Chemical Engineering Journal 420 (2021) 127715

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Chemical Engineering Journal

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Electrochemical lithium recovery system through the simultaneous lithium

enrichment via sustainable redox reaction
Nayeong Kim a, b, Xiao Su b, *, Choonsoo Kim a, *
a
Department of Environmental Engineering and Institute of Energy/Environment Convergence Technologies, Kongju National University, 1223-24, Cheonan-daero,
Cheonan-si 31080, Republic of Korea
b
Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign, IL 61801, United States

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

Keywords: With the drastic increase in the demand for lithium, electrochemical lithium recovery has gained significant
Lithium recovery attention as an alternative for lime soda evaporation. Despite its high selectivity and efficiency, the industrial
Redox reaction application of electrochemical systems remains limited because of its discontinuous operation and the low
Lithium enrichment
lithium concentration in the source water. Hence, this study proposes a redox-mediated system for selective
Desalination
Ferricyanide and ferrocyanide
lithium recovery in tandem with the continuous enrichment of the source water via a sustainable redox reaction.
Continuous separation In the proposed system, the reversible redox reaction of ferri-/ferrocyanide enables continuous enrichment of the
source water, while lithium-selective adsorbent (λ-MnO2) selectively recovers the enriched lithium simulta­
neously. The redox-mediated lithium recovery system successfully concentrated lithium ions up to 37 mM Li+ in
an equimolar mixture of 5 mM Li+ and 5 mM Na+, and up to 0.6 mM Li+ even from extremely dilute lithium-
containing solutions (0.1 mM Li+: 9.9 mM Na+). With the introduction of λ-MnO2 as a chemical adsorbent,
this system exhibited an exceptional selectivity (selectivity coefficient (αLi-Na) of 57) toward lithium from an
equimolar mixture, and high lithium selectivity coefficients (αLi-Na: 804 and αLi-Mg: 387) in a synthetic solution
equivalent to the Salar de Atacama brine in Chile. Therefore, this study represents progress towards the industrial
application of the lithium recovery process, with potential applications for critical metal recovery in general.

1. Introduction increased attention in recent years, as summarized in Table 1. Tradi­

tional solvent extraction has been widely used for lithium recovery from
Since the 21st century, lithium-ion batteries have become an integral a mixture of alkaline and alkaline earth metals [10-14]. However, sol­
part of daily life owing their ubiquitous applications in energy storage, vent extraction utilizes a large amount of organic solvents and acids as
ranging from their use in portable devices to electric vehicles. According extractants, for example, organophosphorus acids and tributyl phos­
to the U.S. Geological Survey, the price of battery-graded lithium car­ phate–kerosene–FeCl3, thus raising concerns regarding sustainability
bonate has skyrocketed from $6,500 to $13,000 per metric ton in the last and associated health problems [13]. In addition, solvent extraction
5 years [1-3]. With the reliability of lithium-ion batteries increasing with chelating extractants such as crown ether conjugates is difficult to
rapidly in the market place, numerous industries have turned their industrialize because of expensive chelating materials and laborious
attention to brine or seawater as a major source of lithium [2-5]. To synthesis [11]. Adsorption is another widely studied method, where
extract lithium from brine (or seawater), lime soda evaporation is widely adsorbents such as spinel manganese oxide (MnO2, λ-MnO2) and tita­
used as the conventional lithium up-concentration method. Highly nium oxide (H2TiO3) selectively sieve lithium from other cations (Na+,
concentrated lithium can be obtained once the source water is evapo­ K+, Mg2+, and Ca2+) [15-20]. Despite exceptional selectivity even in
rated under sunlight and other co-cations precipitate. However, lime dilute lithium solutions, the adsorption can be inefficient because it
soda evaporation has several disadvantages, including a long production requires multiple weeks for the entire process [7,12]. Electrodialysis has
time (1–2 years), high water usage, and low separation efficiency [2,6- also been studied as an alternative lithium recovery method because of
10]. its simple and environmentally benign operation [2,6,21-25]. Lithium-
Therefore, alternative lithium production methods have attracted selective membranes allow the enrichment of lithium in alternative

* Corresponding authors.
E-mail addresses: x2su@illinois.edu (X. Su), choonsoo@kongju.ac.kr (C. Kim).

