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org/journal/ascecg Research Article

Li2CO3 Recovery through a Carbon-Negative Electrodialysis of

Lithium-Ion Battery Leachates
Meng Shi, Luis A. Diaz,* John R. Klaehn, Aaron D. Wilson, and Tedd E. Lister
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ABSTRACT: Recycling of lithium-ion batteries (LIB) has focused on the

recovery of metals such as Co and Ni due to their intrinsic values. Among these
Downloaded via UNIV LIBRE DE BRUXELLES on April 26, 2023 at 08:56:06 (UTC).

metals, recycling of Li requires hydrometallurgical routes that are not widely

implemented due to the higher costs associated with energy and chemical
consumptions. This makes Li recovery from recycling less economical than
obtention from mineral ores. In the present study, Li as well as Mn were
recovered through electrodialysis (ED) from the leachates of spent LIBs by
employing a CO2-capture agent N-methyldiethanolamine as a regenerable
catholyte. Surrogate solutions and Li-rich leachates were tested for the
separation and recovery of Li and Mn as Li2CO3 and MnCO3, respectively.
The purity of recovered Li2CO3 99.6% achieved battery-grade purity levels from
both surrogate and leachate solutions. It was observed that MnO2 was deposited
on the Pt anode only from the surrogate solutions. Energy consumption of the
ED was low at 0.5 kW h/g Li. The overall process recovered high-purity Li from LIB leachate, with CO2 being the only chemical
consumed. This process is presented as an environment-friendly and energy-effective method in Li2CO3 recovery from LIB materials.
KEYWORDS: Li2CO3, lithium-ion battery recycling, electrodialysis, carbon-negative, carbon capture and utilization

■ INTRODUCTION
Recovery of Li from lithium-ion batteries (LIB) has attracted
provide lithium aluminum silicate mineral, where Li2CO3 can
be extracted through a series of steps such as flotation,
increasing attention from academia, industry, and research pulverization, leaching in hot solutions, and precipitation.14
institutes in recent decades, driven by the growing demands This extraction process is more expensive than brine’s
and prices of materials.1−4 78,000 metric tonnes of Li2CO3 evaporation. Similar to pegmatites, Li in sedimentary rock is
(equivalent) were consumed in 2016, which is 2.7 times that of present in compounds such as Li2O, hectorite, and jadarite.14
2010. It is forecasted that global Li demand will reach 509,000 In addition to primary resources, Li can also be extracted from
metric tonnes by the year 2025.5 In addition, the sky-rocketing spent Li-containing products. 35% of the global Li products
price of Li is a challenge to the cost-effective LIB were used for LIB manufacturing in 2017, and this number is
estimated to rise to 66% by 2025.15 Therefore, to maintain a
manufacturing. Due to the growing popularity of electric
sustainable Li supply chain, a greater focus on LIB recycling is
vehicles, the price of Li2CO3 increased 413% and the price of
necessary. To satisfy market demands, primary and reusable
LiOH grew 254% in North Asia in 2021.6 Statistics in Europe
sources of Li have been investigated.16
show that less than 5% of spent LIBs are being recycled, from
To recover Li from LIB leachates, various methods have
which only 1% of Li is recovered.7 As a result, there are
been investigated, including precipitation,17,18 membrane
opportunities and needs to develop effective and practical
separation,15,19−22 combination of membrane separation and
methods to recover Li from recycled LIBs.
ion exchange,23,24 and solvent extraction.25,26 However,
The global Li reserve is estimated to be 39 million metric
excessive chemical use, waste generation, and limitations in
tonnes, which is sufficient to support the demand of 20 million
selectivity or adsorption capacities have hindered the
metric tonnes per year expected up to the year 2100.8 Li comes
implementation of these approaches.27 Electrochemical sepa-
from three primary resources: brines, pegmatites, and
sedimentary rocks.8 Evaporation of brines is a common
method to precipitate Li9−11 and corecover Na, Mg, K, and Received: April 8, 2022
B.8,12 However, there are disadvantages in Li extraction from Revised: August 16, 2022
brines associated with the location and accessibility of brines, Published: August 26, 2022
such as salt flats in Chile and Argentina, or in deep oil
reservoirs. Moreover, Li obtention from brines takes at least 12
months to complete one producing cycle.13 Pegmatite deposits
© 2022 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acssuschemeng.2c02106
11773 ACS Sustainable Chem. Eng. 2022, 10, 11773−11781
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

