pubs.acs.

org/journal/ascecg Research Article

Development of a Novel Solvent Extraction Process to Recover

Cobalt, Nickel, Manganese, and Lithium from Cathodic Materials of
Spent Lithium-Ion Batteries
Wen Xuan, Antônio de Souza Braga, and Alexandre Chagnes*

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ABSTRACT: Lithium-ion batteries (LIBs) are widely used in industry today and their recycling
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turns out to be very important. This paper is focused on the selective recovery of cobalt(II),
nickel(II), and manganese(II) contained in a leach solution obtained by digesting a cathodic
material from spent LIB (NMC111, LiNi1/3Mn1/3Co1/3O2) with hydrochloric acid. After leaching
the cathodic material, cobalt(II) was selectively extracted toward manganese(II) by liquid−liquid
extraction with 0.4 mol L−1 Alamine 336 (tri-octyl/decyl amine) diluted in kerosene modified using
10% (vol) 1-dodecanol at an optimized phase volume ratio between the organic phase and the
aqueous phase of O/A = 1/2. Afterward, manganese(II) was extracted from the cobalt-depleted
aqueous phase using 0.7 mol L−1 Alamine 336 diluted in kerosene modified with 10% (vol) 1-
dodecanol at O/A = 2. The resulting nickel(II)-lithium(I) acidic solution was neutralized at pH 8
with sodium hydroxide in order to precipitate almost all the nickel as nickel(II) hydroxide. The
process can recover more than 99.9% cobalt(II) and produce an aqueous phase for further
precipitation step containing 94.6% cobalt(II) and 5.4% manganese(II). Manganese(II) was
recovered from the cobalt-depleted stream to produce manganese(II) solution, the purity of which
was greater than 99.9%. Furthermore, this process allowed extracting more than 97.0% nickel(II) from the leach solution, which was
precipitated as nickel(II) hydroxide. This precipitate contained 55.6% nickel(II), 7.85% chloride, 2.42% sodium(I), and 0.02%
lithium(I). The effluent containing 0.649 g L−1 lithium(I) and 79.0 g L−1 sodium(I) could be processed by appropriate solvent
extraction with Cyanex 936, that is, a phosphorus-based extractant specifically formulated for lithium−sodium separation from
chloride media such as brines, or by implementing a precipitation stage to selectively recover lithium toward sodium.
KEYWORDS: lithium-ion batteries, NMC, cathode, recycling, hydrometallurgy, leaching, solvent extraction, precipitation

■ INTRODUCTION
Lithium-ion batteries (LIBs) are the best energy storage
technology for the development of electric vehicles.1−3
Although this technology is used in many applications, there
are still many challenges to face including the increase in
energy density and the improvement of their safety. The
increase in energy density can be achieved by developing new
cathodic materials exhibiting high voltage. The safety risks can
be reduced using cathodic materials exhibiting low reactivity
toward the liquid electrolyte or by replacing the liquid
electrolyte with a solid electrolyte. However, there are many
other challenges in the development of LIBs including the
development of environmentally sustainable batteries. Indeed,
nowadays, the LIB technology mainly relies on the use of
nickel, manganese, cobalt, and lithium in NMC cathodes,
which are critical and/or strategic resources. The substitution
of these metals with other metals by designing other cathode
technologies and the implementation of circular economy may
be some of the solutions. In particular, the reuse and the
recycling of spent LIBs must be promoted to decrease
environmental impact, to contribute to the supply of raw
materials and to reduce tensions on mineral resources for the
production of LIBs.
In the last decade, many hydrometallurgical and pyrome-
tallurgical processes were developed to recover valuable metals
from spent LIBs.4 The hydrometallurgical processes rely on
different types of chemistry and the implementation of several
operations including crushing/grinding, physical concentra-
tion, leaching, liquid−liquid and solid−liquid extraction, and
precipitation. Hydrometallurgical processes are more and more
environmentally sustainable, but the zero waste is impossible.
Leaching and precipitation stages use reagents and generate
effluents, which are reused in the process as much as possible.
The leaching operation must be efficient and selective as much
Received: October 18, 2021
Revised: December 3, 2021
Published: December 17, 2021

