Separation and Purification Technology 237 (2020) 116325

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

A novel approach for the selective extraction of Li+ from the leaching T
solution of spent lithium-ion batteries using benzo-15-crown-5 ether as
extractant
Yue Suna, Meiying Zhua, Yonglin Yaoa,b, , Huanwei Wanga, Bihai Tonga,b, Zhuo Zhaoa,b
⁎

a
School of Metallurgical Engineering, Anhui University of Technology, Maanshan, Anhui 243032, China
b
Anhui Province Key Laboratory of Metallurgy Engineering & Resources Recycling, Anhui University of Technology, Maanshan, Anhui 243002, China

ARTICLE INFO ABSTRACT

Keywords: In order to selectively extract Li+ from the leaching solution of spent lithium-ion batteries, benzo-15-crown-5
Spent lithium-ion batteries ether (B15C5) is synthesized and used as a lithium extractant. The selectivity of B15C5 to Li+ is studied from the
Recovery two aspects of experiment research and density functional theory (DFT) calculation. Under the experimental
Crown ether conditions of pH of 6.0, temperature of 30 °C and extraction time of 2 h, the extraction rate of Li+ is 37%, which
Extraction
is well above that of the possible impurity ions Co2+, Ni2+ and Mn2+. The DFT calculation about structure
Density functional theory
Sustainability
optimization, charger transfer, electron density difference, natural bond orbital (NBO) analysis, binding energy
and free energy change are carried out, and the extraction mechanism of B15C5 is revealed. The results show
that B15C5 should combine Li+ preferentially in solution. The calculated values are consistent to the experi-
mental results. Therefore, this paper provides a new feasible method to recover Li from the leaching solution of
spent lithium-ion batteries, and it is conducive to the sustainability of the lithium resources.

1. Introduction methods, hydrometallurgy is considered to be the most promising

In the past several decades, lithium-ion batteries (LIBs) have gra-
dually replaced lead-acid batteries, nickel-metal hydride batteries and
nickel cadmium batteries, and then became the most widely used re-
chargeable batteries, due to their excellent properties [1–3]. Up to now,
LIBs have been largely used in many portable electronics such as mobile
phones, video cameras, laptops and so on. In recent years, with the
rapid development of new energy vehicles (pure electric vehicles and
plug-in hybrid vehicles), the global LIBs market maintained fast growth
[4]. China is the largest producer and consumer of LIBs in the world. In
2018, China's LIBs production has exceeded 12 billion units, with an
average growth rate of over 20% in the last three years. In considera-
tion of the limited charge-discharge cycles of LIBs, it can be predicted
that a great number of spent LIBs will emerge prominently in the near
future.
The spent LIBs contain plenty of valuable metals (Li, Co, Ni, Mn, Cu,
Al) and toxic materials (organic electrolytes and binders). Therefore, it
has become a worldwide concern to recycle the spent LIBs from the
standpoint of sustainable development [5]. Presently, many methods
including pyrometallurgy, hydrometallurgy and combined processes
have been employed for the recycling of spent LIBs. Among these
technology, due to its low energy consumption, high metal recovery
rates and high product purity [4,6]. In hydrometallurgy processes, most
reported studies mainly focused on the recovery of Co, Ni and Mn from
the leaching solution of spent LIBs by precipitation, solvent extraction
or electrochemical deposition. As for Li, it was generally recovered in
the form of Li2CO3 using Na2CO3 as a precipitant, after all the other
valuable metals were removed from the leaching solution. However, it
is difficult to obtain a satisfactory recovery rate of Li (most of the re-
ported recovery rates are less than 80%) by this method due to its low
concentration in the leaching solution [7–9].
Recently, a few new efforts have been made to selectively separate
Li from the leaching process of spent LIBs. Oxalic acid has been used as
the leaching agent to selectively leach Li from the cathode active ma-
terials of spent LIBs, due to that Li2C2O4 is soluble, while MC2O4·2H2O
(M = Co, Ni, Mn) are insoluble precipitates [10–12]. Similarly, H3PO4
was also used as both a leaching agent and a precipitant to treat LiCoO2
and LiFePO4 [13,14]. The Co and Fe in the cathode materials were
recovered in the form of Co3(PO4)2 and FePO4·2H2O precipitates re-
spectively, while the Li still existed in the solution due to the high so-
lubility of LiH2PO4. Higuchi et al. [8] and Zhang et al. [15] reported
methods for the selective leaching of Li by using Na2S2O8 as an oxidant,