https://doi.org/10.1016/j.cej.2020.127715
Received 29 August 2020; Received in revised form 29 October 2020; Accepted 10 November 2020
Available online 17 November 2020
1385-8947/© 2020 Elsevier B.V. All rights reserved.
N. Kim et al. Chemical Engineering Journal 420 (2021) 127715

channels driven by electrochemical reactions, often via water-splitting sustainable redox reaction in the electrode channel, allowing continuous
reactions [21,23]. However, even after several days of operation, the desalination by balancing the charge neutrality in the electrolyte [35].
concentration of lithium remains insufficient for recovery, requiring The key systematic features of the system were analogous to the redox-
sequential processes. In addition, the use of high-priced lithium-selec­ flow battery system: both systems use flowable redox couple, reversible
tive membranes and its poor durability makes electrodialysis difficult to redox reaction, and separable channels [36-38]. For the currently pro­
commercialize [25]. Thus, numerous studies have been conducted to posed system, we combine a redox-mediated continuous system with a
develop fast, energy-efficient, and highly selective electrosorption-based lithium-selective chemical adsorbent. By redesigning the redox-flow
recovery methods for lithium. These approaches rely on lithium- process to continuously enrich the desalinated ions as well as selec­
selective electrodes such as λ-MnO2 and HFePO4 as positive electrodes tively recover the desired ions, we show for the first time the applica­
to selectively extract lithium ions during the charging step, followed by bility of this concept to lithium up-concentration and extraction, thus
recovery during the discharging step [7,26-29]. Lithium extraction has overcoming the longstanding challenges involved in the up-
also been explored through integration with electrokinetic methods for concentration and extraction of lithium from discontinuous electro-
multicomponent separation and selective extraction of lithium from swing processes.
radioactive streams [30]. Our redox-mediated lithium recovery system consists of three
In general, a major obstacle for the industrial application of elec­ different channels: a feed channel (FC), an ion-concentrated channel
trosorption methods is the significant decrease in the lithium recovery (CC), and the redox reaction channel (RC). The FC inputs treating water
performance from brine and seawater because of the extremely low in a large volume of 2,000 mL, while the CC enriches desalted ions from
lithium concentration and the presence of competing cations. In addi­ the FC in a substantially smaller volume of 11 mL. Therefore, when the
tion to the economic feasibility, discontinuous lithium production is a reversible redox couple reacts with the positive and negative electrodes
critical limitation, originating from the sequential charging and dis­ (in the RC), both continuous desalination (from the FC) and accumula­
charging steps. The feed solution needs to be replaced in every tion of the desalted ions (in the CC) can be achieved simultaneously. The
sequential step, leading to an inconvenient process. For instance, during lithium-selective chemical adsorbent in the CC enables the selective
the lithium capturing step, a lithium-containing solution (e.g., brine or recovery of lithium ions from other cations. As a proof of concept, we
seawater) is fed into the system in large volumes, while during the investigated the desalination and the enrichment performances at
lithium recovery step, this solution is replaced by the lithium recovery various operating voltages (0.6–1.2 V) and various ratios between Li+
solution (often KCl) in a much smaller volume [2,31]. Therefore, further and Na+ (from 0.1:9.9 to 9:1). Finally, we achieved molecular selectivity
research is crucial to overcome these limitations of electrochemical toward lithium through a chemical adsorbent, λ-MnO2. High lithium
methods to pave the way for practical industrial use. selectivity using the proposed system was achieved using an equimolar
Hence, in this study, we propose a sustainable redox-mediated solution of 5 mM Li+ and 5 mM Na+ under conditions simulating the
lithium recovery system to enhance the economic feasibility of selec­ synthetic solution of the Salar de Atacama brine, the largest source of
tive lithium recovery by enriching the lithium-containing source water lithium in the world.
simultaneously (Fig. 1). Our proposed system has several distinctive
features compared with existing recovery methods. As it utilizes a 2. Experimental section
reversible redox reaction to enrich lithium under low operating voltages
(<1.2 V), this system can overcome the discontinuity of the electro­ 2.1. Description of the cell configuration
chemical lithium recovery system in an energy-efficient manner, which
is considered to be the major obstacle for industrial applications. The redox-mediated lithium recovery system consists of three
Moreover, instead of using expensive lithium-selective membranes or channels as depicted in Fig. 1. In the outer-most channels, the RC, the
relatively complicated lithium-selective electrodes, the system utilizes redox couple of ferricyanide (Fe(CN)3- 4-
6 ) and ferrocyanide (Fe(CN)6 )
lithium-selective adsorbents that have been widely used in industrial flows around both electrode chambers (Fig. 1a). In the RC, the redox
applications with high capacity and selectivity towards lithium [25]. couple of ferri-/ferrocyanide continuously reacts with the electrodes to
In general, redox-active electrochemical systems have emerged as an maintain a balance between the oxidized and reduced forms. The RC is
efficient method for enhancing energy efficiency and molecular selec­ separated from the feed channel (FC) and the ion-concentrated channel
tivity [32-34]. However, most of these systems have been limited to (CC) by anion exchange membranes (AEMs), whereas the FC and the CC
discontinuous swing operations in batch, single-channel systems. In our are separated by a cation exchange membrane (CEM). In the CC, ions
recent work, we proposed a redox-mediated continuous system via a from the FC are concentrated, and then lithium ions are selectively

