| 1. |
- Balachandran, Srija, et al.
(författare)
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Comparative study for selective lithium recovery via chemical transformations during incineration and dynamic pyrolysis of EV li-ion batteries
- 2021
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Ingår i: Metals. - : MDPI AG. - 2075-4701. ; 11:8
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Tidskriftsartikel (refereegranskat)abstract
- Selective leaching of Li from spent LIBs thermally pretreated by pyrolysis and incineration between 400 and 700 °C for 30, 60, and 90 min followed by water leaching at high temperature and high L/S ratio was examined. During the thermal pretreatment Li2CO3 and LiF were leached. Along with Li salts, AlF3 was also found to be leached with an efficiency not higher than 3.5%. The time of thermal pretreatment did not have a significant effect on Li leaching efficiency. The leaching efficiency of Li was higher with a higher L/S ratio. At a higher leaching temperature (80 °C), the leaching of Li was higher due to an increase in the solubility of present Li salts. The highest Li leaching efficiency of nearly 60% was observed from the sample pyrolyzed at 700 °C for 60 min under the leaching condition L/S ratio of 20:1 mL g−1 at 80 °C for 3 h. Furthermore, the use of an excess of 10% of carbon in a form of graphite during the thermal treatment did not improve the leaching efficiency of Li.
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| 2. |
- Lombardo, Gabriele, 1990, et al.
(författare)
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Chemical Transformations in Li-Ion Battery Electrode Materials by Carbothermic Reduction
- 2019
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Ingår i: ACS Sustainable Chemistry & Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 7:16, s. 13668-13679
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Tidskriftsartikel (refereegranskat)abstract
- The effects of pyrolysis on the composition of the battery cell materials as a function of treatment time and temperature were investigated. Waste of Li-ion batteries was pyrolyzed in a nitrogen atmosphere at 400, 500, 600, and 700 degrees C for 30, 60, and 90 min. Thermodynamic calculations for the carbothermic reduction of active materials LiCoO2, LiMn2O4, and LiNiO2 by graphite and gas products were performed and compared to the experimental data. Ni, Mn, and Co (NMC) cathode materials recovered from spent Li-ion batteries were also studied. The results indicate that the organic compounds and the graphite are oxidized by oxygen from the active material and provide the reductive atmosphere. Such removal of the organic components increases the purity of the metal bearing material. Reactions with C and CO(g) led to a reduction of metal oxides with Co, CoO, Ni, NiO, Mn, Mn3O4, Li2O, and Li2CO3 as the main products. The reduction reactions transformed the metal compounds in the untreated LiB black mass to more soluble chemical forms. It was concluded that the pyrolysis can be used as an effective tool for the battery waste pretreatment to increase the efficiency of the leaching in hydrometallurgical processing of the black mass. The results obtained can help to optimize the parameters in the industrial processing already used for Li-ion battery recycling, especially if followed by hydrometallurgical treatment. Such optimization will decrease the energy demand and increase the metal recovery rate and utilization of the byproducts.
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| 3. |
- Lombardo, Gabriele, 1990
(författare)
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Comparison of incineration and pyrolysis of NMC-lithium-ion batteries – determination of the effects on the chemical composition, and potential formation of hazardous by-products.