⁎
Corresponding author at: School of Metallurgical Engineering, Anhui University of Technology, Maanshan, Anhui 243032, China.
E-mail address: yaoyonglin@ahut.edu.cn (Y. Yao).

https://doi.org/10.1016/j.seppur.2019.116325
Received 15 August 2019; Received in revised form 11 October 2019; Accepted 17 November 2019
Available online 19 November 2019
1383-5866/ © 2019 Elsevier B.V. All rights reserved.
Y. Sun, et al.
in which Li was converted to water-soluble Li2SO4, whereas Mn, Co, Ni
and Fe were oxidized to insoluble precipitates. Hu et al. [16] used
carbonated water to treat the cathode materials after reduction
roasting. Li2CO3 in the roasted products turned to soluble LiHCO3,
while Co, Ni and Mn were retained in the residues. All of the above
methods will produce precipitates with complex components due to the
various types of LIBs, which makes the subsequent processes very
complicated. Therefore, it is still a challenge to selectively separate the
Li from the spent LIBs leaching process.
Crown ether is a kind of macrocyclic ligand containing
[eCH2eCH2eOe] structural units, which has strong ability of selective
extraction of metal ions, especially alkali and alkaline earth metals
through the ion-dipole interaction. In the past decades, crown ethers
have been widely used in isotope separations [17,18], ions determi-
nation sensors [19,20], phase transfer catalysts [21,22], and ions se-
paration [23,24], since it was discovered by Pedersen in 1967 [25].
Among these researches, it is found that B15C5 has a good coordination
ability with Li+ [26,27]. On the contrary, the coordination ability be-
tween B15C5 and Co2+, Ni2+ and Mn2+ may be weak according to the
hard and soft acids and bases (HSAB) theory. Therefore, it is hopeful to
selectively separate Li+ from the spent LIBs leaching solution by using
B15C5 as extractant.
In this paper, B15C5 was synthesized and its extraction property to
Li+ from the solution containing Li+, Co2+, Ni2+ and Mn2+ was stu-
died. Fe2+ may also exist in the leaching solution, however, it can be
removed completely by a simple precipitation process [28]. So it was
not considered in this work. The selective extraction mechanism of
B15C5 to Li+ was revealed through the theoretical calculation based on
the density functional theory.
2. Experimental and computational methods
2.1. Synthesis of B15C5
B15C5 was synthesized through the route as shown in Fig. 1. In a
typical process, 0.1 mol catechol was first dissolved in 100 mL n-bu-
tanol in a round-bottom flask, and then 0.1 mol NaOH was added at
90 °C to form a slurry. When the slurry was heated up to 130 °C,
0.0525 mol diethylene glycol bis(2-chloroethyl) ether (dissolved in
20 mL n-butanol) was added into the flask drop by drop under stirring.
Subsequently, the system was continued to be stirred for 2 h under
refluxing. When the reflux reaction was finished, repeating the previous
steps, 0.1 mol NaOH and 0.0525 mol diethylene glycol bis(2-chlor-
oethyl) ether were added again. In the whole reaction process, the
system was protected in a N2 atmosphere. When the second reflux re-
action was finished, 1 mL HCl (37 wt%) was added into the flask. After
stirring for 0.5 h, the n-butanol was removed by reduced pressure
distillation. The residue was successively extracted with di-
chloromethane and recrystallized from heptane, and then the B15C5
can be obtained.
1
H NMR (400 MHz, CDCl3): δ 6.93–6.86 (m, 4H, ArH), 4.17–4.12
(m, 4H, eOeCH2e), 3.95 –3.90 (m, 4H, eOeCH2e), 3.81–3.74 (m, 8H,
eOeCH2e). ESI-HRMS: m/z 269.14 for [M+H]+ (268.31 calculated
for C14H20O5).
