Journal Pre-proof

Lithium recovery from effluent of spent lithium battery recycling process

using solvent extraction

Licheng Zhang (Conceptualization) (Writing - original draft) (Writing

- review and editing) (Investigation), Li Lijuan (Supervision)
(Funding acquisition), Hongming Rui (Investigation), Dong Shi
(Investigation), Xiaowu Peng (Investigation), Lianmin Ji
(Investigation), Xuexue Song (Visualization)

PII: S0304-3894(20)30829-3
DOI: https://doi.org/10.1016/j.jhazmat.2020.122840
Reference: HAZMAT 122840

To appear in: Journal of Hazardous Materials

Received Date: 9 December 2019

Revised Date: 31 March 2020
Accepted Date: 23 April 2020

Please cite this article as: Zhang L, Li L, Rui H, Shi D, Peng X, Ji L, Song X, Lithium recovery
from effluent of spent lithium battery recycling process using solvent extraction, Journal of
Hazardous Materials (2020), doi: https://doi.org/10.1016/j.jhazmat.2020.122840

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© 2020 Published by Elsevier.

Lithium recovery from effluent of spent lithium
battery recycling process using solvent extraction

Licheng Zhanga,b*, Lijuan Lia,b*, Hongming Ruic, Dong Shia,b, Xiaowu Penga,b,
Lianmin Jia,b, Xuexue Songa,b

a
Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake
Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, 810008
Xining, China
b
Qinghai Engineering and Technology Research Center of Comprehensive Utilization
of Salt Lake Resources, 810008 Xining, China
c
School of Advanced Materials and Nanotechnology, Xidian University, 710071,

of
Xi'an, China

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*Corresponding author at: Qinghai Institute of Salt Lakes, Chinese Academy of
Sciences, 810008 Xining, China
Tel: 0971-6304812
Fax: 0971-6306002 -p
Email address: zhanglc@isl.ac.cn (L. Zhang); lilj@isl.ac.cn (L. Li)
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Graphical abstract
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Highlights
 A novel process of lithium recovery from effluent of spent LIBs was proposed.
 Lithium recovery is about 90% through three-stage countercurrent extraction.
 Lithium of lithium-rich solution is 30 g/L, total impurity is less than 0.5 g/L.
  Application pH range of HBTA/TOPO system was broadened after saponification.
 The lithium extraction mechanism by β-diketone was proposed via FT-IR.

Abstract
A novel process of lithium recovery from effluent of spent lithium batteries recycling
by solvent extraction was proposed. The β-diketone extraction system used in the
experiment was composed of benzoyltrifluoroacetone (HBTA), trioctylphosphine
oxide (TOPO) and kerosene. The effective parameters such as solution pH value,
saponification degree, initial lithium concentration and phase ratio were evaluated by
experiments. More than 90% of lithium could be extracted by saponified organic
phase through three-stage countercurrent extraction. The loaded organic phase was
first eluted by dilute HCl solution to remove nontarget sodium, and then stripped by 6
mol/L HCl at a large phase ratio to obtain lithium-rich solution with 4.322 mol/L

of
lithium. The lithium-rich solution from the process could be used to prepare lithium
carbonate or lithium chloride. The stripped organic phase can be recycled and no

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crud or emulsification was observed during the process. The extraction mechanism of
HBTA-TOPO was investigated via FT-IR spectroscopy, and the results indicated the
two extractants showed strong synergistic effect. The thermodynamic study revealed

extraction of lithium.
-p
lithium extraction is an exothermic process, which meant lower temperature promotes

This work provided a novel approach to recover lithium from effluent of spent lithium
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battery recycling.

