Junjie Shi, Changle Hou, Jingjing Dong, Dong Chen, and Jianzhong Li, Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO2 cathode material, Int. J. Miner. Metall. Mater., 32(2025), No. 1, pp.80-91. https://dx.doi.org/10.1007/s12613-024-2898-4
Cite this article as: Junjie Shi, Changle Hou, Jingjing Dong, Dong Chen, and Jianzhong Li, Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO2 cathode material, Int. J. Miner. Metall. Mater., 32(2025), No. 1, pp.80-91. https://dx.doi.org/10.1007/s12613-024-2898-4
Research Article

Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO2 cathode material

Author Affilications
  • Corresponding author:

    Junjie Shi      E-mail: junjieshi@126.com

  • With the continuous increase in the disposal volume of spent lithium-ion batteries (LIBs), properly recycling spent LIBs has become essential for the advancement of the circular economy. This study presents a systematic analysis of the chlorination roasting kinetics and proposes a new two-step chlorination roasting process that integrates thermodynamics for the recycling of LIB cathode materials. The activation energy for the chloride reaction was 88.41 kJ/mol according to thermogravimetric analysis–derivative thermogravimetry data obtained by using model-free, model-fitting, and Z(α) function (α is conversion rate). Results indicated that the reaction was dominated by the first-order (F1) model when the conversion rate was less than or equal to 0.5 and shifted to the second-order (F2) model when the conversion rate exceeded 0.5. Optimal conditions were determined by thoroughly investigating the effects of roasting temperature, roasting time, and the mass ratio of NH4Cl to LiCoO2. Under the optimal conditions, namely 400°C, 20 min, and NH4Cl/LiCoO2 mass ratio of 3:1, the leaching efficiency of Li and Co reached 99.43% and 99.05%, respectively. Analysis of the roasted products revealed that valuable metals in LiCoO2 transformed into CoCl2 and LiCl. Furthermore, the reaction mechanism was elucidated, providing insights for the establishment of a novel low-temperature chlorination roasting technology based on a crystal structure perspective. This technology can guide the development of LIB recycling processes with low energy consumption, low secondary pollution, high recovery efficiency, and high added value.
  • Lithium-ion batteries (LIBs), with their high energy density, long cycle life, small size, and high safety, are widely used in electric vehicles and consumer battery products [1], contributing to the mitigation of greenhouse gas emissions [25]. As the popularity of electric vehicles and consumer electronics continues to increase, the demand for LIBs and raw materials, such as Li and Co, has considerably increased. Thus, the number of spent LIBs generated after their life cycles end has substantially increased [67]. In China alone, the production of LIBs reached 108 GWh in 2018 and increased to 324 GWh in 2021, and by 2030, the global LIB recycling market is predicted to reach $23.72 billion [8]. Furthermore, the content of valuable metals, such as Li and Co, in spent LIBs is much higher than that of natural minerals [912]. This situation highlights the importance of recycling spent LIBs as sustainable raw materials for producing new LIBs. This approach alleviates the demand for virgin resources. Additionally, the disposal of spent LIBs poses environmental and health risks because they contain high amounts of heavy metals and fluoride-bearing electrolytes [1315]. Therefore, the recovery of spent LIBs is crucial for the circular economy, resource conservation, and environmental sustainability. Global efforts have been dedicated to the development of various technologies that maximize the recovery rates of valuable metals from spent LIBs [1617].

