ISSN: 0304-128X ISSN: 2233-9558
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Received January 17, 2024
Revised June 25, 2024
Accepted June 26, 2024
articles This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/bync/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
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친환경 구연산처리를 통한 폐흑연 재활용 연구

A Study of Recycling Lithium-ion Battery Graphite by Eco-friendly Citric Acid Treatment Method

한국자동차연구원
Korea Automotive Technology Institute (KATECH)
E-mail: jehyun@katech.re.kr
Korean Chemical Engineering Research, August 2024, 62(3), 246-252(7), 10.9713/kcer.2024.62.3.246 Epub 1 August 2024
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Abstract

본 연구에서는 구연산 처리를 통하여 폐흑연의 Li, F 등의 불순물을 제거하였으며, 이에 따른 재생 흑연의 구조적

특성, 용량 및 내구성 변화를 관찰하였다. 질소 분위기에서 전처리를 진행한 재생 흑연은 구연산에서 산처리를 진행하

였고 SEM (Scanning Electron Microscope), FT-IR (Fourier Transform Infrared spectroscopy), XRD (X-ray Diffraction),

XPS (X-ray Photoelectron Spectroscopy)를 통해 구조와 특성 분석을 진행하였다. 산처리를 진행하지 않은 폐흑연은 70

사이클 이전에서 용량이 급격하게 감소하였으나 구연산 처리를 진행한 흑연은 100 사이클에서 302.9mAh g-1의 용량과

93.1%의 용량 유지율을 나타내었다. 또한 Rate performance의 전류 밀도 변화에도 구연산 처리한 샘플은 용량의 변화

없이 1.0C에서 340.2 mAh g-1의 성능을 나타내었다. 결과적으로 구연산 처리는 효과적으로 불순물을 제거하여 높은 용

량 유지율을 나타내었을 뿐만 아니라 높은 전류 밀도에서도 안정적인 모습을 나타내는 것으로 확인하였다.

In this study, impurities such as Li and F were removed from waste graphite through citric acid treatment,

and changes in structural properties, capacity, and cycle stability of regenerated graphite were observed accordingly.

Regenerated graphite pretreated in a nitrogen atmosphere was treated with citric acid, and its structure and characteristics were

analyzed through SEM (Scanning Electron Microscope), FT-IR (Fourier Transform Infrared spectroscopy), XRD (X-ray

Diffraction), and XPS (X-ray Photoelectron Spectroscopy). Waste graphite that was not treated with acid had a rapid

decrease in capacity before 70 cycles, but graphite that had been treated with citric acid showed a capacity of 302.9 mAh g-1

and a capacity retention rate of 93.1% at 100 cycles. In addition, despite changes in current density in rate performance,

samples treated with citric acid showed 340.2 mAh g-1 performance at 1.0C without change in capacity. As a result, it

was confirmed that citric acid treatment not only effectively removed impurities and showed a high capacity retention

rate, but also showed stability even at high current densities.