- 2020
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Several industrial lithium battery recycling processes use thermal pre-treatment in an oxidative or inert atmosphere, or in a vacuum, to separate the battery components and remove organic material. However, a comparison of these pre-treatments on the microstructure and composition of waste material and production scrap LiBs has not been explored as well as there is a scarcity of information about the character of by-products generated during the processing. In this work the effects of incineration and dynamic pyrolysis on the composition of spent Li-ion batteries (LiBs) and the effects of incineration, dynamic pyrolysis, and pyrolysis under vacuum on the composition of production scrap Li-ion batteries (LiBs) were investigated. LiBs with cathode active material based on Li(NixMnyCoz)Oj, i.e. NMC-LiBs, were treated from 15 to 180 minutes at a temperature between 400-700°C. During the pyrolysis, reactions with C and CO(g) led to a reduction of metal oxides, with Co, CoO, Ni, NiO, Mn, Mn3O4, Li2O, and Li2CO3 as the main products. During the incineration, the organic material was removed more efficiently than in pyrolysis and the lithium metal oxides were subjected to both carbothermic reduction and oxidation. During pyrolysis at 700°C for 180 minutes, the carbon content decreased to 15w%, in comparison to the initial 41w%. The incineration performed under the same conditions resulted in almost complete removal of the graphite and organic species, ~0.6w%. Gas and organic oil by-products from the decomposition of the organic components were characterized. The presence of HF was detected and fluorine was identified also in the oil by-products. The decomposition of the binder facilitated the separation by mechanical treatment of the active material from the current collector. The best method to recover cathode material was shown to be incineration at a temperature range between 550˚ and 650˚ C for at least 90 minutes, followed by ball milling. The recovered fraction of active material was >95%. The formation of HF in the case of high temperature accident involving NMC-LiB was also determined. Four commercial refrigeration liquids containing halogens were investigated. The presence of these refrigeration liquids leads to an increase of the quantity of HF released during a simulated fire.
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| 4. |
- Lombardo, Gabriele, 1990, et al.
(författare)
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Comparison of the effects of incineration, vacuum pyrolysis and dynamic pyrolysis on the composition of NMC-lithium battery cathode-material production scraps and separation of the current collector
- 2021
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Ingår i: Resources, Conservation and Recycling. - : Elsevier BV. - 0921-3449 .- 1879-0658. ; 164
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Tidskriftsartikel (refereegranskat)abstract
- The rising demand for lithium batteries is challenging battery producers to increase their production. This is causing an accumulation of production scrap which must be treated to allow re-utilization of cathode material in production. Several industrial lithium battery recycling processes use thermal pre-treatment in an oxidative or inert atmosphere, or in a vacuum, to separate the battery components and remove organic material. However, a comparison of the effects of incineration, dynamic pyrolysis (under a constant flow of inert gas), and pyrolysis under vacuum on the microstructure and composition of scrap cathode material has not been explored. Scrap cathodes, with active material based on Li(NixMnyCoz)Oj, were subjected to incineration, dynamic pyrolysis, and pyrolysis under vacuum at 450˚, 550˚, and 650°C for 30, 60, 90, and 150 min to determine the best approach to cathode material recovery. While the incineration did not cause any chemical transformation of cathode material, under pyrolysis conditions the organic components in the cathodes triggered carbothermic reduction of the active material, yielding Co3O4, NiO, Mn3O4, and Li2CO3 as products. In the gas by-products, formed from the decomposition of the organic material, CO, CO2, and HF were determined. The decomposition especially of the binder in polyvinylidene fluoride (PVDF) facilitated the separation of the active material from the current collector by mechanical treatment. By subsequent ball milling, the best technique to recover cathode material is the incineration at a temperature higher than 550˚ C and below 650˚ C for at least 90 min, with >95% of recovered active material.
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| 5. |
- Lombardo, Gabriele, 1990, et al.
(författare)
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Determination of Hydrofluoric Acid Formation During Fire Accidents of Lithium-Ion Batteries with a Direct Cooling System Based on the Refrigeration Liquids
- 2023
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Ingår i: Fire technology. - : Springer. - 0015-2684 .- 1572-8099. ; 59:5, s. 2375-2388
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Tidskriftsartikel (refereegranskat)abstract
- To avoid overheating of the batteries, which could lead to a fire, Lithium-ion batteries are provided with a thermal management system using refrigeration liquids. Since some of the commercial dielectric liquids used as refrigeration liquids contain halogens, their presence will contribute to a formation of hazardous emissions such as hydrofluoric acid during a potential fire. In this study, a simulation of a high temperature accident has been performed for lithium-ion batteries cooled with the direct immersion cooling systems using single-phase dielectric liquids to define their contribution to HF formation. Four commercial refrigeration liquids based on perfluoropolyethers, hydrofluoroether and polyalphaolefin were investigated in this work. By simulation of a fire, it was observed that the refrigeration liquids delayed the smoke formation by a factor of 2 to 2.5 in comparison to the case when the battery was burned without the cooling liquid. By analysis of the fluoride concentration in the washing system, it was determined that without the refrigeration liquid approximately 46.8 mmol/l of [F] was captured after the fire. When refrigeration liquids based on two perfluoropolyethers and hydrofluoroether were applied, the fluoride concentration in the washing system was 259 mmol/l, 173 mmol/l and 145 mmol/l, respectively. This work also proposed the reaction mechanisms of the refrigeration liquid ' s decomposition during a fire. It was concluded that the refrigeration liquid based on polyalphaolefin does not contribute to the additional formation of hydrofluoric acid due to the chemical stability and low content of fluoride and can be considered as a more sustainable alternative for a direct cooling system for Lithium-ion batteries.