    In chlorination roasting, the metal compound in a material is converted into the corresponding metal chloride through calcination with a chlorination agent in a specific atmosphere. The method is widely used in the extraction of metals from tailings [1819], electronic waste [2021], and industrial solid waste [2223]. Liu et al. [20] developed a vacuum chlorinating process by using CaCl2 and SiO2 as reagents to simultaneously fix sulfur and recover high-purity PbCl2 from spent lead paste; the PbCl2 recovery rate reached 99.7wt% at 350°C under vacuum. Liu et al. [22] extracted Fe and Mn selectively by destroying the typical encompassed structure with NH4Cl; the manganese and iron chlorination ratios reached 95% and 72%, respectively, under the following optimal conditions: NH4Cl/slag mass ratio of 2:1, NaCl/NH4Cl mass ratio of 0.308:1, 800°C, and 4 h; their method had the advantages of having a low roasting temperature requirement, simple operation, high selectivity, and strong adaptability. The potential application of chlorination roasting in the recovery of LIB cathode materials has been explored. Currently, chlorination roasting involves the use of additives, such as Cl2 [2425], CaCl2 [2627], and NH4Cl [2831]. Li et al. [32] revealed the pyrolysis kinetics and reaction mechanism of spent LiCoO2, showing that reactions involving electrode materials (LiCoO2 and C) primarily occur within a temperature range of 500–800°C. Qu et al. [33] demonstrated that the reaction model of the LiCoO2 chlorination stage adheres to the random nucleation and nucleus growth modes after roasting the black mass in the presence of CaCl2; the mechanism function was g(α) = [−ln(1 − α)]3/4, with activation energy (Ea) and pre-exponential factor (A) values of 196.107 kJ/mol and 3.575 × 106, respectively. Fan et al. [34] proposed a method in which spent LiCoO2 was roasted with NH4Cl acting as a fluxing agent. Over 99% of Co and Li were successfully recovered under optimal conditions: temperature of 350°C, reaction time of 2 min, and LiCoO2/NH4Cl mass ratio of 1:2. Existing studies have focused on examining a single facet of the LIB-recycling process, failing to integrate findings from kinetics and thermodynamics systematically to thoroughly explore the reaction mechanism during the chlorination roasting of spent LIBs with NH4Cl as the chlorinating agent.

    Therefore, this study endeavors to provide comprehensive insight into the kinetics and thermodynamic behavior underpinning chlorination reactions, particularly during chlorination roasting for recycling spent LIBs. The study delves into the thermodynamic stability of Li and Co chlorides to affirm the high efficiency and viability of synchronous metal extraction via chlorination roasting. The potential mechanisms driving the chlorination reactions are elucidated using various characterization techniques, including microscopy, spectroscopy, and other analytical methods. The aim is to obtain invaluable insights into reaction pathways and transformations transpiring throughout a chlorination reaction. Beyond shedding light on the chlorination roasting mechanism, this study may facilitate research on chlorination roasting technologies for LIB recycling.

    High-purity LiCoO2 powders were obtained from Aladdin Chemical Reagent Co. Ltd. and used as simulated cathode materials for the experiments. Spent LiCoO2 cathode powders were obtained from spent LIBs through disassembly, crushing, and separation. Table 1 shows the composition of the high-purity LiCoO2 and spent LiCoO2 cathode powders. The spent powder has a lower Co content than the high-purity powder, and the spent materials contains impurities, including Fe, C, and Al. NH4Cl powders obtained from Sinopharm Chemical Reagent Co. Ltd. were used as the reaction’s chlorination additive.

    Table  1.  Compositions of different LiCoO2 powders wt%
    Material Li Co Cu Fe C Al
    Pure LiCoO2 6.95 60.4
    Spent LiCoO2 6.86 47.3 <0.01 0.039 1.32 1.08
     | Show Table
    DownLoad: CSV

    Fig. S1 shows the XRD pattern of the spent LiCoO2 powder, indicating that the main component of the raw material is LiCoO2, which still maintains a layered structure according to the standard card of LiCoO2.

    FactSage [35] is widely used in various fields, such as metallurgy, corrosion, glass technology, combustion, ceramics, geology, and environmental studies. It offers a comprehensive database, multiple computing modules, and user-friendly operation. In this study, the “Reaction” module of FactSage 8.2 was utilized to calculate the Gibbs free energy for potential chloride reactions. The module facilitates thermodynamic calculations and provides valuable information about the stability and feasibility of different responses involving chlorides. Additionally, the “Predom” module of FactSage 8.2 was employed to generate predominance phase diagrams, which visually represent the distribution of different phases under specific conditions and provide a clear and intuitive display of the phase behavior and stability of a system [36].

    Thermogravimetric experiments were conducted using a simultaneous thermal analysis (STA) instrument (NETZSCH STA449F3) in an air atmosphere. Thermogravimetry (TG) and derivative thermogravimetry (DTG) curves were obtained to provide valuable information about the sample’s thermal decomposition and weight loss behavior, which can be further analyzed for the identification of the kinetic parameters of related reactions for subsequent kinetic analysis. Approximately 6 mg of a mixed powder sample with a NH4Cl to LiCoO2 mass ratio of 2:1 was used for the experiments. The sample was heated from 30 to 800°C with three heating rates (5°C/min, 10°C/min, or 20°C/min). Change in the sample’s weight and the corresponding weight change rate as a temperature function were simultaneously obtained with the STA instrument.