Table 1
Summary of lithium recovery methods from brine and seawater: key features of operation and key advantages and disadvantages.
Recovery methods Mechanisms Advantages Disadvantages ref

Lime soda evaporation Evaporating solvent under sunlight and • Simple operation • Long operation time [2,6–10]
precipitating co-cations • Use of sunlight as an energy source • High water usage
• Low separation efficiency
Solvent extraction Separating Li+ using extractantsor chelating • High lithium recovery • Use of volatile organic solvents [10-14]
materials (organophosphorus acids, crown • Strong acidic condition
ether conjugates) • Expensive chelating materials
Adsorption Using lithium-selective adsorbents • Applicable in diluted solutions • Long operation time [7,12,21]
(Li-Mn-O, Li-Ti-O, LiCl⋅2Al(OH)3) • High selectivity • Inefficient operation
• Re-usable
• (pre- and post-treatment)
Electrodialysis Using lithium-selective membranes to • Low capital cost • Expensive membrane [2,6,22–26]
enrich lithium using electrical energy • Simple operation • Poor membrane durability
• Eco-friendly • Operated at high voltages
• Hard to industrialize
Electrosorption Using lithium-selective electrodesto capture • Fast recovery • Inconvenient operation [7,26-29,31]
lithium electrochemically (λ-MnO2, HFePO4) • Energy efficient • Discontinuous lithium production
• Simple operation • Hard to industrialize
• Eco-friendly

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N. Kim et al. Chemical Engineering Journal 420 (2021) 127715

Fig. 1. Cell architecture of the redox-mediated lithium recovery system: (a) schematic illustration of the system and (b) its cell components.

