Fusion Engineering and Design 88 (2013) 2956–2959

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Fusion Engineering and Design

journal homepage: www.elsevier.com/locate/fusengdes

Development of technology for recovering lithium from seawater by

electrodialysis using ionic liquid membrane
Tsuyoshi Hoshino ∗
Breeding Functional Materials Development Group, Fusion Research and Development Directorate, Japan Atomic Energy Agency, 2-166 Obuchi, Omotedate,
Rokkasho-mura, Kamikita-gun, Aomori 039-3212, Japan

h i g h l i g h t s

• I propose a new method for Li recovery from seawater by electrodialysis using an ionic liquid.
• The divalent ions were removed for producing concentrated seawater.
• Almost all Li ions remain on the anode side, whereas the other ions in the concentrated seawater permeate to the cathode side through the ionic liquid
with an applied electric voltage of 2–3 V.
• The Li survival ratio remained high and was 63% after electrodialysis.

a r t i c l e i n f o a b s t r a c t

Article history: Tritium fuel for fusion reactors is produced by reacting lithium-6 (6 Li) with neutrons in tritium
Received 4 February 2013 breeders. This study demonstrates a method for Li recovery from seawater, wherein Li does not
Received in revised form 17 June 2013 permeate from the anode side to the cathode side through an ionic liquid N,N,N-trimethyl-N-
Accepted 18 June 2013
propylammonium–bis(trifluoromethanesulfonyl) imide. Almost all Li ions remain on the anode side
Available online 23 July 2013
(seawater), whereas the other ions in the seawater permeate to the cathode side through the ionic liquid
with an applied electric voltage of 2–3 V.
Keywords:
© 2013 Elsevier B.V. All rights reserved.
Tritium breeder
Lithium resource
Fusion reactor
Seawater
Ionic liquid

1. Introduction for approximately 70% of the global Li production [4,5]. In addi-

Tritium fuel for fusion reactors is produced by the neutron
capture reaction of lithium-6 (6 Li) in tritium breeders. Natural
Li contains approximately 7.6 at.% 6 Li and, consequently, large
amounts of lithium (Li) are needed to obtain the required 30–90%
enrichment of 6 Li for tritium breeding material in fusion reactors
[1–3]. In addition, concerning global warming, the use of Li-ion bat-
teries in electric vehicles and houses is increasing; therefore, the
need for Li is growing.
Li, one of the 31 rare metal elements among the 112 known
elements, is rapidly becoming a valuable commodity. In South
America, Li is recovered from salt lakes and is currently being pro-
duced at the Atacama Salt Lake in Chile and the Hombre Muerto
Salt Lake in Argentina. The production in these two lakes accounts
∗ Tel.: +81 175 71 6703; fax: +81 175 71 6502.
E-mail addresses: hoshino.tsuyoshi@jaea.go.jp, hoshino.tsuyoshi@gmail.com
tion, there are more than 100 salt lakes in the Puna plateau, which
is surrounded by the Andes, located at an altitude more than or
equal to 3500 m. Areas such as the Uyuni Salt Lake, Rincon Salt
Lake, and Olaroz Salt Lake are expected to be developed for Li
production. South American countries such as Chile, Bolivia, and
Argentina have abundant Li resources (brine water). And Li reserves
in these countries account for more than half of the global Li
reserves. Although Li extraction from chloride brine water is easy,
the quantity of natural resources is limited. On the other hand, the
quantity of natural resources in sulfate brine water is large, but the
processing technology has not yet been established.
In contrast, there are virtually inexhaustible Li resources in sea-
water, totalling approximately 230 billion tons, although the Li
concentration is low. Therefore, Li recovery from seawater using
Li adsorbents has been studied [6–8]. However, the efficiency of
Li absorption must be improved to enable cost-effective produc-
tion. In addition, Li-ion selective membranes using crown ethers
have been developed [9–13]. These membranes are unsuitable for

0920-3796/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fusengdes.2013.06.009
 T. Hoshino / Fusion Engineering and Design 88 (2013) 2956–2959 2957

continuous Li recovery from seawater because the chemical reac-

tion rate depends on the absorption and desorption of Li.
At present, Japan solely relies on Li imports. However, Li is
abundant in seawater. Therefore, efficient methods for its stable
recovery from seawater are highly desirable. Hoshino and Terai
developed a novel Li isotope separation technique using organic
membranes impregnated with an ionic liquid [14,15]. This tech-
nique can also be used to recover Li from seawater. On the basis of
this study, a new method for Li recovery from seawater by electro-
dialysis using an ionic liquid is reported.

