Citation: Ling HUANG, Cheng-Zhi ZHANG, Jun TAN, Sui-Min LI. Recycling FePO₄·2H₂O from waste LiFePO₄ powders and formation mechanisms of the impurities during precipitation process[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(2): 357-366. doi: 10.11862/CJIC.2022.288 shu

Recycling FePO₄·2H₂O from waste LiFePO₄ powders and formation mechanisms of the impurities during precipitation process

Jihua Laboratory, Foshan, Guangdong 528200, China

Corresponding author: Jun TAN, tanjun@jihualab.ac.cn
Received Date: 9 September 2022
Revised Date: 18 November 2022

Figures(4)

Applying waste LiFePO₄ powders as raw material, the FePO₄·2H₂O precursor was effectively recycled through chemical precipitation. Thereafter, the formation mechanisms of the impurities were discussed. The potential (φ)-pH diagram of the Fe-P-Li-H₂O system was investigated and the result demonstrated that FePO₄·2H₂O could form at a temperature of 298-363 K under a pH value of 0-5.0 by precipitation. The experiment results indicated that the Fe₃PO₇ phase started to form through the reaction of Fe(OH)₃ and FePO₄·2H₂O during the sintering process. When the molar ratio of Fe and P (n_Fe∶n_P) was 1∶1, pH=1.5-2.2, some Fe³⁺ ions will form Fe(OH)₃, and the yield coefficient increased with the pH and temperature. This is because the solubility product constant (K_sp) of Fe(OH)₃ was much less than the one of FePO₄·2H₂O, suggesting that the precipitate rate of Fe(OH)₃ was faster than FePO₄·2H₂O. Based on thermodynamic principles, aging may be an effective way to convert Fe(OH)₃ into FePO₄ ·2H₂O according to the φ-pH diagram of the Fe-P-Li-H₂O system. Unfortunately, the rate of Fe(OH)₃ conversion was slowed, resulting in some Fe(OH)₃ in precipitation. Therefore, low pH value and temperature are essential to avoid Fe(OH)₃ generation during the co-precipitation process. Also, when n_Fe∶n_P=1∶2, some H₃PO₄ could react with NaOH to form NaH₂PO₄, which would further react with FePO₄·2H₂O to produce NaFeP₂O₇ during the sintering process. At 333 K, the equimolar ratio of co-precipitation precursor FePO₄·2H₂O can be obtained by adjusting the pH value at 1.5, matching the molar ratio of 1∶1 of Fe to P. The purity of this as-prepared FePO₄·2H₂O was 99.97%. Besides, the synthesized LiFePO₄ which used this FePO₄·2H₂O as a precursor exhibited a reversible capacity of 154.1 mAh·g^-1 and excellent capacity retention of 96.79% after 100 cycles at 0.2C (1C=180 mA·g^-1). FePO₄·2H₂O obtained from waste LiFePO₄ powders can be used as precursor to synthesize LiFePO₄ cathode material, which greatly improves the economic effi-ciency of recycling the spent LiFePO₄ battery.
- lithiumion battery,
- spent lithium iron phosphate battery,
- co-precipitation,
- LiFePO₄,
- recycle
1. [1]
  Wang W, Wu Y F. An overview of recycling and treatment of spent LFP batteries in China[J]. Resour. Conserv. Recycl., 2017,127:233-243. doi: 10.1016/j.resconrec.2017.08.019
2. [2]
  Liu P W, Zhang Y N, Dong P, Zhang Y J, Meng Q, Zhou S Y, Yang X, Zhang M Y, Yang X. Direct regeneration of spent LFP cathode materials with pre-oxidation and V-doping[J]. J. Alloy. Compd., 2021,860157909. doi: 10.1016/j.jallcom.2020.157909
3. [3]
  Gaogong Lithium Battery Research Institute (GGⅡ). Research and analysis report on cathode materials for lithium battery in China, 2021. https://www.gg-lb.com/art-44605-yj.html
4. [4]
  Sun Q F, Li X L, Zhang H Z, Song D W, Shi X X, Song J S, Li C L, Zhang L Q. Resynthesizing LFP/C materials from the recycled cathode via a green full-solid route[J]. J. Alloy. Compd., 2020,818153292. doi: 10.1016/j.jallcom.2019.153292
5. [5]
  Li H Y, Ye H, Sun M C, Chen W J. Process for recycle of spent lithium iron phosphate battery via a selective leaching-precipitation method[J]. J. Cent. South Univ., 2020,27(11):3239-3248. doi: 10.1007/s11771-020-4543-3
6. [6]
  He K, Zhang Z Y, Zhang F S. A green process for phosphorus recov-ery from spent LFP batteries by transformation of delithiated LFP crystal into NaFeS₂[J]. J. Hazard. Mater., 2020,395122614. doi: 10.1016/j.jhazmat.2020.122614
7. [7]
  Dai Y, Xu Z D, Hua D, Gu H N, Wang N. Theoretical-molar Fe³⁺ recovering lithium from spent LFP batteries: An acid-free, efficient, and selective process[J]. J. Hazard. Mater., 2020,396122707. doi: 10.1016/j.jhazmat.2020.122707
8. [8]
  Li H, Xing S Z, Liu Y, Li F J, Guo H, Kuang G. Recovery of lithium, iron, and phosphorus from spent LFP batteries using stoichiometric sulfuric acid leaching system[J]. ACS Sustain. Chem. Eng., 2017,5(9):8017-8024. doi: 10.1021/acssuschemeng.7b01594