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582 ACS Sustainable Chem. Eng. 2022, 10, 582−593
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as possible. Sulfuric acid, hydrochloric acid, and organic acids
have been extensively studied as leaching agents. Weak organic
acids such as citric acid have also been reported as efficient
reagents for blackmass leaching, eliminating the need for
harsher acids.5 Recently, the use of formic acid and its
corresponding deep eutectic solvent (DES) was reported to
leach efficiently cobalt and manganese from cathodic materials
of spent LIBs.6 An oxalic acid-based DES was reported to
uptake lithium and cobalt from spent LIBs and separate metal
ions after extraction.7 These organic acids are of great interest
for the development of a novel hydrometallurgical process, as
they pave the way to new chemistry to uptake and separate
metals.
The choice of the leaching reagent directly impacts the
purification stage, as it influences the metal speciation in
solution. Solvent extraction of cobalt, nickel, and manganese
has been extensively studied in acidic sulfate media in the
presence of hydrogen peroxide.8−13 Yang et al. (2021)
investigated another approach to recycle cathodic materials
from spent LIBs.14 In such an approach, transition metals were
co-extracted (no separation) using solvent extraction, while
lithium was recovered separately by precipitation in order to
directly regenerate cathode materials. Less studies addressed
the usage of hydrochloric acid for leaching cathodic materials.
However, hydrochloric acid may be a good alternative toward
sulfuric acid despite its corrosive properties and chlorine
generation. Indeed, chloride medium paves the way to new
chemistry, which can make manganese−cobalt−nickel separa-
tion easier by taking advantage of anionic exchange extraction
with amine extractants. Furthermore, metal extraction using
amines permits us to reduce reagent consumption because no
pH adjustment is necessary since amines can extract metals
even at low pH.
Corrosion can be avoided or delayed using equipment made
of resistant materials such as graphite, titanium, and nickel
alloy like Hastelloy C or rubber-lined steel. The chlorine
generated during leaching can be recycled to produce the
hydrochloric acid needed for the leaching operation and
decrease the reagent consumption in the leaching process.15
Many studies addressed the liquid−liquid extraction of
nickel, manganese, and cobalt. The extraction solvent used in
liquid−liquid extraction is composed of kerosene and
extractant molecules (amine, organophosphorus compounds,
oxime, etc.), but the extraction solvent is used for many years
without being changed, as it is recycled in the liquid−liquid
extraction unit operation. Furthermore, the effluents from
stripping and scrubbing are always recycled somewhere in the
process to reduce the operation cost and the effluent treatment
and to save water as much as possible. Even if solvent
extraction generates effluents (as all other unit operations in
hydrometallurgical processes), it is clear that the environ-
mental footprint of solvent extraction is lower than that of
other unit operations implemented in hydrometallurgical
processes. Therefore, the implementation of liquid−liquid
extraction in hydrometallurgical processes makes sense to
develop sustainable recycling processes provided that the
process works under optimized conditions and streams are
recycling in the process as much as possible.
The most frequently used extracting agents to recover
cobalt(II), manganese(II), and/or nickel(II) are reported in
Table 1, that is, Cyanex 272 (bis-(2,4,4-trimethylpentyl)
phosphinic acid), PC88A (2-ethylhexyl-phosphonic acid
mono-2-ethylhexyl ester), and D2EHPA (bis-2-ethyl-hexyl-
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Table 1. Main Composition of Some Common Extracting
Agents
extractant main composition
Alamine 336 tri-octyl/decyl amine
Cyanex 272 bis-(2,4,4-trimethylpentyl) phosphinic acid
Cyanex 301 bis (2,4,4-trimethylpentyl)-dithiophosphinic
Cyanex 302 bis(2,4,4-trimethylpentyl) monothiophosphinic acid
Cyanex 936 phosphorus-containing organic compounds
D2EHPA bis-2-ethyl-hexyl-phosphoric acid
PC88A 2-ethylhexyl-phosphonic acid mono-2-ethylhexyl ester
phosphoric acid).16 Two thiophosphinic extractants, that is,
Cyanex 301 (bis (2,4,4-trimethylpentyl)-dithiophosphinic) and
Cyanex 302 (bis(2,4,4-trimethylpentyl) monothiophosphinic
acid), also demonstrated their ability to recover nickel(II) and
cobalt(II).17 More recently, several studies were devoted to the
design of new organophosphorus cationic exchangers in order
to understand the influence of the chemical structure of the
extractants on the extraction behavior of cobalt(II), nickel(II),
and manganese(II).18
It is clear that organophosphorus cationic exchangers have
been extensively studied, whereas only several studies have
discussed the use of amines and the development of the
corresponding flowsheets for the recovery and the separation
of cobalt(II), nickel(II), and manganese(II) from acidic
chloride media. Nonetheless, amine extractants exhibit
interesting behaviors, as they can extract metals efficiently
even if the leach solution is very acidic unlike organo-
phosphorus acids.19 Table 2 gathers several amine systems for
the recovery of cobalt, nickel, and manganese from acidic
chloride media. It is interesting to point out that these systems
usually require high chloride concentration.
Liquid−liquid extraction can easily separate cobalt(II) from
nickel(II) using Cyanex 272. but it is more difficult to separate
cobalt(II) from manganese(II) without increasing drastically
the operating cost of the process. For the first time, this study
aims to develop an alternative flowsheet taking advantage of
the chloride chemistry for separating cobalt(II)−manganese-
(II), nickel(II), and lithium(I) from leach solution of NMC
cathodic materials from spent LIBs.
Alamine 336 must be contacted with an inorganic acid
before being used in solvent extraction to protonate the tri-n-
octylamine, which is the main active compound of Alamine
336
H+ + Cl− + R3N F R3NH+Cl− (1)
where the overbar denotes that the species is in the organic
phase and the absence of an overbar indicates that the species
is in the aqueous phase.
Liquid−liquid extraction of cobalt(II) and manganese(II)
(M = Co or Mn) occurs according to the following
reaction20,21
MCl4 2 − + 2R3NH+Cl− F (R3NH)2 MCl4 + 2Cl− (2)
It is interesting to highlight that nickel cannot be efficiently
extracted using Alamine 336 because nickel cannot form easily
extractable anionic species such as NiCl42−.22
The apparent extraction constant for the reaction reported
in eq 2 can be written as