Keywords: spent lithium battery; lithium extraction process; β-diketone extraction

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system

1. Introduction
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With the popularity of electric vehicles and explosive development of portable

intelligent devices, lithium batteries are getting more and more indispensable in
people's daily life for its high voltage, high energy density and light weight[1]. Lithium
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batteries production of China reached 5.287 billion units in 2014 and with the increase
of the demand, the market will exceed 35 billion USD before 2020[2-4]. The global
electric car (including EVs and PHEVs) stock is projected to range between 9 million
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and 20 million by 2020 and between 40 million and 70 million by 2025[5]. Natural
lithium resources mainly exist in ores and salt lake brines but the reservation is very
limited, it is reasonable to predict that lithium will confront serious shortage in the
foreseeable future[6-8]. The lithium recovery from the salt lakes requires large-scale
solar ponds and high energy consumption in the evaporation stage[9,10], while the
recovery of lithium from ores will cause environmental pollution in the process of
mineral processing[11].
With the thriving development of lithium battery, massive spent LIBs containing
hazardous metal elements and flammable electrolytes are inevitably generated, which
are environmentally damaging and jeopardize human health. Several metals in spent
LIBs (e.g., Co, Ni and Li) are very precious and recoverable. By recycle of these
metal components in spent LIBs, serious environmental issues can be solved, while
the shortage of resources is relieved. Efficient recovery of metals from spent LIBs are
urgently required and of high implication to environment and economy[12-15].
In the respect of environment protection and green process, hydrometallurgical
treatment is more favorable for recycling of valued metals from spent LIBs for its
advantages like high selectivity, low energy consumption and no harmful gas
emission compared with pyrometallurgical treatment[16,17].
Some researchers and companies have exploited a number of hydrometallurgy
technologies to recover valuable metal from spent LIBs, which include discharge,
dismantling, separation of metals and organic stuffs, leaching, extraction and chemical
precipitation, through these processes, majority of Co, Ni, Mn, Cu and Al could be
recovered as metal or salt form[4,12,18-22]. However, as an important raw material of

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LIBS, lithium recovery from the spent LIBs was devoid of corresponding recognition
and comprehensive study.

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In recent years, some researchers have proposed some ideas for lithium recovery from
solutions, among which adsorption, chemical precipitation and solvent extraction are
proved to be effective[6].
-p
Adsorption is widely used in the detection and recovery of metal ions because of its
high selectivity, high adsorption efficiency and stable chemical properties [23-27]. The
research on lithium adsorption mainly focuses on the separation and recovery of
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lithium from salt lakes with high Mg/Li ratio[28-30], and the adsorbents revealed great
separation effect of lithium and magnesium, while the adsorption equilibrium requires
a long time, which is unfavorable to continuous operation.
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In recent years, researchers have developed many extraction systems suitable for
extracting lithium from salt lake brine. Among them, TBP based extraction system is
the most studied. TBP extraction systems demonstrate a good effect on extracting
lithium, and have made some successful applications[31,32]. However, FeCl3 must be
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added to the organic phase as a co-extractant when extracting lithium and the solution
is required to be acidic[33,34], so the extraction system is unable to be applied to neutral
or alkaline solutions like effluent of waste lithium battery recycling.
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Precipitation by adding sodium carbonate is the most commonly used method to

prepare lithium carbonate[18,20,35], while lithium ion could not be completely
precipitated due to the solubility of Li2CO3 in aqueous phase, which means about
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0.216-0.360 mol/L lithium will be left in aqueous phase at room temperature. Besides,
to improve precipitation economy, the solution was often concentrated to a certain
extent by forced evaporation, which is high energy consuming[36]. NaF and Na3PO4
were also employed as the precipitation reagent[37,38] and the lithium recovery effect is
satisfactory, while the price of these reagent is relative expensive, so the application is
constrained.
In the present work, lithium recovery from effluent of spent LIBs by solvent
extraction was first proposed. HBTA-TOPO extraction system was employed as
extractant, through saponification, extraction, elution, striping and precipitation,
lithium in aqueous phase was recovered as lithium carbonate. This work will provide
a new approach for lithium recovery from spent LIBs.

2. Experimental section
2.1 Reagents and materials
The effluent liquor used in the experiments was obtained from local spent lithium
batteries recycling factory, the spent LIBs were leached by H2SO4, and valued metal
in the leaching liquor like cobalt and nickel were recovered before. The main ions in
the effluent were shown in Table1.
HBTA(4,4,4-trifluoro-1-phenyl-1,3-butanedione) and TOPO(trioctylphosphine oxide)
used in the experiments were both of 98% purity without further purification(from
Aladdin Industry Corporation), the organic phase used in the experiments was

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composed by 0.4 mol/L HBTA and 0.4 mol/L TOPO and kerosene. All the aqueous
solutions were prepared in deionized water and all the inorganic reagents were of
analytical grade.

