DOI: 10.1002/ente.
201700488
Electrochemical Lithium Recovery with a LiMn2O4–Zinc
Battery System using Zinc as a Negative Electrode
Seongsoo Kim,[a] Jaehan Lee,[a, b] Seoni Kim,[a] Seonghwan Kim,[a, b] and
Jeyong Yoon*[a, b]
Securing lithium resources is an emerging issue owing to the
widespread use of lithium-ion batteries. Recently, an electro-
chemical lithium recovery method based on the principle of
a lithium-ion battery using a lithium-capturing electrode and
silver as a negative electrode was proposed to meet the in-
creased demand for lithium. However, the high cost of silver
is one hindrance to facilitating the practical use of this elec-
trochemical lithium recovery. In this study, zinc, which has a
Introduction
Lithium consumption has dramatically increased worldwide
owing to its versatile use in smartphones, electric automo-
biles, and nuclear fusion reactors. The demand for lithium is
likely to continue its upward trend in the years ahead be-
cause the electric vehicle market is predicted to grow. There-
fore, a stable supply of lithium resources has become a great
concern, and global competition for securing lithium resour-
ces has intensified.[1]
Generally, lithium can be obtained from brines and miner-
als. Of the two, lithium dissolved in brines accounts for more
than 66 % of global lithium reserves, and at present most of
the lithium is produced (about 83 %) from brines.[2] The most
conventional method for lithium production is lime soda
evaporation, which simply uses solar energy to evaporate
brine water. However, this method is time consuming and
strongly affected by climate factors such as rainfall, illumi-
nance, and humidity. Additionally, it requires a tremendously
large site for its operation as well as a substantial amount of
chemicals and water to purify the lithium. These restraints
make it difficult to steadily supply lithium as well as cause
environmental problems.
As part of an effort to overcome the limitation of the con-
ventional method, Kanoh et al. first reported an electro-
chemical lithium-recovery system using a l-MnO2/Pt elec-
trode, demonstrating the possibility of selective lithium re-
covery from brines.[3] For a more efficient process, systems
based on the principle of a lithium secondary batteries were
developed.[4] These systems include LiMn2O4 (LMO) or
LiFePO4 (LFP) for lithium capture as a positive electrode
and silver as a negative electrode. Positive electrodes selec-
tively recover lithium in a few hours, that is, lithium can be
obtained consistently without any other purification process.
However, the high price of silver is one of the obstacles to
achieving a large-scale system and practical application.
Energy Technol. 2018, 6, 340 – 344 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
low price, large capacity, and stable redox potential, was pro-
posed as an alternative negative electrode material. Using a
LiMn2O4–zinc (LMO-Zn) battery system, lithium was selec-
tively recovered with an energy consumption of 6.3 Wh mol@1
of lithium recovered. Zinc was reversibly oxidized and re-
duced during the lithium-recovery process without side reac-
tions and weight loss.
Several candidate materials for replacing the silver elec-
trode such as activated carbon, I@/I3@ redox couple, and
nickel hexacyanoferrate (NiHCF) have been proposed.[5]
However, the capacity of activated carbon is fairly small
compared with that of a silver electrode.[5a] An I@/I3@ redox
couple appears to be inadequate in an aqueous system be-
cause an organic solvent is required as an electrolyte.[5b] The
systems with NiHCF appear to be energy-efficient battery-
like systems, although the energy consumption varies de-
pending upon the choice of cathode materials such as LFP or
LMO. However, it was noted that the cation concentration
such as Na + , K + in the recovery solution needs to be proper-
ly adjusted all the time so that NiHCF does not react with
Li + .[5c,d]
Herein, zinc, which is a low-cost, large-capacity material
and stable in aqueous solution,[6] is proposed as an alterna-
tive negative electrode material for an electrochemical lithi-
um recovery system.
[a] S. Kim, Dr. J. Lee, Dr. S. Kim, Dr. S. Kim, Prof. Dr. J. Yoon
School of Chemical and Biological Engineering, Institute of Chemical Process-
es (ICP)
Seoul National University
World Class University (WCU) Program of Chemical Convergence for Energy
& Environment (C2E2)
Gwanak-gu, Daehak-dong, Seoul 151-742 (Republic of Korea)
E-mail: jeyong@snu.ac.kr
[b] Dr. J. Lee, Dr. S. Kim, Prof. Dr. J. Yoon
Asian Insititute for Energy, Environment & Sustainability (AIEES)
Seoul National University
Gwanak-gu, Daehak-dong, Seoul 151-742 (Republic of Korea)
Supporting Information for this article can be found under:
https://doi.org/10.1002/ente.201700488.