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| 6. |
- Lombardo, Gabriele, 1990
(författare)
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Effects of pyrolysis and incineration on the chemical composition of Li-ion batteries and analysis of the by-products.
- 2019
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In the present work, the effects of pyrolysis and incineration on the composition of Li-ion battery cell materials and their dependence on treatment time and temperature were investigated. Waste from Li-ion batteries was treated at 400˚, 500˚, 600˚, and 700˚C for 30, 60, and 90 minutes. Thermodynamic calculations for the carbothermic reduction of the active materials LiCoO2, LiMn2O4, and LiNiO2 by graphite and the gas products were performed, and the results compared with the experimental data obtained by processing the pure oxides. This allowed for a very exact investigation of the behaviour of the oxides and has brought novel knowledge to the processing of Li-ion batteries. Moreover, to determine the behaviour of the real waste, NMC cathode material recovered from spent Li-ion batteries was studied. The results indicate that the organic compounds and the graphite are oxidized, by oxygen from the active material during the pyrolysis, and during incineration by the oxygen in the air present in the system, forming an atmosphere rich in CO(g) and CO2(g). Removal of the organic components increases the purity of the metal-bearing material. During the pyrolysis, reactions with C and CO(g) led to a reduction of metal oxides, with Co, CoO, Ni, NiO, Mn, Mn3O4, Li2O, and Li2CO3 as the main products. The reduction reactions transformed the metal compounds in the untreated LiB black mass into chemical forms that were more soluble. It was concluded that pyrolysis can be used as an effective tool for pre-treatment of battery waste in order to increase the efficiency of leaching in a hydrometallurgical processing of the black mass. During incineration, it was observed that the organic material was removed more efficiently than in pyrolysis and the lithium metal oxides were subjected to both carbothermic reduction and oxidation. During heat treatment, organic by-products were formed by the decomposition of the polypropylene separator and the PVDF binder. The organic residue contained both non-polar and polar compounds. One of the most important outputs of the current work is the observation of the fluorine behaviour during the thermal treatment, and detection of its presence in the oil product. It was shown that the decomposition of the PVDF facilitates the separation of the active material from the metallic layers of the electrodes by means of a mechanical treatment. An almost complete recovery of the black mass from the foils was achieved following the thermal treatment. The results obtained can help to optimize the parameters in the industrial process that is already used for Li-ion battery recycling, since this research provides novel information about the effects of the thermal treatment and defines the most favourable conditions for the processing. The results could contribute to an increased recycling rate, especially if this process is followed by a hydrometallurgical treatment. Such optimization will decrease the energy demand and increase the metal recovery rate and the utilization of the by-products.
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| 7. |
- Lombardo, Gabriele, 1990, et al.