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Table 2. Amines Systems for Cobalt(II), Nickel(II), and Manganese(II) Recovery from Acidic Chloride Media
organic phase
tridecylamine/trioctylamine
Alamine 336 and Aliquat 336 in diethylbenzene modified by 3 v %
tridecanol
Aliquat 336 in xylene
Ashland 383 (10% triisooctylamine)
25% Alamine 336 and 15% 1-dodecanol in a kerosene
tertiary amine
0.3 M Adogen 381 in naphtha 90/100 and containing 3% by volume of
shell octylol
Alamine 336 m-xylene
1.3 M methyltrioctylammonium in sulfonated kerosene, and 5% v/v
isopropyl alcohol
0.4 M Alamine 336/0.5 M trioctylamine in kerosene
1.0 M Aliquat 336 in kerosene and decanol
[(R3NH)2 MCl4][Cl−]2 DM [Cl−]2
Kex = = kerosene to avoid any third-phase formation when Alamine 336 was
[MCl4 2 −][R3NH+Cl−]2 [R3NH+Cl−]2
where DM is the distribution ratio of M defined as follows
provided that MCl42− is the only metal complex in the aqueous
solution
[(R3NH)2 MCl4]
DM =
[MCl4 2 −]
The distribution ratio can be rewritten as
log(DM ) = log(Kex ) + 2log[R3NH+Cl−] − 2log[Cl−]
Equation 5 shows that the distribution ratio depends on the
extractant concentration in the organic phase and the chloride
concentration in the aqueous phase at the equilibrium.
The influence of the extractant and chloride concentrations
on the extraction efficiency and the selectivity has been studied
in the present paper in order to design solvent extraction stages
capable of extracting and separating cobalt(II), nickel(II),
manganese(II), and lithium(I) from acidic chloride solution.
Based on these results, a novel hydrometallurgical flowsheet
including leaching, solvent extraction, and precipitation steps is
presented for processing lithium−nickel−manganese−cobalt
oxide cathodic materials (NMC) contained in spent LIBs.
■
EXPERIMENTAL SECTION
Leaching Experiments. The leaching experiments were
performed in a homemade double-jacketed 1 L-glassware reactor
thermostated with water heated by means of a Lauda thermostat. The
experimental leaching conditions were studied in our previous
studies.23,24 The leach solutions were prepared by digesting 20 g of
NMC111 (LiNi1/3Mn1/3Co1/3O2, provided by Xiamen Tob New
Technology Co., Ltd.) in 1 L of 4−7 mol L−1 HCl (HCl solutions
were prepared by diluting appropriate amounts of 37% weight HCl
(Sigma-Aldrich) in deionized water (resistivity = 18 MΩ)). Leaching
experiments were conducted at 80 °C for 1 h under agitation at 230
rpm by means of a mechanical steel agitator coated with PTFE.
Solvent Extraction. All solvent extraction experiments were
performed at room temperature, as no improvement in extraction
efficiency was observed when the temperature was risen from 25 to 55
°C. The extraction solvent was prepared by diluting appropriate
amounts of extractant (Alamine 336, tri-octyl/decyl amine, provided
by BASF and Cyanex 301 (bis (2,4,4-trimethylpentyl)-dithiophos-
phinic)) and Cyanex 272 ((bis-(2,4,4-trimethylpentyl) phosphinic
acid) provided by Solvay) in aliphatic kerosene (Alfa Aesar). 1-
pubs.acs.org/journal/ascecg Research Article
aqueous phase reference
8 M Cl; 0.06 g L−1 Co Sato, 1966
6−10 M Cl; 0.06 g L−1 Co Seeley and Crouse,
1966
6−8 M Cl; Fe, Co, Mn Aly et al., 1972
4.5 M Cl; 165 Ni; 2 g L−1 Co/Fe/Cu Lo et al., 1982
5.6 M Cl Lo et al., 1982
3.1 M Cl; Co and Ni Lo et al., 1982
7.3 M Cl; 56 g L−1 Ni; 22 g L−1 Co; 36 g L−1 Fe; 0.15 g L−1 Cu; Lo et al., 1982
55 g L−1 Na
10 M Cl; Co Filiz et al., 2006
5.5 M Cl; 10.19 g L−1 Co; 0.42 g L−1 Ni; 0.03 g L−1 Li Cheng et al., 2009
6 M Cl; 1 g L−1 Co; 0.35 g L−1 Li; 0.4 g L−1 Cu; 0.1 g L−1 Al and Torkaman, 2007
0.1 g L−1 Ni
5 M Cl; 0.9 g L−1 Co; 0.15 g L−1 Mn; 0.1 g L−1 Ni Nguyen et al., 2020
Dodecanol (Sigma-Aldrich, purity = 98%) was added in aliphatic
(3) used as an extractant. The organic phase was preconditioned with 1
mol L−1 hydrochloric acid.
The organic and aqueous phases were contacted in a mechanical
shaker at 200 rpm for 10 min at various volume phase ratios O/A (O
= volume of the organic phase, A = volume of the aqueous phase).
The pH values of the aqueous phases were adjusted using sodium
hydroxide (Merck, purity = 98%). After settlement, centrifugation was
performed at 3000 rpm for 3 min. Metal concentrations in the
(4)
aqueous phases were determined by means of a microwave plasma−
atomic emission spectrometer (Agilent 4210 MP-AES) at 460.289,
497.175, and 610.365 nm for Li, 352.454 nm for Ni, 345.351 nm for
Co, and 403.076 nm for Mn after diluting the samples in 2% (vol)
nitric acid (analytical grade, Merck). Standards for elemental analyses
(5)
of cobalt, nickel, manganese, and lithium were provided by Sigma-
Aldrich (1000 mg L−1 metals in 2% (vol) HNO3). Standard
compositions were adjusted by adding hydrochloric acid in order to
have the same chloride concentration as in the sample to analyze and
reduce interference phenomena. The metal concentrations in the
aqueous solutions before and after solvent extraction were used to
calculate the extraction efficiency of the metal M (M = Li, Ni, Mn, or
Co)
[M]F − [M]aq
% E(M) = × 100%
[M]F (6)
where [M]F and [M]aq denote the initial concentration of the metal M
in the feed solution and the metal concentration in the aqueous phase
in contact with the organic phase at the equilibrium, respectively.
The selectivity for M1 toward M2, that is, S(M1/M2), was written as
DM1
S(M1/M 2) =
DM2 (7)
where DM1 and DM2 denote the distribution ratios of the metal M1 and
M2 between the aqueous phase and the organic phase, respectively.
During cobalt extraction, the aqueous solution was the leachate of
NMC111. During the other steps, the aqueous solutions were
prepared by dissolving appropriate amounts of anhydrous lithium(I)
chloride (Alfa Aesar, purity = 99%), manganese(II) chloride (Acros
Organics, purity = 97%), and nickel(II) chloride (Sigma-Aldrich,
purity = 98%) in hydrochloric acid.
Extraction Isotherm and Computing. The extraction isotherms
of cobalt(II) and manganese(II) were obtained by mixing the leachate
solutions with the organic phase (Alamine 336 diluted in kerosene
modified by adding 10% 1-dodecanol in volume) under optimal
extraction conditions for a series of phase volume ratios ranging from
O/A = 0.2 to 5.
Computer simulations were carried out on a PC with free
mathematical software Scilab (SciLab, Copyright© 1989−2005,
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Figure 1. Extraction efficiencies of cobalt(II), nickel(II), manganese(II), and lithium(I) as a function of (a) hydrochloric acid concentration (0.2
mol L−1 Alamine 336, phase volume ratio O/A = 2) and (b) Alamine 336 concentration (aqueous phase = 1441 mg L−1 Li(I), 3599 mg L−1 Ni(II),
3613 mg L−1 Mn(II), and 3670 mg L−1 Co(II) in 7 mol L−1 HCl, organic phase = 0.1−0.8 mol L−1 Alamine 336 in kerosene modified with 10%
(vol) 1-dodecanol; phase volume ratio O/A = 2).