ration and purification methods have been proposed to tackle monohydrate (Li2SO4·H2O, Alfa Aesar, 99%) and manganese (II)
the technical issues associated to the traditional separation sulfate monohydrate (MnSO4·H2O, Ward’s Science, 100%) in 0.01 M
methods, but implementation is still limited by low technical sulfuric acid (H2SO4, Fisher Scientific, 95−98 wt %) to concen-
maturity.27 Bae et al. developed a stacked electrochemical trations of both Li and Mn ions around 700 mg/L. Real LIB leachate
was produced through the sequence of metal leaching from LIB black
system to recover Li2CO3 from waste Li-containing materi- mass, followed by Ni and Co removal through ion exchange, as
als.28 They produced Li2CO3 at a purity of 99% and a yield described elsewhere.35,36 The composition of the LIB real leachate is
close to 25%, but the use of LiPF6 electrolyte made the shown in Table S1. LIB black mass was provided by Retriev
generation of toxic HF possible. Hwang and colleagues used a Technologies. The black mass was a mixture of shredded anodes and
Li-ion desorption bipolar membrane module to recover Li cathodes, as well as small fractions of other components of LIB, such
from lithium manganese oxide (LMO).29 The study showed as current collectors and wrapping foils. Catholyte solution was a 30
that a high desorption efficiency could be achieved at a high wt % N-methyldiethanolamine (MDEA, Sigma-Aldrich, ≥99%)
applied potential, a low flow rate, and a strong acidic condition. solution sparged with carbon dioxide (CO2, Norco, 100%) for 48 h
This work proved that a faster Li electrochemical extraction prior to use. The estimated CO2 loading was 0.63 mol CO2/L
catholyte.37,38 Nano-pure water used in this study was obtained from
could be achieved in comparison with chemical desorption the PURELAB Flex 1 (18.2 MΩ) and hydrochloric acid (HCl, Fisher
systems. Jang applied electrochemical methods to Li separation Scientific, 36.5−38%) and was used as received.
from LIB leachate (Li: 13.2 g/L) through adsorption on a Electrodialysis Tests. The ED cell was fabricated in-house with a
LMO electrode.30 Li was separated from the leachate through trough (open top) design, as shown in Figure 1. The cell was divided
intercalation in the MnO2 lattice. Lithiated MnO2 was analyzed
as the final products, and the highest purity of adsorbed Li in
this study was 92.2%. Electrochemical adsorption of Li in
MnO2 still requires posttreatment on the product to isolate
and improve the purity of Li for future use. Song’s group also
recovered Li2CO3 from LIB leachate through a series of
chemical and electrochemical steps.31 The LIB leachate
solution was purified by pH adjustment to 12 with NaOH to
remove most of the metal ions except Li. Li was separated from
the leachate as Li3PO4 precipitates, which were then
redissolved in H2SO4. The dissolved Li in the anolyte passed
the cation-exchange membrane to a NaNO3 catholyte to be
finally precipitated out via a reaction with Na2CO3. This
process consumed a large amount of chemicals and heating
energy, and the purity of the final Li2CO3 product was 99.3%,
Figure 1. Sketch of an ED cell. Anolyte was a 100 mL leachate or
lower than the desired battery grade of 99.5%.32 Addition of surrogate solution that contained majorly Li and Mn in the metal
Na2CO3 is a widely applied method to precipitate Li2CO3. The composition. Catholyte featured a CO2-loaded MDEA solution.
pH condition was a key factor in the process. At pH 3.5, high- Continuous CO2 sparging during the ED was from a stainless-steel
purity Li2CO3 (>99%) could be achieved at about 95% sparge filter. The two electrolytes were separated by a monovalent
recovery ratio from LiCoO2 leachate.33 Comparatively speak- selective membrane. The anolyte was cycled in a loop between the
ing, electrodialysis (ED), which was found to be effective and anodic cell and the anolyte reservoir. Both the cathode and anode
environment friendly in other research area, has not been were Pt-plated Ti meshes.
systematically applied in the field of Li recovery from LIB
materials. into two chambers by a monovalent selective membrane (Selemion
In the present study, leachate from end-of-life LIBs was CSO membrane). A monovalent membrane was used with the
intention to favor the transfer of monovalent ions such as Li+, over
investigated as the source to obtain the proof-of-concept of an
other multivalent ions present in the leachate (i.e., Mn2+, Fe2+/3+, and
intensified Li separation process that combines ED with Al3+).39 A separated reservoir contained the bulk anolyte (surrogate or
carbon capture and utilization. The experiments employed a leachate). The total volume of the anolyte was 100 mL. The cathodic
monovalent selective cation-exchange membrane that sepa- bath contained 18 mL of CO2-loaded MDEA solution, and CO2 was
rated the anolyte (LIB leachate) and the catholyte (an amine- sparged at a flow rate of 17 sccm through a stainless-steel sparge filter
based CO2 capture solution). The resulting Li2CO3 was (2 μm porosity, RESTEK). The ED cell employed a waterfall design
recovered and separated by introducing CO2 as the only on the anolyte side, which permitted a constant volume on the anode
consumed chemical. With direct CO2 consumption, this study compartment. Anolyte was pumped from the reservoir to the bottom
avoided other carbonate resources such as Na2CO3 which of the anode chamber using a Masterflex peristaltic pump. Both
cathode and anode were Pt-plated Ti meshes (area: 2 × 3 cm). For
would increase the cost of Li recovery,31,34 and it provided a
cleaning, the electrodes were washed through sonication in acetone
green alternative for carbon-negative Li2CO3 production. for 10 min, in ethanol for 10 min, and in nano-pure water for 10 min.
Moreover, the captured CO2 also assisted with Mn separation After washing, the electrodes were dried in an oven at 75 °C and
and recovery as MnCO3. Purity of recovered Li2CO3 reached cooled in air before use.
up to 99.6% (metal basis), which was higher than the battery- A potentiostat (Ametek Scientific Instruments, Solartron Analytical
grade 99.5%.32 Energy consumption of Li separation through 1287) was used as a power supply and voltage control. CorrWare
ED was calculated as 0.5 kW h/g Li. (Ametek Scientific Instruments) was the interface for potentiostat
control and data acquisition. A constant cell potential of 5 V was

