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Magnesium-Doped Manganese Oxide with Lithium Ion-Sieve Property:

Lithium Adsorption from Salt Lake Brine

Article  in  Bulletin of the Chemical Society of Japan · April 2013

DOI: 10.1246/bcsj.20130019

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850 Bull. Chem. Soc. Jpn. Vol. 86, No. 7, 850­855 (2013) © 2013 The Chemical Society of Japan

Magnesium-Doped Manganese Oxide with Lithium Ion-Sieve Property:

Lithium Adsorption from Salt Lake Brine

Ramesh Chitrakar,1 Yoji Makita,1 Kenta Ooi,2,³ and Akinari Sonoda*1

1
Health Research Institute, National Institute of Advanced Industrial Science and Technology (AIST),
2217-14 Hayashi-cho, Takamatsu, Kagawa 761-0395
2
National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565

Received January 27, 2013; E-mail: a.sonoda@aist.go.jp

Magnesium-doped lithium manganese oxides LimMgxMnIIIyMnIVzO4 (0 < x ¯ 0.5) with cubic spinel structure were
synthesized by a coprecipitation method followed by calcination at 450 °C in air. Protonated samples were obtained after
treatment with HCl solution. Chemical stability is very important for lithium uptake in industry. We used 0.5 M HCl for
desorption of lithium, then dissolution of Mn decreased from 5.8 wt % for a sample without Mg to 1.0 wt % for a Mg-doped
sample (Mg/Mn = 0.33). Raw brine was collected from the Salars de Uyuni, Bolivia. The effects of magnesium-doping
on lithium adsorptive properties of the protonated samples in NaHCO3 containing brine were studied by a batch method.
The results showed that lithium adsorptive capacity and chemical stability of the protonated samples increased with
increase in Mg/Mn ratio. The regeneration of the sample with Mg/Mn = 0.33 up to 10 cycles showed good performance
with lithium adsorptive capacity of 23­25 mg g¹1 at pH 6.6, and the dissolution of manganese ca. 0.25 wt % Mn.

