Abstract
Thermal treatment offers an alternative method for the separation of Al foil and cathode materials during spent lithium-ion batteries (LIBs) recycling. In this work, the pyrolysis behavior of cathode from spent LIBs was investigated using advanced thermogravimetric Fourier transformed infrared spectroscopy coupled with gas chromatography-mass spectrometer (TG-FTIR-GC/MS) method. The fate of fluorine present in spent batteries was probed as well. TG analysis showed that the cathode decomposition displayed a three-stage process. The temperatures of maximum mass loss rate were located at 470 °C and 599 °C, respectively. FTIR analysis revealed that the release of CO2 increased as the temperature rose from 195 to 928 °C. However, the evolution of H2O showed a decreasing trend when the temperature increased to above 599 °C. The release of fluoride derivatives also exhibited a decreasing trend, and they were not detected after temperatures increasing to above 470 °C. GC-MS analysis indicated that the release of H2O and CO displayed a similar trend, with larger releasing intensity at the first two stages. The evolution of 1,4-difluorobenzene and 1,3,5-trifluorobenzene also displayed a similar trend—larger releasing intensity at the first two stages. However, the release of CO2 showed a different trend, with the largest release intensity at the third stage, as did the release of 1,2,4-trifluorobenzene, with the release mainly focused at the temperature of 300–400 °C. The release intensities of 1,2,4-trifluorobenzene and 1,3,5-trifluorobenzene were comparable, although smaller than that of 1,4-difluorobenzene. This study will offer practical support for the large-scale recycling of spent LIBs.
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References
Antolini E, Ferretti M (1995) Synthesis and thermal stability of LiCoO2. J Solid State Chem 117(1):1–7
Cao Y, Liang M, Liu Z, Wu Y, Xiong X, Li C, Wang X, Jiang N, Yu J, Lin CT (2016) Enhanced thermal conductivity for poly (vinylidene fluoride) composites with nano-carbon fillers. RSC Adv 6(72):68357–68362
Chen X, Zhou T (2014) Hydrometallurgical process for the recovery of metal values from spent lithium-ion batteries in citric acid media. Waste Manag Res 32(11):1083–1093
Cheng S, Qiao Y, Huang J, Wang W, Wang Z, Yu Y, Xu M (2019) Effects of Ca and Na acetates on nitrogen transformation during sewage sludge pyrolysis. Proc Combust Inst 37(3):2715–2722
Cho T, Han C, Jun Y et al (2013) Formation of artificial pores in nano-TiO2 photo-electrode films using acetylene-black for high-efficiency, dye-sensitized solar cells. Sci Rep 3:1496
Choi S, Kim Y (2012) Microstructural analysis of poly (vinylidene fluoride) using benzene derivative pyrolysis products. J Anal Appl Pyrolysis 96:16–23
Danilich MJ, Burton DJ, Marchant RE (1995) Infrared study of perfluorovinylphosphonic acid, perfluoroallylphosphonic acid, and pentafluoroallyldiethylphosphonate. Vib Spectrosc 9(3):229–234
Duan C, Li F, Yang M et al (2018) Rapid synthesis of hierarchically structured multifunctional metal-organic zeolites with enhanced volatile organic compounds adsorption capacity. Ind Eng Chem Res 57(45):15385–15394
Escribano RM, Caro GMM, Cruz-Diaz GA et al (2013) Crystallization of CO2 ice and the absence of amorphous CO2 ice in space. Proc Natl Acad Sci 110(32):12899–12904
Gao W, Liu C, Cao H, Zheng X, Lin X, Wang H, Zhang Y, Sun Z (2018) Comprehensive evaluation on effective leaching of critical metals from spent lithium-ion batteries. Waste Manag 75:477–485
He Y, Zhang T, Wang F, Zhang G, Zhang W, Wang J (2017) Recovery of LiCoO2 and graphite from spent lithium-ion batteries by Fenton reagent-assisted flotation. J Clean Prod 143:319–325
Kai X, Li R, Yang T, Shen S, Ji Q, Zhang T (2017) Study on the co-pyrolysis of rice straw and high density polyethylene blends using TG-FTIR-MS. Energy Convers Manag 146:20–33
Kar E, Bose N, Das S, Mukherjee N, Mukherjee S (2015) Enhancement of electroactive β phase crystallization and dielectric constant of PVDF by incorporating GeO2 and SiO2 nanoparticles. Phys Chem Chem Phys 17(35):22784–22798
Liu C, Lin J, Cao H, Zhang Y, Sun Z (2019) Recycling of spent lithium-ion batteries in view of lithium recovery: a critical review. J Clean Prod 228:801–813
Ma J, Haque RI, Larsen RM (2012) Crystallization and mechanical properties of functionalized single-walled carbon nanotubes/polyvinylidene fluoride composites. J Reinf Plast Compos 31(21):1417–1425
Mann DE, Acquista N, Plyler EK (1954) Vibrational spectrum of Bromotrifluoroethylene. J Chem Phys 22(7):1199–1202
Natarajan S, Aravindan V (2018) Recycling strategies for spent Li-ion battery mixed cathodes. ACS Energy Letters 3(9):2101–2103
Nie H, Xu L, Song D, Song J, Shi X, Wang X, Zhang L, Yuan Z (2015) LiCoO2: recycling from spent batteries and regeneration with solid state synthesis. Green Chem 17(2):1276–1280