recovered by the chemical adsorbent, λ-MnO2 (refer to Section 2.3). recovery system was also evaluated considering several aspects, such as
Each cell component is arranged as shown in Fig. 1b and S1. In the the enrichment ratio, charge efficiency, and energy consumption. The
RC, activated carbon clothes (ACC 5092–20, Kynol, Japan) were used as enrichment ratio was calculated using Eq. (1):
both positive and negative electrodes (area: 3.5 × 3.5 cm2, average
Cf ,CC
weight: 200 mg). Both CEM and AEM (CMV and AMV, Selemion, Japan) Enrichment ratio = (1)
Co,FC
had an area of 5 × 5 cm2. While the CC was a batch container with a size
of 4 × 4 × 0.8 cm3, both RC (4 × 4 × 0.2 cm3) and FC (4 × 4 × 0.5 cm3)
where Cf,CC is the final concentration at the CC after the 4 h enrichment
were flowable channels. As the redox-mediated lithium recovery system
test, and Co,FC is the initial concentration at the FC.
is modified from the multichannel flow membrane capacitive deion­
Then, the charge efficiency and energy consumption were estimated
ization system (MC-MCDI) and the multichannel redox capacitive
using Eqs. (2) and (3), respectively:
deionization system (MC-RCDI), further details can be found in our
(∫ )
previous studies [35,39-42]. Idt
Charge efficiency = (nLi,CC + nNa,CC )/ (2)
F
∫
2.2. Analysis of the enrichment performance Energy consumption (J/mol) =
V
Idt (3)
nLi,CC + nNa,CC
The continuous enrichment performance of the redox-mediated
lithium recovery system was evaluated at various operating voltages where nLi,CC and nNa,CC are the final amounts of lithium and sodium ions
(0.6–1.2 V) and various mixture ratios between lithium and sodium at the CC (mol), respectively, I is the current (A), F is the Faradaic
(from 0.1:9.9 to 9.0:1.0 of mM Li+: mM Na+). To study the enrichment constant (96,485C/mol), and V is the operating voltage (V). All exper­
performance at various operating voltages, an equimolar mixture of 5 iments were repeated thrice to insure reproducibility.
mM LiCl (Sigma-Aldrich, USA) and 5 mM NaCl was continuously fed
into the FC. Then, as the RC electrolyte, 100 mM NaCl (Sigma-Aldrich, 2.3. Evaluation of the selective lithium recovery
USA) and 100 mM Na4Fe(CN)6⋅10H2O (Sigma-Aldrich, USA) were
continuously circulated in the positive and negative electrode chambers. Prior to the selective lithium recovery test, λ-MnO2, an efficient
Both the RC and FC were continuously flowing with volume of 100 mL adsorbent for selective lithium sieving, was prepared via the leaching
and 2,000 mL, respectively, at a flow rate of 5 mL/min using a peristaltic process. Spinel-type lithium manganese oxide (LiMn2O4, LMO, Sigma-
pump (Miniplus 3, Gilson, USA). In the CC, 11 mL of 10 mM KCl (Alfa Aldrich, USA) was leached in 20 mL sulfuric acid (H2SO4, Sigma-
Aesar, USA) was used as an inert solution. Using a battery cycler Aldrich, USA) under four conditions: 1 M H2SO4-1 h, 2 h and 2 M
(WBCS3000, WonATech Co., Korea), a constant operating voltage was H2SO4-1 h, 2 h. Based on the observed changes in the scanning electron
applied to the system for 4 h. Moreover, to validate the industrial microscopy (SEM) images, the pristine spinel-type LMO became rough
application of the redox-mediated lithium recovery system, the enrich­ on surface after acid leaching (Fig. S2). Moreover, as the applied
ment performance was investigated at various feed compositions of Li+ leaching conditions became stronger and longer (e.g., 2 M H2SO4 for 2
and Na+. Considering the approximate molar ratio between lithium and h), noticeable right shifts in the X-ray diffraction (XRD) patterns were
sodium in the salt lake (1Li+:15Na+) and seawater (1Li+:16,500Na+) observed (Fig. S3). Based on previous studies, the right shift (lower d-
[6,43], the feed concentration of lithium and sodium was varied from value) in the XRD peaks indicates the successful synthesis of λ-MnO2
0.1 mM:9.9 mM to 9 mM:1 mM for Li+: Na+ (molar ratio of 1:99 and 9:1) [44-46]. Hence, λ-MnO2 leached in 2 M H2SO4 for 2 h was utilized in the
at a voltage of 1.2 V. redox-mediated lithium recovery system as a chemical adsorbent to
To investigate the ionic enrichment of lithium and sodium, the CC investigate the selective recovery of lithium.
solution was sampled 0, 10, 20, 30, 60, 120, 180, and 240 min, and For selective lithium recovery, 0.15 g of prepared λ-MnO2 was added
evaluated using ion chromatography (ICS-1100, DIONEX, USA). to the CC along with 11 mL KCl solution. Then, the system was operated
Furthermore, the effluent solution at the FC was analyzed using con­ at 1.2 V for 4 h using a feed solution of 5 mM:5 mM of Li+: Na+. For
ductivity (3574-10D, Horiba, Japan) and pH meters (9615S-10D, comparison, conventional adsorption was performed in 11 mL of the
Horiba, Japan). The performance of the redox-mediated lithium mixture feed solution of 5 mM LiCl and 5 mM NaCl for 4 h. After the test,

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N. Kim et al. Chemical Engineering Journal 420 (2021) 127715