The demand for lithium in making lithium-ion batteries for
electric vehicles is expected to increase in coming years
because a wide range of electric vehicles has entered the
market.1 Lithium is present in seawater, brines, and ores. The
lithium in seawater is attractive as a future source of lithium
(2.4 © 1011 t), but the concentration is only 0.17 mg dm¹3,
which is about ten thousand times less than South American
brine deposits.1 Lithium recovery from salt lake brine on
industrial scale is being carried out in Chile, Argentina, the
USA, and China, and all processes are based on solar evapo-
ration.2 Very recently, a hydrometallurgical process was used
to study the adsorption of lithium from brine of Bolivia.3
Adsorption of lithium from brine of China was also studied by
addition of Al(OH)3 in brine.4 Ion exchange using ion-sieve
materials with excellent selectivity for lithium ions can be
feasible for lithium adsorption from salt lake brine.
Ion-sieve manganese oxides of various compositions derived
from lithium manganese oxide spinels have been studied in
detail for adsorption of lithium ions from aqueous solutions or
seawater.5­16 Lithium extraction/insertion reactions in aqueous
solutions proceed through redox reaction on LiMn2O4 or ion-
exchange reaction on Li1.33Mn1.67O4 and Li1.6Mn1.6O4.5­9 The
H1.33Mn1.67O4 and H1.6Mn1.6O4 are attractive ion-exchange
materials as seen from high lithium adsorptive capacity.7,9
Recently, we studied lithium adsorption from salt lake brine on
H1.33Mn1.67O4 and H1.6Mn1.6O4.16
Lithium manganese oxide spinels may be unstable during
long-term lithium extraction/insertions cycles as seen from
³ Present address: The Institute for Environmental Management
Technology (EM-TECH), National Institute of Advanced
Industrial Science and Technology (AIST), 16-1 Onogawa,
Tsukuba, Ibaraki 305-8569
the dissolution of manganese by acid treatment.17 Metal-doped
LiMzMn2¹zO4 spinels (M = Mg, Fe, Co, Ni, Ti, etc.) may
improve the chemical stability of the spinel, because strong
chemical bonds between substituted cations and oxygen may be
formed, thereby preventing the dissolution of manganese in the
solution.18,19 Only a few studies related to lithium extraction/
insertion reactions in aqueous solutions or seawater using
metal-doped LiMzMn2¹zO4 spinels (M = Mg, Zn, Fe, Al) had
been reported.20­25 The literature20­25 has focused only on the
lithium adsorptive properties of samples, and has not discussed
the impact of the metal-doped sample on the dissolution of
manganese during acid treatment.
A review of literature shows that there has been no study
undertaken for the adsorption of lithium ions from salt lake
brine by ion-sieve magnesium-doped manganese oxides. The
present study reports the calcination of the precursors at 450 °C
to prepare magnesium-doped lithium manganese oxides. After
acid-treatment, the samples were studied for lithium adsorption
from the NaHCO3-added brine by a batch method.
Experimental
Synthesis of Magnesium-Doped Lithium Manganese
Oxides. Magnesium-doped lithium manganese oxide with
Mg/Mn molar ratio of 0.10 was prepared as follows: solid
Mg(NO3)2¢6H2O (0.77 g, 3.0 mmol Mg) and solid MnCl2¢
4H2O (5.94 g, 30.0 mmol Mn) were dissolved in deionized
water to make 100 cm3 solution. The metal salt solution was
transferred into a 500 cm3 beaker. Solid LiOH¢H2O was slowly
added to the mixed metal salt solution until the pH of the
suspension reached ca. 11 under magnetic stirring at room
temperature. 30% H2O2 (30 cm3) was slowly added to the
suspension for oxidation of Mn(II) ions. After stirring for 2 h,
the suspension was poured into a dish for evaporation of water