INRIA ENPC, www.scilab.org). The set of non-linear equations
derived from the extraction isotherms and from the mass balance was
solved using the Newton−Raphson method.25
For each mixer settler (i), the extraction is given by eq 8
extraction stage, respectively. S and F represent the organic phase flow
rate and the aqueous feed flow rate, respectively.
By solving the set of equations corresponding to a set of mixer
settlers in series, it was therefore possible to calculate the extraction
performance of the process defined as

ij xout, n yz
% P = 100jjj1 − zz
yout, i = fext (xout, i)

(8)
where xout,i and yout,i are the metal concentrations in the aqueous and
organic phases at the outlet of the mixer settler i, respectively. The
function fext is the mathematical equation of the extraction isotherm.
The mass balance leads to eq 9
S Salt Precipitation. A synthetic solution was prepared to simulate
xout, i = xin, i − (y − yin, i )
F out, i (9)
where the subscripts “out,i” and “in,i” correspond to the outlet and
inlet flows across the mixer settler (i), respectively. x and y denote the
metal concentration in the aqueous and organic phases in the
z
j x0 z{
k (10)
where x0 and xout,n are the metal concentrations at the entrance of the
flowsheet and at the outlet of the last mixer settler (n) of the
flowsheet, respectively.
the leach solution of NMC111 in 7 mol L−1 HCl after complete
removal of Co and Mn. A solution of NaOH at 7 mol L−1 was added
into the solution under agitation to reach different pH values. After
centrifugation, the chemical composition of the overflow solution was
analyzed. The precipitation efficiency of each element M (% PE(M))

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Figure 2. Effect of the phase volume ratio (O/A) on the extraction efficiency of cobalt(II), manganese(II), nickel(II), and lithium(I) (organic
phase = 0.4 mol L−1 Alamine 336 in kerosene modified with 10% (vol) 1-dodecanol; aqueous phase = 1441 mg L−1 Li(I), 3599 mg L−1 Ni(II),
3613 mg L−1 Mn(II), and 3670 mg L−1 Co(II) in 7 mol L−1 HCl).
was defined by eq 11, assuming that the volume change in the liquid
phase during precipitation is negligible
[M]F − [M]O
% PE(M) = × 100%
[M]F (11)
where [M]F is the concentration of the metal M in the feed leachate in
mol L−1 and [M]O is the concentration of the metal M in the overflow
after precipitation in mol L−1.
■
RESULTS AND DISCUSSION
Liquid−Liquid Extraction of Cobalt. The extraction of
cobalt(II) and manganese(II) from HCl media with Alamine
336 depends on the chloride concentration as shown in eq
5.26−28 The variation of the extraction efficiency of these
metals as a function of the hydrochloric acid concentration was
investigated by mixing Alamine 336 diluted in kerosene
modified with 10% (v/v) 1-dodecanol with the leach solutions
produced by digesting NMC111 in 4−7 mol L−1 HCl at 80 °C
at a solid−liquid ratio of S/L = 20 g L−1.
Figure 1a shows that high extraction efficiency of cobalt(II)
and manganese(II) was achieved under these conditions,
whereas nickel(II) and lithium(I) extraction was negligible.
The use of 7 mol L−1 hydrochloric acid permits to extract
around 70% cobalt(II) in one stage with limited co-extraction
of manganese(II) and almost no co-extraction of nickel(II) and
lithium(I).
The influence of Alamine 336 concentration on the
extraction efficiency was determined at a phase volume ratio
of O/A = 2 in Figure 1b. The extraction efficiency of cobalt(II)
and manganese(II) increases with the increase in the Alamine
336 concentration. It is interesting to point out that the
increase in the Alamine 336 concentration does not increase
nickel(II) and lithium(I) co-extraction. Finally, the use of 0.4
mol L−1 Alamine 336 is a good compromise, as a good
selectivity for cobalt(II) versus manganese(II) was reached
(SCCo/Mn = 25.7), whereas no co-extraction of nickel(II) and
lithium(I) occurred. Furthermore, cobalt(II) was fully stripped
from the organic phase using 0.1 mol L−1 or 0.01 mol L−1 HCl.
Figure 1b shows that high cobalt(II) extraction efficiency (%
E(Co) = 96.2%) and moderate manganese(II) co-extraction
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(%E(Mn) = 49.8%) were achieved when 0.4 mol L−1 Alamine
336 was used for solvent extraction (HCl concentration in the
leachate in contact with the extraction solvent = 7 mol L−1
HCl, O/A = 2).
The affinity of the extractant for specific metal ions is
strongly linked with the chemical structure of the extractant
(size of the alkyl chains, steric hindrance by the presence of
ramification in the alkyl chain, presence of heteroatoms, etc.),
the speciation in the aqueous phase, the ionic strength in the
aqueous phase, the nature of the diluent used in the extraction
solvent, and so forth. The high extraction efficiency of
cobalt(II) and manganese(II) toward nickel(II) may be
explained by higher extractability of CoCl42− and MnCl42−
than NiCl42− according to eq 2. Furthermore, although nickel
belongs to the first transition series like cobalt and manganese,
nickel exhibits a high ligand field stabilization energy that
makes difficult the formation of NiCl42− aqueous complexes.29
No lithium(I) extraction occurs because lithium(I) ions do not
form extractable anionic species in acidic chloride media.
The extraction efficiency of cobalt(II) and manganese(II) as
a function of the phase volume ratio O/A was determined by
mixing the feed solutions initially containing 3854 mg L−1
cobalt(II), 3675 mg L −1 manganese(II), 3899 mg L−1
nickel(II), and 1441 mg L−1 lithium(I) in 7 mol L−1
hydrochloric acid with the organic phase (0.4 mol L−1 Alamine
336 diluted in kerosene modified with 10% (v/v) 1-
dodecanol), for a series of phase volume ratios (O/A) ranging
from O/A = 0.2 to 5 (Figure 2). The extraction isotherms of
cobalt(II) and manganese(II) reported in Figure 3 were then
calculated from Figure 2.
The following empirical function fext was used to plot the
extraction isotherm (Figure 3a for cobalt(II) and Figure 3b for
manganese(II))
For cobalt(II)
fext,Co (x) = A[1 − exp( −ax)] + B[1 − exp( −bx)] (12)
−1
where fext,Co(x) in mg L is equal to the cobalt(II)
concentration in the organic phase at the equilibrium when
the organic phase is in contact with an aqueous phase
containing x mg L−1 cobalt(II) at the equilibrium. The
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Figure 3. Extraction isotherms of (a) cobalt(II) and (b) manganese(II) (organic phase = 0.4 mol L−1 Alamine 336 in kerosene modified with 10%
(vol) 1-dodecanol; aqueous phase = 1441 mg L−1 lithium(I), 3899 mg L−1 nickel(II), 3675 mg L−1 manganese(II), and 3854 mg L−1 cobalt(II) in
7 mol L−1 HCl).
parameters A = 2587.2 mg L−1, B = 9198.3 mg L−1, a = 5.36
10−3 L mg−1, and b = 3.24 10−4 L mg−1 were deduced by fitting
the experimental data with eq 12. The sum A + B corresponds
to the cobalt concentration in the organic phase at saturation.
The value of A + B was deduced from eq 2 with M = Co, that
is, A + B = 11 786 mg L−1.
For manganese(II)
fext,Mn (x) = cx 2 + dx (13)
where fext,Mn(x) in mg L−1 is the manganese(II) concentration
in the organic phase at the equilibrium after contacting the
organic phase with an aqueous phase containing x mg L−1
manganese(II). The parameters c = −2.973 10−4 and d = 1.095
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were deduced by fitting the experimental data of the extraction
isotherm with eq 13.
The shape of the extraction isotherm of cobalt(II) in Figure
3a is classical, as there is little competition between cobalt(II)
extraction and manganese(II) extraction (the extraction
solvent has more affinity for cobalt(II)). The extraction
isotherm of manganese(II) exhibits a bell-shaped curve [Figure
3b], which evidences a competition between manganese(II)
and cobalt(II) extraction.
Equations 12 and 13 describe fairly well the experimental
data as the standard deviation (R2) is equal to 0.999 and 0.952
for cobalt(II) and manganese(II) extraction, respectively. Such
an accordance can be used to determine the number of mixer
settlers in the solvent extraction stage.
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Figure 4. Extraction performance of the process (% P in eq 10) for (a) cobalt(II) and (b) manganese(II) as a function of the flowrate ratio S/F
between the extraction solvent and the feed solution when the number of mixer settlers (n) varies between 2 and 4 (organic phase = 0.4 mol L−1
Alamine 336 in kerosene modified by 10% (vol) 1-dodecanol; aqueous phase = 1441 mg L−1 lithium(I), 3899 mg L−1 nickel(II), 3675 mg L−1
manganese(II), and 3854 mg L−1 cobalt(II) in 7 mol L−1 HCl).