2. Experimental

2.1. Removal of divalent ions and the production of concentrated

seawater

Many ions exist in seawater, and the concentration of Li ion is

very low. For high-efficiency Li recovery, the divalent ions were
removed for producing concentrated seawater.
Fig. 1 shows the experimental setup for electrodialysis.
SELEMIONTM CSO was used as the separation membrane for the
divalent ions. The monovalent ions (Na, K, and Li) in seawa-
ter permeated from the anode side to the cathode side through
SELEMIONTM CSO, and the divalent ions (Ca and Mg) remained
on the anode side. Furthermore, 15 L seawater in the anode side
was concentrated to a 3.8 L solution in the cathode side. This con-
centrated solution was used in recovering Li from seawater by
electrodialysis using an ionic liquid.

2.2. Li recovery using an ionic liquid

Fig. 2 shows the proposed method for Li recovery from seawater.

The ions in seawater permeate from the anode side to the cathode
side during electrodialysis. The permeation speed of the major
ions, including Na, Mg, Ca, and K, is faster than that of Li. Therefore,
Li ions remain on the anode side and can be recovered. N,N,N-
trimethyl-N-propylammonium–bis(trifluoromethanesulfonyl)
imide (TMPA–TFSI) was selected as the ionic liquid because it
exhibits low Li conductivity. For accurately measuring the Li
residual characteristics, seawater was added to the anode side, and
a solution without major elements was added to the cathode side.
The SELEMIONTM CMV membrane was installed on both ends
of the ionic liquid flow. It is possible to prevent the outflow of the
ionic liquid by SELEMIONTM CMV because both water and ionic
liquid cannot permeate through SELEMIONTM CMV. This membrane
is permeable to all cations (Na, Mg, Ca, and K) present in seawater,
enabling the major ions in seawater to permeate the membrane
and become concentrated on the cathode side.
Fig. 1. Electrodialysis for removing divalent ions and producing concentrated sea-
water.
2.3. Experimental conditions

Fig. 3 shows the Li recovery system using TMPA–TFSI (Koei
Chemical Co. Ltd) consisting of an electrodialysis setup and a poten-
tiostat (1470E of Solartron CellTest System). The latter was used to
supply electric potential between the cathode (working electrode
(WE)) and anode (counter electrode (CE)).
The concentrations of the concentrated seawater on the anode
side and the 0.1 M HCl solution on the cathode side were mea-
sured by inductively coupled plasma atomic emission spectrometry
(Optima7000DV of PerkinElmer Co., Ltd) and inductively coupled
plasma mass spectrometry (ELAN DRC-e of PerkinElmer Co., Ltd),
respectively.
The applied dialysis voltage was 2–3 V, and the duration of dial-
ysis was up to 15 h. The area of the Pt-covered Ti electrode was
21 cm2 .
3. Results and discussion
3.1. Removal of divalent ions and concentration of seawater
The stabilized electrical potential for electrodialysis was sup-
plied from cathode into anode with a potentiostat. A Ag–AgCl/KCl
electrode (silver–silver chloride electrode: SSE) was used as the ref-
erence electrode (RE). The limit value of the electrical potential was
3 V to prevent the resolution of TMPA–TFSI.
Table 1 shows the results of the removal of seawater divalent
ions (Ca and Mg) and the concentration of seawater by electro-
dialysis. The applied dialysis voltage was 3 V, and the duration of
dialysis was approximately 5 h. SELEMIONTM CSO essentially pre-
vents permeation of Ca and Mg ions from anode to the cathode
2958 T. Hoshino / Fusion Engineering and Design 88 (2013) 2956–2959

Table 1
Ion concentrations in seawater before and after electrodialysis.

side. The concentration of Na, K, and Li ions on the cathode side

was two times the initial concentration. The volume of seawater
decreased from 15 to 3.8 L. These observations suggest that the sep-
aration of Ca and Mg ions is easily achieved by electrodialysis using
SELEMIONTM CSO.