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2.2 Experimental and analysis
The extraction, scrubbing and stripping process were conducted in the separatory
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funnel with PTFE plugs, the organic phase and aqueous phase were mixed and shaken
for 6 minutes at 25℃ unless otherwise stated.
The metal ions in aqueous phase were measured using Atomic Absorption
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Spectrometer after properly diluted and the ion concentration in organic phase was
calculated according to mass balance. The morphology of Li2CO3 was observed by a
scanning electron microscope (SEM, SU8010,Hitachi Corp.), the crystal structures of
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solid materials were characterized by an X-ray diffractometer (X’pert PRO,

PANalytical) with Cu Kα radiation, organic phase was measured by FT-IR(Nexus,
Thermo Scientific Corp.)
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The distribution ratio (D) is the ratio of the concentration of the metal ion M in
organic phase to metal ion concentration in aqueous phase, at equilibrium:
[𝑀]𝑜𝑟𝑔 𝐶0 − 𝐶𝑒 𝑉𝑎𝑞
D= = × Eq.(1)
[𝑀]𝑎𝑞 𝐶𝑒 𝑉𝑜𝑟𝑔
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Where Co and Ce(mol/L) are initial and equilibrium concentrations of metal ions in
the aqueous phase, respectively. Vaq and Vorg(mL) represent the volume of the aqueous
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phase and organic phase, respectively. The extraction efficiency (E) is defined as the
amount of metal extracted to the organic phase over the total amount of metal in both
phases and is given by the following expression:
𝐶0 − 𝐶𝑒
E= × 100% Eq.(2)
𝐶0

3. Results and discussion

3.1 Effect of saponification degree on lithium extraction
Former study indicated that pH value of aqueous phase played very important role in
lithium extraction from solution due to the keto-enol tautomerization of the
extractants[22,23].
To investigate the effect of pH value on lithium extraction, extraction experiments
were conducted with 0.4 M HBTA+0.4 M TOPO and feed solution at different pH
value. Fig. 1 revealed the relationship of pH value of aqueous phase and metal
extraction, it could be concluded from the experiment data that in the range of
pH=8.5-13.0 lithium extraction was positively associated with pH value of aqueous
phase, lithium extraction reached 80% only when initial pH = 13.0. The strict
requirement of pH restricts the application of β-diketone extraction system, to expand
the application scope, a saponification process of the organic phase was proposed
according to the extraction mechanism proposed by Zhang[39,40] et al. and the
extraction principle of other extraction system[41]，the following extraction pattern was
proposed:

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RH + 𝑁𝑎+ + 𝑂𝐻 − ⇌ 𝑅𝑁𝑎 + 𝐻2 𝑂 Eq.(3)
+ +
RNa + 𝐿𝑖 ⇌ 𝑅𝐿𝑖 + 𝑁𝑎 Eq.(4)

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Since β-diketone extractant HBTA is a hard base, and Pearson hardness of lithium
ion(ηA=35.1 eV) is stronger than that of sodium ion(ηA=21.1 eV)[42,43], so Li+ is easier
to chelate with the extractant when mixing together. Furthermore, the ion radius of
-p
lithium ion is smaller than that of sodium ion, so the length of Li-O bond in the
complex is smaller than Na-O bond, in other words, the complex formed by Li+ and
HBTA will be more stable. Therefore, it is reasonable to deduce that lithium in water
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phase can effectively replace sodium in organic phase.
Herein the description of saponification degree Rs is introduced,
𝐶𝑁𝑎𝑂𝐻 × 𝑉𝑁𝑎𝑂𝐻
𝑅𝑠 = × 100% Eq.(5)
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𝐶𝐻𝐵𝑇𝐴 × 𝑉𝑜𝑟𝑔
Where CNaOH is the molar concentration of NaOH, VNaOH is the volume of NaOH
CHBTA is molar concentration of HBTA in organic phase, Vorg is the volume of organic
phase.
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The experimental data with different saponification were revealed in Fig.2 and Table2.
It is clear that lithium extraction increased with increase of saponification degree,
while the increase of lithium extraction slowed down when saponification degree
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exceeded 70%. From data in Table 2 it could be read that utilization of sodium
hydroxide became lower and lithium in organic phase was almost unchanged when
the saponification degree is over 70%, so 70% saponification of organic phase would
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be appropriate accordingly.
In order to verify the applicability of saponified organic to solutions with different pH
value, extraction experiments with solutions with pH=1.17-13.00 were carried out,
and the experimental results were given in Fig.3. From the experimental results, the
extraction effect of lithium by saponified organic is relatively unsatisfactory when the
solution pH is less than 5, while it revealed good extraction effect for solutions with
pH value higher than 6. It can be inferred that the replacement between lithium in the
aqueous phase and sodium in the organic phase requires that the equilibrium pH of the
aqueous phase should be in the neutral or alkaline condition. By comparing Fig. 1 and
Fig. 3, it can be concluded that the application pH scope of the system is obviously
expanded