By solving the set of eqs 8 and 9 corresponding to a set of
mixer settlers in series and using the mathematical expressions
of the extraction isotherms fext (eqs 12 and 13), it was possible
to calculate the extraction performance of the process (% P, eq
10) as a function of the number of mixer settlers in series in the
flowsheet.
Figure 4 displays the extraction performance (% P) as a
function of the flowrate ratio between the solvent (organic
phase) and the feed solution (aqueous phase) (S/F) when the
number of mixer settlers in the flowsheet varies between 2 and
4. This figure shows that the use of four mixer settlers in series
at a flowrate ratio S/F = 1/2 leads to an extraction efficiency
greater than 99.9% cobalt(II), while nearly 6% manganese(II)
588
is co-extracted. Therefore, the implementation of four mixer
settlers in series at S/F = 1/2 produces an aqueous solution at
the outlet of the liquid−liquid extraction stage containing
94.6% (w/w) cobalt and 5.4% (w/w) manganese.
Further separation of manganese(II) from cobalt(II) can be
performed by solvent extraction, ion exchange, or precipitation.
D2EHPA (bis-2-ethyl-hexylphosphoric acid) is a suitable
extractant for Co(II)−Mn(II) separation from acidic chloride
media as the pH1/2 values (pH at which the extraction
efficiency is 50%) for Mn(II) and Co(II) are equal to 2.2 and
3.2, respectively.30 It has also been reported that manganese-
(II) can be completely removed from LIB waste leachate,
leaving lithium(I), nickel(II), and cobalt(II) in the raffinate by
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ACS Sustainable Chemistry & Engineering
two-step elution of the aminomethylphosphonic acid func-
tional resin (Lewatit TP260) with 2.0 mol L−1 H2SO4 and 0.4
mol L−1 potassium oxalate, resin being loaded at a feed pH of
1.8 at 60 °C.31 Besides, the use of SO2/O2 as an oxidant was
also reported to be able to selectively recover manganese by
oxidizing Mn(II) and precipitating it as MnO2/Mn2O3 in the
pH range of 3−4 and temperature range of 25−80 °C, with
less than 1% co-precipitation of cobalt and nickel.32
Liquid−Liquid Extraction of Manganese. The resulting
cobalt-depleted stream contained 3613 mg L−1 manganese(II),
3599 mg L−1 nickel(II), and 1515 mg·L−1 lithium(I). Figure
5a,b shows that manganese(II) can be selectively extracted
from the cobalt-depleted stream using 0.7 mol L−1 Alamine
336 at O/A = 2.
Figure 5. Effect of (a) Alamine 336 concentration (O/A = 2) on
manganese(II) extraction and (b) phase volume ratio O/A on
manganese(II), nickel(II), and lithium(I) extraction from the cobalt-
depleted stream (organic phase = 0.1−0.9 mol L−1 Alamine 336 in
kerosene modified with 10% (vol) 1-dodecanol; aqueous phase =
1534 mg L−1 lithium(I), 3218 mg L−1 nickel(II), and 3863 mg L−1
manganese(II), in 7 mol L−1 HCl).
589
pubs.acs.org/journal/ascecg Research Article
The McCabe−Thiele diagram in Figure 6 shows that only
three theoretical counter-current stages are required to achieve
a complete recovery of manganese(II) from the cobalt-
depleted stream at O/A = 2.
Nickel Recovery. Gibson and Rice reported successful
extraction of nickel(II) with Cyanex 301 from chloride leach
liquors produced from lateritic nickel ores.33 Wang and Lee
reported that an almost full extraction of nickel(II) can be
achieved at pH 1 with Cyanex 301, and nickel(II) can be
completely stripped using 10 mol L−1 HCl.34
Liquid−liquid extraction of nickel(II) from the cobalt−
manganese-depleted leach solution was performed using 10%
(v/v) Cyanex 301 diluted in kerosene at pH 7 adjusted with
ammonia at O/A = 0.5 (full extraction efficiency, SCNi/Li =
395). Full stripping was performed using 10 mol L−1 HCl.
Despite the high extraction efficiency of nickel(II) and the
good selectivity coefficient, this use of Cyanex 301 was
excluded because of an important chemical degradation of
Cyanex 301.35 Cyanex 272 was also tested to recover nickel(II)
from the cobalt−manganese-depleted solution. However, the
addition of NaOH to reach pH 9 was responsible for nickel(II)
precipitation during the liquid−liquid extraction step.
Nickel(II) precipitation was also performed with sodium
hydroxide to selectively recover nickel(II) toward lithium(I)
from the cobalt−manganese-depleted solution. Figure 7 shows
that nickel(II) precipitation started at pH 7. It is interesting to
point out that 98.5% nickel(II) and 10.7% lithium(I)
precipitated at pH 8. A significant increase in lithium lost
was observed when the pH was greater than 8. For instance,
15.4% lithium was lost in the precipitate at pH 9. Therefore,
pH 8 is a good compromise to achieve an efficient nickel−
lithium separation.
Finaly, the precipitate contains nickel(II), lithium(I), and
sodium(I). It was possible to purify the nickel(II) precipitate
using diluted sodium hydroxide as lithium(I) and sodium(I)
solubilites are much higher than those of nickel(II) in weak
alkaline media at room temperature. Therefore, the precipitate
was washed several times according to the following
procedure:
•90% in volume of the overflow solution was replaced
with diluted sodium hydroxide at pH 8;
•The solid/liquid mixture was mixed for 10 min before
centrifugation.
Figure 8 shows the variation in nickel(II), lithium(I), and
sodium(I) concentrations in the overflow after several washing
steps. Lithium(I) was almost fully dissolved after the first
washing step, but the sodium(I) content in the overflow was
still very high, that is, 8672 ppm. After the second washing
step, almost all lithium(I) and sodium(I) were removed from
the precipitate. Beyond the second stage, nickel(II) dissolution
was greater than sodium(I) dissolution, as 245 ppm nickel(II)
and 119 ppm sodium(I) were solubilized in the overflow
solution. Therefore, the implementation of two washing stages
is enough to purify nickel(II) hydroxide without loosing too
much nickel(II) in the overflow solution.
After two washing stages, dewatering and drying the
precipitate at 105 °C for 24 h, the overall nickel recovery
calculated using eq 11 reached 97.0%. Table 3 shows that the
precipitate contained 55.6% nickel(II) (equivalent to 87.9%
Ni(OH)2), 7.85% chloride, 2.4% sodium(I) (equivalent to
6.4% NaCl), and 0.02% lithium(I).
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Figure 6. McCabe−Thiele diagram applied to manganese(II) extraction from the cobalt-depleted streams for the determination of the theoretical
number of mixer settlers.