■ EXPERIMENTAL SECTION
Materials and Reagents. Surrogate and real LIB leachate
applied between the anode and cathode. The total applied charge was
achieved from integration of current and time by CorrView. ED was
carried out for 48 h in surrogate studies and 24 h in leachate studies.
obtained after the separation of Co and Ni were used as Li sources. Other Electrochemical Tests. A Biologic potentiostat (SP-300)
Surrogate leachate was prepared by mixing lithium sulfate was used to perform cyclic voltammetry (CV) measurements. The

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ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

working electrode was either a Pt plate (1.9 × 1.9 cm) or a graphite X-ray diffraction (XRD) spectroscopy was performed on a Bruker
sheet (2.7 × 2.5 cm). The counter electrode was a Pt plate (1.9 × 1.9 AXS D8 ADVANCE spectrometer with a LYNXEYE XE-T detector
cm), and the reference electrode was Ag/AgCl. The scan rate was 20 in 1D mode. A Cu target (λ = 1.54 Å, 40 kV and 40 mA) was used for
mV/s. CV measurements started at the open-circuit potential (OCP), the characterization of the precipitates obtained, including MnO2,
scanned forward to the anodic potential, moved reverse to the MnCO3, and Li2CO3. Scans were operated at 0.01°/min between 20
cathodic setpoint, and finally stopped at the initial OCP. Surfaces of and 90° (2θ) in a coupled 2θ/θ mode.
electrodes were cleaned with HCl between measurements. Theory of the Electrochemical Production of Li2CO3. The
When necessary, MnO2 deposition was performed by chronoam- described process is intended to transfer Li from LIB leachates
perometry (CA) at 1.2 V vs Ag/AgCl using a Biologic potentiostat (anolyte) to the cathode side of the ED cell, recovering Li2CO3 as a
(SP-300) in a MnSO4 solution (Mn: 700 mg/L in 0.01 M H2SO4) for solid in the cathode compartment employing captured CO2 as the
5 min. Both the working and counter electrodes were Pt plates (1.9 × only consumable reagent.
1.9 cm). The MnO2-coated Pt was dipped in water to clean the A mixture of MDEA (30 wt %) in water was used as the CO2-
surface. All the electrochemical operations were conducted at room capture catholyte solution. MDEA is a commercial tertiary amine,
temperature. which has been widely tested for pre- and postcombustion CO2
ED Material Processing and Analysis. Processing of the ED capture due to its low absorption enthalpies, stability, and competitive
products is described in Figure 2. After the applied potential was CO2 loading.40,41 CO2 absorption in tertiary amines such as MDEA
occurs through a reaction with water and amine protonation to form
HCO3− (eq 1)42
+
MDEA (aq) + H 2O + CO2(g) MDEAH(aq) + HCO3(aq) (1)
During ED, water electrolysis takes place, including the oxygen
evolution reaction (OER) and hydrogen evolution reaction (HER) at
the anode and cathode, respectively. The applied potential imparts
cation migration toward the cathode for which a monovalent cation-
Figure 2. Scheme of isolating MnCO3 and Li2CO3 with CO2- selective membrane is used to separate the anode and cathode
facilitated ED and associated processes. favoring the transfer of monovalent cations such as Li+. At the
cathode, Li+ is expected to react with available HCO3− and OH− ions
(produced from the HER) to form Li2CO3 and the deprotonated
ceased, both electrodes were removed slowly from the cell to avoid amine (eq 2)
dislodging of electrode deposits. Deposit layers on the anode were
scraped from the electrode after the anode was dried in air. Then, 2Li+(aq) + 2OH (aq)
+
+ MDEAH(aq) + HCO3(aq)
both electrodes were washed with HCl to remove any additional
material to clean the electrodes. The acidic wash solutions were Li 2CO3(s) + MDEA (aq) + 2H 2O (2)
collected to assist with the determination of the material balance of
each experiment. Collected catholyte and catholyte precipitates were Note that the solutions fed to the anode compartment also
sparged with CO2 for 5 h, and the remaining precipitate was filtered contained Mn in comparable concentrations to Li, as well as traces of
and dried. After filtration, the catholyte solution was heated at 75 °C Ni, Co, and other impurities such as Fe, Al, Cd, and Zn present in real
for 2 h. The precipitate after heating was the recovered Li2CO3. LIB leachate. It was anticipated that Mn would form MnO2 at the
Surrogate leachate tests used fresh anolyte (leachate feed) in each anode, as predicted in the Pourbaix diagram.43
experiment, but the catholyte was regenerated and reused from the
previous experiment. To regenerate catholyte, 0.5 mL of fresh MDEA
and water were added to reach 18 mL of the total volume. The
■ RESULTS AND DISCUSSION
Sequential Electrodialysis of Surrogate Anolytes. To
amount of MDEA added was selected to address possible material loss
(from evaporation and transfer) during ED post-treatments. This simplify the system and isolate the electrochemical behavior of
MDEA solution was sparged with CO2 overnight to achieve Li+ and Mn2+ under an ED environment, preliminary Li
saturation. recovery experiments were performed with a surrogate mixture
In LIB leachate electrodialysis, the anolyte was a fresh batch of of Li2SO4 and MnSO4 in 0.01 M H2SO4.
leachate mixed with the catholyte precipitates (mostly MnCO3) ED tests with surrogate solutions were carried out by
obtained from the previous test. The catholyte was also recycled, and applying a cell voltage of 5 V. After 48 h of ED, 5860 C was
the regeneration method was the same as that described above. applied in the first test with a fresh anolyte and a fresh
All the products were sampled, and elemental analysis was catholyte (Table 1, test 1). On the anode, a black deposit layer
performed with an Agilent, 240FS atomic absorption spectrometer was formed (Figure 3b). XRD analysis (Figure 3a) identified
(AAS). Liquid products were diluted with 3% HCl, and solid products
were first dissolved in concentrated HCl and then diluted with 3% the anode black deposit as manganese oxides where β-MnO2
HCl. Calibration standards were prepared for each metal from was the predominant phase.44−46 The Pourbaix diagram43
commercially available standard solutions (Agilent). Prepared stand- predicts that the formation of β-MnO2 (eq 3) was favored over
ard solution was 1 mg/L for Cd and Zn, 40 mg/L for Al, and 5 mg/L OER at pH > 0. In the pH range of 1−2, three oxidation
for all other metals. reactions might occur, water electrolysis, solid manganese