Published on the web April 6, 2013; doi:10.1246/bcsj.20130019

R. Chitrakar et al. Bull. Chem. Soc. Jpn. Vol. 86, No. 7 (2013) 851

at 90 °C, and further dried at 150 °C to obtain the precursor
solid. The solid was ground to powder and then calcined at
450 °C for 4 h in air. After cooling, the powder was washed
with deionized water, and finally dried at room temperature.
We obtained about 3 g of powder on this scale. Similarly,
magnesium-doped lithium manganese oxides with Mg/Mn
molar ratios of 0, 0.20, and 0.33 were prepared (about 3 g). The
samples were designated as Mg-0, Mg-0.1, Mg-0.2, and Mg-
0.3 for Mg/Mn ratios of 0, 0.10, 0.20, and 0.33, respectively.
Physical Analysis. Powder X-ray diffraction analysis was
carried out using an X-ray diffractometer (RINT 2100; Rigaku
Corp.) operated at 40 kV and 24 mA with Cu K¡ radiation.
The XRD patterns were recorded in the range of 5­70° (2ª)
at a scanning rate of 1° (2ª) min¹1. The cubic lattice constant
(a) for samples was determined using a JADE 3.0 package.
Thermogravimetric-differential thermo analysis data (TG-DTA)
were collected using thermal analyzer system 001 (TG-DTA
2000, MAC Science Co., Ltd., Japan) at a heating rate of 10
°C min¹1 in air.
Chemical Analysis. Sample (0.05 g) was dissolved in
5 mol dm¹3 HCl containing a few drops of 30% H2O2 and then
heated at ca. 80 °C to dissolve magnesium and manganese.
The solutions were analyzed for their lithium, magnesium
and manganese contents by atomic absorption spectrometry
(AAnalyst 300; Perkin-Elmer) after appropriate dilution. The
mean oxidation state of Mn (ZMn) was evaluated after deter-
mination of active oxygen by standard oxalic acid method.7
Brine. The raw brine from Salar de Uyuni, Bolivia
collected by Japan Oil, Gas and Metals National Corporation
(JOGMEC) was used for the lithium adsorption experiments
in the present study. The raw brine was analyzed for its Li, Na,
K, Mg, and Ca contents (three replicate analyses) by atomic
absorption spectrometry, and Cl, NO3, and SO4 (three replicate
analyses) by ion chromatography (761 Compact IC: Metrohm
AG). In lithium adsorption experiments to be discussed below,
solid NaHCO3 was added to the raw brine (25 g NaHCO3 in
1.0 dm3 brine). Since NaHCO3 acts as a buffer in brine, the pH
of brine before and after lithium adsorption maintained a nearly
constant value (pH 6.4­6.6).
Extraction of Lithium. Extraction of lithium in magne-
sium-doped lithium manganese oxides was carried out by
stirring 2.5 g of sample in 0.5 mol dm¹3 HCl (250 cm3) for 1 d
at room temperature. The samples were filtered, washed with
deionized water, and finally dried at room temperature. The
protonated samples were designated as Mg-0(H), Mg-0.1(H),
Mg-0.2(H), and Mg-0.3(H) for Mg-0, Mg-0.1, Mg-0.2, and
Mg-0.3, respectively.
Rate of Lithium Adsorption. Rate of lithium adsorption
from the NaHCO3 containing brine was carried out at various
reaction times (1, 2, 4, 6, 8, and 24 h). For each experiment,
Mg-0.3(H) (0.20 g) was dispersed in 10.0 cm3 of the brine, and
the suspension was kept under magnetic stirring at room
temperature for the designated times. The suspensions from
various reaction times were filtered using a 0.45 ¯m syringe-
driven filter unit. The filtrates were analyzed for their lithium
contents.
Lithium Adsorption/Desorption. For lithium adsorp-
tion, 1.0 g of protonated samples with various Mg/Mn ratios
was immersed in the NaHCO3 containing brine (40.0 cm3),
and kept under magnetic stirring at room temperature for 1 d.
The suspension was filtered, washed with deionized water and
finally the sample was dried at room temperature. The filtrates
were analyzed for their lithium contents. For lithium desorption,
lithium adsorbed sample (1.0 g) was treated with 0.5 mol dm¹3
HCl (100 cm3) for 1 d at room temperature. The filtrates were
analyzed for their lithium and manganese contents.
Sample Dose. The effect of sample dose on lithium adsorp-
tion from the NaHCO3 containing brine was carried out by
dispersing 0.20­0.80 g protonated samples with Mg-0.3(H)
in the brine (20.0 cm3), and the suspension was kept under
magnetic stirring for 1 d at room temperature. The filtrates were
analyzed for their lithium contents.
Regeneration. Regeneration of Mg-0.3(H) up to 10 cycles
was performed by dispersing 5.0 g of the sample in the
NaHCO3 containing brine (200 cm3) as described above
(Lithium adsorption/desorption).
Results and Discussion
Synthesis of Magnesium-Doped Lithium Manganese
Oxides. Figure 1A shows the powder X-ray diffraction
patterns of magnesium-doped lithium manganese oxides with
various Mg/Mn ratios prepared by calcination of the precursors
at 450 °C for 4 h in air. In conventional procedures, calcination
of the precursors at temperature 400­450 °C is favorable for the