Figure 7. Precipitation efficiency (% PE) of nickel(II) and lithium(I) as a function of pH adjusted by adding sodium hydroxide (initial
concentration of the aqueous phase = 1406 mg L−1 lithium(I) and 4219 mg L−1 nickel(II), in 7 mol L−1 HCl).

The XRD pattern reported in Figure 9 confirms the presence
of Ni(OH)2 as the main component. The presence of NaCl
was also confirmed. It was difficult to confirm the presence of
LiOH or LiCl, as their XRD peaks were likely masked by the
Ni(OH)2 peak.
The precipitation of nickel hydroxide can be further
optimized in terms of precipitation efficiency and purity by
changing the temperature, adding seeds, or using another
neutralizing agent such as MgO instead of sodium hydroxide.36
Global Flowsheet. The preceding results showed that
stream containing sodium(I) and lithium(I) can be efficiently
separated using Cyanex 936 (a phosphorus-based extractant
specifically formulated for lithium−sodium separation from
chloride media such as brines) diluted in kerosene at pH above
10 according to the paper published by Fritz, which
demonstrated the high selectivity of Cyanex 936 for lithium(I)
toward sodium(I).37 Another option to extract lithium(I)
consists in precipitating lithium carbonate using saturated
sodium carbonate at 50 °C.38 All of these results lead to the
global flowsheet reported in Figure 10.

Alamine 336 can be used to separate cobalt(II) and
manganese(II) by optimizing the Alamine 336 concentration
and the phase volume ratio O/A. Furthermore, nickel(II)
hydroxide can be produced by precipitation with sodium
hydroxide without significant loss of lithium. The resulting
590
■
CONCLUSIONS
After full leaching of NMC111 in hydrochloric acid, cobalt(II)
can be efficiently extracted using Alamine 336 at a low phase
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ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Figure 8. Evolution of the overflow composition as a function of the number of washing steps of the Ni(OH)2 precipitate at pH 8 (adjusted using
NaOH).

Table 3. Chemical Composition of the Precipitate volume ratio O/A = 0.5 without significant co-extraction of
(*Equivalent to 87.9% Ni(OH)2) manganese(II) and no co-extraction of nickel(II) and lithium-
element % Ni* % Li % Na % Cl (I). McCabeThiele analysis showed that the use of two mixer
content in weight 55.64 0.02 2.42 7.86 settlers in series allows extracting 99.9% cobalt(II) and 6%
manganese(II). After stripping the loaded organic phase with
0.1 mol L−1 hydrochloric acid, an aqueous phase containing

Figure 9. XRD pattern of the precipitate.