the used λ-MnO2 was carefully washed with DI (1.5–2.0 L) and dried As the hydrated ionic radius of sodium is smaller than that of lithium, its
overnight. The fully dried adsorbents were leached with 1 M HCl solu­ passage through the cation exchange membranes is easier [29].
tion (20 mL) for 2 h. The leached solution was then collected to analyze Accordingly, the enrichment rates for lithium and sodium showed
the amount of adsorbed lithium and sodium using an inductively different trends (Fig. 2a and 2b and Tables S2 and S3). For instance, as
coupled plasma atomic emission spectrometer (ICP, ICPS-8100, Shi­ the experiment duration crossed 60 min, the enrichment rate of lithium
madzu, Japan). With the prepared λ-MnO2, an additional investigation increased four times more than that at the beginning of the experiment
was conducted using the synthetic solution of Salar de Atacama brine in (0–30 min). On the other hand, the enrichment rate of sodium decreased
Chile. The composition of the synthetic solution is listed in Table S1. by over 22% as the experiment continued. Thus, at the beginning of the
Along with other evaluations, the selectivity coefficient (αLi-M) was experiment, sodium was enriched approximately seven times faster than
calculated to understand the lithium selectivity with respect to the other lithium, whereas as the experiment continued, the difference in the rate
cations using Eq. (4): of sodium and lithium enrichment was within 30%. Therefore, our
system would become much more effective by using a membrane that is
(QLi /QM )
αLi− M = (4) favorable towards lithium ions or by extending the experimental dura­
(Q’ Li /Q’M )
tion [2,22-24].
The effective enrichment performance of the redox-mediated lithium
where QLi and QM are the amount of adsorbed lithium and other metal
recovery system could be explained by its unique mechanism as depicted
ions, respectively, and Q’Li and Q’M are the amounts of lithium and other
in Fig. 1a and 3. While the redox couple of ferricyanide (Fe(III)(CN)3- 6)
metal ions in the feed solution, respectively.
and ferrocyanide (Fe(II)(CN)4-
6 ) kept reacting in the RC, positively (e.g.,
Li+ and Na+) and negatively (e.g., Cl–) charged ions preferred to move
3. Results and discussion
toward the negative and positive electrode chambers, respectively.
Although the negative ions enter the positive electrode chamber, the
3.1. Investigation of the enrichment performance at various operating
positive ions could not reach the negative electrode chamber due to the
voltages
AEM. As the AEM was placed between the negative electrode chamber
and the CC, the positive ions were trapped in the CC. Eventually, all of
Fig. 2 illustrates the continuous enrichment performance of the
the desalted ions were concentrated in the CC. Thus, the system effi­
redox-mediated lithium recovery system at operating voltages ranging
ciently leverages the reversible redox reaction to continuously desalt
from 0.6 to 1.2 V. Under the various operating voltages, both lithium
ions from the FC and concentrates them in a much compact chamber
and sodium ions were successfully enriched at the CC, showing linear
(CC). This is well supported by the continuous desalination in the FC,
trends throughout the experiments (Fig. 2a and 2b). As the operating
which was examined by the effluent conductivity and current mea­
voltage increased, both lithium and sodium were concentrated at faster
surements (Fig. 4). As shown in Fig. 4a, the decrease in the effluent
rates, because the utilization of the redox reaction highly depends on the
conductivity at the FC was steady throughout the experiment, indicating
operating voltage [35]. The lithium and sodium ions were enriched up
that the reversible redox couple of ferri-/ferrocyanide continuously
to 17 mM Li+ and 28 mM Na+ at an operating voltage of 0.6 V (Fig. 2c).
desalinated ions from the FC. In addition, as the operating voltage
This performance was enhanced to 37 mM Li+ and 51 mM Na+ at an
increased, the change in effluent conductivity was greater (Fig. 4a), and
operating voltage of 1.2 V, indicating a two-fold enhanced performance.
the specific current increased (Fig. 4b). These results are consistent with
In the same manner, as the operating voltage increased from 0.6 V to 1.2
the linear trends of lithium and sodium enrichments in the CC (Fig. 2a
V, the enrichment ratios increased from 3.4 and 5.6 to 7.0 and 10 for
and 2b). Furthermore, the effects of operating voltages on charge effi­
lithium and sodium, respectively. Note that by applying voltage, both
ciency and energy consumption are presented in Table 2. The redox-
lithium and sodium could be concentrated up to ten-fold compared to
mediated lithium recovery system is highly efficient (charge effi­
the open-circuit voltage (3.5 mM and 5.1 mM for Li+ and Na+, respec­
ciencies of approximately 83–100%) and consumed reasonable energy
tively; Fig. S4). This result highlights that a sufficient driving force
(57–140 kJ/mol) over the investigated range of operating voltages. All
(operating voltage) is necessary for the optimal usage of the redox re­
these features confirm that the redox-mediated lithium recovery system
action for enrichment (Fig. 3).
could effectively overcome the limitations of electrochemical recovery
Throughout the experiment, we noticed that sodium is more favor­
system. While enriching the ions in the CC, this system also desalinates
ably enriched at the CC than lithium. This result is due to the size of the
the feed solution in the FC. As demonstrated in our previous paper, the
hydrated ion, which affects the rate of penetration through membranes.
system has a high potential as an economically feasible continuous

Fig. 2. Enrichment performance results at various operating voltages (from open-circuit voltage o 1.2 V): enrichment profiles for (a) Li+ and (b) Na+ and (c)
summary of the total enrichment of Li+ and Na+ at the CC and their enrichment ratios. The enrichment test was performed using a mixed feed solution of 5 mM LiCl
and 5 mM NaCl with a flow rate of 5 mL/min. An electrolyte with 100 mM NaCl and 100 mM Na4Fe(CN)6 was used at the RC, while 10 mM KCl was used as the base
solution in the CC.