340
Description of the electrochemical lithium recovery system with
zinc
Scheme 1 shows the two-step process of the electrochemical
lithium recovery system with LMO and a zinc electrode
(LMO-Zn system). The reactor of this system is divided into
two compartments by an anion exchange membrane (AEM).
The LMO electrode, which is used as a positive electrode, is
immersed in one compartment, and a zinc foil as a negative
electrode is dipped into the other compartment, which is
filled with a ZnCl2 solution with a concentration above 1 m
for reversible redox reactions (refer to Table S1 in the Sup-
porting Information).
In the discharging step, the LMO electrode is filled with
brine water (Scheme 1 a). Lithium ions in the brine are selec-
tively captured by the l-MnO2 structure, and simultaneously
the zinc metal is oxidized to zinc ions. These reactions occur
spontaneously, that is, electrical energy is generated. The
overall reaction is as follows:
2 l-MnO2 þ Liþ þ ZnðsÞ Ð LiMn2 O4 þ Zn2þ þ e@ ð1Þ
In the charging step, the LMO electrode is moved to the
charging solution, which then releases Li + to obtain a highly
pure lithium solution. At the same time, zinc ions are re-
duced to zinc metal (Scheme 1 b). This step is the energy-
consuming process [the reverse reaction of Eq. (1)]. The
charge neutrality of this system is balanced by the transfer of
anions through the AEM.
Scheme 1. Diagrams of the electrochemical lithium recovery process with the
LMO-Zn system. (a) Discharging step: lithium ions are selectively captured
from the brine water, and zinc oxidation occurs. (b) Charging step: lithium
ions are released into the charging solution, and zinc reduction occurs.
Energy Technol. 2018, 6, 340 – 344 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Results and Discussion
Figure 1 shows the results of the selective lithium recovery
from artificial brine the chemical composition of which was
intended to simulate that of the Salar de Atacama in Chile
(refer to Table S2 in the Supporting Information) with the
LMO-Zn system in which zinc is used as a negative elec-
trode. The suitability of zinc in the LMO-Zn system was con-
firmed with cyclic voltammetry (refer to Figure S1 in the
Supporting Information). As shown in Figure 1, lithium was
selectively recovered from brine water and extracted into the
charging solution. On the other hand, other ions (Na + , K + ,
and Mg2 + ) were not significantly recovered despite their
high concentration in the brine water. This result is attribut-
ed to the preference of lithium insertion into the l-MnO2
spinel structure; insertion of lithium is structurally and ener-
getically favorable compared with other ions.[7] The lithium
selectivity in the LMO-Zn system appears to be low in com-
parison with the previous study,[5d] and a good explanation
for this difference other than the difference of the solution
concentration between the two studies is not available at
present. The crossover of zinc ions through the anion-ex-
change membrane was 3 % (refer to Table S3 in the Support-
ing Information for details).
Figure 1. Selective lithium recovery with the LMO-Zn system in the presence
of other cations (Na + , K + , and Mg2 + ): the concentration changes in the
charging solution during 3 cycles (Atacama brine for lithium source water,
CaCl2 (0.1 m) for charging solution, current density: 0.5 mA cm@2).
Figure 2 shows the respective voltage profiles of the LMO
and zinc electrodes during the lithium recovery process. The
electrode potential of LMO varies with two plateaus whereas
lithium ions are intercalated and de-intercalated. On the
other hand, the electrode potential of zinc remains almost
constant during the discharging and charging steps with a
small overpotential. This result implies that it would be easy
to construct a two-electrode system for practical application
when zinc is used as a negative electrode because zinc can
function as a potential reference for the system.
Figure 3 shows the cell voltage of the LMO-Zn system
plotted in terms of the charge delivered during the lithium-
341
Figure 2. Respective voltage profiles of the LMO and zinc electrodes during
the electrochemical lithium recovery process in the LMO-Zn system.