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Separation and Purification Technology 237 (2020) 116325
2.2. Solvent extraction of Li+
The organic phase used for the solvent extraction was prepared by
dissolving B15C5 in dichloromethane (0.05 mol L−1). The aqueous
solutions (Li 0.005 mol L−1, Co 0.005 mol L−1) were employed as the
simulated leaching solution. The solvent extractions were operated in a
water bath with magnetic stirring. The O/A was controlled at 1:1, and
the pH of the solutions were adjusted by 1 mol L−1 HCl.
2.3. Analytical methods
The structure of the synthesized B15C5 was determined with
Nuclear magnetic resonance (NMR) analysis (AVANCE 400, Bruker,
Switzerland) and mass spectrographic analysis (GC–MS 2010 PLUS,
Shimadzu, Japan). The mixed solutions after solvent extraction were
separated into organic and aqueous solutions using a separating funnel.
The metal ions concentrations in the aqueous solutions were analyzed
using an inductively coupled plasma optical emission spectrometer
(ICP-OES, ICPS-7510 PLUS, Shimadzu, Japan). The extraction rate of
metal ions can be calculated according to Eq. (1):
co Vo
q=
co Vo + c w Vw (1)
where q is the extraction rate, co and cw are metal ions concentrations in
organic and aqueous solutions after extraction, respectively. Vo and Vw
are the volumes of organic and aqueous solutions, respectively. The
separation coefficients between Li+ and Co2+ can be obtained ac-
cording to Eq. (2):
coLi/ c wLi
=
Li/Co
coCo/ c wCo (2)
where β is the separation coefficient, coLi and cwLi are Li+ concentra-
tions in organic and aqueous solutions after extraction, respectively.
coCo and cwCo are Co2+ concentrations in organic and aqueous solutions
after extraction, respectively.
2.4. DFT calculation
The geometrical structures of B15C5 and B15C5-M (Li+, Co2+, Ni2+
and Mn2+) were optimized based on the DFT with the B3LYP hybrid
functional at def2-SVP level [29–31]. The frequency calculation was
carried out at the same functional and basis set level, and the optimized
structures were confirmed to be real minima by that there were no
imaginary frequencies. In order to get higher computational accuracy,
B3LYP/def2-TZVP level was used to calculate the single point energies
of B15C5 and the complexes in gas phase [29–31]. The dispersion
correction of DFT-D3 was considered in both of structure optimization
and single point energy calculation [32]. The Gibbs free energy in
solvents was calculated according to Eq. (3):
Gsolv = Ggas + Gsolv + 1.89 kcal/mol (3)
where Gsolv and Ggas are the Gibbs energies of B15C5, metal ions and
B15C5-M in solvents (CH2Cl2 or H2O in this work) and gas phase, re-
spectively. ΔGsolv is the dissolving free energy change from gas phase to
a solvent. The dissolving free energy change ΔGsolv was calculated
based on the M052X/6-31G* level [33–35]. The solvation model based
on density (SMD) was employed in all the calculations of structure
optimization, vibration frequency and dissolving free energy change
Fig. 1. Synthetic route of B15C5.
Y. Sun, et al.
Fig. 2. Effects of pH (a), temperature (c) and time (d) on the extraction rates and separation coefficient, solubility products of the hydroxides of Co2+, Ni2+ and
Mn2+ (b).
[36].
All of above DFT calculations were carried out with Gaussian 16
program package [37]. The NBO analysis was performed with the NBO
3.1 program implemented in Gaussian [38]. The electron density dif-
ference of B15C5-M and the Hirshfeld charges were calculated with
Multiwfn program package [39].
3. Results and discussion
3.1. Solvent extraction of Li+