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ACS Sustainable Chemistry & Engineering
Figure 10. Simplified flowsheet to recover cobalt(II), manganese(II), nickel(II), and lithium(I) from NMC111.
94.6% cobalt(II) and 5.4% manganese(II) was produced. This
stream can be purified by solvent extraction, ion exchange, or
precipitation to produce high-grade cobalt products.
Afterward, manganese(II) contained in the cobalt-depleted
stream can be selectively extracted toward nickel(II) and
lithium(I) using Alamine 336 at O/A = 2. The loaded organic
phase can be efficiently stripped with 0.1 mol L−1 hydrochloric
acid. The manganese(II) extraction/stripping stage permits us
to recover more than 94.6% manganese(II) with a purity
greater than 99.9%.
The remaining aqueous phase after manganese(II) extrac-
tion contains nickel(II) and lithium(I). Nickel(II) can be
precipitated as nickel(II) hydroxide using NaOH at pH 8.
After dewatering, the overflow contains sodium(I) and
lithium(I). The precipitate is mainly composed of Ni(OH)2.
Most of the lithium(I) and sodium(I) contained in the
precipitate can be washed away using water. This process can
recover more than 97.0% nickel(II) contained in the solution.
The resulting precipitate contains 55.64% Ni (equivalent to
87.9% Ni(OH)2), 7.85% chloride, 2.42% sodium, and 0.02%
lithium. The lithium remaining in the resulting aqueous phase
can be recovered by precipitation or by solvent extraction with
the new organosphosphorus reagent Cyanex 936, which was
initially developed for the selective extraction of lithium(I)
from brines.
■
AUTHOR INFORMATION
Corresponding Author
Alexandre Chagnes − Université de Lorraine, CNRS,
GeoRessources, 54505 Vandoeuvre-les-Nancy, France;
orcid.org/0000-0002-4345-6812; Phone: +33(0)
372744544; Email: alexandre.chagnes@univ-lorraine.fr
Authors
Wen Xuan − Université de Lorraine, CNRS, GeoRessources,
54505 Vandoeuvre-les-Nancy, France
Antônio de Souza Braga − Université de Lorraine, CNRS,
GeoRessources, 54505 Vandoeuvre-les-Nancy, France
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.1c07109
Notes
The authors declare no competing financial interest.
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pubs.acs.org/journal/ascecg Research Article
■ ACKNOWLEDGMENTS
This work was supported by the French National Research
Agency through the national program “Appel à Projet
Générique 2018” (ANR-18-CE08-0005-03) and the national
program “Investissements d’avenir” with the reference ANR-
10-LABX-21-RESSOURCES21. The authors acknowledge the
European Union within the framework of the operational
programme FEDER-FSE Lorraine et Massif des Vosges 2014−
2020 for their contribution in funding the Hydroval and
Hydrolab facilities. The authors thank BASF and Solvay for
providing the extracting agents. The authors are grateful to
Jérôme Marin (PGM laboratory) and Renaud Gley (LIEC
laboratory) for their support in the analyses of few samples.
■
REFERENCES
(1) Armand, M.; Tarascon, J.-M. Building Better Batteries. Nature
2008, 451, 652−657.
(2) Chagnes, A.; Pospiech, B. A Brief Review on Hydrometallurgical
Technologies for Recycling Spent Lithium-Ion Batteries: Technolo-
gies for Recycling Spent Lithium-Ion Batteries. J. Chem. Technol.
Biotechnol. 2013, 88, 1191−1199.
(3) Hannan, M. A.; Hoque, M. M.; Hussain, A.; Yusof, Y.; Ker, P. J.
State-of-the-Art and Energy Management System of Lithium-Ion
Batteries in Electric Vehicle Applications: Issues and Recommenda-
tions. IEEE Access 2018, 6, 19362−19378.
(4) Chagnes, A.; Swiatowska, J. Lithium Process Chemistry: Resources,
Extraction, Batteries, and Recycling; Elsevier Science: San Diego, CA,
USA, 2015.
(5) Xiao, X.; Hoogendoorn, B. W.; Ma, Y.; Ashoka Sahadevan, S.;
Gardner, J. M.; Forsberg, K.; Olsson, R. T. Ultrasound-assisted
extraction of metals from Lithium-ion batteries using natural organic
acids. Green Chem. 2021, 23, 8519−8532.
(6) Chen, L.; Chao, Y.; Li, X.; Zhou, G.; Lu, Q.; Hua, M.; Li, H.; Ni,
X.; Wu, P.; Zhu, W. Engineering a tandem leaching system for the
highly selective recycling of valuable metals from spent Li-ion
batteries. Green Chem. 2021, 23, 2177−2184.
(7) Lu, Q.; Chen, L.; Li, X.; Chao, Y.; Sun, J.; Ji, H.; Zhu, W.
Sustainable and Convenient Recovery of Valuable Metals from Spent
Li-Ion Batteries by a One-Pot Extraction Process. ACS Sustainable
Chem. Eng. 2021, 9, 13851−13861.
(8) Stefaniak, J.; Karwacka, S.; Janiszewska, M.; Dutta, A.; Rene, E.
R.; Regel-Rosocka, M. Co(II) and Ni(II) Transport from Model and
Real Sulfate Solutions by Extraction with Bis(2,4,4-Trimethylpentyl)-
Phosphinic Acid (Cyanex 272). Chemosphere 2020, 254, 126869.
(9) Ocaña, N.; Alguacil, F. J. Cobalt-Manganese Separation: The
Extraction of Cobalt(II) from Manganese Sulphate Solutions by
Cyanex 301. J. Chem. Technol. Biotechnol. 1998, 73, 211−216.
https://doi.org/10.1021/acssuschemeng.1c07109
ACS Sustainable Chem. Eng. 2022, 10, 582−593
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