    The model-free method is a valuable approach for determining the apparent activation energy (Ea) of complex and multiple reactions even when the mechanism function g(α) of the reactions is unknown. This method does not require knowledge of a specific reaction mechanism and is based on equal conversion methods. Table 2 lists various model-free methods, all of which are equivalent conversion methods and involve the analysis of TG/DTG data obtained at different heating rates within the temperature ranges of reactions. By comparing the weight loss behavior at different heating rates, the Ea value of a reaction can be calculated without relying on a specific reaction mechanism.

    Table  2.  Common model-free methods and corresponding equations
    Method Equation Ref.
    Flynn Wall Ozawa (FWO) lnβ=ln[AEaRg(α)]5.3311.052EaRT [3739]
    Kissinger Akahira and Sunose (KAS) ln[βT2]=ln[AREag(α)]EaRT [4042]
    Starink ln[βT1.92]=C1.0008ln(EaRT) [43]
    Friedman ln[β(dαdT)]=ln[Af(α)]EaRT [4041]
    Note: β—heating rate (°C/min); A—pre-exponential factor; Ea—apparent activation energy (kJ/mol); R—gas constant (8.314 J·mol–1·K–1); g(α)—dominant mechanism function in integral form; T—temperature (K); α—conversion rate; f(α)—dominant mechanism function in differential form; C—constant.
     | Show Table
    DownLoad: CSV

    The conversion rate α in the chlorination roasting process could be deduced by Eq. (1) using TG data.

    α=m0mtm0m
    (1)

    where m0 and m are the initial and final weights of the sample at the beginning of the reaction temperature interval of a TG curve, respectively; mt is the remaining sample weight at reaction time t.

    The dominant mechanism function of chlorination roasting processes can be determined by combining the model-fitting and Z(α) master-plot methods. The model-fitting method was used to narrow down the possible g(α) functions listed in Table 3, and the function with a high coefficient of determination (r2) close to 1 was selected. This method enables the identification of the most suitable mechanism function that describes the reaction kinetics.

    Table  3.  Kinetic models commonly used for thermal decomposition reactions
    Model Tpye Symbol Differential form f(α) Integral form g(α)
    Geometrical contraction
    models
    Contracting area R2 2(1α)1/2 1(1α)1/2
    Contracting volume R3 3(1α)2/3 1(1α)1/3
    Diffusion models Parabolic law, one–dimensional diffusion D1 1/2α α2
    Valesi, two–dimensional diffusion D2 [ln(1α)]1 (1α)ln(1α)+α
    Jander, three–dimensional diffusion D3 (3/2)(1α)2/3[1(1α)1/3]1 [1(1α)1/3]2
    Ginstling–Brounshtein, three–
    dimensional diffusion
    D4 (3/2)[(1α)1/31]1 12α/3(1α)2/3
    Reaction–order models First order F1 1α ln(1α)
    Second order F2 (1α)2 (1α)11
    Third order F3 2(1α)3 [(1α)21]/2
     | Show Table
    DownLoad: CSV

    After the appropriate g(α) function was selected, the Coats–Redfern equation (Eq. (2)) was employed in a specific form for the calculation of the pre-exponential factor and the apparent activation energy for each g(α) function. The calculation was performed through the linear fitting of experimental data.

    ln[g(α)T2]=ln[ARβEa]EaRT
    (2)

    The dominant mechanism function can be further confirmed by comparing the theoretical Z(α) of each g(α) with the experimental Z(α) of each heating rate. Eq. (3) represents the theoretical expression of Z(α), which provides a mathematical relationship between Z(α) and the conversion rate of the reaction. Eq. (4) represents the experimental expression of Z(α) obtained from the experimental data (where t represents time), enabling the calculation of the actual values of Z(α) at different conversion rates. In Eq. (5), π(u) represents the fourth-order Senum–Yang approximation of the temperature integral. This approximation calculates the integral term in the Z(α) equation and is based on a specific mathematical formulation. Finally, Ea is calculated using the model-free method (Eq. (6)). This method utilizes the TG/DTG data obtained at different heating rates for the calculation of the activation energy without relying on a specific reaction mechanism.