References

1. Arumugam Manthiram, “Materials Challenges and Opportunities
of Lithium Ion Batteries,” J. Phys Chem Lett., 2(3), 176-184(2011).
2. Arumugam Manthiram, “An Outlook on Lithium ion Battery
Technology,” ACS Cent. SCI. 3, 1063-1069(2017).
3. Michael Green, Aspects of Battery Legislation in Recycling and
Re-use,” Johnson Matthey Technol. Rev., 61(2), 87-92(2017).
4. Dornbusch, D. A., Hilton, R., Lohman, S. D. and Suppes, G. J.,
“Experimental Validation of the Elimination of Dendrite Shortcircuit
Failure in Secondary Lithium-metal Convection Cell Batteries,”
J. Electrochem. Soc., 162, 262-268(2015).
5. Jana, A., Ely, D. R. and Garcia, G. E., “Dendrite-separator Interactions
in Lithium-based Batteries,” J. Power Sources., 275, 912-
912(2015).
6. Nazerian, M., B-Hoerh, N. and Mousavi, S. M., “Enhanced
Bioleaching of Valuable Metals From Spent Lithium-ion Batteries
Using Ultrasonic Treatment,” Korean J. Chem. Eng., 40(3),
584-593(2023).
7. Lv, W. G., Wang, Z. H., Cao, H. B., Zheng, X. H., Jin, W., Zhang, Y.
and Sun, Z., “A Sustainable Process for Metal Recycling from
Spent Lithium-ion Batteries Using Ammonium Chloride,” Waste
Manag., 79, 545-553(2018).
8. Ma, X., Chen, M., Chen, B., Meng, Z. and Wang, Y., “High-performance
Graphite Recovered From Scrapped Lithium-ion Batteries,”
ACS Sustain. Chem. Eng., 7, 19732-19738(2019).
9. Mayyas, A., Steward, D. and Mann, M., “The Case for Recycling :
Overview and Challenges in the Material Supply Chain for Automotive
Li-ion Batteries,” Sustain Mater. Technol., 19, e00087(2019).
10. Moradi, B. and Botte, G., “Recycling of Graphite Anodes for the
Next Generation of Lithium ion Batteries,” J. Appl. Electrochem., 46,
123-148(2016).
11. Rothermel, S., Evertz, M., Kasnatscheew, J., Qi, X., Gretzke,
M., Winter, M. and Nowak, S., “Graphite Recycling From Spent
Lithium ion Batteries,” ChemSusChem., 9, 3473-3484(2016).
12. Niu, B., Xiao, J. and Xu, Z., “Advances and Challenges in Anode
Graphite Recycling from Spent Lithium-ion Batteries,” Journal
of Hazard Mater., 439(5), 129678(2022).
13. Arshad, F., Li, L., Amin, K., Fan, E., Manurkar, N., Ahmad, A.,
Yang, J., Wu, F. and Chen, R., “A Comprehensive Review of the
Advancement in Recycling the Anode and Electrolyte From Spent
Lithium ion Batteries,” ACS Sustain. Chem. Eng., 8, 13527-13554
(2020).
14. Gao, Y., Zhang, J., Jin, H., Liang, G., Ma, L., Chen, Y. and Wang,
C., “Regenerating Spent Graphite from Scrapped Lithium-ion
Battery by High-temperature Treatment,” Carbon., 189(15), 493-
502(2022).
15. Wang, H., Huang, Y., Huang, C., Wang, X., Wang, K., Chen, H.,
Liu, S., Wu, Y., Xu, K. and Li, W., “Reclaiming Graphite from
Spent Lithium ion Batteries Ecologically and Economically,”
Electrochim. Acta. 313, 423-431(2019).
16. Ma, X., Chen, M., Chen, B., Meng, Z. and Wang, Y., “High Performance
Graphite Recovered from spent Lithium-Ion Batteries,”
ACS Sustainable Chem. Eng., 7(24), 19732-19738(2019).
17. Xu, Y. J., Song, X. H., Chang, Q., Hou, X. L., Sun, Y., Feng, X.
Y., Wang, X. R., Zhan, M., Xiang, H. F. and Yu, Y., “The Regeneration
of Graphite Anode from Spent Lithium-ion Batteries by
Washing with a Nitric Acid/ethanol Solution,” New Carbon Materials.
37(5), 1011-1020(2022).
18. Yang, Y., Song, S., Lei, S., Sun, W., Hou, H. S., Jiang, F., Ji, X.
B., Zhao, W. and Hu, Y. H., “A Process for Combination of
Recycling Lithium and Regenerating Graphite from Spent Lithium-
ion Battery,” Waste Manag., 85(15), 529-537(2019).
19. Ruan, D., Wu, L., Wang, F., Du, K., Zhang, Z., Zou, K., Wu, X.
and Hu, G., “A Low-cost Silicon-graphite Anode Made from Recycled
Graphite of Spent Lithium-ion Batteries,” J. Electroanal.
Chem., 884(1), 115073(2021).
20. Liu, K., Yang, S., Luo, L., Pan, Q., Zhang, P., Huang, Y., Zheng,
F., Wang, H. and Li, Q., “From Spent Graphite to Recycle Graphite
Anode for High-performance Lithium ion Batteries and Sodium
ion Batteries,” Electrochim Acta. 356(1), 136856(2020).
21. Yu, J., Lin, M., Tan, Q. and Li, J., “High-value Utilization of Graphite Electrodes in Spent Lithium-ion Batteries : From 3D Waste
Graphite to 2D Graphene Oxide,” Journal of Hazardous Materials.
401(5), 123715(2021).
22. Li, H., Peng, J., Liu, P., Li, W., Wu, Z., Chang, B. and Wang, X.,
“Re-utilization of Waste Graphite Anode Materials From Spent
Lithium-ion Batteries,” J. Electroanal. Chem., 932(1), 117247(2023).
23. Gao, Y., Zhang, J., Jin, H., Liang, G., Ma, L., Chen, Y. and Wang,
C., Regenerating Spent Graphite From Scrapped Lithium-ion
Battery by High-temperature Treatment,” Carbon., 189(15), 493-
502(2022).
24. Yang, J., Fan, E., Lin, J., Arshad, F., Zhang, X., Wang, H., Wu,
F., Chen, R. and Li, L., “Recovery and Reuse of Anode Graphite
from Spent Lithium-Ion Batteries via Citric Acid Leaching,”
ACS Appl. Energy Mater., 4(6), 6261-6268(2021).
25. Xiao, H., Ji, G., Ye, L., Li, Y., Zhang, J., Ming, L., Zhang, B. and
Ou, X., Efficient Regeneration and Reutilization of Degraded
Graphite as Advanced Anode for Lithium-ion Batteries,” J.
Alloys Compd., 888(25), 161593(2021).
26. Shin, Y.-R., Jung, S.-M., Jeon, I.-Y. and Baek, J.-B., “The Oxidation
Mechanism of Highly Ordered Pyrolytic Graphite in a
Nitric Acid/sulfuric Acid Mixture,” Carbon., 52, 493-498(2013).
27. Mazarji, M., Mahmoodi, N. M., Bidhendi, G. N., Minkina, T.,
Sushkova, S., Mandzhieva, S., Bauer, T. and Soldatov, A., “Visible-
Light-Driven Reduced Graphite Oxide as a Metal-Free Catalyst
for Degradation of Colored Wastewater,” Nanomaterials, 12(3),
374(2022).
28. Quinlan, R. A., Lu, Y. C., Kwabi, D., Horn, Y. S. and Mansour,
A. N., “XPS Investigation of the Electrolyte Induced Stabilization
of LiCoO2 and “AlPO4”-Coated LiCoO2 Composite Electrodes,”
J. Electrochem Society, 163, 2(2016).
29. Limcharoen, A., Pakpum, C. and Limsuwan, P., “An X-ray Photoelectron
Spectroscopy Investigation of Redeposition from Fluorine-
based Plasma Etch on Magnetic Recording Slider Head
Substrate,” Procedia Eng., 32, 1043-1049(2012).
30. Gao, Y., Zhang, J., Chen, Y. and Wang, C., “Improvement of the
Electrochemical Performance of Spent Graphite by Asphalt
Coating,” Surf Interfaces, 24, 101089(2021).

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