20000 (i)
400
311
111

(A) (B)
440
222

331

511
111

531

(d)
400
311

16000
Intensity / cps

440
511
222

531
331

(h)
12000
(c) (g)
8000
(b) (f)
4000
(a) (e)
0
5 15 25 35 45 55 65 5 15 25 35 45 55 65
2θ / degree (Cu Kα )
Figure 1. XRD patterns of magnesium-doped lithium manganese oxides (A) and their protonated samples (B). (a) Mg-0, (b) Mg-0.1,
(c) Mg-0.2, (d) Mg-0.3, (e) Mg-0(H), (f ) Mg-0.1(H), (g) Mg-0.2(H), (h) Mg-0.3(H), and (i) Mg-0.3(H) after regeneration (10
cycles) *Mn2O3.
852 Bull. Chem. Soc. Jpn. Vol. 86, No. 7 (2013)
Table 1. Composition and Lattice Parameter of the Samples
Sample Mg/Mna) Li/Mna) H/Mna)
Mg-0 (0) 0.49
Mg-0(H) (0) 0.02 0.52
Mg-0.1 0.10 (0.10) 0.63
Mg-0.1(H) 0.08 0.04 0.58
Mg-0.2 0.20 (0.20) 0.61
Mg-0.2(H) 0.15 0.18 0.48
Mg-0.3 0.33 (0.33) 0.58
Mg-0.3(H) 0.24 0.09 0.46
a) Mole ratio, parentheses denote starting Mg/Mn ratios.
preparation of lithium selective materials.26 All the diffraction
patterns of Mg-0.3 could be attributed to the expected cubic
spinel phase (Figure 1A, d).27 Although the XRD patterns of
Mg-0, Mg-0.1, and Mg-0.3 exhibited peaks of spinel phase
(Figure 1A, a, b, c), peaks from Mn2O3 impurity (weak peak
indicated in Figure 1A by a star) were also observed, simi-
lar to the XRD patterns of the LiMn2O4 spinel prepared by
coprecipitation/heat treatment of the precursor at 400 °C.28
Pure LiMn2O4 or magnesium-doped LiMgzMn2¹zO4 spinel
(z = 0­0.2) with well developed crystallinity without Mn2O3
impurity can be prepared only after calcination of the pre-
cursor at high temperature (800 °C).27,28 The diffraction peaks
of Mg-0.3 could be indexed to cubic spinel structure of
magnesium-doped LiMg0.5Mn1.5O4 with space group Fd3m of
(PDF# 32-0573). In this spinel structure, lithium occupies the
8a tetrahedral sites, and magnesium and manganese occupy the
16d octahedral sites of a cubic closed packed oxygen frame-
work.21 The lattice constants (a) of the samples are given in
Table 1. The lattice constants (a = 0.8152­0.8183 nm) of the
samples increased with increase in Mg/Mn ratio. In contrast to
the present results, the lattice constant (a = 0.8226­0.8200 nm)
decreased linearly with increasing Mg content for well-crystal-
lized magnesium-doped Li1.05Mn1.95¹zMgzO4 spinel prepared
via a two-step calcination at 800 °C for 18 h in air.19,27 It was
reported that one-step calcination at 800 °C may not be enough
for the preparation of well-crystallized magnesium-doped
Li1.05Mn1.95¹zMgzO4 spinel with scattered distribution of the
lattice constants.27 These XRD results are only shown for
the crystal parts, so our samples might have different well-
crystallized spinels, since higher temperature (over 500 °C)
treatment decreased lithium ion selectivity.
Chemical analysis data of the magnesium-doped lithium
manganese oxides are shown in Table 1. The Mg/Mn ratios in
the solid phase were close to the starting Mg/Mn ratios in the
solutions. A general chemical formula LimMgxMnIIIyMnIVzO4
can be used to denote the spinels and the values of m, x, y, and
z can be estimated from the experimental values of Li/Mn,
Mg/Mn ratios, and mean oxidation state of manganese (ZMn)
under the condition of electroneutrality:21,29
m þ 2x þ ðy þ zÞZMn ¼ 8 ð1Þ
3y þ 4z ¼ ZMn ðy þ zÞ ð2Þ
m ¼ ðy þ zÞðLi=MnÞ ð3Þ
x ¼ ðy þ zÞðMg=MnÞ ð4Þ
The chemical formulae of the magnesium-doped lithium
