by XRD, FE-SEM and XPS. The electrochemical performances of modified CTP were investigated by constant current charge/discharge test, rate performance, cyclic voltammetry and impedance tests using the electrolyte of $LiPF_6$ dissolved in the mixed organic solvents (ethylene carbonate : dimethyl carbonate = 1 : 1 vol% + vinylene carbonate 3 wt%). The coin cell using modified CTP ($H_3PO_4/CTP$ = 3 : 100 in weight) has better initial capacity and initial efficiency (489 mAh/g, 82%) than those of other composition coin cells. Also, it was found that the capacity retention was 86% after 30 cycles and the rate capability was 87% at 2 C/0.1 C.

음극소재의 전기화학적 성능을 향상시키기 위해, 인산의 화학처리를 통한 헤테로 원자를 도입함으로써 석탄계 피치의 표면 개질을 수행하였다. 제조된 표면 개질 피치 음극소재의 물리적 특성은 XRD, FE-SEM, XPS 분석을 통하여 수행되었으며, 전기화학적 특성은 $LiPF_6$ (EC : DMC = 1 : 1 vol% + VC 3 wt%) 전해액을 사용하여 충 방전 테스트, 율속 테스트, 순환 전압 전류 테스트와 임피던스 테스트를 통해 조사하였다. 인산 3 wt% 첨가된 표면 개질 피치 전지의 초기 충전 용량 및 초기효율은 489 mAh/g, 82%로 다른 조성의 음극소재보다 우수하였다. 또한 3 wt% 인산으로 표면개질된 CTP 음극소재의 용량 보존율은 30사이클 후에 86%를 나타냈으며, 2 C/0.1 C에서 87%의 우수한 율속 특성을 보여줌을 알 수 있었다.

Keywords

References

  1. R. Yazami, Surface chemistry and lithium storage capability of the graphite-lithium electrode, Electrochim. Acta, 45, 87-97 (1999). https://doi.org/10.1016/S0013-4686(99)00195-4
  2. W. J. Zhang, A review of the electrochemical performance of alloy anodes for lithium-ion batteries, J. Power Sources, 196, 13-24 (2011). https://doi.org/10.1016/j.jpowsour.2010.07.020
  3. J. Y. Park and J. D. Lee, 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
  4. L. Wang, Z. Liu, Q. Guo, G. Wang, J. Yang, P. Li, X. Wang, and L. Liu, Electrochemical properties of carbon nanocoils and hollow graphite fibers as anodes for rechargeable lithium ion batteries, Electrochim. Acta, 199, 204-209 (2016). https://doi.org/10.1016/j.electacta.2016.03.160
  5. A. Bai, L. Wang, J. Li, X. He, J. Wang, and J. Wang, Composite of graphite/phosphorus as anode for lithium-ion batteries, J. Power Sources, 289, 100-104 (2015). https://doi.org/10.1016/j.jpowsour.2015.04.168
  6. J. G. Kim, F. Liu, C. W. Lee, Y. S. Lee, and J. S. Im, Boron-doped carbon prepared from PFO as a lithium-ion battery anode, Solid State Sci., 34, 38-42 (2014). https://doi.org/10.1016/j.solidstatesciences.2014.05.005
  7. I. Mochida, Y. Korai, C. H. Ku, F. Watanabe, and Y. Sakai, Chemistry of synthesis, structure, preparation and application of aromatic-derived mesophase pitch, Carbon, 38, 305-328 (2000). https://doi.org/10.1016/S0008-6223(99)00176-1
  8. H. J. Ko, Y. S. Lim, and M. S. Kim, Fabrication and characterization of pitch/cokes/natural graphite composites as anode materials for high-power lithium secondary batteries, Korean J. Mater. Res., 25, 279-287 (2015). https://doi.org/10.3740/MRSK.2015.25.6.279
  9. M. S. Park, J. Lee, J. W. Lee, K. J. Kim, Y. N. Jo, S. G. Woo, and Y. J. Kim, Tuning the surface chemistry of natural graphite anode by $H_3PO_4$ and $H_3BO_3$ treatments for improving electrochemical and thermal properties, Carbon, 62, 278-287 (2013). https://doi.org/10.1016/j.carbon.2013.05.065
  10. L. K. Putri, W. J. Ong, W. S. Chang, and S. P. Chai, Heteroatom doped graphene in photocatalysis: A review, Appl. Surf. Sci., 358, 2-14 (2015). https://doi.org/10.1016/j.apsusc.2015.08.177
  11. Y. S. Yun and H. J. Jin, Electrochemical performance of heteroatom-enriched amorphous carbon with hierarchical porous structure as anode for lithium-ion batteries, Mater. Lett., 108, 311-315 (2013). https://doi.org/10.1016/j.matlet.2013.07.026
  12. M. S. Park, J. H. Kim, Y. N. Jo, S. H. Oh, H. Kim, and Y. J. Kim, Incorporation of phosphorus into the surface of natural graphite anode for lithium ion batteries, J. Mater. Chem., 21, 17960-17966 (2011). https://doi.org/10.1039/c1jm13158c
  13. Y. N. Jo, E. Y. Lee, M. S. Park, K. J. Hong, S. I. Lee, H. Y. Jeong, Z. Lee, S. M. Oh, and Y. J. Kim, A study on the $H_3PO_4$-treated soft carbon as anode materials for lithium ion batteries, J. Korean Electrochem. Soc., 15(4), 207-215 (2012). https://doi.org/10.5229/JKES.2012.15.4.207
  14. H. Song, N. Li, H. Cui, and C. Wang, Enhanced storage capability and kinetic processes by pores-and hetero-atoms-riched carbon nanobubbles for lithium-ion and sodium-ion batteries anodes, Nano Energy, 4, 81-87 (2014). https://doi.org/10.1016/j.nanoen.2013.12.017
  15. A. M. Puziya, O. I. Poddubnaya, R. P. Socha, J. Gurgul, and M. Wisniewski, XPS and NMR studies of phosphoric acid activated carbons, Carbon, 46, 2113-2123 (2008). https://doi.org/10.1016/j.carbon.2008.09.010
  16. X. Liu, D. Teng, T. Li, Y. Yu, X. Shao, and X. Yang, Phosphorus-doped tin oxides/carbon nanofibers webs as lithium-ion battery anodes with enhanced reversible capacity, J. Power Sources, 272, 614-621 (2014). https://doi.org/10.1016/j.jpowsour.2014.08.084
  17. H. Zhao, Y. Gao, J. Wang, C. Chen, D. Chen, C. Wang, and F. Ciucci, Egg yolk-derived phosphorus and nitrogen dual doped nano carbon capsules for high-performance lithium ion batteries, Mater. Lett., 167, 93-97 (2016). https://doi.org/10.1016/j.matlet.2015.12.147
  18. Y. P. Wu, E. Rahm, and R. Holze, Effects of heteroatoms on electrochemical performance of electrode materials for lithium ion batteries", Electrochim. Acta, 47, 3491-3507 (2002). https://doi.org/10.1016/S0013-4686(02)00317-1
  19. J. Ou, Y. Zhang, L. Chen, H. Yua, and D. Xiao, Heteroatom doped porous carbon derived from hair as an anode with high performance for lithium ion batteries, RSC Adv., 4, 63784-63791 (2014). https://doi.org/10.1039/C4RA12121J