Resources Recycling (자원리싸이클링)

The Korean Institute of Resources Recycling (한국자원리싸이클링학회)
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A Study on the Synthesis Behavior of Lithium Hydroxide by Type of Precipitant for Lithium Sulfate Recovered from Waste LIB

폐리튬이차전지에서 회수된 황산리튬 전구체로부터 침전제 종류별 수산화리튬 제조 거동 연구

  • Joo, Soyeong (Materials Science and Chemical Engineering Center, Institute for Advanced Engineering (IAE)) ;
  • Kim, Dae-Guen (Materials Science and Chemical Engineering Center, Institute for Advanced Engineering (IAE)) ;
  • Byun, Suk-Hyun (SungEel HiTech Co., Ltd.) ;
  • Kim, Yong Hwan (Research Institute of Advanced Manufacturing Technology, Korea Institute of Industrial Technology) ;
  • Shim, Hyun-Woo (Materials Science and Chemical Engineering Center, Institute for Advanced Engineering (IAE))
  • 주소영 (고등기술연구원 융합소재연구센터) ;
  • 김대근 (고등기술연구원 융합소재연구센터) ;
  • 변석현 (성일하이텍(주) 부설연구소) ;
  • 김용환 (한국생산기술연구원 뿌리산업기술연구소) ;
  • 심현우 (고등기술연구원 융합소재연구센터)
  • Received : 2020.10.29
  • Accepted : 2021.01.21
  • Published : 2021.02.28
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Abstract

This study investigated the effect of the type of alkaline precipitant used on the synthesis of lithium hydroxide by examining the behavior of lithium hydroxide produced using lithium sulfate recovered from a waste lithium secondary battery as a raw material. The double-replacement reaction (DRR) process was used to remove the impurities contained in the lithium salt precursor of lithium sulfate and to improve the efficiency of the synthesis of lithium hydroxide. The experiment was conducted by control the molar ratio of the precursor ([Li]/[OH]), the reaction temperature, and the composition of the alkaline precipitant (KOH, Ca(OH)2, Ba(OH)2) used for the production of highly-crystalline lithium hydroxide. A secondary solid-liquid separation was performed following the reaction to remove the impurities generated, and the purified aqueous solution of lithium hydroxide was evaporated to remove the moisture and obtain the product as a powder. The crystallinity and synthesis behavior of the product were examined.

본 연구에서는 알칼리성 침전제 종류 따라 제조되는 수산화리튬 결정화 정도 확인을 위해 폐리튬이차전지로부터 회수된 황산리튬을 원료로 사용하여 수산화리튬 제조 거동을 확인하였다. 황산리튬의 리튬염 전구체에 포함되어 있는 불순물 제거 및 높은 수산화리튬 합성효율을 위해 2차 침전법인 Double replacement reaction(DRR) 공정을 사용하였으며, 결정성 높은 수산화리튬 제조를 위하여 알칼리성 침전제(KOH, Ca(OH)2, Ba(OH)2)를 포함하여 전구체 몰비 ([Li]/[OH]) 및 합성온도 조건을 변수로 두어 실험을 진행하였다. 반응 후 생성된 불순물 제거를 위해 2차 고/액 분리를 실시하였고 불순물이 제거된 수산화리튬 수용액은 증발을 통해 수분 제거하여 분말을 수득하였다. 최종적으로 수득한 분말의 결정성 평가 및 제조 거동을 확인하였다.