3.2 Effect of organic phase composition on lithium extraction

To determine the best composition of the organic phase for lithium extraction, a series
of experiments were conducted. Since Li+ is a hard acid according to Pearson’s
theory[44,45] and is difficult to chelate with single extractant. TOPO is a strong electron
donor which could enhance the combination of lithium and HBTA. By keeping the
total concentration of organic phase constant at 0. 8 mol/L and varying the proportion
of two extractants, the effect of proportion of HBTA and TOPO in the organic phase
on lithium extraction was investigated, and HBTA was 70% saponified before. Data in
Fig.4 and Table S1 indicated that extractants HBTA and TOPO showed strong
synergist effect and the synergist coefficient reach the peak when the concentration of
HBTA and TOPO was at the same level. The synergistic coefficient Rsc was

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calculated according to Eq.(6) and the peak value of Rsc reached 30.029 when
concentration of HBTA and TOPO was both 0.4 mol/L
𝐷𝐴+𝐵

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𝑅𝑠𝑐 = Eq.(6)
𝐷𝐴 + 𝐷𝐵
Combined with the experimental results, it can be inferred that the complex formed
-p
during the extraction of lithium ion by HBTA-TOPO is shown in scheme 1. Lithium
ion is sp3 hybridized to form four empty orbits, which are coordinated with four
oxygen atoms in the extractant and the synergistic extractant respectively to form a
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tetrahedral structure. The oxygen atom of the P=O bond in TOPO has two pairs of
unbound electrons, which can coordinate with two lithium ions to form a complex
with the chemical formula of Li•BTA•TOPO.
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3.3 Effect of extraction time on Li and Na extraction

Effect of extraction time of metal extraction was studied with the saponified organic
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phase consisting of 0.4 M HBTA and 0.4 M TOPO and the feed solution at O/A=1: 1.
The extraction of lithium reached near equilibrium in 2 minutes with about 80%
extraction efficiency, further increase of contacting time had almost no effect on
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lithium extraction. It was clearly seen from Fig.5 that 75% of sodium in organic phase
was replaced by lithium after 2 minutes extraction, while the exchange of lithium and
sodium almost stopped with the extraction went on. Due to the high concentration of
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sodium in aqueous phase, more sodium will probably transfer to the organic if the
extraction duration is too long. In order to ensure lithium extraction and avoid too
much sodium entering to organic phase, 2 minutes is enough for the extraction.

3.4 Effect of initial lithium concentration on metal extraction

The effect of lithium concentration was carried out by changing the initial lithium
concentration from 0.029 mol/L to 0.720 mol/L at constant concentration of sodium
(1.370 mol/L) considering the variation range of different leaching conditions. The
 extractant was 70% saponified and the operating phase ratio O/A=1: 1. It could be
found from Fig. 6 that lithium capacity of the extractants increased from 0.027 mol/L
to 0.261 mol/L with the increase of lithium concentration from 0.029 mol/L to 0.720
mol/L, while sodium in organic decreased from 0.239 mol/L to 0.005 mol/L. A
higher lithium concentration accelerates the chelate of lithium with the extractants
due to high concentration difference between aqueous and organic phase. Meanwhile,
the extractants was almost saturated with lithium when mixed with high-lithium feed
solution, resulting in less capacity for other metal ions such as sodium. It could be
concluded from the experimental data that HBTA-TOPO system is suitable for
lithium extraction with a wide concentration range just by choosing the appropriate
phase ratio.