manganese oxides are given in Table 1. The ZMn values in
Lithium Adsorption from Salt Lake Brine
ZMn a0/nm Atomic ratio for oxygen as 4
3.57 0.8152 Li0.97MnIII0.84MnIV1.13O4
3.83 0.8070 Li0.04H0.99MnIII0.32MnIV1.58O4
3.79 0.8156 Li1.10Mg0.17MnIII0.36MnIV1.37O4
3.92 0.8076 Li0.07H1.03Mg0.14MnIII0.13MnIV1.64O4
3.81 0.8172 Li1.01Mg0.33MnIII0.31MnIV1.35O4
3.84 0.8127 Li0.31H0.74Mg0.26MnIII0.27MnIV1.45O4
3.92 0.8183 Li0.90Mg0.51MnIII0.12MnIV1.43O4
3.95 0.8168 Li0.15H0.76Mg0.40MnIII0.08MnIV1.59O4
Dissolution of Mg2+ and Mn2+ / wt%
50 10
Extraction of Li+ / mg g–1
40 8
30 6
20 4
10 2
0 0
0 0.1 0.2 0.3 0.4
Mg/Mn ratio
Figure 2. Extraction of Li+, and dissolution of Mg2+ and
Mn2+ from magnesium-doped lithium manganese oxides
with various Mg/Mn ratios using 0.5 mol dm¹3 HCl.
( ) Li+, ( ) Mg2+, and ( ) Mn2+.
the LimMgxMnIIIyMnIVzO4 samples increased with increase in
Mg/Mn ratio from 3.57 for Mg-0 to 3.96 for Mg-0.3, and
almost all manganese ions became Mn(IV) at Mg/Mn ratio of
0.3. The calculated values of total cations (m + x + y + z) from
the chemical formulae were 2.93­3.0. The mole ratio of oxygen
to total cations for the spinels may be larger than 4:3 from the
chemical analysis.18 In fact, it is very difficult to prepare or
control magnesium-doped lithium manganese oxide spinel
[Li]8a[MgxMn2¹x]16d[O4]32e with both exact oxygen stoichiom-
etry and no cation vacancies.18
Lithium Extraction. Figure 2 shows the extraction of
lithium and the dissolution of magnesium and manganese ions
from the magnesium-doped lithium manganese oxides with
various Mg/Mn ratios after treatment with 0.5 mol dm¹3 HCl.
When magnesium was not present, the Mg-0 showed lithium
extractability 40 mg g¹1 with high dissolution of manganese
(5.8 wt % Mn) because of its high Mn(III) content. The Mg-
0.1 exhibited lower dissolution of manganese (2.5 wt % Mn)
with lithium extractability of 43.7 mg g¹1. The extractability
of lithium and the dissolution of manganese in the samples
decreased with further increase in Mg/Mn ratio of the samples.
The dissolution of magnesium increased with increase in Mg/
Mn ratio of the samples (Mg extractability = 17­23%). The
magnesium-doped sample (Mg/Mn > 0.1) reduced the lithium
extractability, but greatly inhibited the dissolution of manga-
nese, which may be due to the higher chemical stability of the
R. Chitrakar et al.
3 Mg-0(H)
0 3
5.1%
2 2
540ºC
1 10
DTA / μV mg –1
0 DTA TG
Mass loss / %
-1 20
3 0
Mg-0.2(H)
4.0%
2 580ºC
580ºC
1 10
250ºC
0 0
-1 20
0 400 800
Temperature / ºC
Figure 3. TG-DTA curves of protonated samples with
various Mg/Mn ratios.
sample. The dissolution of manganese in the samples during
lithium extraction is due to the disproportionation reaction
of Mn(III) in the acidic medium taking place as 2Mn(III) ¼
Mn(II) + Mn(IV).6,7 For LiMn2O4 spinel, lithium extraction
with acid is mainly a redox reaction with high dissolution of
manganese (25 wt % Mn) to form ­-MnO2 with tetrahedral
vacant sites,5­7 while in Li1.33Mn1.67O4, Li1.6Mn1.6O4, and
LiMg0.50Mn1.5O4 spinels, it is an ion-exchange reaction with
low dissolution of manganese (1­2 wt % Mn) forming lattice
proton sites.7,21,26 Since the present samples except Mg-0
exhibited low dissolution of manganese (1­2.5 wt % Mn)
similar to Li1.33Mn1.67O4, Li1.6Mn1.6O4, and LiMg0.50Mn1.5O4
spinels,7,21,26 it can be expected that the lithium extraction
occurred via ion exchange as major reaction in addition to
