Journal of Cleaner Production 417 (2023) 138043

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Journal of Cleaner Production

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A novel method for recovering valuable metals from spent lithium-ion

batteries inspired by the mineral characteristics of natural spodumene
Youqi Fan a, b, Hu Li b, Chang Lu b, Shiliang Chen a, b, *, Yonglin Yao b, Hanbing He b, c, **,
Shuai Ma b, Zhen Peng b, Kangjun Shao b
a
Key Laboratory of Metallurgical Emission Reduction and Comprehensive Utilization of Resources, Ministry of Education, Maanshan, 243000, China
b
School of Metallurgical Engineering, Anhui University of Technology, Maanshan, 243000, China
c
School of Metallurgy and Environment, Central South University, Changsha, 410083, China

A R T I C L E I N F O A B S T R A C T

Handling Editor: Zhen Leng Based on the unique crystal structure characteristics of natural spodumene (LiAlSi2O6) with six coordination of Li
at the M2 position and monoclinic crystal system, an innovative approach is developed for the simultaneous
Keywords: recovery of Co, Ni, and Cu, while selectively enriching Li into the slag. The slag system was designed and
Lithium-ion battery controlled according to thermodynamic simulations and calculations to provide the theoretical basis for subse­
Recycling
quent experiments. The effects of the ratio of Al2O3 to SiO2, temperature, and ratio of raw material to oxidizer
Spodumene
addition on metal recovery were systematically investigated. The results showed that Li, Co, Ni, and Cu recovery
Pyrometallurgy
Leaching efficiencies could exceed 99%, while Li was concentrated in the slag with a high grade of Li2O (6.0–9.0 wt%)
under the experimental conditions, which is about 1.0–1.6 times that of the commercially available spodumene
concentrate (Li2O, 5.5 wt%). By sulfation roasting-leaching of this lithium-rich slag, a leaching efficiency of Li
can be achieved to 93%. This study provides valuable insights into shortening the recycling process of spent
lithium-ion batteries and increasing the comprehensive utilization rate of high-value metals.

1. Introduction The recovery of valuable metals from SLIBs is currently accom­

plished through three main methods (Table 1): pyrometallurgy (Fan
Lithium-ion batteries (LIBs) are used as crucial energy storage et al., 2020), hydrometallurgy (Zhang et al., 2018), and a combination of
components in automobiles, communications, and electronic devices the two (Arshad et al., 2020). Hydrometallurgical processes are capable
(Al-Thyabat et al., 2013) due to their lightweight properties, high ca­ of producing high-purity metals with a high recovery efficiency. (Assefi
pacity, and long lifespan (Miao et al., 2022). However, the growing et al., 2020). However, these processes can be time-consuming and may
electric vehicle market is expected to result in a significant increase in lead to secondary pollution (Yao et al., 2018) and waste disposal chal­
spent lithium-ion batteries (SLIBs) (Choubey et al., 2017; Chen et al., lenges (Lv et al., 2018). The pyrometallurgy method offers the benefits
2022), with projections of 253 million electric vehicles on the roads by of a short process and high adaptability to raw materials (Zhang et al.,
2030 (Liu et al., 2019). SLIBs contain valuable elements such as Co, Ni, 2021), as well as a larger processing capacity (Kwon and Sohn, 2020).
Cu, Li, and others (Chen et al., 2016), which if not properly recycled, can However, it requires high energy consumption (Popien et al., 2022). The
result in wasted resources (Jin et al., 2022) and toxic waste (Harper combined method provides the benefits of both pyrometallurgy and
et al., 2020). Therefore, to protect the environment (Chagnes et al., hydrometallurgy (Lu et al., 2021; Lin et al., 2020). In the pyrometal­
2013) and alleviate the shortage of resources (Chen et al., 2019), there is lurgical mothed, SLIBs are directly smelted to produce Co–Ni–Cu–Fe
an urgent need to develop environmentally friendly recycling technol­ alloy or Co–Ni matte and then recovered through hydrometallurgical
ogies for the effective and safe treatment and recovery of SLIBs (Lu et al., separation. This technology, which has promising prospects for indus­
2014). trial application, is currently being used to treat SLIBs in Umicore

* Corresponding author. Key Laboratory of Metallurgical Emission Reduction and Comprehensive Utilization of Resources, Ministry of Education, Maanshan,
243000, China.
** Corresponding author. School of Metallurgical Engineering, Anhui University of Technology, Maanshan, 243000, China.
E-mail addresses: [email protected] (S. Chen), [email protected] (H. He).

https://doi.org/10.1016/j.jclepro.2023.138043
Received 2 February 2023; Received in revised form 8 June 2023; Accepted 8 July 2023
Available online 10 July 2023
0959-6526/© 2023 Elsevier Ltd. All rights reserved.
Y. Fan et al. Journal of Cleaner Production 417 (2023) 138043

Table 1
The main methods of SLIBs are (a) Typical hydrometallurgy methods, (b) Typical treatment under high temperature.
(a)Typical hydrometallurgy methods

Raw material Leaching Recycling Leaching conditions Characteristic Ref.