    Z(α)=f(α)g(α)
    (3)
    Z(α)=π(u)(dαdt)Tβ=π(u)(dαdT)T
    (4)
    π(u)=u3+18u2+86u+96u4+20u3+120u2+240u+120
    (5)
    u=EaRT
    (6)

    Fig. 1 shows a schematic diagram of the chlorination roasting–water leaching process for treating spent LiCoO2 powder. Approximately 1.5 g of powder was mixed thoroughly with a certain amount of NH4Cl, and the mixture was transferred to a 20-mL crucible. The crucible was then placed in a muffle furnace for a certain period after the furnace had been preheated to the designated preset temperature. The roasted samples were removed after the furnace cooled to room temperature. The roasted sample was ground for 30 min with a mortar. Subsequently, the ground sample was subjected to 30 min of water leaching at 25°C with a solid–liquid ratio of 20 g/L for the extraction of valuable metals.

    Fig. 1.  Experimental process of chlorination roasting and water leaching.

    The surface morphology and microstructure of the spent LiCoO2 and roasted product were observed using a scanning electron microscopy (SEM) system (ZEISS Gemini 300 instrument). The phase composition of the spent LiCoO2, roasted product, and filter residue was determined through X-ray diffraction (XRD) analysis with a Panalytical X’Pert’3 Powder instrument. The crystal structure and phase composition of the materials were determined with an XRD system equipped with a Cu Kα radiation source. The specific phases were identified by analyzing the XRD data with the search–match method. The valences of Li and Co in the roasted products were characterized using X-ray photoelectron spectroscopy (XPS) with a Thermo Scientific K-Alpha instrument. XPS employs an Al Kα radiation source for the analysis of the chemical composition and valence states of elements on the surfaces of samples. An inductively coupled plasma emission spectrometer (ICP-OES, Agilent 5110) was used in obtaining the initial and residual concentrations of Li and Co in the leaching solution. This instrument can accurately measure the concentration of metal elements in the solution. The leaching rate of metal was calculated using Eq. (7).

    Ri=CiViMi×100%
    (7)

    where Ri is the leaching rate of metal i, Ci is the concentration of element i obtained in the leaching solution, Vi is the volume of the leaching solution, and Mi is the total mass of element i in the raw material.

    The relationship between standard Gibbs free energy change (ΔG) and temperature (0–1000°C) for possible decomposition reactions was obtained using Factsage 8.2. The results are presented in Table 4, and the corresponding relationship between ΔG and temperature is plotted in Fig. 2. The thermodynamic data for LiCoO2 was calculated by a group-contribution method [4445]. Reaction (1) shows that NH4Cl can spontaneously decompose into NH3 and HCl at a temperature higher than 364°C; that is, gas–solid reactions occur at temperatures above 364°C. The decomposition reaction of LiCoO2 remains thermodynamically stable up to 1000°C. The reaction between LiCoO2 and NH4Cl or HCl is thermodynamic feasible according to reactions (3)–(7). Reaction (3) indicates that LiCoO2 can be converted into LiCl and CoCl2 at a temperature higher than 0°C in the presence of HCl gas, and reaction (4) proves that the chloride reaction occurs at a temperature higher than 285°C in the presence of NH4Cl. Reactions (5) and (6) demonstrate that LiCoO2 is probably converted into LiCl, CoO, or Co3O4. Reaction (7) indicates that the roasted product may contain LiOH and CoCl2. Furthermore, the Gibbs free energy change of reaction (3) is lower than that of reactions (4)–(7) at low temperatures, indicating that reaction (3) is favorable at low temperatures. The stability of CoCl2 and LiCl below 1000°C is demonstrated by reactions (8)–(10), demonstrating that these compounds remain thermodynamically stable within a specific temperature range in the air atmosphere. However, reactions (11), (12), and (13) show that CoCl2 and LiCl easily form hydrates with H2O at low temperatures, whereas LiCl·H2O, CoCl2·2H2O, and CoCl2·2H2O cannot maintain thermal stability above 184°C. Therefore, the co-chlorination reactions of LiCoO2 by roasting with NH4Cl are thermodynamically favorable.