(författare)
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Incineration of EV Lithium-ion batteries as a pretreatment for recycling – Determination of the potential formation of hazardous by-products and effects on metal compounds
- 2020
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Ingår i: Journal of Hazardous Materials. - : Elsevier BV. - 1873-3336 .- 0304-3894. ; 393
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Tidskriftsartikel (refereegranskat)abstract
- In several industrial Lithium-ion batteries recycling processes, a thermal treatment with oxidative atmosphere is used to separate the battery components and to remove the organic components. This method is often combined with hydrometallurgical processes with the aim to increase the metal recovery rate or to improve the efficiency of the existing processes. Despite such efforts, the effects of a thermal treatment in an oxidative atmosphere on the microstructure and composition on cathode and anode materials has not been explored. In this manuscript, spent batteries which cathode active material has the composition Li(NixMnyCoz)Oz, i.e. NMC-LiBs, were subjected to thermal treatment at 400˚, 500˚, 600˚, and 700 °C for 30, 60, and 90 min. The microstructure and the composition were studied using XRD and ICP-OES. Thermodynamic calculations were performed to forecast the trend of the carbothermic reduction of active materials. It was observed the formation of gas and organic oil by-products from the decomposition of the polypropylene separator and the polyvinylidene fluoride binder. The identification of the composition of these by-products has great importance since they have a corrosive and toxic behavior. It was observed the fluorine behavior during the thermal treatment and its presence in the oil by-products.
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| 8. |
- Petranikova, Martina, 1983, et al.
(författare)
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Recovery of critical metals from EV batteries via thermal treatment and leaching with sulphuric acid at ambient temperature
- 2022
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Ingår i: Waste Management. - : Elsevier BV. - 0956-053X .- 1879-2456. ; 140, s. 164-172
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Tidskriftsartikel (refereegranskat)abstract
- In the upcoming years, todaýs e-mobility will challenge the capacity of sustainable recycling. Due to the presence of organic components (electrolyte, separator, casings, etc.), future recycling technologies will combine thermal pre-treatment followed by hydrometallurgical processing. Despite the ongoing application of such treatment, there is still a lack of information on how applied parameters affect subsequent metal recovery. In this study, both oxidative and reductive conditions in dependence on temperature and time were studied. Qualitative and quantitative characterizations of the samples after treatment were performed followed by leaching with 2 M sulphuric acid at ambient temperature to determine the leachability of valuable metals such as Co, Mn, Ni and Li. Moreover, the negative or positive effect of treatment on the leachability of the main impurities (Cu and Al) was determined. Since the presence of carbon affects the degree of active material reduction, it's content after each thermal treatment was determined as well. If all variables, temperature and time of thermal processing are taken into account, pyrolysis at 700 °C for 30 min is the optimal treatment. Under these conditions, full recovery is reached after 2 min for Li, 5 min for Mn and 10 min for both Co and Ni. In the case of the incineration, only processing at 400 and 500 °C promoted higher recovery of metals, while the treatment at 600 and 700 °C led to the formation of less leachable species.
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| 9. |
- Vieceli, Nathalia Cristine, 1989, et al.
(författare)
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Hydrometallurgical recycling of EV lithium-ion batteries: Effects of incineration on the leaching efficiency of metals using sulfuric acid
- 2021
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Ingår i: Waste Management. - : Elsevier BV. - 0956-053X .- 1879-2456. ; 125, s. 192-203
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Tidskriftsartikel (refereegranskat)abstract
- The growing demand for lithium-ion batteries will result in an increasing flow of spent batteries, which must be recycled to prevent environmental and health problems, while helping to mitigate the raw materials dependence and risks of shortage and promoting a circular economy. Combining pyrometallurgical and hydrometallurgical recycling approaches has been the focus of recent studies, since it can bring many advantages. In this work, the effects of incineration on the leaching efficiency of metals from EV LIBs were evaluated. The thermal process was applied as a pre-treatment for the electrode material, aiming for carbothermic reduction of the valuable metals by the graphite contained in the waste. Leaching efficiencies above 70% were obtained for Li, Mn, Ni and Co after 60 min of leaching even when using 0.5 M sulfuric acid, which can be linked to the formation of more easily leachable compounds during the incineration process. When the incineration temperature was increased (600–700 °C), the intensity of graphite signals decreased and other oxides were identified, possibly due to the increase in oxidative conditions. Higher leaching efficiencies of Mn, Ni, Co, and Li were reached at lower temperatures of incineration (400–500 °C) and at higher leaching times, which could be related to the partial carbothermic reduction of the metals.
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