agents elements

Cathode powder obtained after the long Ascorbic Co, Ni, and Mn T = 70 ◦ C, L/S = 25:1 t Long process, with high acid consumption, but a Fan et al.
process of pretreatment = 20 min high recovery efficiency (2020)
Citric acid Co, Ni, Mn, and T = 60 ◦ C, L/S = 100:1, (Joo et al.,
Li t = 2h 2016)
HCl Co, Li T = 60 ◦ C, L/S = 8:1, t = Li et al.
1h (2009)
H2SO4 Co T = 60 ◦ C, L/S = 100:1, Kang et al.
t=1h (2010)

(b)Typical treatment under high temperature

Raw material Critical Recycling Smelting Characteristic Ref

Processes elements conditions

Cathode powder obtained after Reduction Co, Ni, and Cu T= Fewer types of metals are recovered, but the recovery (Cheret et al., 2007) (
the long process of roasting 1400–1500 ◦ C efficiency will be high Wang et al., 2016)
pretreatment Sulfate Li, Co T = 600 ◦ C, t =
roasting 0.5 h
SLIBs without pretreatment Direct slag Co, Ni, Fe T = 1450 ◦ C, t = CaO–Al2O3–SiO2 slag system short process, high (Georgi-Maschler et al.,
melting 1.0 h recovery efficiency, a large amount of slag, Li is not 2012)
recovered.
Co, Ni, Fe, and T = 1450 ◦ C, t = FeO–Al2O3–SiO2 slag system short process, high Ren et al. (2017)
Cu 1.0 h recovery efficiency, a large amount of slag, Li is not
recovered.
Co, Ni, Cu, Mn T = 1500 ◦ C, t = Li2O–Al2O3–SiO2 slag system short process, the high This work
and, Li 0.5 h recovery efficiency, small slag volume, high recovery
rate of Li

Hoboken (Belgium) (Cheret et al., 2007) and Chaoda Sudbury (Canada) 2.5–4.0% wt% (Xiao et al., 2017). Scholars have primarily focused on
(Georgi-Maschler et al., 2012) smelters. recovering Co, Ni, and Cu metals during the melting of SLIBs. However,
The success of pyrometallurgical recycling of SLIBs relies on the se­ due to the large volume of slag produced and the high efficiency of Li
lection of an appropriate slag system. Researchers have developed volatilization, the Li2O content in the slag is typically very low, it is often
various using slag systems such as CaO–Al2O3–SiO2 and FeO­ lower than the Li2O content found in natural spodumene concentrates,
–Al2O3–SiO2 slag systems to achieve high levels of recycling efficiency which means that the slag does not have any significant recovery value
(Cheret et al., 2007). The Val’Eas process combines single SLIBs with for Li. Most of the Li in the slag exists in a complex form with low Li
other cobalt concentrate materials at 1400–1500 ◦ C without prior me­ content (typically 1–3 wt%) (Zhang et al., 2016), and it often ends up
chanical dismantling or physical sorting. The resulting product is a being disposed of in landfills (Chan et al., 2021) or used as raw material
Co–Ni–Cu–Fe alloy. The Inmetco process (Georgi-Maschler et al., 2012) for construction (Graedel et al., 2011). This results in a waste of valuable
fuses discarded Li-ion/nickel-hydrogen batteries with Fe-containing raw Li resources. The complex composition and large volume of the tradi­
materials, adds flux SiO2 and limestone to form a CaO–Al2O3–SiO2 slag tional slag system led to complex Li phase and low Li content in the slag,
system, and uses graphite and organic matter from the batteries as making it difficult to connect with the existing Li extraction process;
heating and reducing agents to produce Fe–Co–Ni alloys. The addition of moreover, due to the high chemical activity of Li, it is easy to get into the
too much slagging, results in a large amount of slag, low Li content, and soot during the smelting process, resulting in partial loss of Li. Therefore,
difficulty to store and reuse. Ren (Ren et al., 2017) used a FeO­ the difficulty of the current pyrometallurgical Li recovery is that no
–Al2O3–SiO2 slag system for the mixed reduction smelting of soft man­ suitable slag system has been developed to enrich Li with high recovery
ganese ores for SLIBs and obtained a Co–Ni–Cu–Fe alloy at 1450 ◦ C. of Cu, Co, and Ni metals.
However, the slag volume was too large, the slag had many phases and Previous studies did not consider Li2O as the main component of the
complex composition, and the Li2O content in the slag was only slag in the slag-making process, resulting in a large slag volume and

Fig. 1. Physical images (a) SLIBs (b) pretreatment material.

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Y. Fan et al. Journal of Cleaner Production 417 (2023) 138043

Table 2
Major metal element content of pre-roasted SLIBs (wt%).
Cu Mn Ni Al* Co Li Fe

15.81 ± 13.91 ± 9.24 ± 8.54 ± 4.50 ± 3.42 ± 0.95 ±

0.39 0.31 0.24 0.21 0.09 0.05 0.01

Note: the results were analyzed by Flame Atomic Absorption Spectroscopy

(FAAS) and * represents the result of Al being tested by Inductively coupled
plasma-optical emission spectrometry (ICP-OES).