3. 5 Effect of phase ratio on lithium separation

The metal extraction under various phase ratios was conducted with same organic and

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aqueous phase as above. The behaviors of both lithium and sodium are investigated,
and it could be seen from Fig.7 that the concentration change of lithium and sodium

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inorganic phase showed absolutely opposite trend with different phase ratio. At
O/A=1:15, almost no sodium remained in organic phase after extraction, the organic
phase was saturated with lithium under that condition though lithium extraction ratio
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is lower than other conditions. Moreover, the phase separation time was getting longer
and lithium concentration in organic phase became less as the phase ratio was over 2:
1. From the perspective of economy and operation, it would be favorable to conduct
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the extraction at O/A=1:1.
In optimum experimental conditions at pH=8.5, 0.4 mol/L HBTA + 0.4 mol/L TOPO
+ kerosene was employed as the organic phase, effluent with 0.266 mol/L Li+ and
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1.36 mol/L Na+ was extracted at an O/A=1:1, the lithium extraction McCabe Thiele
diagram was constructed and presented in Fig.8 and Fig. S1, it was found that at an
operation O/A=1: 1, three theoretical stages were required to extract more than 90%
lithium from the tail liquor which contained 0.267 mol/L lithium ion. Table 3 showed
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average concentration of aqueous and organic phase through three-stage

counter-current extraction at O/A=1: 1. It could be concluded from the data that
lithium extraction reached 97%, about 94% of sodium in saponification extractant was
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replaced to aqueous phase. Though molar ratio of lithium and sodium in equilibrium
organic phase reached 17.98, scrubbing of sodium from organic phase is still
necessary to obtain high purity lithium product.
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3.6Metal eluting study of organic phase

In eluting study, hydrochloric acid and lithium chloride solution were used as the
elution reagent according to extraction subsequence (see in Fig.S2) of HBTA-TOPO
extraction system: H+>>Li+>Na+>K+, namely sodium ion in organic phase would be
eluted before lithium by hydrogen ion or lithium ion. Elution experiments were
conducted using loaded organic phase and eluting solutions with various
concentration at O/A=20: 1, the eluting performance of elution solutions were
illustrated in Fig.9. HCl solution revealed better ability of sodium removal, about 95%
of sodium could be eluted by 1.0 mol/L HCl and 15% of lithium was eluted to
aqueous phase simultaneously. While using lithium chloride as scrubbing reagent not
only removed sodium in organic phase, but also improved lithium concentration in
organic phase due to high lithium concentration of eluting solution. About 90% of
sodium was replaced by lithium and some extra lithium in eluting solution was
extracted into organic phase, resulting in improvement of lithium in organic phase.

3.7 metal stripping study of organic phase

The stripping study was carried out using organic phase eluted by HCl(organic A) and
LiCl(organic B) solution, and HCl solution with various concentration was used as
stripping reagent at O/A=20: 1. It was found from Fig.10 that lithium was easily
stripped to the aqueous phase, and obviously, both lithium stripping ratio and lithium
concentration in stripping solution increased as the increase of HCl concentration.

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Since stripping process was designed to obtain lithium chloride solution with high
concentration, stripping process should be conducted with high concentration HCl

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solution. By comparing the experimental data of organic A and organic B, it is
obvious that lithium in stripping solution obtained from organic B is higher than
organic A at the same stripping condition (6 mol/L HCl and O/A=20: 1). While Table
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4 showed the main composition of the stripping solution, as described in section3.6,
sodium in organic phase could not be eluted thoroughly by LiCl solution, so sodium
in stripping solution obtained from organic B is higher than that of organic A, while
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the lithium-rich solution obtained from two approaches could be directly used to
Li2CO3 production after deep purification by ultrasonic method. It should be noted
that chloride anion in aqueous phase is much lower than stripping acid, especially in
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stripping solution from organic A, a reasonable explanation is the HCl is extracted by

the organic phase in a molecular form[30], the specific extraction mechanism needs
further investigation.
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3.8 Li2CO3 preparation and characterization