Figure 3. Voltage versus capacity profile during the electrochemical lithium re-
covery process in the LMO-Zn system. The area between the discharging-
charging curves shows the consumed energy during the process
(6.3 Wh molLi@1).
recovery process. The energy consumption per cycle was cal-
culated by the circular integration of the plot as follows:
I
W ¼ @ DEdq ð2Þ
c
where W is the energy (J), DE is the cell voltage (V), and q
is the delivered charge (C).
In terms of energy, 6.3 Wh is required to recover 1 mol of
lithium during the electrochemical lithium recovery process
with the LMO-Zn system (the mechanical energy consumed
for moving the LMO electrode was not considered).
Figure 4 shows how the lithium selectivity of the LMO is
affected by the applied current densities in the electrochemi-
cal lithium recovery process. The lithium-selective coefficient
(L) is defined as follows:
cLi;C
L¼ ð3Þ
cLi;B
Energy Technol. 2018, 6, 340 – 344 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 4. Effect of the intensity of the current density on lithium selectivity in
the electrochemical lithium recovery process with the LMO-Zn system.
where cLi,C is the cationic mole fraction of Li + in the charg-
ing solution after the lithium recovery process, and cLi,B is
the cationic mole fraction of Li + in the brine water (Ataca-
ma brine). As shown in Figure 4, the lithium selectivity tends
to decrease with a higher current density. The lithium-selec-
tive coefficient is 14.4 for 0.5 mA cm@2, 9.2 for 0.75 mA cm@2,
and 6.6 for 1.0 mA cm@2. This result implies that as a higher
current density is applied, more impurity ions gain enough
energy for insertion and co-intercalate into the l-MnO2
structure.
To demonstrate the cyclability and stability of the LMO-
Zn system, 100 cycles of discharging–charging steps with a
current density of 1 mA cm@2 were repeated in the LMO-Zn
cell. Figure 5 shows the capacity retention of the LMO-Zn
cell during the cycles. After 100 cycles, the LMO-Zn cell re-
tained 73 % of its initial capacity.
Capacity fading is an inevitable feature of the lithium-ion
storage material owing to intercalation-induced stress and is
significantly intensified when the system is exposed to
oxygen.[8] The high concentration of impurity ions in the
electrolyte used in this study is presumed to be another
Figure 5. Capacity retention of the LMO-Zn cell during 100 cycles of the dis-
charging and charging step (Atacama brine for LMO side solution, ZnCl2
(3.2 m) for zinc side, 1 mA cm@2).
342
factor for the decrease in capacity because the structural
stress is assumed to be enhanced by the insertion of other
cations that have bigger ionic radii. The zinc electrode was
repeatedly oxidized and reduced during the 100 cycles and
maintained its mass (1675 mg). The zinc electrode was ana-
lyzed by X-ray diffraction to confirm whether the reversible
redox reaction between Zn2 + and Zn0 occurs (Figure S2 in
the Supporting Information). Peaks for zinc metal were
clearly detected; as a result, the zinc electrode showed great
stability during long-term operation.
Conclusions
This study demonstrated the feasibility of an electrochemical
lithium recovery system using zinc as a negative electrode,
which is an inexpensive and large-capacity material. In the
LiMn2O4–zinc (LMO-Zn) battery system, lithium was selec-
tively recovered from brine water that contained high con-
centrations of impurities with an energy consumption of
6.3 Wh per 1 mol of lithium recovered. By storing a high con-
centration of ZnCl2 in the confined compartment, the zinc
electrode was reversibly oxidized and reduced without side
reactions and electrode-potential variation. The stability of
the LMO-Zn system was examined through 100 cycles of dis-
charging–charging, and the LMO-Zn cell retained 73 % of its
initial capacity without loss of zinc.