Fig. 4. Li2O–Al2O3–SiO2 ternary phase diagram.

spodumene concentrates, which makes it a valuable artificial lithium

concentrate (Zeng et al., 2014), and the slag can be connected with the
current lithium concentrate smelting treatment process.
This work is to recover valuable metals such as Cu, Co, Ni, and Li
from SLIBs. Based on the composition of Cu, Co, Ni, Al, and Li in SLIBs
and the properties of natural spodumene, the Cu–Co–Ni alloy was suc­
cessfully recovered through theoretical design and mechanistic study,
Fig. 2. XRD pattern of SLIBs after pretreatment. and a lithium-rich slag with Li2O content greater than 7% was also ob­
tained, and the lithium extraction effect of the lithium-rich slag was
evaluated.

2. Materials and methods

2.1. Raw materials

The SLIBs were supplied by a battery processing company and they

have dimensions 130 mm × 80 mm x 8 mm (Fig. 1(a)). Chemical
analysis of the main metal elements in the SLIBs, including Co, Ni, Cu,
Al, and Li, is presented in Table 2, and pretreated SLIBs were used as raw
materials in this research (Fig. 1(b)). The pretreated SLIBs (Fig. S1)
consist mainly of metal oxides, Li-containing oxides, and C powder
(Fig. (2), Fig. (3)).

2.2. Design of the experimental procedures

In this study, the slag is made for the enrichment of Li, so for equi­
librium analysis and calculation, Li is set as the slag component. The
study designed the Li2O–Al2O3–SiO2 slag system based on the compo­
Fig. 3. SEM image of pretreated SLIBs.
sition of SLIBs. The ternary phase diagram of Li2O–Al2O3–SiO2 (Gal­
akhov, 1959) was analyzed to determine the regions of slag phase
composition in Fig. 4.
complex and unstable structure of the Li-containing phase in the slag.
SiO2 was selected as a flux (Cheng, 2021) in the reduction smelting
However, by using both Li2O and Al2O3 as the main components of the
process of SLIBs to efficiently enrich Li in the slag phase. From the B
slag and avoiding the addition of other metal oxides, the volume of the
point in Fig. 4, when the molar ratio of Li2O, Al2O3, and SiO2 was 1:1:4,
slag can be reduced, to increase the content of Li2O in the slag. More­
the spodumene (LiAlSi2O6) phase was formed. The theoretical content of
over, the lithium-rich slag phase will have a simple and stable compo­
Li2O in spodumene is 8 wt% and the smelting temperature was
sition, resulting in a simple and stable Li-bearing phase. By analyzing the
approximately 1500 ◦ C. Since a portion of the added SiO2 will form
phase diagram of Li2O–Al2O3–SiO2 (Galakhov, 1959), the slag system
other silicate products, to ensure the formation of the spodumene phase
was determined concerning the phase characteristics of natural spodu­
must be considered the ratio of Al2O3 and SiO2 (Qu et al., 2023). Due to
mene ore, and the temperature required to form this slag system is
the high C content in the raw material, the reduction is too strong, so O2
suitable and the slag quantity is small. Spodumene, one of the vital
is introduced to adjust the atmosphere in the furnace (Fig. 5).
natural Li-bearing resources, is currently processed through mature
methods like sulfation roasting (Kuang et al., 2018), alkali roasting
(Chen et al., 2011), and sulfate roasting (Li et al., 2019). Smelting slag 2.3. Thermodynamics
has fewer impurities and a higher lithium content compared to natural
The molar Gibbs free energy of generation ΔfGθm (oxygen potential)

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Y. Fan et al. Journal of Cleaner Production 417 (2023) 138043

Fig. 5. Smelting and Sulphated roasting - leaching experimental flow chart.

Fig. .6. Oxygen potential of different elements as a function of temperature.

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Y. Fan et al. Journal of Cleaner Production 417 (2023) 138043

Fig. 7. Simulation calculation - distribution of elements (Cu, Co, Ni, Mn, Li, F, P) in the alloy, slag, and gas.

versus temperature T (Fig. 6) for the oxides of the main elements of the slagging flux is necessary to form stable compounds with Al2O3, Li2O,
LIBs roasting products and investigated the smelting process of all and MnOx.
components of SLIBs (valuable metal elements and F/P hazardous Based on the main composition of the pretreated SLIBs samples
components) in the slag, alloy, and flue gas during the smelting process (Table 2), according to the analysis of the ternary phase diagram and the
(Fig. 7) were calculated using Facsage 7.0 software. simulation data performed by Factsage 7.0 under weak reducing at­
The study aims to efficiently enrich and recover lithium by first mosphere conditions, the following experimental conditions were
ensuring the efficient enrichment of high-value metals Co and Ni in determined: PO2 = 10− 13–10− 7 atm, T = 1500 ◦ C, Al2O3/SiO2 = 0.7
lithium ions. To achieve this, the experimental sample is divided into (Haccuria et al., 2015).
three parts: alloy, smelting slag, and flue gas, and high-temperature
smelting at 1500 ◦ C is used as an example analysis. Therefore, to
ensure the alloying of transition group metals, the selection of the 2.4. Smelting
optimal reducing atmosphere is a necessary condition in the smelting
process. The content of Al and Mn in the pretreated SLIBs was high, 8.5% This study investigates the influence of three key variables on
and 13.9%, respectively, and the content of Li was 3.4%; these three smelting, namely the oxygen potential, temperature, and raw material
elements are the main components of the slag, and selecting a suitable composition. It is noteworthy that an additional oxidant is typically
introduced during the pyrometallurgical process to facilitate the