Table 1. Analysis of Products from Surrogate Experiments Performed for 48 Ha

Li2CO3 MnCO3 MnO2 used catholyte
test charge/C Li/Mn separation factor Li/mg purity/% Mn/mg purity/% Mn/mg purity/% Li/mg Mn/mg
1 5860 0.57 33.9 100 92.9 92.9 28.2 100 6.98 0.05
2 6438 0.75 26.6 99.8 72.7 96.5 15.9 99.7 21.98 0.06
3 9669 1.38 24.1 99.8 45.6 95.4 2.3 99.3 17.23 0.04

a
Initial composition of both Li and Mn in the surrogate anolytes was kept at around 700 mg/L for all three tests.

11775 https://doi.org/10.1021/acssuschemeng.2c02106
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light brown MnCO3 powder was 92.9 wt % (metal basis). XRD

analysis confirmed the formation of MnCO3 as the primary
phase with traces of Li2CO3 present (Figure 3a). A small
amount of Li and traces of Mn remained in the catholyte after
MnCO3 and Li2CO3 separation.
Mass balance of metals showed that 48.4 wt % of Li from the
anolyte was recovered in the form of Li2CO3 dried product. A
recent literature on membrane-based Li separation and
recovery reports Li recoveries in that range of 5.9−99%, but
this information only accounts for the Li reported in the
catholyte and not as a final solid product.27,47,48 Nevertheless,
improvements in Li2CO3 yields are necessary in order to make
this technology industrially relevant. Due to the OER and
MnO2 formation, the pH of the anolyte decreased from 2.10 to
Figure 3. (a) XRD patterns of achieved anode deposits (β-MnO2), 1.28, while the pH of the catholyte increased from 8.15 to 9.92.
Li2CO3 product, and MnCO3 product. (b) Picture of the MnO2- Two consecutive repetitions of the ED experiments (Table
deposited anode after electrodialysis, (c) picture of obtained Li2CO3, 1, tests 2 and 3) were performed with fresh anolyte, in which
and (d) picture of obtained MnCO3. all the operational parameters as well as the procedures in
recovering products were the same as those of test 1. Li and
oxide generation, and MnO4− formation. Water electrolysis Mn salts, accumulated in the catholyte from previous
generates oxygen bubbles. MnO4− in the liquid phase is not a experiments, acted as supporting electrolyte for the catholyte,
significant product during the experiments. Therefore, among thus these experiments featured higher currents and therefore
these possible oxidation products, it can be deduced that more charges (Table 1). However, this increase in current did
manganese oxides are the only solids that show a dark color not translate in higher Li- or Mn-transfer rates as the greater
and can deposit a layer on the anode. The β-MnO2 deposit number of protons generated from the combined OER and Mn
could be mechanically removed from the anode after drying. In oxidation (eq 3) could also compete for charge transfer
some experiments, the black sediment was also found at the through the cation-exchange membrane. Mn diffusion to the
bottom of the anolyte chamber, likely dislodged by O2 catholyte was also hindered as evidenced by the decreasing
formation at the anode surface. amount of MnCO3 recovery with each subsequent test.
2+ Nevertheless, the purity of the recovered Li2CO3 in the two
Mn(aq) + 2H 2O MnO2(s) + 4H+(aq) + 2e (3) repetitions was 99.8%.
At the cathode side of the membrane, a layer of light brown Recovery of Li2CO3 from the catholyte after ED required
deposit was formed (Figure 3d). Analysis of this product, additional processing as Li was predominantly present as
obtained in preliminary tests, showed that the deposit LiHCO3. Heating this catholyte released CO2 generating
contained Li and Mn, indicating that Li was not the only Li2CO3 (reverse of eq 5). Li2CO3 precipitated due to its lower
metal crossing the monovalent selective membrane. Since Mn solubility compared with that of LiHCO3 (1.27 g/100 mL at
also passed across the membrane, formation of MnCO3 is 25 °C vs 5.74 g/100 mL at 20 °C), which decreases with
expressed in eq 4 temperature.49 A typical heating process was carried out at 75
°C for 2 h. Heating above 75 °C might increase the yield of
2+ +
Mn(aq) + 2OH (aq) + MDEAH(aq) + HCO3(aq) Li2CO3, but it could lead to the MDEA degradation. Heating
for longer than 2 h also impacted the recyclability of the
MnCO3(s) + MDEA (aq) + 2H 2O (4) catholyte (likely through MDEA evaporation) and afforded
minimum additional recoveries of Li2CO3.
Liquid and solid phases at the cathode side were collected. Both Li and Mn were detected in all products collected at
CO2 was sparged to the catholyte suspension to dissolve the cathode compartment. From the experiments in Table 1, in
Li2CO3 as LiHCO3 (eq 5) and isolate MnCO3. After filtration, average 59.4% of Li, along with 54.9% of Mn, was transferred
the filtrate was heated at 75 °C for 2 h to release CO2, which to the cathode side, indicating that the expected monovalent
promoted the reverse reaction of eq 5 and precipitated Li2CO3 selectivity of the Selemion CSO was not achieved. For the
(Figure 3c). purpose of Li-only permeability, the Selemion CSO cation-
Li 2CO3(s) + CO2(g) + H 2O 2LiHCO3(aq) exchange membrane consists of a porous structure with
(5)
covalently bound sulfonate groups (R−SO3−).39 Cations, both
MnO2, Li2CO3, and MnCO3 products recovered in the monovalent and divalent ions, are attracted to the surface of
anode and cathode, respectively, were characterized with XRD the membrane through electro-osmotic force. Compared with
(Figure 3a). The elemental composition of the recovered the monovalent ions, the divalent ions should be preferentially
products was measured by AAS and is listed in Table 1. The adsorbed on the surface. Thus, a positive electric layer,
XRD pattern of MnO2 powder matched with β-MnO2, and the consisting mostly of divalent ions, is formed on the interface.
elemental analysis showed 100% Mn in metal basis, meaning Since the positive charge density and the local electrostatic
the deposit on the anode was pure β-MnO2. The XRD pattern repulsive force on divalent ions are higher, it is more difficult
of the Li2CO3 product showed sharp peaks, which matched the for divalent ions to permeate the positive electric layer and
Li2CO3 standard. Furthermore, the concentration of Li in the travel across the membrane.24 When the divalent ions have a
white Li2CO3 powders approached 100%. Therefore, the higher concentration than that of the monovalent, the
combined results from AAS and XRD identified that high- transport for divalent ions is slowed.50 However, Mn molar
purity Li2CO3 was produced. The concentration of Mn in the concentration in the tested solution is 1 order of magnitude
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Figure 4. Scheme of isolating Li2CO3 and MnCO3 with CO2 facilitated sequential leachate ED and associated processes. Five ED cycles were
performed from LIB leachate recovering Li2CO3 and MnCO3.