(10) Mohapatra, D.; Hongin, K.; Nam, C.; Park, K. Liquid−Liquid Manganese from Acidic Chloride Media. RSC Adv. 2017, 7, 5660−
Extraction of Aluminium(III) from Mixed Sulphate Solutions Using 5668.
Sodium Salts of Cyanex 272 and D2EHPA. Sep. Purif. Technol. 2007, (31) Virolainen, S.; Wesselborg, T.; Kaukinen, A.; Sainio, T.
56, 311−318. Removal of Iron, Aluminium, Manganese and Copper from Leach
(11) Guimarães, A. S.; da Silva, P. S.; Mansur, M. B. Purification of Solutions of Lithium-Ion Battery Waste Using Ion Exchange.
Nickel from Multicomponent Aqueous Sulfuric Solutions by Hydrometallurgy 2021, 202, 105602.
Synergistic Solvent Extraction Using Cyanex 272 and Versatic 10. (32) Zhang, W.; Singh, P.; Muir, D. Oxidative precipitation of
Hydrometallurgy 2014, 150, 173−177. manganese with SO2/O2 and separation from cobalt and nickel.
(12) Kang, J.; Senanayake, G.; Sohn, J.; Shin, S. M. Recovery of Hydrometallurgy 2002, 63, 127−135.
Cobalt Sulfate from Spent Lithium Ion Batteries by Reductive (33) Rice, N. M. A hydrochloric acid process for nickeliferous
Leaching and Solvent Extraction with Cyanex 272. Hydrometallurgy laterites. Minerals Eng. 2016, 88, 28.
2010, 100, 168−171. (34) Wang, L. Y.; Lee, M. S. Separation of Co(II) and Ni(II) from
(13) Nathsarma, K. C.; Devi, N. Separation of Zn(II) and Mn(II) Chloride Leach Solution of Nickel Laterite Ore by Solvent Extraction
from Sulphate Solutions Using Sodium Salts of D2EHPA, PC88A and with Cyanex 301. Int. J. Miner. Process. 2017, 166, 45−52.
Cyanex 272. Hydrometallurgy 2006, 84, 149−154. (35) Wieszczycka, K.; Tomczyk, W. Degradation of Organo-
(14) Yang, Y.; Xu, S.; He, Y. Lithium Recycling and Cathode thiophosphorous Extractant Cyanex 301. J. Hazard. Mater. 2011,
Material Regeneration from Acid Leach Liquor of Spent Lithium-Ion 192, 530−537.
Battery via Facile Co-Extraction and Co-Precipitation Processes. (36) Mubarok, M. Z.; Lieberto, J. Precipitation of Nickel Hydroxide
Waste Manage. 2017, 64, 219−227. from Simulated and Atmospheric-Leach Solution of Nickel Laterite
(15) Bates, J. R. The Reaction of Hydrogen Atoms with Oxygen and Ore. Procedia Earth Planet. Sci. 2013, 6, 457−464.
the Hydrogen Chlorine Reaction. Proc. Natl. Acad. Sci. U.S.A. 1933, (37) Fritz, A. Q. CYANEX 936/TAT-Li Process, A new technology
19, 81−85. for Lithium extraction. XV Congreso Internacional Expomin 2018,
(16) Sarangi, K.; Reddy, B. R.; Das, R. P. Extraction studies of cobalt Innovation for Mining Development, 2018.
(II) and nickel (II) from chloride solutions using Na-Cyanex 272. (38) Han, B.; Anwar UI Haq, R.; Louhi-Kultanen, M. Lithium
Hydrometallurgy 1999, 52, 253−265. Carbonate Precipitation by Homogeneous and Heterogeneous
(17) Tait, B. K. Cobalt-Nickel Separation: The Extraction of Reactive Crystallization. Hydrometallurgy 2020, 195, 105386.
Cobalt(II) and Nickel(II) by Cyanex 301, Cyanex 302 and Cyanex
272. Hydrometallurgy 1993, 32, 365−372.
(18) Chagnes, A.; Omelchuk, K. Liquid-Liquid Extraction of
Cobalt(II), Nickel(II) and Manganese(II) from Acidic Chloride
Media. Extraction; Springer, 2018.
(19) Aly, H. F.; El-Garhy, M.; El-Reefy, S. Extraction of Iron, Cobalt,
and Manganese from Hydrochloric Acid with Quaternary Amine,
Aliquat-336. Microchem. J. 1972, 17, 431−435.
(20) Good, M. L.; Bryan, S. E. Extraction of Group VIII Metals by
Long Chain Alkyl AminesII. J. Inorg. Nucl. Chem. 1961, 20, 140−
146.
(21) D’yakova, L. V.; Kasikov, A. G. Manganese(II) Extraction from
Chloride Nickel Solutions with the Use of Trioctylamine. Russ. J.
Appl. Chem. 2013, 86, 1090−1093.
(22) Shen, Y.-f.; Xue, W.-y.; Niu, W.-y.W. Recovery of Co(II) and
Ni(II) from Hydrochloric Acid Solution of Alloy Scrap. Trans.
Nonferrous Met. Soc. China 2008, 18, 1262−1268.
(23) Xuan, W.; Otsuki, A.; Chagnes, A. Investigation of the leaching
mechanism of NMC 811 (LiNi0.8Mn0.1Co0.1O2) by hydrochloric
acid for recycling lithium ion battery cathodes. RSC Adv. 2019, 9,
38612−38618.
(24) Xuan, W.; de Souza Braga, A.; Korbel, C.; Chagnes, A. New
Insights in the Leaching Kinetics of Cathodic Materials in Acidic
Chloride Media for Lithium-Ion Battery Recycling. Hydrometallurgy
2021, 204, 105705.
(25) Ypma, T. J. Historical Development of the Newton-Raphson
Method. SIAM Rev. 1995, 37, 531−551.
(26) Seeley, F. G.; Crouse, D. J. Extraction of Metals from Chloride
Solutions and Amines. J. Chem. Eng. Data 1966, 11, 424−429.
(27) Zhu, Z.; Yoko, P.; Cheng, C. Y. Recovery of Cobalt and
Manganese from Nickel Laterite Leach Solutions Containing Chloride
by Solvent Extraction Using Cyphos IL 101. Hydrometallurgy 2017,
169, 213−218.
(28) Cheng, J.; Lu, T.; Wu, X.; Zhang, H.; Zhang, C.; Peng, C.-A.;
Huang, S. Extraction of cobalt(ii) by methyltrioctylammonium
chloride in nickel(ii)-containing chloride solution from spent lithium
ion batteries. RSC Adv. 2019, 9, 22729−22739.
(29) Logeat, M.; Mankowski, G.; Molinier, J.; Lenzi, M. Complete
Separation of Copper from Cobalt by Solvent Extraction with
Triisooctylamine. Hydrometallurgy 1982, 9, 105−113.
(30) Omelchuk, K.; Szczepański, P.; Shrotre, A.; Haddad, M.;
Chagnes, A. Effects of Structural Changes of New Organophosphorus
Cationic Exchangers on a Solvent Extraction of Cobalt, Nickel and

593 https://doi.org/10.1021/acssuschemeng.1c07109
ACS Sustainable Chem. Eng. 2022, 10, 582−593