Keywords

References

  1. Whittingham, M. S., 2004 : Lithium batteries and cathode materials. Chemical reviews, 104, pp.4271-4302. https://doi.org/10.1021/cr020731c
  2. Zhou, L., Zhang, K., Hu, Z., et al., 2018 : Recent developments on and prospects for electrode materials w ith hierarchical structures for lithium-ion batteries. Advanced Energy Materials, 8, pp.1701415. https://doi.org/10.1002/aenm.201701415
  3. Wang, R. C., Lin, Y. C., & Wu, S. H., 2009 : A novel recovery process of metal values from the cathode active materials of the lithium-ion secondary batteries. Hydro-metallurgy, 99, pp.194-201.
  4. Mortgat, B., 1999 : Piles et accumulateurs: Filieres et procedes se multiplient a deux ans de l'obligation de traitement. Environnement & technique, 183, pp.20-26.
  5. Mortgat, B., 2000: Procedes de recyclage du lithium des piles et accumulateurs. Environnement & techniqu, 193, pp.41-44.
  6. Li, L., Ge, J., Chen, R., et al., 2010 : Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries. Waste management, 30, pp.2615-2621. https://doi.org/10.1016/j.wasman.2010.08.008
  7. Swain, B., Jeong, J., Lee, J. C., et al., 2007 : Hydro-metallurgical process for recovery of cobalt from waste cathodic active material generated during manufacturing of lithium ion batteries. Journal of Power Sources, 167, pp.536-544. https://doi.org/10.1016/j.jpowsour.2007.02.046
  8. Grimes, S. M., Donaldson, J. D., Chaudhary, A. J., et al., 2000 : Simultaneous recovery of metals and destruction of organic species: cobalt and phthalic acid. Environmental science & technology, 34, pp.4128-4132. https://doi.org/10.1021/es990784k
  9. Musariri, B., Akdogan, G., Dorfling, C., et al., 2019 : Evaluating organic acids as alternative leaching reagents for metal recovery from lithium ion batteries. Minerals Engineering, 137, pp.108-117. https://doi.org/10.1016/j.mineng.2019.03.027
  10. Dorella, G., & Mansur, M. B., 2007 : A study of the separation of cobalt from spent Li-ion battery residues. Journal of Power Sources, 170, pp.210-215. https://doi.org/10.1016/j.jpowsour.2007.04.025
  11. Song, Y. J., 2018 : Recovery of Lithium as Li3PO4 from Waste Water in a LIB Recycling Process. Korean Journal of Metals and Materials, 56, pp.755-762. https://doi.org/10.3365/KJMM.2018.56.10.755
  12. Xu, J., Thomas, H. R., Francis, R. W., et al., 2008 : A review of processes and technologies for the recycling of lithium-ion secondary batteries. Journal of Power Sources, 177, pp.512-527. https://doi.org/10.1016/j.jpowsour.2007.11.074
  13. Kim, K. J., 2008 : Recovery of lithium hydroxide from spent lithium carbonate using crystallizations. Separation Science and Technology, 43(2), pp.420-430. https://doi.org/10.1080/01496390701784088
  14. Parsa, N., Moheb, A., Mehrabani-Zeinabad, A., et al., 2015 : Recovery of lithium ions from sodium-contaminated lithium bromide solution by using electrodialysis process. Chemical Engineering Research and Design, 98, pp.81-88. https://doi.org/10.1016/j.cherd.2015.03.025
  15. Yuan, B., Wang, J., Cai, W., et al., 2017 : Effects of temperature on conversion of Li2CO3 to LiOH in Ca(OH)2 suspension. Particuology, 34, pp.97-102. https://doi.org/10.1016/j.partic.2017.01.005
  16. Wen_huang, H. U. A. N. G., Yu_shun, Y. A. N., Chun_rong, W. A. N., et al., 2000 : Study on the Effect of Sodium Ion on Cycle Performance of Lithium/Improved Graphite Lithium Ion Cell. Journal of Electrochemistry, 6, pp.212.
  17. Nemkov, N. M., Ryabtsev, A. D., Kotsupalo, N. P., et al., 2020 : Preparing High-Purity Lithium Hydroxide Monohydrate by the Electrochemical Conversion of Highly Soluble Lithium Salts. Theoretical Foundations of Chemical Engineering, 54, pp.710-718. https://doi.org/10.1134/S0040579519050166
  18. Joo, S. Y., Kang, Y. B., Shim, H. W., et al., 2019 : Study on Preparation of High Purity Lithium Hydroxide Powder with 2-step Precipitation Process Using Lithium Carbonate Recovered from Waste LIB Battery. Journal of the Korean Institute of Resources Recycling, 28, pp.60-67.
  19. Joo, S. Y., Shim, H. W., Choi, J. J., et al., 2020 : A Method of Synthesizing Lithium Hydroxide Nanoparticles Using Lithium Sulfate from Spent Batteries by 2-Step Precipitation Method, Korean Journal of Metals and Materials, 58, pp.286-291. https://doi.org/10.3365/kjmm.2020.58.4.286
  20. Kang, D. J., Jeong, B. G., Yoon, M. H., et al., 2012 : KR. 1011585270000.