lower than that of Li, which affects the selectivity of the solution contains high concentrations of Li, Mn, Co, and Ni, as
membrane. well as small amounts of impurities, such as Fe, Al, Zn, and Cd.
In our study, the molar concentration of monovalent Li ions The metal impurities can be removed through a precipitation
was much higher compared with that of divalent Mn ions. The step as either phosphoric salts (US Prov. 63/260,988) or
positive electric layer was weak, and the transfer of divalent hydraulic salts.56−58 The valuable metals such as Ni and Co
ions was not hindered, so the selectivity of Li ions was low. As can be separated through ion-exchange and other ap-
the result, almost the same ratios of Li and Mn transferred proaches.36,59−61 The obtained processed leachate is Li-rich
through the membrane. There are no known ED membranes and can be utilized in this study.
with greater selectivity reported of monovalent ions over Fresh leachate (anolyte) was used in each repetition,
divalent. It may be possible to achieve a greater separation with whereas fresh catholyte was only used for the first experiment
monovalent selective nanofiltration, but the difference in and then regenerated and reused for the following four
solubility of the transition-metal elements (i.e., Mn, Co, or Ni) batches. Operating parameters were similar to those used in
in CO2-loaded catholytes was found to be an effective method the surrogate studies, except that each individual batch was
to obtain high-purity Li2CO3. performed for 24 h, and no electrode deposit was removed
To recover Li2CO3, energy was required in two aspects, for until the end of batch 5. Moreover, Li in the light brown
ED and catholyte heating. Based on the total charge applied, powder was not redissolved into the catholyte until after the
the energy consumptions for ED were 0.24, 0.34, and 0.56 kW end of batch 5. Instead, the light brown powder directly
h/g Li in the three tests presented above, respectively. separated from catholyte after ED was added to the new
Comparing with values reported in the literature of over 192 anolyte before the beginning of the following batch. A diagram
kW h/g Li through a different ED method,51 lower energy of the operation is presented in Figure 4.
consumptions show the primary benefits of the proposed The pH of the anolyte feed was 2.02, which decreased to
process. To precipitate Li2CO3, the catholyte was heated at 75 around 1.2 after ED. The volume of anolyte after the reaction
°C for 2 h. As a result, the heating step consumed 17 kW h/g reduced to about 90% of the starting volume as the result of
Li, which was over 98% of the total energy provided. Various water electrolysis and evaporation. The black deposit (MnO2,
heating sources have been reported, including energy from Figure 3b) which generated on the anode in the surrogate tests
nuclear reactors, radiant panels, and other renewable and green did not form with LIB leachate, instead only a light brown
sources that have been studied and applied to practical use for coating on the anode was observed at the end of batch 5.
decades.52−54 By introducing these heating methods, the Further investigations were performed, as presented below, to
process will be much lower in energy consumption and more gain insights into the absence of MnO2 formation on the anode
promising for commercial adoption. when the ED anolyte was LIB leachate. It was learned from the
Based on the studies with surrogates, it was expected that surrogate study that there was Li in the MnCO3 product, and a
MnO2 formed on the anode, and MnCO3 and Li2CO3 were be higher Mn concentration might benefit the selectivity of the Li
achieved in catholyte. It was also found that since Li and Mn over Mn. Therefore, in the studies with leachate solutions, the
ions were retained in the processed catholyte, recycling MnCO3 separated from the catholyte was redissolved in the
catholyte resulted in a better material balance. next-batch anolyte. Concurrently, as there was no MnO2
Electrodialysis of LIB Leachates. A series of five deposition, and most of the Mn transferred to the cathode
consecutive ED experiments were conducted using Li-rich cell was captured as MnCO3 and redissolved in the next
leachate (Table 1). The leachate was originally obtained from batches starting anolyte feed, Mn concentrations in the used
LIB black mass through an electrochemical leaching process.35 anolyte did not show a significant change.
The leachate solutions can be prepared through different On the cathode side, a dark deposit layer formed on the
approaches from a variety types of battery cathodes, such as cathode. This was not observed from the surrogate experi-
lithium cobalt oxide (LCO), lithium nickel manganese cobalt ments. At the end of batch 5, both anode and cathode were
oxides (NCM), and lithium iron phosphate (LFP).33,55 The rinsed with concentrated HCl for analysis. AAS analysis of this
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Table 2. Analysis of Li2CO3 and MnCO3 Products

Li2CO3
mass/mg Li composition/% Mn composition/% Co composition/%
1st ED 67.0 99.1 0.8 0.1
2nd ED 62.0 99.6 0.3 0.1
3rd ED 95.0 99.6 0.3 0.1
4th ED 88.0 99.6 0.3 0.2
5th ED 133.0 99.9 0.1 0.0
total 445.0 99.6 0.3 0.1
MnCO3
total 77 2.4 95.5 2.1

Figure 5. (a) CV curves of 0.01 M H2SO4, surrogate, and leachate solutions with a Pt working electrode. (b) First and second CV cycles of the
leachate solution using the MnO2/Pt working electrode formed by chronoamperometric MnO2 coating. Counter electrode: Pt and reference
electrode: Ag/AgCl. Scan rate: 20 mV/s.