The precipitation of Li2CO3 was conducted by adding sodium carbonate to 0.05 L
lithium-rich solution with 4.44 mol/L Li+, and the operation was in a beaker immersed
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in a waterbath with magnetic stir at 80℃. The total lithium in the solution is 0.222
mol, to precipitate lithium as much as possible, the dosage of sodium carbonate is 120%
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of the theoretical amount according to Eq.(7). After 1h stirring, the precipitation is

filtrated and washed with 80℃ water to remove sodium, then the precipitation is
dried in a vacuum oven at 80℃.The SEM and XRD results were displayed in Fig. 11,
the SEM images revealed the average size of Li2CO3 is 100 um, the XRD pattern
showed all the diffraction peaks are indexed as a monoclinic phase of Li2CO3.
2𝐿𝑖𝐶𝑙(𝑎𝑞) + 𝑁𝑎2 𝐶𝑂3 (𝑎𝑞) → 𝐿𝑖2 𝐶𝑂3 (𝑠) + 2𝑁𝑎𝐶𝑙(𝑎𝑞) Eq. (7)

3.9 Whole process of Li recovery from tailing liquor

The whole process containing of saponification, extraction, scrubbing, stripping for
lithium recovery from effluent of spent LIBs recycling was designed according to
above studies, the process flowchart is shown in Fig. 12, and main composition of
different solutions were listed in Table 5. The mother liquor of Li2CO3 precipitation
and elution residue had similar composition with the feed solution, so the mother
liquor and elution residue could be returned to extraction section as feed solution to
improve yield of lithium further. It could be concluded from the experimental results
that more than 96% of lithium was recovered in the extraction section, and the
comprehensive yield of lithium through the whole process is about 90%

3.10 FT-IR spectrum study

FT-IR spectroscopy is sensitive to small differences in the chemical
microenvironment of complex systems, and can be used to characterize different

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functional group information. These measurements were carried out to clarify the
existence of interactions between metal ions and extractants.

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FT-IR spectra of organic phase before and after the extraction process were recorded
and the results were shown in Fig.13. In Fig.13A the peaks at 1604 and 1289 cm-1
were considered as characteristic peak of vc-o and vco in the hexatomic ring
-p
respectively [46]. The peaks showed red shift in varying degrees after extraction of
lithium or sodium, this is due to the electron transfer between metal ions and the
organic ligand when HBTA chelated with the metal ion. The transfer of electron
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enhanced the conjugation of chelating rings, and reduced the electron density of
ligands, and thus causes the vibration frequency to move to the low frequency
direction. In Fig.13B, the peaks at 1450 and 1150 cm-1 belonged to v-CH2P and v-P=O
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respectively [47], and the characteristic peaks at 1150 cm-1 remained unchanged before
and after extraction, which meant TOPO was unable to chelate with alkali metal ions.
In Fig.13C, the main characteristic peak of -P=O appeared obvious split towards the
high wave number direction, which indicated the complex between -P=O and alkali
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metal ion had taken place, thus caused the electron cloud density of oxygen atom
changed. The FT-IR results were in accordance with the experimental results.

3.11 Thermodynamic parameter study

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To investigate thermodynamic parameter of lithium extraction by HBTA-TOPO

extraction system, the extraction experiments were conducted under various
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temperatures.
The enthalpy change(ΔH) during an extraction can be determined based on the slop of
a plot of lgD versus 1/T(K-1) using the van't Hoff equation:
∆𝐻
lgD = − +𝐶 Eq.(8)
2.303𝑅𝑇
Where R is the universal gas constant and C is the integration constant. In this study,
the integration constant was assumed to be constant at a particular temperature under
the experimental conditions.
The enthalpy change of the extraction system is found to be -5.73 kJ•mol-1 according
to Fig.14, highlighting the exothermic nature of the extraction reaction, which means
that lower temperature is better for lithium extraction. While considering poor fluidity
of organic phase in low temperature and difficulty in phase separation, room
temperature (293K) would be appropriate for lithium extraction.