9. [9]
  Yang Y X, Meng X Q, Cao H B, Lin X, Liu C M, Sun Y, Zhang Y, Sun Z. Selective recovery of lithium from spent lithium iron phosphate batteries: A sustainable process[J]. Green Chem., 2018,20(13):3121-3133. doi: 10.1039/C7GC03376A
10. [10]
  Fan E S, Li L, Zhang X X, Bian Y F, Xue Q, Wu J W, Wu F, Chen R J. Selective recovery of Li and Fe from spent lithium-ion batteries by an environmentally friendly mechanochemical approach[J]. ACS Sustain. Chem. Eng., 2018,6(8):11029-11035. doi: 10.1021/acssuschemeng.8b02503
11. [11]
  Kumar J, Shen X, Li B, Liu H Z, Zhao J M. Selective recovery of Li and FePO₄ from spent LFP cathode scraps by organic acids and the properties of the regenerated LFP[J]. Waste Manage., 2020,113:32-40. doi: 10.1016/j.wasman.2020.05.046
12. [12]
  Institute of rare metals, Guangdong academy of sciences. A method for synthesis iron phosphate for battery materials from spent lithium iron phosphate batteries: CN201811327545.8. 2018-11-08.
13. [13]
  He L H, Zhao Z W, Liu X H, Chen A L, Si X F. Thermodynamics analysis of LFP precipitation from Li-Fe(Ⅱ)-P-H₂O system at 298 K[J]. Trans. Nonferrous Met. Soc. China, 2012,22(7):1766-1770. doi: 10.1016/S1003-6326(11)61385-X
14. [14]
  ZHAO Z W, LIU X H. Thermodynamics analysis of Li-Fe-P-H₂O system[J]. The Chinese Journal of Nonferrous Metals, 2006,16(7):1257-1263.
15. [15]
  Gal'perin Y L, Kosmynin B P. The crystalline structure of polyvinyli-denefluoride[J]. Polym. Sci. U.S.S.R., 1969,11(7):1624-1629. doi: 10.1016/0032-3950(69)90199-3
16. [16]
  Churikov A V, Ivanishchev A V, Ushakov A V, Gamayunova I M, Leenson I A. Thermodynamics of LFP solid-phase synthesis using iron(Ⅱ)oxalate and ammonium dihydrophospate as precursors[J]. J.Chem. Eng. Data, 2013,58(6):1747-1759. doi: 10.1021/je400183k
17. [17]
  Nriagu J O. Stability of vivianite and ion-pair formation in the system Fe₃(PO₄)₂-H₃PO₄-H₂O[J]. Geochim. Cosmochim. Acta, 1972,36(4):459-470. doi: 10.1016/0016-7037(72)90035-X
18. [18]
  ZHAO Z W, LIANG X X, LIU X H, HE L H, CHEN X Y, SI X F, CHEN A L. Thermodynamics analysis of Li-extraction from brine using FePO₄ ion-sieve[J]. The Chinese Journal of Nonferrous Metals, 2013,23(2):559-567.
19. [19]
  Speight J G. Lang's handbook of chemistry. 6th ed. Los Angeles: McGraw-Hill, 2004: 1.253-1.261
20. [20]
  Lide D R. CRC Handbook of chemistry and physics. 77th ed. Florida: CRC Press, 2019.
21. [21]
  JING Q K. Basic research on wet chemical recovery and regeneration of typical cathode materials of lithium⁃ion batteries. Beijing: Univer-sity of Science and Technology Beijing, 2020: 33-38
22. [22]
  Tremaine P R, Leblanc J C. The solubility of magnetite and the hydrolysis and oxidation of Fe2+ in water to 300℃[J]. J. Solution Chem., 1980,9(6):415-442. doi: 10.1007/BF00645517
23. [23]
  YANG M. Dephosphorization mechanism of the raw and as ⁃ roasted Huiming high phosphorus limonite through sulfuric acid leaching. Beijing: Institute of Process Engineering Chinese Academy of Science, 2015: 44-45
24. [24]
  HG/T 4701-2014. Iron phosphate for battery materials. China Indus-try Standards. 2015-6-1.
25. [25]
  Šušić M V, Minić D M. Electric and electrochemical properties of solid LiH₂PO₄[J]. Solid State Ionics, 1981,2(4):309-314. doi: 10.1016/0167-2738(81)90032-1
26. [26]
  Wurm C, Morcrette M, Rousse G, Dupont L, Masquelier C. Lithium insertion/extraction into/from LiMX₂O₇ compositions (M=Fe, V; X= P, As) prepared via a solution method[J]. Chem. Mater., 2002,14(6):2701-2710. doi: 10.1021/cm020168e
27. [27]
  Gabelica-Robert M, Goreaud M, Labbe P, Raveau B. The pyrophos-phate NaFeP₂O₇: A cage structure[J]. J. Solid State Chem., 1982,45(3):389-395. doi: 10.1016/0022-4596(82)90184-0
28. [28]
  Lou W B, Zhang Y, Zhang Y, Zheng S L, Sun P, Wang X J, Li J Z, Qiao S, Zhang Y, Wenzel M, Weigand J J. Leaching performance of Al-bearing spent LFP cathode powder in H₂SO₄ aqueous solution[J]. Trans. Nonferrous Met. Soc. China, 2021,31(3):817-831. doi: 10.1016/S1003-6326(21)65541-3
29. [29]
  Zheng R J, Zhao L, Wang W H, Liu Y L, Ma Q X, Mu D Y, Li R H, Dai C S. Optimized Li and Fe recovery from spent lithium-ion batter-ies via a solution-precipitation method[J]. RSC Adv., 2016,6(49):43613-43625. doi: 10.1039/C6RA05477C
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Recycling FePO₄·2H₂O from waste LiFePO₄ powders and formation mechanisms of the impurities during precipitation process