rinse showed that the anode deposit contained majorly 56.9% In terms of materials balance, the analysis of the anolyte,
of Mn, 41.2% of Li, and 1.7% of Co. The cathode deposit was before and after ED, along with the anode deposits showed
made of an almost equal amount of Li, Mn, and Co with trace that 22.4% of the Li was transferred to the cathode. Most of
quantities of Ni, Zn, and Fe. The cathode deposits contained the other metals, including Mn, remained in the anolyte. 90.4%
79% of the total Co transferred to the cathodic side but less of the total Li balance was accounted in all the products
than 10% of the Mn and 3% of the Li transferred. Almost all analyzed for this test. 86.0% of the Li transferred to the
the detectable Ni, Zn, and Fe that passed to the cathode side cathode side was collected as Li2CO3. Only 4.5% of Mn was
were captured in the cathode deposit, and nothing was converted to MnCO3.
detected in the used catholyte. As noted, the MnO2 deposit was not observed on the anode
Table 2 shows the amount of Li2CO3 recovered through using real LIB leachate as the anolyte in all five experiments,
each ED experiment and the weight percentage of Li, Mn, and unlike observed in surrogate experiments. Therefore, addi-
Co in metal basis. After the electrodialysis, impurity metals (Al, tional CV studies were carried out to establish a better
Fe, Cd, and Zn) distributed in different products, and in some understanding of this phenomenon.
of the products, the concentrations of these metals are at a CV Measurements in Surrogate and Leachate
trace amount or lower than the detectable levels of the AAS. Solutions. Figure 5a shows the CVs of both surrogate and
Most of the accounted Al, Cd, Fe, and Zn were detected in the leachate compared against a background solution (0.01 M
processed anolyte. Average compositions of Li2CO3 products H2SO4) in the absence of any metal (Figure 5a, solid blue
obtained during the first four batches were 99.5, 0.4, and 0.1% line). The CV of the surrogate electrolyte (Figure 5a, dashed
for Li, Mn, and Co, respectively. A higher Li purity of 99.9% orange line) shows a clear redox couple with an oxidation peak
was achieved at the final step. The difference in purity was the onset at 0.9 V vs Ag/AgCl and another oxidation reaction
result of the final procedures for isolating Li2CO3, which starting at 1.2 V vs Ag/AgCl corresponding to the oxygen
involved redissolution with sparging CO2, followed by filtration evolution reaction. The oxidation peak starting at 0.9 V vs Ag/
to separate MnCO3 and precipitation at 75 °C. Batch 5 AgCl corresponded to the oxidation of Mn2+ to form MnO2
recovered 77 mg of MnCO3 at 95.5% purity. Through a (eq 3) confirming that at the tested pH, the MnO2 formation is
sequential of five batches, each batch produced Li2CO3 in an thermodynamically more favorable than water oxidation. Black
increasing quantity and quality, which could be attributed to deposit was observed on the Pt working electrode at potentials
either the build-up of a base level of Li in the reused catholyte higher than 0.9 V vs Ag/AgCl. In the reverse scan, a large
or the increase of Mn and Li concentration in the anolyte by reduction peak at 1 V vs Ag/AgCl was attributed to reduction
the addition of the brown carbonates produced in the previous of the MnO2 film, reverse of the reaction shown in eq 3,
cycle. This result proved that a regenerated catholyte was featured by the redissolution of the black coating formed
qualified for multiple uses. during the anodic scan.
11778 https://doi.org/10.1021/acssuschemeng.2c02106
ACS Sustainable Chem. Eng. 2022, 10, 11773−11781
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Under the same parametric control, CVs were also commercial membranes, and ED cell architecture. MnCO3 was
performed in the leachate electrolyte (Figure 5a, dotted grey another product recovered from the leachate with a purity over
line). An LIB leachate with similar concentrations to the 95%. Existence of Mn in the catholyte indicated the
surrogate, 700 mg/L of Li and Mn, was used for the CV tests. permeability of Mn2+ through the Selemion CSO monovalent
A small oxidation peak was observed at around 1 V vs Ag/AgCl selective membrane due to a high Li/Mn ratio in the anolyte.
before the onset of the oxygen evolution. The charge of this The CV studies indicated that surrogate anolyte could deposit
oxidation peak was substantially smaller than that of the MnO2 on the Pt electrode surface, but a leachate-derived
surrogate Mn2+ oxidation peak. Moreover, no observable black anolyte could not. To generate MnO2 from LIB leachates, a
deposit formed on the working electrode during the CV carbon-based anode was identified as an option. Multiple
measurements, consistent with the leachate ED experiments. cycling tests showed that the catholyte (CO2-capture solution)
An increase in the water oxidation current is observed when could be reused multiple times with minor replenishments.
comparing with the background solution, followed by an