Experimental Section
The LMO-Zn system in this study consisted of the LMO elec-
trode, a zinc electrode, and an anion-exchange membrane
(AEM; AMX, ASTOM Co., Japan). AEM was used in the
LMO-Zn system as the production cost of AEM continues to be
greatly lowered to 4.84 $ m@2 owing to its mass production and
technological developments in recent years.[9] The distance be-
tween the LMO and zinc was 5 cm. The LMO electrode was fab-
ricated by mixing LiMn2O4 (Sigma–Aldrich, Korea), carbon
black (Super P, Timcal, Switzerland), and polytetrafluoroethylene
(PTFE, Sigma–Aldrich, Korea) at a weight ratio of 8:1:1 with
ethanol. The resulting mixture was roll-pressed to 300 mm thick-
ness and dried in a vacuum oven at 80 8C for 12 h to evaporate
the solvent. The dried electrode was cut into 2.5 cm by 4 cm
shape and attached to a titanium foil with carbon paint (DAG-T-
502, Ted Pella, USA). Zinc foil (Alfa Aesar, Korea), which was
cut to the same dimensions as the LMO electrode without any
other fabrication processes, was used as the negative electrode.
The properties of the AEM, which separates the reactor of the
LMO-Zn system into two compartments, are described in
Table S4 in the Supporting Information.
The LMO electrode was converted into the l-MnO2 phase with
an electrochemical method, the form of which is susceptible to
capture lithium ions in the brine. The aqueous solution on the
LMO electrode side was Atacama brine (50 mL) in the discharg-
ing step so that the l-MnO2 is supposed to capture lithium ions
selectively, and in charging step, it was replaced with CaCl2
(0.1 m) for quantifying the amounts of lithium ions released from
the LMO electrode. The cycle of discharging–charging, which is
the lithium recovery process, were repeated galvanostatically
with a battery cycler (WBCS3000, WonATech, Korea) with a
constant current of 0.5 mA cm@2 in the 1.38–1.93 V range. The
Energy Technol. 2018, 6, 340 – 344 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
zinc-side solution was 1.8 m ZnCl2, which was determined experi-
mentally for a favorable reversible redox reaction in discharg-
ing–charging step. The voltage profiles of LMO and Zn during
the lithium recovery were measured simultaneously with two dif-
ferent Ag/AgCl (KCl sat.) reference electrodes, which were lo-
cated in a LMO-side compartment and a Zn-side compartment,
respectively. The potential of LMO was measured with a three-
electrode system, which was comprised of LMO as working elec-
trode, Zn as counter electrode, and Ag/AgCl (KCl sat.) in the
LMO-side compartment as reference electrode. At the same
time, the open circuit potential between Zn and another Ag/
AgCl reference in the Zn-side compartment was measured. Ion
concentrations in the charging solution were measured by ion
chromatography (DX-120, DIONEX, USA). Cyclic voltammetry
was performed to confirm the redox properties of zinc with a po-
tentiostat (PARSTAT 2273, Princeton Applied Research, USA)
in a potential range from @0.8 V to @1.9 V and a scan rate of
5 mV s@1. Zinc foil and Ag/AgCl (KCl sat.) were used as the
working and reference electrode, respectively. The Ag/AgCl
counter electrode was prepared with the same method used in
the previous study.[4b]
For the long-term stability test of the LMO-Zn system, capacity
retention was measured repeatedly up to 100 times between
1.93 V and 1.38 V as Atacama brine was in the LMO-side com-
partment regardless of discharging–charging step (Atacama brine
was not replaced even in the charging step) and 3.2 m ZnCl2 was
in the zinc electrode side. This long-term stability test focused on
whether the capacity retention is maintained. The high concen-
tration of ZnCl2 (3.2 m) was chosen to minimize the osmotic pres-
sure between the two compartments. XRD patterns of the zinc
electrode after the long-term stability test of the LMO-Zn
system were obtained with the Rigaku D-MAX2500, Japan.
Acknowledgments
This research was supported by a grant (code 17IFIP-
B065893-05) from the Industrial Facilities & Infrastructure
Research Program funded by Ministry of Land, Infrastructure
and Transport of Korean government and Basic Science Re-
search Program through the National Research Foundation of
Korea (NRF) funded by the Ministry of Education (NRF-
2016R1D1A1A02937469), and by the “Foundation of IN-
NOPOLIS Daegu Project” funded by Ministry of Science,
ICT and Future Planning of the Korean government
(2015DG0016).
Conflict of interest
The authors declare no conflict of interest.
Keywords: batteries · lithium manganese oxide · lithium
recovery · membranes · zinc
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Manuscript received: July 18, 2017
Revised manuscript received: August 21, 2017
Accepted manuscript online: August 30, 2017
Version of record online: January 17, 2018
344