    Table  4.  Possible reactions during roasting (0–1000°C)
    No. Reaction Reaction temperature / °C
    1 NH4Cl(s) = NH3(g) + HCl(g) 364–1000
    2 2LiCoO2(s) = Li2O(s) + 2CoO(s) + 1/2O2(g)
    3 LiCoO2(s) + 4HCl(g) = LiCl(s) + CoCl2(s) + 2H2O(g) + 1/2Cl2(g) 0–1000
    4 LiCoO2(s) + 4NH4Cl(s) = LiCl(s) + CoCl2(s) + 2H2O(g) + 1/2Cl2(g) + 4NH3(g) 285–1000
    5 LiCoO2(s) + 2NH4Cl(s) = LiCl(s) + CoO(s) + H2O(g) + 1/2Cl2(g) + 2NH3(g) 125–1000
    6 6LiCoO2(s) + 8NH4Cl(s) = 6LiCl(s) + 2Co3O4(s) + 4H2O(g) + Cl2(g) + 8NH3(g) 0–1000
    7 LiCoO2(s) + 3NH4Cl(s) = LiOH(s) + CoCl2(s) + H2O(g) + 1/2Cl2(g) + 3NH3(g) 192–1000
    8 CoCl2(s) + 1/2O2(g) = CoO(s) + Cl2(g)
    9 3CoCl2(s) + 2O2(g) = Co3O4(s) + 3Cl2(g)
    10 2LiCl(s) + 1/2O2(g) = Li2O(s) + Cl2(g)
    11 LiCl(s) + H2O(g) = LiCl·H2O(s) 0–184
    12 CoCl2(s) + 2H2O(g) = CoCl2·2H2O(s) 0–147
    13 CoCl2(s) + 6H2O(g) = CoCl2·6H2O(s) 0–113
     | Show Table
    DownLoad: CSV
    Fig. 2.  (a) ΔG values of chlorination reactions and (b) the decomposition reaction of raw material and roasted product.

    The stability regions of various phase assemblies in the Li–Co–H–Cl–O system were determined through calculations in FactSage 8.2. The results, based on ΔG, are presented in Fig. 3(a)–(d) and show the stability of chloride compounds at temperatures ranging from 200 to 500°C. As shown in Fig. 3(a), the predominance area diagram can be divided into five phase domains: LiCl + CoCl2, LiCl + Co3O4, LiCl + CoCl2·6H2O, LiCl + CoCl2·2H2O, and LiOH + CoCl2·2H2O at 200°C. The target product area comprises LiCl + CoCl2, LiCl + CoCl2·2H2O, and LiCl + CoCl2·6H2O. Notably, target products often manifest at low temperatures.

    Fig. 3.  Predominance area diagram of Li–Co–H–Cl–O at (a) 200°C, (b) 300°C, (c) 400°C, and (d) 500°C.

    The TG-differential scanning calorimetry (DSC) and TG-DTG curves of the mixed powders of LiCoO2 and NH4Cl at a heating rate of 5°C/min are presented in Fig. 4. Fig. 4(a) shows the first weight-loss stage with three endothermic peaks, which are weaker than the thermogravimetric curve of NH4Cl [46]. This result indicates that LiCoO2 facilitates NH4Cl decomposition by reacting with HCl, consistent with reaction (3). Although no endothermic peaks were observed during the second and third weight-loss stages in TG-DSC curves, them can be found in the TG-DTG curves (Fig. 4(b)). Given that Co2+ readily forms (NH4)3CoCl5, (NH4)2CoCl4, and NH4CoCl3 in the NH4Cl–NH3 medium [4748], the full decomposition temperature of NH4Cl increases to 500°C, resulting in the second chlorination reaction during the second weight-loss stage [49]. Before the third weight-loss stage, NH4Cl fully decomposes, causing a weight decrease. Thus, the maximum reaction temperature limit is 500°C, at which product decomposition is prevented.

    Fig. 4.  TG-DSC (a) and TG-DTG (b) curves of the mixed powders of LiCoO2 and NH4Cl at 5°C/min heating rate.

    The thermogravimetric results show that chlorination mainly occurs in the first weight-loss stage: 177–362°C. The TG and DTG curves for the mixture of NH4Cl and LiCoO2 are presented in Fig. S2(a) and (b) for different heating rates.

    Fig. 5(a) shows the relationship between temperature and conversion rate α. The graph demonstrates that the conversion rate increases with temperature, indicating that the reaction becomes favorable and progresses toward completion at high temperatures. Notably, this trend is consistent at different heating rates, but the conversion rate decreases when the heating rate increases at a fixed temperature.

    Fig. 5.  (a) Conversion rate changing with temperature at different heating rates; (b) Ea calculated by model-free methods listed in Table S1.