redox as minor reaction due to the presence of Mn(III) in the
samples.29
Figure 1B shows the XRD patterns of the protonated sam-
ples preserving the cubic spinel structure with a slight decrease
of lattice constant (a) compared to the original samples
(Figure 1A). The acid treatment greatly reduced the Mn2O3
phase initially present in the original samples (Figure 1A). The
peak intensities in the XRD patterns of Mg-0.1(H), Mg-0.2(H),
and Mg-0.3(H) were nearly the same as the original samples.
The fraction of tetravalent manganese increased with increase
in Mg/Mn ratio, resulting in stable metal oxide framework of
the spinel.29 The lattice constants (a) of the protonated samples
also increased with increase in Mg/Mn ratio similar to the
original samples (Table 1).
TG-DTA curves of the protonated samples are shown in
Figure 3. The small endothermic peaks around 250 °C with
mass loss could be ascribed to the dissipation of water by con-
densation of the lattice hydroxy groups of the spinel structure.21
In the case of ­-MnO2 prepared from LiMn2O4 spinel, TG-
DTA curves showed a little weight loss (<1%) up to 400 °C
indicating the presence of the tetrahedral vacant sites, and an
exothermic peak at 270 °C due to phase transformation of
­-MnO2 to ¢-MnO2.5,7 The endothermic peaks at 540 °C in
Mg-0(H), 580 °C in Mg-0(0.2), and Mg-0.3(H), and 600 °C
in Mg-0.1(H) could be ascribed to the transformation from
manganese(IV) to manganese(III).21 The TG-DTA data con-
firmed the formation of lattice protons accompanying lithium
Bull. Chem. Soc. Jpn. Vol. 86, No. 7 (2013) 853
(H)Mg-0.1
0 Table 2. Analysis of Common Ions in Brine
5.4%
Components Concentration/mg dm¹3 (n = 3)
600ºC
1
250ºC
10 Li+ 1630 « 30
Na+ 59100 « 500
DTA / μV mg –1
0
Mass loss / %
-1
K+ 18700 « 200
20
3 0 Mg2+ 29200 « 100
Mg-0.3(H)
4.0% Ca2+ 230 « 5
2
Cl¹ 235000 « 100
1 10 SO42¹ 26300 « 50
250ºC
NO3¹ 970 « 1
-1 20
0 400 800 extraction via ion-exchange reaction on the present protonated
samples. The lattice protons were 4.0­5.4% calculated from the
mass loss between 120­300 °C.21
A general formula LimHnMgxMnIIIyMnIVzO4 can be written
for the protonated samples. The chemical formulae of the
protonated samples estimated from the experimental values of
Li/Mn, H/Mn, and Mg/Mn ratios and ZMn under the condition
of electroneutrality21,29 are shown in Table 1. The ZMn value
increased with increase in Mg/Mn ratio reaching a value of
3.95 for Mg-0.3(H). The calculated values of cations (m + n +
x + y + z) from the chemical formulae were close to 3 (2.92­
3.02) for all samples except Mg-0(H) indicating the protonated
samples satisfied the general condition for spinel structure.29
Raw Brine. In Bolivia, there are two wide salt crusts: the
Salar de Uyuni, which is probably the largest salt pan in the
world (10000 km2) and the Salar de Coipasa (2500 km2).30 Both
crusts are made from porous halite filled with interstitial brine
very rich in Li, K, Mg, and B, whose concentrations depend on
the depths within the halite crust.30 In the Salar de Uyuni, the
lithium concentration ranges from 250 to 4700 mg dm¹3.30
Brines collected from different locations of the Salar de Uyuni
were essentially saturated with halite (density > 1.2 g cm¹3),
and moderately high in sulfate (3200­19000 mg dm¹3 SO4), but
low in carbonate (<500 mg dm¹3 HCO3).31 The raw brine from