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Y. Fan et al. Journal of Cleaner Production 417 (2023) 138043

Fig. 8. Effect of M/O on metals recovery and S/A (a) Recovery of metals; (b) Metals content in lithium-rich slag; (c) S/A.

combination of Li and Al with the slagging agent SiO2 in the form of 2.6. Characterization
oxides (Li2O, Al2O3) to create artificial spodumene. Abbreviations like
M/O (ratio of raw material to oxidizer addition), Al2O3/SiO2 (mass ratio The main phases and phase characterization results of the raw ma­
of Al2O3 in the raw material to the added flux SiO2), and S/A (mass ratio terials were shown in Figs. 1(a) and Fig. 2. The roasted products of SLIBs
of slag to the alloy) were used to simplify the description of reaction were cold mounted in resin and then subjected to SEM-EDS (Scanning
conditions. Electron Microscope-Energy Dispersive Spectrometer, JSM-63620LV),
The steps of the experimental procedure (Fig. 5(a)) were as follows: and the results were showed in Fig. 3 and Table S2. The SLIBs used in
(1) Weighing the appropriate amount of pretreated SLIBs sample pow­ this study were obtained from a battery processing company, and all
der and flux SiO2; (2) Thoroughly mixing based on the Al2O3/SiO2 (0.25, other chemical reagents used were of analytical purity and sourced from
0.3, 0.4, 0.7, 1.1, 1.6, and 2.2) in an agate mortar; (3) Compress the Sinopharm (China National Pharmaceutical Group Co. Ltd).
mixture into a compact cylinder using a die and a sample press; (4) Insert The phase and microscopic characterization of all solid samples in
the cylinder into an alumina crucible within a vacuum tube furnace that this study were determined using XRD (Bruke, D8ADVANCE, Germany)
has continuous oxygen input; (5) Heat the crucible at the set tempera­ and SEM-EDS (JEOL, JSM-63620LV, Japan). The composition of the
ture (1350 ◦ C, 1400 ◦ C, 1450 ◦ C, 1500 ◦ C, and 1550 ◦ C) for 30 min; (6) solids was determined using XRF (Thermo Fisher Scientific, ARL
Slowly cool the samples to room temperature. Advant’X Intellipower TM 3600, USA), FAAS (Thermo Fisher Scientific,
ICE3500 GF AA, Inc GFS35Z, USA), and ICP-OES (PerkinElmer, PE
2.5. Recovery of lithium Optima 8000, USA). The concentrations of the major elements in the
solutions were determined by a combination of FAAS and ICP-OES
The Li extraction experiment was carried out to evaluate the effect of methods.
Li recovery from the lithium-rich slag. The procedure (Fig. 5(b))
involved mixing the slag with 150% of the theoretical amount of 3. Results and discussion
concentrated sulfuric acid and roasting the mixture in a muffle furnace
at 250 ◦ C for 40 min. The sulfation roasting slag was then transferred to a 3.1. Thermodynamic analysis of smelting reactions and simulation
beaker for leaching, with a solid-liquid ratio of 1:10 (g/mL), a duration calculations
of 180 min, and a stirring speed of 300 rpm. After solid-liquid separa­
tion, leaching solution and residue were collected. The Li leaching ef­ The ΔfGθm for CuO, NiO, MnO2, Fe3O4, FeO, and P2O5 are lower than
ficiency was calculated using Equation. The residue was dried at 105 ◦ C that for SiO2, Li2O, and Al2O3 in the range of 1350–1600 ◦ C, indicating
for 10 h before being analyzed and characterized. they can be reduced by C into the alloy melt, whereas SiO2, Li2O, and
Al2O3 then create target slag. During the reduction smelting process,
ELi=C Li × VLi / (mLi × wLi) (1) MnO was reduced spontaneously as the temperature exceeded 1400 ◦ C
where ELi: leaching efficiency of Li; CLi: concentration of Li in leachate; (Fig. 6). However, MnO tends to combine with SiO2 easily, which re­
VLi: volume of leachate; mLi: mass of lithium-rich slag; wLi: mass per­ duces its activity and requires a higher temperature for complete
centage of Li in the lithium-rich slag. reduction. Therefore, during the actual smelting experimental process,
MnO is partially transformed into slag and partially reduced into the
alloy phase. In summary, from a thermodynamic perspective, it is

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Fig. 9. XRD patterns of lithium-rich slag under different M/O.

