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202 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208 Spent lithium batteries Neutralization Leaching & washing Recovered chemical substances Fig. 6. Batrec Industrie AG process flowsheet. 3.3.1.7. OnTo Technology (USA). Spent batteries are discharged before dismantling. Batteries are cleaned and then placed in a high pressure extraction container filled with liquid CO2 and some additives like alkyl ethers, ammonia etc. The CO2 is transformed into a supercritical fluid by increasing the pressure and temperature in the container. With an increase in pressure, the battery casings are breached by fluid. When the desired pressure and temperature are reached the electrolyte extrac- tion can either be carried out by circulating CO2 through the system or by soaking the batteries in the supercritical fluid. Batteries without function- al potential are subsequently recycled through pulverization and the var- ious materials separated and recovered based on the physical properties. 3.3.1.8. Umicore process (Belgium and Sweden). Also called as the ValÉas process, this is a combined pyro-and-hydro-metallurgical process to separate nickel and cobalt without recovering lithium. The spent batte- ries are smelted in a furnace. Plastic, solvent and graphite are burnt off while the metals are reduced and collected in a melt. The process is operated in Sweden while the molten metal consisting of Ni, Co, Cu and Fe is cooled and processed in Belgium by sulfuric acid leaching and solvent extraction. NiSO4 and CoCl2 are separated from the solution from which cobalt oxide and Ni(OH)2 are obtained. A disadvantage of pyrometallurgical recycling processes including that of Umicore is that lithium recovery is not targeted and for which a combination of pyrometallurgical and hydrometallurgical processing steps are necessary. The Umicore process has another drawback of losing base metals which are slagged off, besides the loss of organic materials as well as carbon. 3.3.2. Recent development in recycling of lithium ion batteries Spent LIBs containing lithium and other metals are mostly treated by the hydrometallurgical process which is used at times in combi- nation with pyrometallurgical treatment. This may have integrated pre-treatment steps like pyrolysis or mechanical processing, i.e. crushing and material separation. In order to investigate the extraction of cobalt, nickel, manganese etc. from LIBs by such processes thermodynamic as- pects particularly the stability regions of different phases in aqueous solu- tion under redox conditions may be examined. For this standard Eh–pH diagrams of Li–H2O, Co–H2O, Mn–H2O and Ni–H2O systems can be re- ferred from literature (Pourbaix, 1966; Schweitzer and Pesterfield, 2010). Leaching of LIBs are carried out with different acids like HCl (Contestabile et al., 2001; Zhang et al., 1998), H2SO4 (Aktas et al., 2006; Dorella and Mansur, 2007; Kang et al., 2010a,b; Nan et al., 2005; Shin et al., 2005; Swain et al., 2007), HNO3 (Lee and Rhee, 2002, 2003), and a few organic acids like DL-malic acid (Li et al., 2010a), citric acid (Li et al., 2010b) etc. The binder (PVDF) which links the cathode material, LiCoO2 with aluminium foils does not dissolve easily in the organic reagents such as fatty hydrocarbon or alcohol at room temperature making the leaching reactions more difficult to proceed. The important developments Protective atmosphere CO2 CO2 Moist air Feeder & Shredder Release of protective atmosphere Acidified aqueous liquid Gases Gas Scrubber SO2(aq), Cl2(aq) Leach liquor Hydrometallurgical processing (SX/Precipitation) Metal fractions & plastics Residue metal oxides and carbon. Lithium is precipitated as Li2CO3 using the CO2 obtained from the mechanical treatment. The suspension of metal oxides is dissolved in H2SO4. Copper is cemented out by the steel shots (Tedjar and Foudraz, 2007). The purified solution is oxidized by NaClO to precipitate cobalt(III) hydroxide (Fig. 5) and cobalt is separat- ed by electrolysis. The remaining lithium in the solution is precipitated with CO2 gas. 3.3.1.6. Batrec Industrie AG process (Switzerland). The company Batrec mainly runs a mechanical processing plant for LIBs. In this process batteries are crushed in CO2 gas atmosphere and the released lithium is neutralized. With the completion of the neutralization step, the protective environment is released and subsequently treated in a gas scrubber to reduce the emission during the process. Scrap material is leached and washed in acidified aqueous liquid and leach liquor is further processed for the recovery of different chemical substances. Metal containing a solid fraction can be separated from liquid and treat- ed to remove impurities. The flowsheet of the process is presented in Fig. 6. Table 9 Extraction and recovery of metals from spent LIBs in hydrochloric acid system. Material Cylindrical- shaped LIBs Spent LIBs LIBs LIBs Ash from LIBs Leaching conditions Acid concentration (M) 4 4 4 3 M acid + 3.5% H2O2 4 Temp. Time Pulp density (°C) (h) (g/L) 80 1 100 80 1 100 80 1 20 80 1 50 90 18 50 Extraction/Separation—parameters SX with 0.29 M D2EHPA and 0.90 M PC-88A Precipitation: pH 6–8 with 4 M NaOH. Synthesis of precursor material by co-precipitation. Precipitation: pH 2 with KMnO4 for Mn(II), pH 9 for Co by DMG and Li2CO3 Precipitation: pH 11–12 with NaOH for Co; Na2CO3 at 100 °C for Li Precipitation by NaClO at pH 3 and base addition at pH 11 Highlights (with merits/demerits) SX: N 99.9 Co and 12.6% Li with 0.9 M PC-88A. Higher selectivity with PC 88A. Co(OH)2 separated easily. NixCoyMnz a precursor to cathode material Purity (%): 96.9 Li, 98.23 Mn, 96.94 Co and 97.43 Ni Recovery (%): 95 Co and 93 Li in precipitate Recovery (%): 100 Co and 99.99 Ni. HCl gives higher leaching efficiency. References Zhang et al. (1998) Contestabile et al. (2001) Wang et al. (2009) Shuva and Kurny (2013) Joulié et al. (2014)PDF Image | Extraction of lithium from primary and secondary sources
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