Conclusion
In this work, a novel process for lithium recovery from effluent of spent LIBs
recycling is developed. HBTA-TOPO extraction system is employed as the extractant,
after saponification, the applicable pH range of saponified organic phase is much
wider than that of original organic phase. In extraction section, the extraction
condition is determined to be 3-stage countercurrent extraction at an O/A=1:1
according to McCabe Thiele diagram, more than 90% of lithium was recovered
through 3-stage countercurrent extraction. In elution section, dilute HCl solution and
LiCl solution is chosen as the elution solutions, the experimental data showed HCl

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had better sodium scrubbing effect, while LiCl solution could remove sodium from
organic and improve lithium concentration at the same time. In stripping section,

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purified organic phase was stripped by 6 mol/L HCl solution, lithium in stripping
solution reached 4.32 mol/L. The lithium-rich solution obtained from stripping
process could be used to prepare Li2CO3 or LiCl according to different demand of the
-p
market. The mechanism study revealed that HBTA and TOPO showed strong
synergistic effect when extracting alkali metal ions. Based on the batch experiments
and the obtained results for lithium extraction, solvent extraction by HBTA-TOPO is
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proved to be a feasible and promising method for lithium recovery from effluent of
spent LIBs recycling.
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Credit author statement

Licheng Zhang: Conceptualization, Writing - Original Draft, Writing - Review & Editing,
Investigation
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Lijuan Li: Supervision, Funding acquisition

Hongming Rui: Investigation
Dong Shi: Investigation
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Xiaowu Peng: Investigation

Lianmin Ji: Investigation
Xuexue Song: Visualization
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All authors read and approved the manuscript.

Declaration of interest

The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

Acknowledgement
This work was supported by the National Natural Science Foundation of China(No.
U1707601), National Key Research and Development Program of China(No.
2018YFC0604800), Natural Science Foundation of Qinghai Province-Youth
Project(2020-ZJ-941Q) and CAS "Light of West China" Program.

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lP
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 10

80
lithium extraction
Equilibrium pH 8
Lithium extraction,% 60

Equilibrium pH
6

40

20

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0
8 9 10 11 12 13

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Initial pH of aqueous phase

Fig. 1 Effect of pH on lithium extraction

-p
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100
lP

13 pH of saponification raffinate
pH of extraction raffinate
12 lithium extraction
pH value of aqueous phase

90
lithium extraction, %
na

11

80
10
ur

9
70
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7 60
50 60 70 80 90 100
Saponification degree,%
Fig.2 Effect of saponification degree on lithium extraction
 100 14
lithium extraction
equilibrium pH of aqueous phase 12

Equilibrium pH of aqueous phase

80
10
lithium extraction, %

60
8

6
40

4
20
2

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0 0
0 2 4 6 8 10 12 14

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Initial pH of aqueous phase

Fig. 3 Effect of pH value on lithium extraction by saponified organic

-p
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8
lP

7
Dmix
6 D1+D2
na

4
DLi

3
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1
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-1
0.0 0.2 0.4 0.6 0.8
HBTA concentration, mol/L

Fig.4 Effect of HBTA concentration on lithium extraction

 90 0.28

0.24
75

metal ion in organic phase, mol/L

0.20
lithium extarction
60
lithium extraction,%

lithium in organic phase

sodium in organic phase 0.16
45
0.12

30
0.08

15 0.04

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0 0.00
0 20 40 60 80 100 120 140 160 180 200

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Extraction time, s

Fig.5 Effect of extraction time on lithium extraction

-p
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lP

0.35 100
lithium in organic phase
sodium in organic phase
Concentration in organic phase, mol/L

0.30
lithium extraction
80
na

0.25
lithium extraction, %

60
0.20
ur

0.15
40

0.10
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20
0.05

0.00 0
0.0 0.2 0.4 0.6 0.8
Liini in aqueous phase, mol/L
Fig.6 Effect of initial lithium in aqueous phase on extraction
 0.35 100
sodium in organic phase
0.30 lithium in organic phase

Metal ion in organic phase, mol/L

lithium extraction 80
0.25

lithium extraction,%
0.20 60

0.15
40
0.10

0.05 20

0.00
0
15:1 10:1 5:1 2:1 3:2 1:1 2:3 1:2 1:5 1:10 1:15
phase ratio O/A

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Fig.7 Effect of phase ration on lithium extraction

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-p
0.28
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Equilibrium line
0.24
Lithium in organic phase, mol/L