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N. Kim et al. Chemical Engineering Journal 420 (2021) 127715

Fig. 3. Schematic diagram of the redox-mediated lithium recovery system, showing the mechanism of the sustainable enrichment at the CC and the desalination at
the FC.

Fig. 4. (a) Change in the effluent conductivity and the pH profiles at the FC and (b) specific current profiles at various operating voltages (0.6–1.2 V). The experiment
was performed with a mixed feed solution of 5 mM LiCl and 5 mM NaCl with a flow rate of 5 mL/min. An electrolyte with 100 mM NaCl and 100 mM Na4Fe(CN)6 was
used at the RC, while 10 mM KCl was used as the base solution in the CC.

4-h experiment such that the AEMs partially turned yellow (Fig. S5).
Table 2
Thus, there is room for improvement in future studies to investigate a
Charge efficiencies and energy consumptions (kJ/mol) with respect to the
more economical and environmentally benign redox couple with opti­
operating voltages (0.6–1.2 V) during the 4-h enrichment process.
mized chemical compatibility.
Operating voltage Charge efficiency Energy consumption (kJ/mol)

0.6 V 1.00 57
0.8 V 0.97 80 3.2. Investigation of the enrichment performance at various mixture
1.0 V 0.92 105
proportions
1.2 V 0.83 140

The redox-mediated lithium recovery system successfully achieved

desalination system [35]. In addition, the undetectable iron concentra­ lithium enrichment at the CC at various lithium concentrations ranging
tions in both FC and CC proved that the redox couple of ferri-/ferrocy­ from 0.1 mM to 9 mM (mixture ratio of 1:99 and 9:1 for Li+: Na+). With a
anide could not pass through both the AEM and CEM because of its large high lithium-containing feed stream (9 mM Li+), the lithium concen­
molecular size (Table S4). This suggests that each channel can be tration reached 46 mM (Fig. 5a). Even when the feed solution contained
maintained without cross-contamination, and that the system can be a limited amount of lithium (0.1 mM Li+), it was successfully enriched
stably operated without loss of the redox couple. Nonetheless, the redox up to six-fold at the CC (0.6 mM of Li+ in the CC, inset graph of Fig. 5a).
couple was partially adsorbed on the ion exchange membranes after the As illustrated in Fig. 5b, within the investigated range of solution mix­
tures, a consistent enrichment ratio of approximately 5.6 was observed.

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N. Kim et al. Chemical Engineering Journal 420 (2021) 127715

Fig. 5. (a) Lithium enrichment profiles and (b) summary of the total lithium enrichment and enrichment ratio with respect to the various feed mixture ratios between
lithium and sodium (from 0.1 mM Li+: 9.9 mM Na+ to 9 mM Li+: 1 mM Na+). The enrichment test was performed at 1.2 V with a flow rate of 5 mL/min. An
electrolyte with 100 mM NaCl and 100 mM Na4Fe(CN)6 was used at the RC, while 10 mM KCl was used as the base solution in the CC.

This observation is meaningful in that our system could be applied to a Considering the experimental precision, the average standard deviation
real brine lake, where extremely small amounts of lithium are dissolved of the experiments was around 5%. However, there might be experi­
along with various metal ions such as Na+, K+, Mg2+, and Ca2+. For mental errors due to systematic limitations and measurement errors. For
instance, in Salar de Atacama brine, the concentration of sodium is 16 instance, unmixing the solution in the CC might be a major cause of
times greater than that of lithium (Table S1) [7,9,47]. Despite being a experimental errors, resulting in an imperfect distribution of enriched
minor component, lithium can be enriched via the redox-mediated solutions. Thus, the CC needs to be further modified so that we could add
lithium recovery system within a much shorter duration compared to a stir bar in the channel. Experimental inaccuracies could also originate
conventional recovery processes such as lime soda evaporation. from measurement errors while sampling the solution in the CC, diluting
Furthermore, during the enrichment of lithium, the feed stream was the sample solutions, and analyzing peaks using ion chromatography.
desalted at a steady rate with a charge efficiency of 82–87% and energy
consumption of 133–141 kJ/mol (Fig. S6 and Table S6). This result
confirmed that the redox-mediated lithium recovery system can be 3.3. Investigation of the selective lithium recovery
highly applicable to industrial streams with low lithium concentrations.
Along with continuous enrichment and desalination, selective