Uyuni belonging to Mg-Cl group30 was analyzed for its Li,
Na, K, Mg, Ca, Cl, NO3, and SO4 contents (Table 2). The
concentrations of lithium and magnesium in the brine of Uyuni,
Bolivia (Li = 1630 mg dm¹3, Mg = 29200 mg dm¹3) were very
high compared to the brine of China (Li = 280 mg dm¹3,
Mg = 1100 mg dm¹3).32
Rate of Lithium Adsorption. Time required to attain
equilibrium for lithium adsorption from brine is necessary
for selecting optimum operating conditions for batch experi-
ments. Figure 4 shows the rate of lithium adsorption from the
NaHCO3 containing brine on Mg-0.3(H). It was observed that
lithium adsorption increased with increase in time attaining
equilibrium in 24 h. Initial adsorption rate of lithium was slow
with 14 mg g¹1 in 1 h. It was apparent that equilibrium was
almost achieved in 24 h with lithium adsorptive capacity of
23 mg g¹1 at equilibrium pH 6.5, which was 61% of the theo-
retical adsorptive capacity of the sample. All the protons in the
sample cannot be re-exchanged for lithium ions because
lithium/proton exchange proceeds only to 60­70% on ion-
sieve manganese oxides.7,26 Prolonged standing up to 48 h did
not result in higher lithium adsorption. Based on the results,
contact time of 24 h was chosen as equilibrium time for
subsequent adsorption experiments.
854 Bull. Chem. Soc. Jpn. Vol. 86, No. 7 (2013)
30
Extraction of Li+ / mg g–1
20
10
0 0
0 12 24 36
Time / h
Figure 4. Rate of Li+ adsorption from the NaHCO3-added
brine on protonated sample Mg-0.3(H).
30
Amount of Li+ / mg g–1
20
10
0 0.0
0.0 0.1 0.2 0.3
Mg/Mn ratio
Figure 5. Adsorption of Li+ from the NaHCO3-added brine
on protonated samples with various Mg/Mn ratios, and
desorption of Li+ with HCl solution. ( ) Li+ adsorption,
( ) Li+ desorption, and ( ) dissolution of Mn2+.
The relatively high selectivity for lithium ions on Mg-0.3(H)
in the presence of high concentrations of sodium, potassium,
and magnesium can be well explained by the ion-sieve effect
of the spinel structure with (1 © 3) tunnels, which are suitable
in size for fixing lithium ions only.5 Although ionic radius of
magnesium (0.072 nm) is close to that of lithium (0.069 nm),
a high energy may be required for dehydration of magnesium
ions to enter tunnel sites of the Mg-0.3(H) because the free
energy of hydration for magnesium ions (¦Gh0 = ¹1980
kJ mol¹1) is 4 times greater than lithium ions (¦Gh0 = ¹475
kJ mol¹1).33
Lithium Adsorption/Desorption. The lithium adsorption
from the NaHCO3 containing brine and lithium desorption
with acid on the samples with different Mg/Mn molar ratios
is shown in Figure 5. Lithium adsorptive capacity increased
slightly from 19 mg g¹1 for Mg-0(H) to 23 mg g¹1 for Mg-
0.3(H). The lithium desorption from the samples was per-
formed with HCl solution. The amount of lithium desorption
was slightly higher than the amount of lithium adsorption
for Mg-0(H), Mg-0.1(H), and Mg-0.2(H), because the original
protonated sample contained lithium ions. The dissolution
Lithium Adsorption from Salt Lake Brine
30 60
Adsorption of Li+ / mg g–1
Recovery of Li + / %
20 40
10 20
0
48 60 0 10 20 30 40 50
Sample dose / g dm–3
Figure 6. Effect of sample dose on adsorption of Li+ from
the NaHCO3-added brine by protonated sample Mg-
0.3(H).
2.0
Dissolution of Mn2+ / wt%
of manganese in the samples decreased continuously with
1.5 increase in Mg/Mn ratio. The Mg-0.3(H) is chemically more