    At a fixed temperature, the model-free method can be used in calculating the activation energy. The activation energy calculated by the four model-free methods is depicted in Fig. 5(b), and the exact values of the calculated activation energy at different conversion rates are listed in Table S1. The activation energy calculated by FWO, KAS, and FWO fluctuates around the average but shows a steady trend, whereas the r-square values of FWO are mostly close to 1. For the precise approximation of temperature integral and proper r-square values, the average activation energyobtained from the FWO method (Ea,FWO = 88.41 kJ/mol) was used as the parameter for the reaction mechanism.

    Model fitting narrows the scope of reaction models, and the Z(α) master-plot method further confirms the exact mechanisms with related kinetic models during reactions. The curve in Fig. 6 represents the theoretical value of Z(α), while the points correspond to the experimental values of Z(α). Table S2 shows the kinetic parameters of common models calculated by model fitting. The point values of Z(α) gradually flatten with increasing heating rate. According to the Z(α) curve of the best-fitting model in Fig. 6(b), the conversion rate increases with temperature, and a reaction is controlled by the first reaction (F1) with an apparent activation energy of 67.84 kJ/mol at α ≤ 0.5. Conversely, the control step shifts as the third reaction (F3) with an apparent activation energy of 194.98 kJ/mol at α > 0.5. The results reveal that the chlorination reaction becomes dominant at higher temperatures.

    Fig. 6.  Comparison of the experimental data with theoretical curves at different heating rates: (a) models with all fitting effects and (b) models with the best fitting effect.

    The effects of roasting temperature on the roasted product and the leaching rate of Li and Co were studied at a roasting time (t) of 30 min and a NH4Cl/LiCoO2 mass ratio (w) of 2:1. The results are shown in Figs. S3 and 7. As shown in Fig. S3, the color of the mixed powders changes from black (0°C) to green (200–250°C) and blue (400–500°C) as temperature increases. This change indicates that chlorination reactions occur as two-step processes. At 200–250°C, only the surface of the roasted product changes color, whereas the interior remains black. The change in color indicates the presence of Co(II) as the roasted product. Notably, the CoCl2 sublimates and adheres to the lid above 450°C, fitting the products decomposed in the third weight-loss stage of the thermogravimetric results. The effects of the roasted products at different roasting temperatures were clarified through XRD. As shown in Fig. 7(a), the diffraction peaks at 200–250°C mainly correspond to LiCoO2, NH4Cl, and (NH4)xCoCl2+x, and the peaks of (NH4)xCoCl2+x are weak, indicating that incomplete chlorination can occur at low temperatures. The green color of (NH4)xCoCl2+x is consistent with the color of the roasted product, proving the existence of (NH4)xCoCl2+x and the occurrence of chlorination. After the temperature increases to 300°C, the diffraction peaks of LiCoO2 and NH4Cl transform entirely into the diffraction peaks of (NH4)xCoCl2+x and LiCl·H2O, respectively. This transformation is consistent with the sharp increase in leaching rate observed in Fig. 7(b) between 250°C and 300°C. The phase remains the same at 300–400°C, and leaching rate slowly increases.

    Fig. 7.  XRD patterns of roasted products (a) and the corresponding leaching rates (b) at different temperatures (t =30 min; w = 2:1).

    At 450–500°C, the diffraction peaks of (NH4)xCoCl2+x and LiCl·H2O transformed into CoCl2·2H2O (fuchsia) and LiCl·H2O, indicating that (NH4)xCoCl2+x decomposes between 400 and 450°C. As shown in Fig. 7(a), the diffraction peaks shift regularly to the left with increasing temperature, indicating that the amount of NH4Cl in (NH4)xCoCl2+x gradually decreases. However, the fuchsia of CoCl2·2H2O does not match the blue color of the product because of the water absorption of CoCl2 (blue) at room temperature when LiCl is under the same situation. XRD analysis corresponds well with the reaction of the second weight-loss stage. The leaching rate of Li remains unchanged after reaching the maximum value (98.27%) at 400°C, and the leaching rate of Co continues to increase with temperature. The results indicate that the chlorination reaction ends at 400°C, and the leaching rate of Co is affected by some unknown factors.

    As shown in Fig. 8(a), the main phase of residue is Co2(OH)3Cl, which results in the low leaching rate of Co. In a previous experiment [50], Co2(OH)3Cl was used as the solid solution of Co(OH)2 and CoCl2 and was prepared in an alkaline solution. The XRD analysis results show that alkaline substances are not produced during roasting. During roasting, NH3 and H2O are not consumed as chlorination products. Thus, NH3 may react with H2O and form NH3·H2O during cooling.