Fig. 6. Application of the λ-MnO2 in the redox-mediated lithium recovery system with the mixed feed solutions: (a) lithium enrichment profiles in the absence and
presence of λ-MnO2, and (b) lithium and sodium uptake in our system and the conventional adsorption process. The test was performed with a mixed feed solution of
5 mM LiCl and 5 mM NaCl with a flow rate of 5 mL/min. An electrolyte with 100 mM NaCl and 100 mM Na4Fe(CN)6 was used at the RC, while 10 mM KCl was used
as the base solution in the CC with the λ-MnO2. The conventional adsorption was performed in 11 mL of the mixed feed solution for 4 h. Lithium and sodium uptakes
were analyzed using ICP.

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recovery of lithium could be achieved in our system by using a lithium-

selective chemical adsorbent. To enable selective recovery from the
enriched solutions in the CC, λ-MnO2 was applied in the redox-mediated
lithium recovery system, as shown in Fig. 6. In the presence of the
adsorbent, the enriched amount of lithium was reduced (Fig. 6a), while
the conductivity, pH, and current profiles were analogous to those in the
absence of λ-MnO2 (Fig. S7). This result indirectly demonstrates that
there is no distinctive change in the electrochemical enrichment per­
formance in the presence of λ-MnO2; however, enriched lithium at the
CC could be recovered by λ-MnO2. To compare the effect of enrichment
on the adsorption capacity, the adsorption capacity in our system was
compared with that of the conventional adsorption process (Fig. 6b).
With the redox-mediated lithium recovery system, 3.1 mg/g_adsorbent of
lithium was successfully recovered from the CC with minor amounts of
sodium (0.18 mg/g_adsorbent). This lithium uptake increased by more
than 53% compared with the conventional adsorption method (2.0 mg/
g_adsorbent). Despite the highly enriched amount of sodium in the CC
(Fig. 2), λ-MnO2 exhibits exceptionally selective adsorption toward
lithium with an insignificant amount of sodium uptake (6% of lithium
Fig. 7. Li+, Na+, K+, Mg2+, and Ca2+ uptakes and their selectivity coefficients
uptake). Consequently, in our system, the selectivity coefficient of
against Li+ in the redox-mediated lithium recovery system. The test was per­
lithium against sodium (αLi-Na) was 57 compared to the selectivity co­
formed using a synthetic solution of Salar de Atacama brine in Chile (Table S1)
efficient 40 for the conventional adsorption process (Fig. 6b). One of the with a flow rate of 5 mL/min. An electrolyte with 100 mM NaCl and 100 mM
major explanations for this enhanced lithium uptake could be the kinetic Na4Fe(CN)6 was used at the RC, while 10 mM KCl was used as the base solution
improvement of adsorption in contact with the enriched lithium solu­ in the CC with the λ-MnO2. Each uptake was analyzed using ICP.
tion. Several kinetic studies have shown that the lithium concentration
near the adsorbent is a decisive factor in the rate of lithiation [4,48-50]. recovery process from e-wastes or mining solutions. The system could
Considering the adsorption mechanism, two well-known lithiation up-concentrate gold ions from the targeting solution to the CC, while
mechanisms are involved, which are significantly influenced by the gold-selective adsorbents, such as glutaraldehyde cross-linked chitosan
lithium concentration near the adsorbents. The first involves a proton beads or mesoporous silica adsorbents, recover gold ions exclusively
(H+) in the spinel structure of λ-MnO2 being replaced with lithium (Li+) [54-56]. Therefore, we envision our system to be widely utilized for
through the ion exchange process [51]. Thus, the ion exchange process is metal recovery processes in subsequent studies. Subsequent studies
more favorable at the high lithium concentrations near the adsorbent should not only improve recovery performance (e.g., more economical
surface. In addition, lithium can diffuse from the adsorbent surface to adsorbent synthesis, parameter optimization, and the anionic effect) but
inner sites as Mn(IV) in the spinel structure of λ-MnO2 reduces to Mn(III) also implement infrastructure design (e.g., scale-up of the system and
[51]. As the diffusion rate is proportional to the concentration of the energy supply system). Overall, the redox-mediated lithium recovery
solution, up-concentration via the redox-mediated lithium recovery system takes us one step closer to the industrial application of the
system enhances lithium uptake. In addition, the XRD pattern of λ-MnO2 electrochemical recovery system.