LiCoO2 is one of the most widely used cathode materials for LIBs in
the past decades. Therefore, the extraction of Li+ was first carried out
in the simulated solution only containing Li+ and Co2+. The effects of
pH on the extraction rates of Li+, Co2+ and their separation coefficient
are shown in Fig. 2(a). It is shown that the extraction rate of Co2+
decreases from 7.38% to 1.65% with the increase of pH value. A lower
pH indicates more hydrogen ions exist in the solution. Therefore, the
enhanced extraction rate of Co2+ at low pH may be due to the salting-
out effect of hydrogen ions. The extraction rates of Li+ are much larger
than that of Co2+ in the whole pH range of −0.5 to 6, and show a
growing tendency with the increased pH except for a weakened ex-
traction rate at pH = 2. In the extraction process, in addition to salting-
out effect, the hydrogen ions will also compete against metal ions to
combine crown ethers, which leads to a negative impact on the ex-
traction rate. The effects of hydrogen ions on Li+ may be more sensitive
due to its higher extraction rate, and then the extraction rate of Li+
fluctuates with the changing pH under the function together with
salting-out effect and competition of hydrogen ions. It also can be seen
from Fig. 2(a) that the separation coefficient of Li+ and Co2+ increases
from 4.27 to 29.49 with the varying pH form −0.5 to 6. However,
further increase of the pH will lead to the precipitation of Co2+ (Ni2+
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Separation and Purification Technology 237 (2020) 116325
and Mn2+) due to the low solubility products of their hydroxides as
shown in Fig. 2(b).
Fig. 2(c) shows the effects of temperature on the extraction rates of
Li+, Co2+ and their separation coefficient. It can be seen that there is a
slight decrease from 5.68% to 1.65% for the extraction rate of Co2+,
when the temperature increased from 15 °C to 30 °C. The combination
of metal ions and crown ether is an exothermic process, therefore, a
lower temperature is conducive to a higher extraction rate. However, a
reverse trend was observed for the extraction rate of Li+. In the ex-
traction process, besides the exothermic process from the combination
of metal ions and crown ether, there are also some endothermic pro-
cesses, including the desolvation of metal ions and the structural re-
arrangement of the complex of metal ions and crown ethers. The ra-
pidly increased extraction rate of Li+ in the temperature of 15–20 °C
and the slight fluctuation in 20–30 °C indicate that the endothermic
processes for the extraction of Li+ is more remarkable than Co2+.
Fig. 2(c) also shows that the separation coefficient of Li+ and Co2+
increases from 4.70 to 29.49 with the increasing temperature from
15 °C to 30 °C.
The effects of reaction time on the extraction rates of Li+ and Co2+
are shown in Fig. 2(d). At the reaction time of 1 h, 33.1% Li+ and a
small amount of Co2+ were extracted. When the reaction time in-
creased to 2 h, the extraction of Li+ increased slightly due to the more
sufficient contact between crown ethers and Li+. However, the ex-
traction of Co2+ was eliminated at this time, which may be caused by
the competition of Li+. When the reaction time increased further to 4 h,
on the one hand, the dichloromethane will volatilize partly due to its
high vapor pressure and low boiling point. On the other hand, a part of
B15C5 will be lost in the water phase because it is water soluble
slightly. Both of the two aspects lead to the decreased extraction rate of
Li+.
Y. Sun, et al. Separation and Purification Technology 237 (2020) 116325