entirely feasible to study the reduction smelting of SLIBs to recover Cu, Co and Cu entered the lithium-rich slag, which was primarily composed
Ni, and Co, while enriching Li in the slag. of LiAlSiO4, Mn2SiO4, and LiAlO2 phases. This indicates significant
As the oxygen partial pressure increased, the recoveries of Mn, Co, changes in the composition of the slag as the M/O ratio increases and the
Ni, and Cu decreased slowly and gradually. The recovery of Li was more disappearance of phases containing Co and Cu. When the M/O ratio was
stable. Additionally, the ratio of F to P entering the slag increased 0.8, the intensity of the diffraction peak suddenly decreased. This phe­
significantly and stabilized during the process (Fig. 7). nomenon is because the cooling rate of the experiment is faster than
other experiments, resulting in the poor crystallinity of the material
phase, which leads to the inconspicuous XRD diffraction peaks and the
3.2. Results and discussion inconspicuous separation of the material phase precipitation in SEM, but
the composition of the material phase is found to be unchanged after the
3.2.1. Effect of M/O on metal recovery detection and analysis, the main phases are still LiAlSi2O6 and Mn2SiO4.
The effect of M/O on reduction smelting was experimentally studied The ease of Li leaching is influenced by the embedding relationship
at 1500 ◦ C and Al2O3/SiO2 = 0.7. In Fig. 8(a), as M/O increased, the between Li-bearing phases and other phases in slag (Fig. 10). The
recoveries of Co, Ni, and Cu increased and stabilized at around 97%, and lithium-rich slag contained small alloy particles of Cu and the CoMnAlO4
the recovery of Mn has gradually increased, but is still very low at less phase of Co (Fig. 10 (a, b) and Table S1). The lithium-rich slag comprised
than 20%, while the recovery of Li is consistently maintained at 20%. LiAlSiO4 and Mn2SiO4, and contained solid solution elements (Fig. 10(d
Notably, when M/O was 6.5–9.5, Co recovery was low due to its high and e) and Table S1). The phase analysis shows that when M/O is below
ΔG, but improved when M/O was 10.5–12.5, with less added oxygen and 9.5, the slag phase composition is more complex, while with M/O above
Li mainly enriched in the slag. These results suggest that increasing M/O 9.5, the slag phase composition is relatively simple without any stray
improves the reducibility of metal oxides in the smelting process. phase that could enclose Li.
With the increase of M/O (Fig. 8(b)), the Co, Ni, and Cu content in After conducting a comprehensive analysis at a temperature of
the slag decreases, making the total mass of the slag decrease, resulting 1500 ◦ C and an Al2O3/SiO2 of 0.7, it was found that higher M/O con­
in the Li2O content in the slag increasing and stabilizing at 8% or more. ditions improved the enrichment of Co, Cu, Ni, and Li in the raw and that
In the experiments, S/A was used to show metal enrichment in the slag. a simple composition of the phase was obtained. Consequently, a M/O
In Fig. 8(c), it shows that S/A gradually decreases with improved M/O, ratio of 10.5 was selected for further experiments.
indicating stronger alloying during smelting with less O2. Within the
experimental range, the S/A decreases sharply with M/O increase from 3.2.2. Effect of temperature on smelting
6.5 to 8.5 but becomes flat afterward. S/A was influenced by oxygen The temperature experiments were conducted using the M/O ratio of
potential, mainly reflected in the reducing atmosphere, which favors 10.5 and two representative slag types: spodumene (Al2O3/SiO2 = 0.3)
metal alloying. Thus, the reducing atmosphere was used in further ex­ and eucryptite (Al2O3/SiO2 = 0.7). As the temperature increased, the
periments as the experimental conditions. recoveries of Cu, Ni, and Co gradually increased (Fig. 11(a and b)).
When M/O was between 6.5 and 7.5, a small amount of Co and Cu However, the overall recovery efficiencies of Cu, Ni, and Co for Al2O3/
entered the slag, which mainly consisted of LiAlSiO4, Mn2SiO4, and SiO2 = 0.7 were lower than those for Al2O3/SiO2 = 0.3. That may be due
CoMnAlO4 phases (Fig. 9), thereby explaining the low recovery of Co to that, high content of SiO2 which increased the slag viscosity (Cheng,
and Cu seen in Fig. 8(a). However, when the M/O ratio was ≥ 8.5, little

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Y. Fan et al. Journal of Cleaner Production 417 (2023) 138043

Fig. 10. SEM images of lithium-rich slag under different M/O (a) 6.5; (b) 7.5; (c) 8.5; (d) 9.5; (e) 10.5.

2021), hindering the settling of metals and is not conducive to metal resulting in a lower slag viscosity and making Li easier to volatilize.
recovery. With an Al2O3/SiO2 = 0.3, Li recovery initially increased from Between 1450 ◦ C and 1550 ◦ C, the melting of SiO2 reduced the viscosity
91.86% (1400 ◦ C) to 99.83% (1500 ◦ C) and then decreased to 82.10% of the slag, improving the release of Li2O in the slag and its reaction with
(1600 ◦ C). In contrast, with an Al2O3/SiO2 of 0.7, Li recovery initially SiO2, resulting in better Li recovery. Overall, higher temperatures tend
decreased from 91.07% (1350 ◦ C) to 65.06% (1450 ◦ C) and then to increase metal recovery but can also increase the volatilization effi­
increased to 75.76% (1550 ◦ C). When Al2O3/SiO2 was 0.3, the high ciency of Li, which makes it less conducive to Li recovery.
content of SiO2 resulted in a decrease in slag O2− and the formation of a As the temperature increased, the recovery of Cu, Co, and Ni slightly
mesh-like structure in the silicate anion. This led to higher viscosity in increased while the S/A ratio slightly decreased and remained stable,
the slag. The structure of silicate ions was disrupted as the temperature resulting in a slight decline in the quality of the lithium-rich slag. Based
increased, making it easier for molecules to be freed in the slag and on the analysis, the temperature has an impact on the S/A, and high
facilitating contact reactions between SiO2 and Li2O. However, as the temperatures are more favorable for metal alloying (as shown in Fig. 11
temperature increased further, the viscosity of the slag decreased, (c, e)). et al.2O3/SiO2 = 0.3 in the slag, the phase is mainly composed of
causing Li to become more volatile and leading to decreased Li enrich­ LiAlSi2O6 and Mn2SiO4, and the phases are well distributed with no
ment in the slag phase. et al.2O3/SiO2 = 0.7 and a temperature range of inclusions. et al.2O3/SiO2 = 0.7 in the slag, the phase consists of LiAl­
1350 ◦ C–1450 ◦ C, the SiO2 may not completely smelt in a short time, SiO4, MnAl2O4, and Mn2SiO4 (Fig. 12). The presence of MnAl2O4 is