revealed a left shift after the chemical adsorption and a right shift after
re-leaching (Fig. S8). This result demonstrates that λ-MnO2 could be 4. Conclusion
regenerated so that it would be reusable. However, current λ-MnO2 is
not stable enough to be used in sequential processes because of the A sustainable redox-mediated lithium recovery system, was pro­
extraction of Mn from the spinel structure. Therefore, further efforts to posed to effectively recover lithium via the enrichment of the feed so­
increase the adsorbent capacities and stabilities are necessary for more lution containing Li+. This system can overcome the discontinuity of the
dramatic lithium recovery and reusability before industrial applications. electrochemical lithium recovery processes, which is a major obstacle in
For instance, maintaining the solution pH between 5 and 9 would be one industrial applications. In addition, it is remarkable that our system
way to enhance the lithium adsorption capacity by reducing the co- allows for desalting the feed stream, even enhancing its value in terms of
intercalation of H+ [2,52,53]. energy consumption, system utilization, and industrial application.
The redox-mediated lithium recovery system exhibited exceptional Various performance tests confirmed that the system continuously
performance in the synthetic solution of Salar de Atacama brine in Chile enriched lithium in the CC up to 37 mM Li+ (at an operating voltage of
(Fig. 7). Note that in the synthetic solution, Li+ coexists with more than 1.2 V) from the feed solution with an equimolar concentration of 5 mM
15-fold Na+ and two-fold K+ and Mg2+ (Table S1). As depicted in Fig. 7, Li+ and 5 mM Na+. Moreover, lithium was successfully enriched over
4.2 mg/g_adsorbent of lithium was recovered from the CC with small six-fold even when the feed solution contained a very limited amount of
amounts of co-ion uptakes (0.27 mg/g_adsorbent Na+ and 0.073 mg/ lithium (0.1 mM Li+: 9.9 mM Na+). Furthermore, the application of
g_adsorbent Mg2+) and undetectable uptakes of K+ and Ca2+ after the 4-h λ-MnO2 in the CC verified the exceptionally selective lithium recovery
experiment. Despite the large amounts of enriched co-ions at the CC from an equimolar mixture of Li+ and Na+ (αLi-Na: 57) and even from the
(Fig. S9), the selectivity coefficient of lithium against sodium (αLi-Na) synthetic solution of Salar de Atacama brine in Chile (αLi-Na: 804 and αLi-
was 804, while that of lithium against magnesium (αLi-Mg) was 387.
Mg: 387). In conclusion, this study is a major stepping stone toward the
Compared with other λ-MnO2-based electrochemical lithium recovery industrial application of an electrochemical recovery system. Tandem
systems shown in Table 3, this study exhibited highly competitive ionic enrichment using the redox-sustainable couple is an innovative
selectivity coefficients against sodium and magnesium. Therefore, by step in the field of redox-mediated separation, translating traditionally
applying a lithium-selective adsorbent, it was confirmed that our system swing-based concepts of lithium recovery into a continuous mode. Long-
is effective for tandem enrichment/desalination and selective recovery term development of redox-active reactions for continuous ion up-
of lithium. One promising advancement of the redox-mediated lithium concentration can have a significant impact in enabling the intensifi­
recovery system is that it can be utilized not only in the lithium recovery cation of sustainable electrochemical processes. In addition to the
process, but also in the recovery of general precious metals (e.g., cobalt, lithium recovery, we envision our system to be widely utilized as a
gold, and silver). For instance, this system could be applied to the gold

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N. Kim et al. Chemical Engineering Journal 420 (2021) 127715

Table 3
Comparisons of the selectivity coefficient of lithium against sodium (αLi-Na) and magnesium (αLi-Mg) among various λ-MnO2-based electrochemical lithium recovery
systems.
Electrode materials(working/counter) Solution (mM) αLi-Na αLi-Mg ref.

Liþ Naþ Kþ Mg2þ

λ-MnO2 / Ag 30 30 30 30 1235 822 [57]

λ-MnO2 / Ag 42 793 108 74 30 7100 [31]
λ-MnO2 / Nickel cyanoferrate 42 793 108 74 58 1633
λ-MnO2 / Activated carbon 210 3300 460 400 994 127 [7]
λ-MnO2 / LMO 21 330 – 40 321 74 [58]
3.2 905 – 91 384 98
Redox couple of ferri-/ferrocyanidewith adsorbent (λ-MnO2) 210 3300 460 400 804 387 This study

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