Fig. 3. Optimized structures of B15C5 (a), (a'), B15C5-Li+ (b), (b′) and B15C5-Co2+ (c), (c′).

Table 1
Calculated geometric parameters of B15C5-Mn+ (Li+, Co2+) complexes.
Complex Bond length/Å Cavity size/Å

MeO11 MeO18 MeO25 MeO32 MeO39

B15C5-Li+ 2.084 2.045 2.066 2.066 2.069 3.440

B15C5-Co2+ 2.130 2.109 2.103 2.107 2.190 3.801

3.2. DFT calculation

The optimized structures of free B15C5 and its complexes with Li+
and Co2+ are shown in Fig. 3. It is shown that the crown ring has un-
dergone only small changes in B15C5-Li+, but huge changes in B15C5-
Co2+, which means the interaction between B15C5 and Co2+ may be
stronger. The corresponding geometric parameters of B15C5-Li+ and
B15C5-Co2+ are shown in Table 1. It can be seen that the cavity sizes of
crown rings in both B15C5-Li+ and B15C5-Co2+ are decreased com-
pared with that of free B15C5 (4.118 Å), which can be attributed to the
interactions between the donor O atoms in crown ring and metal ions.
The matching degree between ion radius and cavity size of crown ethers
also has great influence on their complex structure. The ion radius of
Co2+ is larger than Li+, therefore, both the bond length of MeO and
the cavity size of B15C5-Co2+ are larger than that of B15C5-Li+.
Fig. 4 shows the surface electrostatic potential of B15C5, which
presents that there is an obvious negative electrostatic potential region
in the center of the crown ring due to the electronegative oxygen atoms
in the ring. It is well known that the highly negative electrostatic po-
tential region has a strong attraction to metal ions, therefore, Li+ and
Co2+ can be captured easily by the crown ring.
When the metal ions were absorbed in the crown ring under the
electrostatic interaction, the charges of metal ions and the atoms in
B15C5 will be redistributed. The Hirshfeld charge distributions of
B15C5, B15C5-Li+ and B15C5-Co2+ were calculated and shown in
Table 2. It is shown that the charges of all the O atoms in B15C5 were
increased after the coordination with Li+ and Co2+. Meanwhile, the
charges of Li+ and Co2+ was decreased. These changes indicate there
were charge transfers (Qt) in the complex formation process. As shown
in Table 2, the charge transfers between metal ions and O18, O25 and
O32 are larger than O11 and O39 for both B15C5-Li+ and B15C5-Co2+,
which means the stronger interaction between metal ions and O18, O25
and O32. This results are consistent with the shorter bond length of
Fig. 4. Surface electrostatic potential of B15C5 (isosurface = 0.001).
MeO18,25,32 compared with MeO11,39 as shown in Table 1. There are
two reasons that account for this phenomenon. First, the benzene ring
in B15C5 is an electron withdrawing group [40], which can restrict the
charge transfers of its directly connected oxygen atoms. Second, the
oxygen atoms connected to the benzene ring have strong rigidity, which
is adverse to their coordination with metal ions. It is also found from
Table 2 that the total charge transfers of O atoms are less than that of
metal ions (Li+: from 1 to 0.2088, and Co2+: from 2 to 0.4890). This
can be ascribed to the inevitable calculation errors and the additional
charge transfers between the metal ions and the C atoms at the crown
ring.
The charge transfers between B15C5 and metal ions were further
proved by the electron density difference as shown in Fig. 5, in which
the solid line and green1 region stand for the area with increased
electron density, and the dashed line and blue region stand for the area
with decreased electron density. Both Fig. 5 and Table 2 show that more
charge transfer occurred between B15C5 and Co2+ due to the higher
valence of Co2+.
The NBO analysis was widely used to describe the donor–acceptor
1
For interpretation of color in Fig. 5, the reader is referred to the web version
of this article.

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Y. Sun, et al. Separation and Purification Technology 237 (2020) 116325

Table 2
Hirshfeld charges of O, Li and Co in B15C5 and its complexes, and the corresponding charge transfer.
O11 O18 O25 O32 O39 Li Co

B15C5 Q −0.1325 −0.1789 −0.1754 −0.1790 −0.1337

B15C5-Li+ Q −0.1122 −0.1341 −0.1347 −0.1340 −0.1123 0.2088
Qt 0.0203 0.0448 0.0407 0.045 0.0214
B15C5-Co2+ Q −0.0820 −0.0961 −0.0960 −0.0964 −0.0845 0.4890
Qt 0.0505 0.0828 0.0794 0.0826 0.0492

Fig. 5. Contour map (a) and isosurface map (b) of the electron density difference of B15C5-Li+; contour map (c) and isosurface map (d) of the electron density
difference of B15C5-Co2+.