    Fig. 8.  (a) XRD pattern of leaching residue; (b) comparison of products with and without lid based on XRD patterns and leaching liquor (T = 350°C, w = 2:1, t = 20 min); (c) leach solution with lid; (d) leach solution without lid.

    As shown in Fig. 8(b), roasting without a lid, which favors NH3 emission, was compared with roasting with a lid. The methods generate the same products, but the leaching solution of the roasted products without a lid is limpid. In conclusion, NH3 and H2O produced by chlorination reactions form ammonia during cooling, which results in an alkaline leaching solution leading to Co precipitation.

    The impact of NH4Cl to LiCoO2 mass ratio on the roasted product and leaching rate of Li and Co was examined under the condition with a roasting time of 30 min and temperature of 350°C, with the results illustrated in Fig. 9. In Fig. 9(a), when the mass ratio of NH4Cl and LiCoO2 was 0.5:1, the predominant compound phases were LiCoO2 due to the insufficient amount of NH4Cl to react with LiCoO2. A mass ratio of 1:1 resulted in the emergence of diffraction peaks of (NH4)xCoCl2+x and LiCl·H2O alongside the presence of mostly LiCoO2. Then LiCoO2 completely transformed to the (NH4)xCoCl2+x and LiCl·H2O at 2:1–3:1. Additionally, a linear correlation between the mass ratio and the leaching rates of Li and Co is evident in Fig. 9(b), with leaching rates reaching 100% for Li and 88.9% for Co at a mass ratio of 3:1. Ultimately, the mass of NH4Cl was conducive to the chlorination reaction without significantly affecting the roasted products.

    Fig. 9.  XRD patterns of roasted products (a) and the corresponding leaching rate (b) at different mass ratio of NH4Cl to LiCoO2 (T = 350°C, t = 30 min).

    The effect of roasting time on the roasted product and the leaching rates of Li and Co in a NH4Cl to LiCoO2 mass ratio of 2:1 were investigated at 350°C. The results are detailed in Fig. 10. As shown in Fig. 10(a), LiCoO2 is completely chlorinated to (NH4)xCoCl2+x and LiCl·H2O after 10 min, and no change in the roasted products occurs with roasting time. The corresponding leaching rate of Li fluctuates within the margin of error, as shown in Fig. 10(b), indicating that chlorination proceeds smoothly.

    Fig. 10.  XRD patterns of roasted products (a) and the corresponding leaching rates (b) at different roasting times (T = 350°C, w = 2:1).

    Different roasting methods were applied to improve the leaching rate of Co. The diffusion of NH3 to the atmosphere was induced by roasting without a lid, ensuring the completion of chlorination. As shown in Fig. S4, the two-step method was developed by integrating the advantages of the other methods, starting with roasting with a lid followed by roasting without a lid after lid removal.

    The results of the leaching rate of Li and Co are shown in Fig. 11. In Fig. 11(a), the roasted products with a lid considerably differ from those obtained by other methods under the following conditions: 350°C, 2:1 NH4Cl/LiCoO2 mass ratio, and 30 min. The products roasted without a lid and with two-step calcination are mainly CoCl2·2H2O. This result indicates that roasting without a lid can promote the decomposition of (NH4)xCoCl2+x. Fig. 11(b) shows that the leaching rate of Li and Co subjected to two-step roasting and roasting without a lid is higher than that after roasting with a lid. The optimal method is two-step roasting with a leaching rate of 95.77% Li and 92.54% Co, which ensures adequate chlorination and NH3 emissions.

    Fig. 11.  Comparison of different roasting methods with (a) XRD pattern of roasted products and (b) leaching rate of Li and Co (T = 350°C; w = 2:1; t =30 min).

    The feasibility of chlorination roasting for spent LIBs was determined with a roasting experiment with the two-step method under the following conditions: 400°C, 3:1 NH4Cl/LiCoO2 mass ratio, and 20 min. As shown in Fig. 12(a), the roasted product of pure LiCoO2 and spent LiCoO2 is consistent and composed of (NH4)xCoCl2+x and LiCl·H2O. The leaching rate of Li and Co in pure LiCoO2 is 99.43% and 99.05% in Fig. 12(b), respectively, proving the correctness of the optimal condition. The leaching rates of Li and Co in the spent LiCoO2 (spent-1 and spent-2 are made with the same experimental materials and conditions) under the same conditions are higher than 99%. Nevertheless, the results demonstrate the feasibility of recovering LiCoO2 by chlorination roasting–water leaching process and show that NH4Cl has a high recovery efficiency for spent LiCoO2.