3.2. Survival ratio of Na, K, and Li in concentrated seawater

The Li recovery test was performed using an ionic liquid, and

the ion survival ratio on the anode side was calculated from the
following formula:

survival ratio (%)

100

Li
80 Na
K
60

40
Approximately 50 %
20

Fig. 2. Li recovery method using an ionic liquid.

0
0 2 4 6 8 10 12 14 16
Time (h)
(a) 2V
100

Li
80 Na
K
60
Approximately 38 %
40

20

0
0 2 4 6 8 10 12 14 16
Time (h)
(b) 3V
Fig. 3. Li recovery system using an ionic liquid and consisting of an electrodialysis
setup and a potentiostat. Fig. 4. Li, Na, and K ion concentrations on the anode side as a function of dialysis
time.
 T. Hoshino / Fusion Engineering and Design 88 (2013) 2956–2959
100
80
60
Approximately 63 %
40
20
0 SELEMIONTM CMV to prevent the outflow of the ionic liquid, the
0 2 4 6 8 10 12
Time (h)
Fig. 5. Li, Na, Mg, and K ion concentrations on the anode side as a function of dialysis
time.
anode ion concentration after electrodialysis
= × 100.
anode ion concentration before electrodialysis
Fig. 4 shows the Li, Na, and K ion concentrations on the anode
side as a function of dialysis time. At 2 and 3 V, the Na and K
ions selectively permeated from the anode side to the cathode
side through the ionic liquid. The Li survival ratio was high for
3 h; however, it decreased as the survival ratios of Na and K
reached 0%. Finally, the Li survival ratio was approximately 50%
and 38% at 2 and 3 V, respectively. Although the permeation of
Na and K ions at 3 V is faster than that at 2 V, the Li survival
ratio is lower at 3 V. Therefore, it was considered that another ion
needs to be added to the anode side to improve the Li survival
ratio.
3.3. Improvement of Li survival ratio
Mg was selected as another ion because a large amount of
Mg was already recovered by concentrating seawater, and it
can remove Li from the recovery solution by chemical precipita-
tion. Therefore, Li recovery was performed by using concentrated
seawater having approximately 9000 ppm Mg and an ionic liq-
uid. A dialysis voltage of 2 V was applied on the basis of the
results in Fig. 4 because the Li survival ratio at 2 V is higher than
at 3 V.
Fig. 5 shows the Li, Na, Mg, and K ion concentrations on the anode
side as a function of dialysis time. Na, Mg, and K ions permeate from
the anode side to the cathode side with time. Furthermore, the Li
survival ratio remained high and was 63% after 11 h. These results
show that the Li survival ratio can be controlled, and the concen-
tration of ions on the anode side can be changed. Subsequently, Li
becomes selectively concentrated on the anode side because the
other ions (Na, Mg, and K) in the concentrated seawater permeate
through TMPA–TFSI.
In the future, the evaluation of the optimization of the Li recov-
ery system configuration for high efficiency will be performed using
multistage electrodialysis and an ionic liquid.
2959
4. Conclusions
Li
In this study, a method for Li recovery from seawater has been
Na proposed. The method involves the use of an ionic liquid through
Mg which only major seawater ions, including Na, Mg, Ca, and K but
K not Li, permeate from the anode side to the cathode side during
electrodialysis. Therefore, the Li ions become concentrated on the
anode side and can be recovered. TMPA–TFSI was selected as the
ionic liquid because it exhibits lower Li conductivity than other
ionic liquids. For accurately measuring the Li recovery character-
istics, concentrated seawater without Mg and Ca ions was added
to the anode side, and a solution without major ions was added to
the cathode side. With both ends of the ionic liquid covered with
14 16
Li survival ratio increased from 38% to 63% after adding Mg to the
anode side to control Li permeation.
Electrodialysis is already used in seawater desalination plants.
Thus, this new recovery method is easily scalable. The recovered
Li could then be used in applications such as in fusion reactors for
fuel production. In addition, this method may also be suitable for
(1) recovering other rare metals from seawater.
Acknowledgments
The author is indebted to Professor Takayuki Terai for help-
ful discussions. The technical assistance of Mr. Fumiaki Oikawa,
Tatsuya Suzuki, and Makiko Sekiya are greatly appreciated. This
study was supported by the Funding Program for Next Generation
World-Leading Researchers (NEXT Program) of the Cabinet Office,
Government of Japan.
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