CO2 was the only chemical consumed in the electrodialysis,
increase in the peak associated to the reduction of surface-
making this Li2CO3 synthesis an alternative possible carbon-
adsorbed oxygen in the reversed scan (c.a, 0.2 V vs Ag/AgCl).
Although we cannot provide a clear explanation on why negative process. This proposed ED method delivers an
MnO2 did not form from the LIB leachate, we hypothesize that environment-friendly and energy-effective pathway in recover-
the presence of unidentified organic components in the real ing Li2CO3 during LIB recycling.
LIB leachate could interact with the Pt surface favoring O2
adsorption against Mn2+ as suggested by the CVs. The multiple
oxidation mechanism increases the complexity of the study.62
■ ASSOCIATED CONTENT
* Supporting Information
sı
To verify this, the surface of the Pt electrode was coated with
MnO2 via CA at 1.2 V vs Ag/AgCl for 5 min in a surrogate The Supporting Information is available free of charge at
solution containing 700 mg/L Mn before performing CVs in https://pubs.acs.org/doi/10.1021/acssuschemeng.2c02106.
the leachate. In the first CV cycle with the MnO2-coated Composition of the LIB leachate used for the ED
electrode (Figure 5b, solid blue line), an intense Mn2+ experiments and CV curves for the graphite working
oxidation peak was found in the CV curve at 1.05 V vs Ag/ electrode in the base electrolyte, surrogate, and LIB
AgCl. In the reverse scan, the large reduction feature caused leachate (PDF)
the dissolution of the MnO2 layer. The charge applied for the
reduction was more than that applied in the Mn2+ oxidation
reaction, indicating that the amount of reduced MnO2 was
larger than the amount of MnO2 formed in the anodic scan.
■ AUTHOR INFORMATION
Corresponding Author
This additional MnO2 was likely from the initial electrode
coating. As the MnO2 coating was reduced, the Pt surface was Luis A. Diaz − Critical Materials Institute, 311 Iowa State
exposed. As a result, the second CV cycle after coating (Figure University, Ames, Iowa 50011, United States; Chemical
5b, dashed orange line) showed the same peak pattern as Pt in Separations Department, Idaho National Laboratory, Idaho
leachate (Figure 5a, dashed orange line), including water Falls, Idaho 83402, United States; orcid.org/0000-0003-
electrolysis peaks and a small Mn2+ oxidation peak. 4895-464X; Phone: (208) 526-7411;
The results presented above show that Pt is not an effective Email: Luis.DiazAldana@inl.gov; Fax: (208) 526-5086
anode if the intention is to recover MnO2 as a byproduct of
Authors
Li2CO3 recovery from LIB leachates. Carbon-based electrodes
have been reported for use in the electrolytic production of Meng Shi − Critical Materials Institute, 311 Iowa State
MnO2.63 Figure S1 shows that usage of a graphite working University, Ames, Iowa 50011, United States; Chemical
electrode allowed the formation of MnO2 in both surrogate Separations Department, Idaho National Laboratory, Idaho
and leachate solutions. Therefore, for the purpose of Falls, Idaho 83402, United States
recovering MnO2, a carbon-based anode would likely be John R. Klaehn − Critical Materials Institute, 311 Iowa State
effective. University, Ames, Iowa 50011, United States; Chemical
Separations Department, Idaho National Laboratory, Idaho
■ CONCLUSIONS
High-purity Li2CO3 was successfully recovered from Li/Mn
Falls, Idaho 83402, United States
Aaron D. Wilson − Critical Materials Institute, 311 Iowa
State University, Ames, Iowa 50011, United States; Chemical
surrogate and recycled-LIB leachates through a novel ED Separations Department, Idaho National Laboratory, Idaho
method. In the ED process, the anolyte was the Li-rich Falls, Idaho 83402, United States; orcid.org/0000-0001-
solution, and the catholyte was a CO2-loaded amine solution. 5865-6537
This method is applicable to leachate solutions generated from Tedd E. Lister − Critical Materials Institute, 311 Iowa State
a variety type of battery cathodes, such as LCO, NCM, and University, Ames, Iowa 50011, United States; Chemical
LFP. Li2CO3, MnCO3, and MnO2 were the products isolated Separations Department, Idaho National Laboratory, Idaho
in these studies. Li2CO3 with purities higher than battery Falls, Idaho 83402, United States; orcid.org/0000-0003-
grade, >99.5%, was recovered from LIB leachates using CO2 as 4844-7787
the only added reagent. Li2CO3 yields as high as 48.4% were
reported in this study. This value is still low for industrial Complete contact information is available at:
application. However, there are still several factors to be https://pubs.acs.org/10.1021/acssuschemeng.2c02106
optimized for the purpose of increasing Li2CO3 yield, such as
anolyte pH, Li2CO3 precipitation temperatures, types of Notes
catholyte tertiary amine solutions, uncovered limitations of The authors declare no competing financial interest.
11779 https://doi.org/10.1021/acssuschemeng.2c02106
ACS Sustainable Chem. Eng. 2022, 10, 11773−11781
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