Table 3
interaction, whose energy can be evaluated by the second-order per-
Selected stabilization energies E(2) (kcal mol−1) for B15C5-Li+ and B15C5-
turbation theory. For each donor NBO (i) and acceptor NBO (j), the
Co2+.
donor-acceptor stabilization energy E(2) associated with i → j deloca-
lization can be defined by Eq. (4): Donor E(2) Donor E(2)
NBO(i) → acceptor NBO NBO(i) → acceptor NBO
F 2 (i , j ) (j) (j)
E (2) = Eij(2) = qi
j i (4) B15C5-Li+ LP1 O11 → LP*Li 8.35 LP2 O11 → LP*Li 0.10
LP1 O18 → LP*Li 7.48 LP2 O18 → LP*Li 2.61
where qi is the donor orbital occupancy, εi, εj are diagonal elements LP1 O25 → LP*Li 7.91 LP2 O25 → LP*Li 2.61
(orbital energies), and F(i,j) is the off-diagonal NBO Fock matrix ele- LP1 O32 → LP*Li 7.30 LP2 O32 → LP*Li 2.77
LP1 O39 → LP*Li 8.46 LP2 O39 → LP*Li 0.08
ment.
In NBO analysis, the larger the stabilization energy E(2) between a B15C5-Co2+ LP1 O11 → LP*Co 14.25 LP2 O11 → LP* Co 6.21
donor bonding orbital and an acceptor antibonding orbital, the stronger LP1 O18 → LP* Co 2.56 LP2 O18 → LP* Co 18.98
LP1 O25 → LP* Co 1.93 LP2 O25 → LP* Co 20.14
the interaction between the two orbitals. Generally, the stabilization LP1 O32 → LP* Co 2.62 LP2 O32 → LP* Co 19.06
energies E(2) of crown ether-metal complexes are mainly from the lone LP1 O39 → LP* Co 12.66 LP2 O39 → LP* Co 5.36
pair electrons of oxygen in the crown ring and the LP* obitals of metal
ions. As shown in Table 3, the stabilization energies between metal ions
and O18, O25 and O32 are larger than O11 and O39 for both B15C5-Li+ B15C5-Co2+ are larger than B15C5-Li+, which means the structure of
and B15C5-Co2+, which is consistent with the aforementioned charge B15C5-Co2+ is more stable.
transfer results. It is also found that the stabilization energies for The binding energy (ΔE) is usually used to characterize the stability

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Y. Sun, et al. Separation and Purification Technology 237 (2020) 116325

dehydration processes before they are combined with extracting agent

as shown in Fig. 6. Therefore, the difficulty degree of dehydration for
one metal ion has an important influence on its selective extraction. In
order to clarify the selectivity of B15C5 to different metal ions, the free
energy changes (ΔG) and equilibrium constants (K) of the exchange
reactions in the extraction processes were calculated according to Eqs.
(7)–(9):
B15C5 Li+ (CH2 Cl2) + M2+ (H2 O) = B15C5 M2 + (CH2 Cl2) + Li+ (H2 O)
(7)

Fig. 6. Migration path of metal ions in the extraction process. G = GB15C5 M2 + (CH2Cl2) + G Li+(H2 O) G B15C5 Li+ (CH2 Cl2) G M2 + (H2O)
(8)
Table 4 G= 2.303RT logK (9)
Gibbs free energy changes and equilibrium constants of Eq. (7).
Table 4 shows the calculated thermodynamic parameters. It can be
Exchange reaction ΔG/kJ mol−1 K seen that B15C5 will extract Li+ preferentially due to the positive ΔG
B15C5/Li+ → B15C5/Co2+ 164.08 1.81E−29 and very small K of the exchange reaction of B15C5/Li+ → B15C5/
B15C5/Li+ → B15C5/Ni2+ 144.65 4.59E−26 Co2+, which is consistent with the results of extraction experiments. In
B15C5/Li+ → B15C5/Mn2+ 235.55 5.47E−42 view of the more stable structure of B15C5-Co2+, it can be concluded
that the hydratability of Co2+ is stronger than Li+, and its dehydration
is more difficult.
of crown ether-metal complexes, and it can be calculated according to In recent years, LiNixCoyMnzO2 was largely produced and used,
Eqs. (5) and (6) as follows: especially in electric vehicles region. Therefore, the extraction of Li+
Mn + + L = L-Mn + (5) from the solution containing Ni2+ or Mn2+ was also studied from the
two aspects of theoretical calculation and experiment research. Fig. 7
E = E (L-Mn+) E (L) E (Mn +) (6) shows the optimized structures and electron density differences of
B15C5-Ni2+ and B15C5-Mn2+, which are similar with that of B15C5-
where E(L-Mn+), E(L) and E(Mn+) are the energy of crown ether-metal Co2+. In order to make it clear if the Ni2+ and Mn2+ will compete with
ion complexes, free crown ethers and metal ions respectively. The Li+ to combine B15C5 in the extraction process, the Gibbs free energy
calculated ΔE is −445.53 kJ·mol−1 for B15C5-Li+, and changes and equilibrium constants of their exchange reactions were
−1388.16 kJ·mol−1 for B15C5-Co2+. Generally, the more negative the calculated. It can be seen from Table 4 that Ni2+ and Mn2+ cannot
binding energy is, the more stable the complex will be. Therefore, the capture B15C5 from the complex of B15C5-Li+ due to the positive
B15C5-Co2+ is more stable than B15C5-Li+, which is consistent with Gibbs free energy changes and very small equilibrium constants. The
the results of geometric structure, charge transfer and NBO analysis. extraction experiments were carried out under the optimum condition
According to the above results, it seems that B15C5 is not suitable in Fig. 2, and the results show that the extraction rates of Ni2+ and
for the selective extraction of Li+ from the solution containing Li+ and Mn2+ are 5.18% and about zero, respectively, which are much less than
Co2+ due to the stronger stability of B15C5-Co2+. However, metal ions the extraction rate of Li+ under this condition. Therefore, both the
always exist in the form of hydrated ions in aqueous solutions. In a theoretical calculation and experiment research indicate that B15C5
solvent extraction process, the metal ions must first go through also has the ability to extract Li+ selectively from the solution