    Fig. 12.  Comparisons of results from using pure LiCoO2 and spent LiCoO2 as raw materials: (a) XRD pattern of chlorination-roasted product; (b) leaching rate of the chlorination-roasted product; (c) XPS spectra of spent LiCoO2 before and after roasting and (d) enlarged in spectra of Co 2p; SEM (e) and energy disperse spectroscopy (f) analyses of CoCl2.

    Fig. 12(c) and (d) indicates that Co(III) is converted into Co(II) after roasting. Fig. 12(e) shows the microstructure of the roasted product, which is a hollow pellet formed by the adhesion of many fine particles, and Fig. 12(f) demonstrates that the primary substance of the pellet is CoCl2.

    The conversion of LiCoO2 cathode powder is demonstrated in Fig. 13. As temperature increases, NH4Cl decomposes to produce NH3 and HCl gases, where HCl only participates in the reaction [46]. As shown in Fig. 7(a), the products of roasting are LiCl and (NH4)xCoCl2+x below 400°C. As temperature increases, (NH4)xCoCl2+x is decomposed into NH3, HCl, and CoCl2. The TG-DSC analysis results in Section 3.2.1 reveal two primary processes in chlorination roasting. Recovery can be categorized as a two-stage reaction: initially, the decomposition of NH4Cl generates HCl and NH3. Concurrently, a reduction reaction involving HCl disrupts the structure of LiCoO2, leading to the reduction of Li and Co and producing LiCl and (NH4)xCoCl2+x, respectively. As temperature increases, the NH4Cl in (NH4)xCoCl2+x gradually decomposes and reacts with LiCoO2. By controlling the appropriate conversion temperature and atmosphere, a chlorination roasting recovery technology can be easily applied to other types of spent LIBs.

    Fig. 13.  Mechanism of chlorination roasting of NH4Cl and LiCoO2 mixed materials.

    This study proposed a new chlorination roasting–water leaching process for recovering spent LIBs. The temperature range of chlorination was divided into two steps: the decomposition of NH4Cl and the decomposition of (NH4)xCoCl2+x by thermogravimetric experiments. The activation energy of chlorination reactions was 88.41 kJ/mol according to the results of kinetic analysis combining model-free, model-fitting, and Z(α) functions, and the chlorination reactions were consistent with F1 (α ≤ 0.5) and F2 (α >0.5). The effects of roasting temperature, roasting time, mass ratio of NH4Cl/LiCoO2, and roasting methods were studied, and the leaching rates of Li and Co for spent LiCoO2 were 95.77% and 92.54%, respectively, under optimal conditions. The feasibility of the chlorination recovery process for spent LIBs was verified with experiments on spent LiCoO2 powder. Finally, the reaction mechanism of NH4Cl and LiCoO2 was determined with thermodynamics, kinetics, and roasting experiment, which included two steps: the decomposition reaction of NH4Cl, the gas–solid reaction between HCl and LiCoO2, and the decomposition reaction of (NH4)xCoCl2+x.

    In summary, the chlorination roasting–water leaching process had the advantages of being environmentally friendly and having low energy consumption, low secondary pollution, high recovery efficiency, and high added value. This work provided theoretical data for the chlorination recovery of LIBs, which is of great significance for constructing a green and sustainable recycling process for LIBs.

    This work was financially supported by the National Natural Science Foundation of China (No. 52204310), the Guizhou Provincial Key Laboratory of Coal Clean Utilization (No. [2020]2001), the China Postdoctoral Science Foundation (Nos. 2020TQ0059 and 2020M570967), the Natural Science Foundation of Liaoning Province (No. 2021–MS–083), the Fundamental Research Funds for the Central Universities, China (No. N2125010), the Open Project Program of Key Laboratory of Metallurgical Emission Reduction & Resources Recycling (Anhui University of Technology), Ministry of Education (No. JKF22–02), the Foundation of Liupanshui Normal University (No. LPSSYZDZK202205), and the Key Laboratory for Anisotropy and Texture of Materials, Ministry of Education, China.

    The authors report no conflicts of interest and the authors alone are responsible for the content and writing of the article.

    The online version contains supplementary material available at https://doi.org/10.1007/s12613-024-2898-4

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