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Y. Fan et al. Journal of Cleaner Production 417 (2023) 138043

Fig. 11. Effect of temperatures on metals recovery and S/A (a, b) Recovery of metals, (a) Al2O3/SiO2 = 0.3, M/O = 10.5; (b) Al2O3/SiO2 = 0.7, M/O = 10.5; (c, d)
Metals content in lithium-rich slag, (c) Al2O3/SiO2 = 0.3, M/O = 10.5 (d) Al2O3/SiO2 = 0.7, M/O = 10.5; (e) S/A.

Fig. 12. XRD patterns of lithium-rich slag at different temperature (A) Al2O3/SiO2 = 0.3, (B) Al2O3/SiO2 = 0.7.

attributed to the deficiency of SiO2 and the high concentration of Al2O3 the microstructure and the relationship between the phases (Fig. 13).
in the slag system. The main phase composition of the lithium-rich slag The detailed results of the Energy-Dispersive Spectroscopy (EDS) anal­
was similar at different temperatures, but differences were observed in ysis are presented in Tables S2 and S3.

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Fig. 13. SEM images of lithium-rich slag at different temperature

(A) Al2O3/SiO2 = 0.3, (B) Al2O3/SiO2 = 0.7.

Fig. 14. Effect of Al2O3/SiO2 on metals recovery and S/A

(a) Recovery of metals, (b) Metals content in lithium-rich slag, (c) S/A.

As the M/O and Al2O3/SiO2 were set to 10.5 and (0.3 and 0.7) decreases slag viscosity and leads to partial volatilization of Li, resulting
respectively, the results showed that the high-value Co, Cu, Ni, and Li in in the formation of a LiAlO2 phase. The recovery of Mn increases slowly
the spent lithium-ion batteries were fully enriched, leading to a lithium- with increasing Al2O3/SiO2 due to the reduced volume and increased
rich slag with simple phases of LiAlSi2O6 (spodumene) and Mn2SiO4. specific surface area of the lithium-rich slag, and the reducing atmo­
sphere reduces Mn oxide in the slag. Although increasing Al2O3/SiO2
3.2.3. Effect of Al2O3/SiO2 on smelting facilitates the recovery of Cu, Ni, Co, and other metals, it hinders the
The critical factor affecting slag smelting is Al2O3/SiO2. With its recovery of Li.
increase, the recoveries of Cu, Ni, and Co improve and stabilize, but As the Al2O3/SiO2 increases, the content of Co, Cu, and Cu in the slag
reduces the recovery of lithium due to reduced SiO2 addition, which gradually decreases, while the content of Li2O gradually increases and

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Fig. 15. XRD patterns of lithium-rich slag under different Al2O3/SiO2.