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Stage 2 Stage 1
0.20

0.16
Operating line
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0.12 O/A=1:1
Stage 3

0.08
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0.04

0.00
0.00 0.04 0.08 0.12 0.16 0.20 0.24 0.28
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Lithium in aqueous phase, mol/L

Fig.8 McCabe Thiele diagram for lithium extraction
 0.35
100

90 0.30

lithium in organic phase, mol/L

80 sodium scrubbing by HCl
Sodium scrubbing, %

sodium scrubbing by LiCl

lithium in organic after HCl scrubbing 0.25
70 lithium in organic after LiCl scrubbing

60
0.20
50

40 0.15

30

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0.10
0.0 0.5 1.0 1.5 2.0
Concentration of scrubbing reagents, mol/L

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Fig. 9 Effect of HCl concentration on scrubbing effect

-p
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8
stripping ratio of Li (organic A)
100
stripping ratio of Li (organic B) 7
lP

Li in stripping solution(organic A)
Li in stripping solution, mol/L

Li in stripping solution(organic B) 6
80
Stripping ratio, %

5
na

60
4

40 3
ur

2
20
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0 0
1 2 3 4 5 6
Concentration of HCl, mol/L
Fig.10 Effect of HCl concentration on lithium stripping
 of
(a) standard Li2CO3
Intensity

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-p
10 20 30 40
(b) precipitated Li2CO3

50 60 70 80
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2 theta(°)
Fig.11 SEM and XRD pattern of Li2CO3
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Fig.12 Flowchart of lithium recovery from effluent of spent LIBs recycling

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-p
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lP

Fig.13 FT-IR of organic phase before and after extraction

0.65
na

0.60

Slope=0.2993
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0.55
R2=0.9796
lgD

4.4

4.0
0.50
3.6
D
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3.2

2.8
0.45 260 280 300 320 340
T,K

2.9 3.0 3.1 3.2 3.3 3.4 3.5 3.6

-1
1000/T, K

Fig. 14 Effect of temperature on lithium extraction

 C8H17
C8H17 C8H17 C8H17
C8H17 C8H17
P P
O CF3 O CF3
O O pH>5 O O
Na Na + 2Li+ Li Li + 2Na+
O O O O
F3C O F3C O
P P
C8H17 C8H17 C8H17 C8H17
C8H17 C8H17

Scheme1 Possible bonding mechanism of lithium and sodium with extractants

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Table 1 Main composition of the effluent
Ions Li Na Ni Co Mg Ca SO42-
Mass Conc.
1.85 31.2 0.025 0.005 0.002 0.005 78.72
g/L
Molar Conc.
0.267 1.36 4.7×10-4 9.1×10-5 8.5×10-5 1.3×10-4 0.82
Mol/L

Table 2 Equilibrium concentration in saponified organic phase

Lithium in
Saponification Saponification Sodium in saponified
organic phase,
degree(Cal.) degree(Exp.) organic phase, mol/L
mol/L
50% 48.28% 0.1931 0.1829
60% 57.66% 0.2306 0.1984

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70% 66.54% 0.2662 0.2141
80% 72.97% 0.2919 0.2170
90% 80.96% 0.3238 0.2205

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100% 79.66% 0.3187 0.2203

Table 3 Main composition of feed solutions

Feed solution
Li, mol/L
0.267
Na, mol/L
1.370
-p SO42-, mol/L
1.66
pH
8.52
Raffinate 0.009 1.602 1.66 8.35
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Loaded organic 0.258 0.014 0 -
lP
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Table 4 Composition of stripping solutions
Li, mol/L Na, mol/L Cl-, mol/L pH
Stripping liquor from organic A 4.445 0.006 4.452 3.482
Stripping liquor from organic B 5.749 0.026 5.776 4.155

Table 5 Main composition of different solutions

Li, mol/L Na, mol/L Cl-, mol/L SO42-, mol/L pH
Feed solution 0.262 1.357 0.02 0.82 8.55
Saponification raffinate 0 0.099 0.02 0 9.45
Extraction raffinate 0.009 1.580 0.02 0.001 8.17
Elution residue 0.239 0.273 0.96 0.001 8.68

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Stripping solution 4.445 0.006 4.46 0.001 3.85
Stripped organic 0.003 0 0 0 -

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