Fig. 7. Optimized structures of B15C5-Ni2+ (a), (b) and B15C5-Mn2+ (c), (d), electron density differences of B15C5-Ni2+ (c) and B15C5-Mn2+ (f).

6
Y. Sun, et al.
containing Ni2+ and Mn2+.
The organic solvent extraction is an important branch of hydro-
metallurgy, and it has been widely used in the separation and pur-
ification of various metal ions in the past decades. After extraction, the
organic phase and aqueous phase can be separated easily through their
density difference. The extracted Li+ in the organic solvent can be
stripped by HCl and then the purified and enriched Li+ can be pre-
cipitated by Na2CO3 for further application. When the Li+ are stripped
from the organic solvent, the organic solvent can be used repeatedly for
the following extraction.
Although the selective extraction of Li+ by using B15C5 as ex-
tractant was proved to be feasible from DFT calculation and pre-
liminary experiment research in this study, there are two issues that
need to be improved. First, the single extraction rate of Li+ (37%) in
this study is smaller than the reported recovery rate (about 80%). But
this value can be improved by multi-stage solvent extraction. Second,
the solubility of B15C5 in organic solvent is not high enough. Therefore,
it cannot be used for the extraction of the solution with higher con-
centration, and so the metal ions concentration in this study is lower
than the practical leaching solution. The solution is to modify the
structure of B15C5 by the side chain alkylation reaction to increase its
solubility in organic solvent. Both the modification of B15C5 and its
performance under multi-stage solvent extraction will be studied in
detail in a further work.
4. Conclusion
B15C5 was synthesized and its ability to selectively extract Li+ from
the leaching solution of spent lithium-ion batteries was studied sys-
tematically based on the experiment research and DFT calculation.
Under the experimental conditions of pH of 6.0, temperature of 30 °C
and extraction time of 2 h, the extraction rate of Li+ is 37%, corre-
sponding to the extraction rate of 5.18% for Ni2+, and about zero for
Co2+ and Mn2+. The DFT calculated results of optimized structure,
charger transfer, electron density difference, NBO analysis and binding
energy show that B15C5-Co2+ is more stable than B15C5-Li+.
However, the strong hydratability of Co2+ lead to that B15C5 should
extract Li+ preferentially. The DFT calculated results of B15C5-Ni2+
and B15C5-Mn2+ are similar with that of B15C5-Co2+. The calculated
free energy changes are found to agree with the experimental results,
which means it is a new feasible method to recover Li from the leaching
solution of spent lithium-ion batteries using B15C5 as extractant.
Declaration of Competing Interest
None.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China [grant number 51604005, U1703130], and the
Open Fund of Anhui Province Key Laboratory of Metallurgy
Engineering & Resources Recycling [grant number SKF19-01].
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