the S/A sharply decreases, then gradually plateaus (Fig. 14(b and c)). Al2O3/SiO2, the physical phase composition of the lithium-rich slag was
When Al2O3/SiO2 was between 0.25 and 0.4, the content of Cu and Co complex.
was higher, with Cu at 3.63%, 1.02%, 1.31%, and Co at 1.05%, 0.91%, At an Al2O3/SiO2 ratio of 0.3, a temperature of 1500 ◦ C, and a M/O
0.32%, respectively, in the lithium-rich slag, which resulted in a slightly ratio of 10.5, high recovery efficiencies for Co, Cu, Ni, and Li in battery
lower alloying rate of Cu and Cu. The content of Mn in the lithium-rich raw material were achieved: 74.05%, 97.30%, 98.81%, and 99.83%,
slag is low and remains steady, which may relate to the drastic decline in respectively. The resulting lithium-rich slag contained two phases
slag volume. As Al2O3/SiO2 increases, the significant decrease in slag (LiAlSi2O6 and Mn2SiO4), simplifying subsequent leaching for Li
volume leads to a gradual increase and leveling of Li2O content in the extraction.
lithium-rich slag (Li2O > 8 wt%), which is favorable for the subsequent
recovery of Li (see Fig. 15). 3.2.4. Proposal of smelting strategies for various SLIBs
The Al2O3/SiO2 has a substantial impact on the phase composition of There is a diverse range of SLIBs, and effective smelting solutions
the lithium-rich slag. As SiO2 addition decreases, it became more chal­ that are operationally feasible and capable of recovering highly valuable
lenging to form Si-containing phases. In the range of Al2O3/SiO2 be­ strategies must be developed for different types of SLIBs. As discussed in
tween 0.25 and 0.7, there was sufficient SiO2 to form LiAlSi2O6. At an sub-sections 3.2.1 to 3.2.3, the key factor affecting the melting process is
Al2O3/SiO2 of 1.1, only a small amount of SiO2 was available to form the oxygen potential and the Al2O3/SiO2, which must be thoroughly
LiAlSiO4 phase. At an Al2O3/SiO2 of 1.6, the LiAlSiO4 phase disappeared analyzed.
completely, and a small amount of SiO2 combined with MnOx formed To control the distribution of Mn in the process, a low oxygen po­
Mn2SiO4. Additionally, a part of Li was present in the form of LiF. Since tential should be maintained in the melting atmosphere. The smelting
traces of F were found in the SEM images, but very few, they were not can be divided into two categories based on the differences in Mn
detected in the XRD pattern spectrum. which is not a focal phase of Li distribution:
and therefore not shown. A small amount of LiPF6 remains in SLIBs, and
it is recognized that LiPF6 can be decomposed into LiF and PF5 at room (i) Smelting process with extremely low oxygen potential: Mn in the
temperature, and PF5 volatilizes directly at melting temperature, while SLIBs is mainly reduced into an alloy to facilitate easier handling.
LiF has a high boiling point and does not volatilize easily, so a small (ii) Smelting process with low oxygen potential: More MnOx enters
amount of LiF exists in the slag (Han and Jung, 2022). The decompo­ the slag. As shown in Fig. 17, the main phases of the lithium-rich
sition equation is LiPF6 → LiF + PF5↑." slag are:
The SEM-EDS characterization results (Fig. 16 and Table S4) show ➢ LiAlSi2O6 (spodumene) and Mn2SiO4 when Al2O3/SiO2 is 0.3
significant differences in the composition of lithium-rich slag phases and (blue area)
the microstructure and relationships among the phases under various ➢ LiAlSiO4 (eucryptite) and Mn2SiO4 when Al2O3/SiO2 is 0.7
Al2O3/SiO2. When Al2O3/SiO2 was in 0.25–0.3 (Fig. 16(a and b)), the (pink area)
phases were evenly distributed, and small metal particles were present ➢ LiAlSiO4 and LiAlO2 (green area).
in the low magnification SEM images, reducing the recovery of Cu and
Co. As the Al2O3/SiO2 increased from 0.4 to 2.2 (Fig. 16(c, g)), the area Various proportions of the Li2O–Al2O3–SiO2 slag system can be
representing LiAlSiO4 in the SEM images gradually decreased. Based on selected for different applications. (1) By regulating the composition of
phase analysis, under low Al2O3/SiO2 conditions, the lithium-rich slag the slag and utilizing LiAlSi2O6 as the primary phase of the lithium-rich
simply consisted of LiAlSi2O6 and LiAlSiO4, whereas, in the case of high slag, the mature industrial method of extracting spodumene concentrate

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Y. Fan et al. Journal of Cleaner Production 417 (2023) 138043

Fig. 16. SEM images of lithium-rich slag at different Al2O3/SiO2 (a) 0.25, (b) 0.3, (c) 0.4, (d) 0.7, (e) 1.1, (f) 1.6, (g) 2.2.

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Y. Fan et al. Journal of Cleaner Production 417 (2023) 138043

Fig. 17. Li2O–Al2O3–SiO2 ternary phase diagram

T = 1500 ◦ C, t = 30 min, M/O = 10.5, a: Al2O3/SiO2 = 0.3, b: Al2O3/SiO2 = 0.7, c: Al2O3/SiO2 = 1.6.

wastes slag and Li recovery through smelting dust can be achieved.

However, it is difficult to interface with existing processes and has high
energy consumption.
In industrial production, raw materials often consist of various spent
lithium-ion batteries in a hybrid state. In addition to the demand for slag
component regulation to obtain the required Li-bearing phase, Mn in the
raw material can be adjusted according to the demand for oxygen po­
tential to change its distribution law. There is a correlation between
industrial production and laboratory research, but significant differ­
ences also exist. To consume excess reducing substances in the raw
material, we added O2 as an oxygen supply agent (Xiao et al., 2017).

3.3. Evaluation of Li recovery effect in lithium-rich slag

The optimal conditions for generating lithium-rich slag and alloy

from SLIBs were determined based on analysis of experimental results.
The conditions were determined to be a M/O ratio of 10.5, a tempera­
ture of 1500 ◦ C, and an Al2O3/SiO2 ratio of 0.3. The produced alloy was
enriched with Co, Ni, and Cu, while the primary phases of the slag were
LiAlSi2O6 and Mn2SiO4.
The degree of embeddedness in the alloy determines the ease of
subsequent leaching of Co, Ni, and Cu. The alloy is generally uniform,
with only slight phase separation (Fig. 18). Point 1 in Fig. 18 shows the
Fig. 18. SEM image of the alloy at the condition of T = 1500 ◦ C, M/O = 10.5, main alloy phase is dominated by Cu with a solid solution of Ni, Co, and
and Al2O3/SiO2 = 0.3. Mn. As shown in point 2 (Fig. 18), the alloy phase is dominated by Ni,
Co, and P with a small amount of Cu and Mn in the solid solution. P was
can be utilized to process the slag, reducing investment risk. However, present in both SLIBs and the slag during the reduction-smelting process,
this method results in a large volume of slag. (2) By choosing LiAlSiO4 as while the remaining P in the alloy melted. The analysis indicates that
the principal phase, a lithium-rich slag with elevated Li content, high Li this alloy fulfills all requirements for atomized acid leaching in indus­
recovery efficiency, and low slag volume can be generated. However, trial production.
the subsequent Li extraction process needs to be developed. (3) By Crushed α-spodumene (Abdullah et al., 2019) transforms into
selecting LiAlO2 as the main phase, the highest Li enrichment, smallest β-spodumene (Peltosaari et al., 2015; Lajoie et al., 2018), which has a
tetragonal crystal structure, at temperatures above 1000 ◦ C. Al replaces