stable among the samples studied.
1.0 Effect of Sample Dose. Sample dose is an important
parameter because it determines the adsorptive capacity of the
sample for a given concentration of the ions. The dependence
0.5 of adsorptive capacity on sample dose was studied at different
amounts of Mg-0.3(H) varying from 10 to 40 g dm¹3 in the
NaHCO3 containing brine (Figure 6). The lithium recovery
increased from 17% to 58% by increasing the sample dose
0.4
from 10 to 40 g dm¹3. For the same initial concentration of
lithium, the number of exchange sites increased because of
the higher sample dose, and hence the lithium recovery (%)
increased. But the lithium adsorptive capacity (mg g¹1) did not
increase with increase in sample dose from 20 to 40 g dm¹3,
which can be related to the establishment of equilibrium
between the exchange sites of the sample and lithium ions in
solution.24 At equilibrium pH 6.5, the Mg-0.3(H) exhibited
lithium adsorptive capacity of 23 mg g¹1, which compared well
with that of magnesium manganese oxide spinels exhibiting
lithium adsorptive capacity of 20­22 mg g¹1 at pH 6­7 from
the single electrolyte (LiCl solution).21,24
Regeneration of the Sample. It is necessary to develop
the sample with a high lithium adsorptive capacity and high
chemical stability that can be effectively regenerated so that
the sample can be used with respect to practical applications.
The lithium adsorption from the NaHCO3 containing brine
on the Mg-0.3(H) was carried out. 0.50 mol dm¹3 HCl was used
to regenerate lithium from lithium adsorbed samples. Good
regeneration ability was achieved as seen from nearly constant
lithium adsorptive capacity of 23­25 mg g¹1 even after 10
adsorption/desorption cycles (Figure 7). More than 96­100%
of lithium was recovered in 10 cycles except in 3 and 5 cycles
(87­90%). The amount of residual manganese in the acidic
solution after lithium extraction was around 0.20 wt % Mn. The
XRD pattern of Mg-0.3 after 10 regenerations showed neither
weakening nor broadening of the peaks (Figure 1B, i) com-
pared to the original one (Figure 1B, h), which indicated the
stability of the sample.
R. Chitrakar et al.
30
Amount of Li+ / mg g–1
20
10
0 0.0
0 1 2 3 4 5 6 7 8 9 10 11
Cycle number
Figure 7. Regeneration of Mg-0.3(H). ( ) Li+ adsorption
from brine with added NaHCO3, ( ) Li+ desorption, and
( ) dissolution of Mn2+.
Conclusion
Among the protonated samples studied, magnesium-doped
manganese oxide with a composition of Li0.15H0.76Mg0.40-
MnIII0.08MnIV1.59O4 was effective for lithium adsorption from
salt lake brine. The rate of lithium adsorption from brine
containing added NaHCO3 was found to attain equilibrium in
24 h. The sample exhibited lithium adsorptive capacity of 23
mg g¹1 at pH 6.5. Regeneration study showed that the lithium
ions can be desorbed with HCl solution, and the efficiency of
adsorptive capacity of the sample did not decrease even after 10
cycles (23­25 mg g¹1). The magnesium-doped sample greatly
inhibited the dissolution of manganese. High concentrations of
sodium, potassium, and magnesium ions in the brine did not
affect the lithium adsorptive capacity of the sample, thereby
confirming lithium ion sieve property.
This work was supported by Japan Oil, Gas and Metals
National Corporation (JOGMEC).
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