■ ACKNOWLEDGMENTS
The authors acknowledge the financial and technical support
(20) Yang, G.; Shi, H.; Liu, W.; Xing, W.; Xu, N. Investigation of
Mg2+/Li+ Separation by Nanofiltration. Chin. J. Chem. Eng. 2011, 19,
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funded by the U.S. Department of Energy, Office of Energy separation from salt lake brines by nanofiltration (NF) and low
Efficiency and Renewable Energy, and Advanced Manufactur- pressure reverse osmosis (LPRO). Desalination 2013, 317, 184−192.
ing Office. The work was conducted at the Idaho National (22) Kumar, J.; Neiber, R. R.; Park, J.; Ali Soomro, R.; Greene, G.
Laboratory (INL) under Battelle Energy Alliance, LLC W.; Ali Mazari, S.; Young Seo, H.; Hong Lee, J.; Shon, M.; Wook
contract no. DE-AC07-05ID14517. The authors would like Chang, D.; Yong Cho, K. Recent Progress in Sustainable Recycling of
to thank the Retriev Technologies for providing the black mass LiFePO4-type Lithium-ion Batteries: Strategies for Highly Selective
materials as well as technical guidance. Lithium Recovery. Chem. Eng. J. 2022, 431, 133993.
(23) Jagur-Grodzinski, J.; Schori, E. Solvent-Polymeric Membranes

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