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Y. Fan et al. Journal of Cleaner Production 417 (2023) 138043

Fig. 19. SEM patterns of lithium-rich slag at different conditions.

part of Si to form [AlO−4 ] tetrahedra and Li+ fills the structural gaps, resulted in the production of a Li-rich slag with the main phase LiAl­
creating a larger crystal volume with improved ion-exchange properties Si2O6. Sulfation roasting-water leaching was utilized to confirm Li re­
and increased chemical activity of β-spodumene (Leroux et al., 2018). covery from the slag, and the leaching efficiency of Li was high at 93%.
Upon roasting with a sulfuric acid mixture at 250–300 ◦ C (Wang et al., The next step will be to optimize the slag type and to conduct an in-
2016), Li exists in the slag as Li2SO4. The thermodynamic calculation depth study on the higher extraction efficiency of Li.
shows that the ΔG of the reaction at 250 ◦ C is − 88.283 J/mol, indicating
that the reaction can proceed. To evaluate the leaching effect of this slag CRediT authorship contribution statement
for Li extraction, conducted sulfation roasting-water leaching experi­
ments (Wu et al., 2018). The main reactions occurring in this type of slag Youqi Fan: Investigation, Methodology, Writing – original draft. Hu
are as follows. Li: Data curation, Writing – original draft. Chang Lu: Formal analysis.
Shiliang Chen: Conceptualization, Writing – review & editing, Funding
α-LiAlSi2O6 → β-LiAlSi2O6 acquisition, Supervision. Yonglin Yao: Funding acquisition. Hanbing
2β-LiAlSi2O6 + H2SO4 → Li2SO4 + 2HAlSi2O6 He: Funding acquisition, Supervision. Shuai Ma: Formal analysis. Zhen
Peng: Formal analysis. Kangjun Shao: Formal analysis.
The XRD results of the lithium-rich slag were analyzed after trans­
formation roasting, sulfation roasting, and water leaching. Following Declaration of competing interest
transformation roasting at 1000 ◦ C, the slag exhibited intense diffraction
peaks of the β-spodumene phase, indicating a successful conversion from The authors declare that they have no known competing financial
the α-spodumene phase. Sulfation roasting resulted in obvious charac­ interests or personal relationships that could have appeared to influence
teristic diffraction peaks of Li2SO4 showing that Li+ from LiAlSi2O6 was the work reported in this paper.
replaced with H+ to form HAlSi2O6 (Fig. 19). On observing the XRD
phases, water leaching caused Li2SO4 to disappear, with a high leaching Data availability
efficiency of 93% for Li. The process is similar to the extraction of nat­
ural spodumene, which also yields a Li extraction efficiency of approx­ We have shared the data in the supporting materials
imately 90% (Gu et al., 2022).
Acknowledgments
4. Conclusion
This work was supported by the Open Fund Project of Key Laboratory
In summary, Li was successfully enriched in the spodumene, and the of Metallurgical Emission Reduction and Comprehensive Utilization of
effective separation of Li from Co, Ni, and Cu was achieved. The Resources, Ministry of Education (JKF20-02); the Universities Natural
modification in metal retrieval, alloy phase, and slag phase was inves­ Science Research Project of Anhui Province (grant number
tigated during the reduction smelting process under various conditions. KJ2020A0224); the Anhui University of Technology Young Teachers’
It was found that the Al2O3/SiO2 ratio plays a significant role in the Research Fund Project (QZ202103); the National College Students’
partitioning of Li, the Li2O content of the slag, and the fugacity of Li in innovation and entrepreneurship training program (S202210360160).
the slag. The optimal conditions were determined to be a M/O ratio of
10.5, a temperature of 1500 ◦ C, and an Al2O3/SiO2 ratio of 0.3, which

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Appendix A. Supplementary data Joo, S., Shin, D., Oh, C., Wang, J., Shin, S.M., 2016. Extraction of manganese by alkyl
monocarboxylic acid in a mixed extractant from a leaching solution of spent lithium-
ion battery ternary cathodic material. J. Power Sources 305, 175–181. https://doi.
Supplementary data to this article can be found online at https://doi. org/10.1016/j.jpowsour.2015.11.039.
org/10.1016/j.jclepro.2023.138043. Kang, J., Senanayake, G., Sohn, J., Shin, S.M., 2010. Recovery of cobalt sulfate from
spent lithium ion batteries by reductive leaching and solvent extraction with Cyanex
272. Hydrometallurgy 100, 168–171. https://doi.org/10.1016/j.
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