O'Shea ML, Morterra C, Low M (1990) Spectroscopic studies of carbons. XVII Pyrolysis of polyvinylidene fluoride. Mater Chem Phys 26(2):193–209
Ouyang Z, Chen E, Wu T (2015) Thermal stability and magnetic properties of polyvinylidene fluoride/magnetite nanocomposites. Materials 8(7):4553–4564
Qi W, Liu G, He C, Liu S, Lu S, Yue J, Wang Q, Wang Z, Yuan Z, Hu J (2019) An efficient magnetic carbon-based solid acid treatment for corncob saccharification with high selectivity for xylose and enhanced enzymatic digestibility. Green Chem 21(6):1292–1304
Rathore S, Madhav H, Jaiswar G (2019) Efficient nano-filler for the phase transformation in polyvinylidene fluoride nanocomposites by using nanoparticles of stannous sulfate. Mater Res Innov 23(4):183–190
Sun C, Xu L, Chen X, Qiu T, Zhou T (2018) Sustainable recovery of valuable metals from spent lithium-ion batteries using DL-malic acid: leaching and kinetics aspect. Waste Manag Res 36(2):113–120
Tran MK, Rodrigues MF, Kato K et al (2019) Deep eutectic solvents for cathode recycling of Li-ion batteries. Nat Energy 4(4):339–345
Wang F, Zhang T, He Y, Zhao Y, Wang S, Zhang G, Zhang Y, Feng Y (2018) Recovery of valuable materials from spent lithium-ion batteries by mechanical separation and thermal treatment. J Clean Prod 185:646–652
Wang M, Tan Q, Liu L, Li J (2019a) A low-toxicity and high-efficiency deep eutectic solvent for the separation of aluminum foil and cathode materials from spent lithium-ion batteries. J Hazard Mater 380:120846
Wang M, Tan Q, Liu L, Li J (2019b) Efficient separation of aluminum foil and cathode materials from spent lithium-ion batteries using a low-temperature molten salt. ACS Sustain Chem Eng 7:8287–8294
Winslow KM, Laux SJ, Townsend TG (2018) A review on the growing concern and potential management strategies of waste lithium-ion batteries. Resour Conserv Recycl 129:263–277
Xiao J, Li J, Xu Z (2017) Novel approach for in situ recovery of lithium carbonate from spent lithium ion batteries using vacuum metallurgy. Environmental Science & Technology 51(20):11960–11966
Xiao J, Li J, Xu Z (2020) Challenges to future development of spent lithium ion batteries recovery from environmental and technological perspectives. Environmental Science & Technology 54(1):9–25
Yao J, Chen J, Shen K, Li Y (2018) Phase-controllable synthesis of MOF-templated maghemite-carbonaceous composites for efficient photocatalytic hydrogen production. J Mater Chem A 6(8):3571–3582
Yu S, Su W, Wu D, Yao Z, Liu J, Tang J, Wu W (2019) Thermal treatment of flame retardant plastics: a case study on a waste TV plastic shell sample. Sci Total Environ 675:651–657
Zeng X, Li J (2014) Innovative application of ionic liquid to separate Al and cathode materials from spent high-power lithium-ion batteries. J Hazard Mater 271:50–56
Zhang Z, He W, Li G et al (2014) Ultrasound-assisted hydrothermal renovation of LiCoO2 from the cathode of spent lithium-ion batteries. Int J Electrochem Sci 9:3691–3700
Zhang G, He Y, Feng Y, Wang H, Zhang T, Xie W, Zhu X (2018a) Enhancement in liberation of electrode materials derived from spent lithium-ion battery by pyrolysis. J Clean Prod 199:62–68
Zhang G, He Y, Feng Y, Wang H, Zhu X (2018b) Pyrolysis-ultrasonic-assisted flotation technology for recovering graphite and LiCoO2 from spent lithium-ion batteries. ACS Sustain Chem Eng 6(8):10896–10904
Zhang W, Xu C, He W, Li G, Huang J (2018c) A review on management of spent lithium ion batteries and strategy for resource recycling of all components from them. Waste Manag Res 36(2):99–112
Zhang X, Li L, Fan E, Xue Q, Bian Y, Wu F, Chen R (2018d) Toward sustainable and systematic recycling of spent rechargeable batteries. Chem Soc Rev 47(19):7239–7302
Zhang G, Du Z, He Y et al (2019) A sustainable process for the recovery of anode and cathode materials derived from spent lithium-ion batteries. Sustainability 11(8):2363
Zhao S, Li G, He W, et al. (2019) Recovery methods and regulation status of waste lithium-ion batteries in China: a mini review. Waste Manag Res DOI: https://doi.org/10.1177/0734242X19857130, 2019-06-27
Zulfiqar S, Zulfiqar M, Rizvi M, Munir A, McNeill IC (1994) Study of the thermal degradation of polychlorotrifluoroethylene, poly (vinylidene fluoride) and copolymers of chlorotrifluoroethylene and vinylidene fluoride. Polym Degrad Stab 43(3):423–430
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This work was financially supported by the Zhejiang Provincial Natural Science Foundation of China (Grant no. LY19B070008).
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Yu, S., Xiong, J., Wu, D. et al. Pyrolysis characteristics of cathode from spent lithium-ion batteries using advanced TG-FTIR-GC/MS analysis. Environ Sci Pollut Res 27, 40205–40209 (2020). https://doi.org/10.1007/s11356-020-10108-4
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DOI: https://doi.org/10.1007/s11356-020-10108-4