materials

Article
Highly Efficient Lithium Recovery from
Pre-Synthesized Chlorine-Ion-Intercalated
LiAl-Layered Double Hydroxides via a Mild
Solution Chemistry Process
Ying Sun, Rongping Yun, Yufeng Zang, Min Pu and Xu Xiang *
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology,
Beijing 100029, China; 2017210404@mail.buct.edu.cn (Y.S.); yuanrp@mail.buct.edu.cn (R.Y.);
xiangxubuct@163.com (Y.Z.); pumin@mail.buct.edu.cn (M.P.)
* Correspondence: xiangxu@mail.buct.edu.cn; Tel.: +86-10-64425385




Received: 13 May 2019; Accepted: 17 June 2019; Published: 19 June 2019


Abstract: Lithium extraction from salt lake brine is critical for satisfying the increasing demand
of a variety of lithium products. We report lithium recovery from pre-synthesized LiAl-layered
double hydroxides (LDHs) via a mild solution reaction. Lithium ions were released from solid
LiAl-LDHs to obtain a lithium-bearing solution. The LiAl-LDHs phase was gradually transformed
into a predominantly Al(OH)3 phase with lithium recovery to the aqueous solution. The lithium
recovery percentage and the concentration of the lithium-bearing solution were dependent on
the crystallinity of LiAl-LDHs, the initial concentration of the LiAl-LDHs-1 slurry, the reaction
temperature, and the reaction time. Under optimized conditions, the lithium recovery reached 86.2%
and the Li+ concentration in the filtrate is 141.6 mg/L. Interestingly, no aluminum ions were detected
in the filtrate after solid–liquid separation with high crystallinity LiAl-LDHs, which indicated the
complete separation of lithium and aluminum in the liquid and solid phases, respectively. The 27 Al
NMR spectra of the solid products indicate that lithium recovery from the lattice vacancies of
LiAl-LDHs affects the AlO6 coordination in an octahedral configuration of the ordered Al(OH)3 phase.
The XPS O 1s spectra show that the Oad peak intensity increased and the OL peak intensity decreased
with the increasing lithium recovery, which indicated that the Al-OH bond was gradually formed
and the metal–oxygen–metal bond was broken.

Keywords: lithium recovery; LiAl-LDHs; reaction-coupled separation technology; salt lake brine

1. Introduction
Lithium is the lightest metal with high electrochemical potential and is commonly used in
lithium-ion batteries. Lithium-ion batteries are widely developed as efficient energy storage devices for
electronic products and electric vehicles because they have a high energy density [1]. Lithium demand
is expected to increase five-fold in the next decade [2]. Lithium-ion batteries account for 37% of the
rechargeable batteries in the global market, and 39% of lithium resources are used to produce and
manufacture batteries [3]. In 2019, global sales of electric vehicles (EVs) are likely to exceed 2.8 million
which is expected to account for 3% of the total passenger car market, of which 68% will be battery
electric vehicles (BEVs), and the rest will be plug-in hybrid electric vehicles (PHEVs) [4].
According to the US Geological Survey report in 2019, there are 62 million tons of lithium resources
worldwide, 70% of which are found in salt lakes [5,6]. In China, there are 4.5 million tons of lithium
resources, and 80% of them are contained in salt lake brine [7]. Therefore, extracting lithium from salt
lake brine is an important way to obtain lithium resources. The great challenge is the high Mg/Li ratio

Materials 2019, 12, 1968; doi:10.3390/ma12121968 www.mdpi.com/journal/materials

Materials 2019, 12, 1968 2 of 13

in extracting lithium from salt lake brine in China. Currently, calcination, adsorption, extraction, and
membrane
Materialstechnology
2019, 12, x FORare PEERthe available industrialized extraction methods. The calcination method
REVIEW 2 of 13 is
suitable for high-grade brines, but the extraction process consumes high energy and produces a large
amountthe ofhigh
HClMg/Li
gas [8]. ratio
The in adsorption
extracting lithium
methodfrom salt lake
involves + selectively
brine inLiChina.
adsorbing Currently,withcalcination,
adsorbent and
adsorption, itextraction,
then dissolving in acid toand separate Li+ from
membrane technology are the
other ions. availablemanganese-based
At present, industrialized extraction [9–11] and
methods. The calcination method is suitable for high-grade brines, but the extraction process
titanium-based [12,13] lithium-ion sieves have attracted the attention of researchers, and precursors
consumes high energy and produces a large amount of HCl gas [8]. The adsorption method involves
include LiMnO2 , +Li2 TiO3 , among others. The extraction method involves selective extraction of lithium
adsorbing Li selectively with adsorbent and then dissolving it in acid to separate Li+ from other
with organic
ions. At solvents.
present, The extractant with
manganese-based tributyl
[9–11] and phosphate
titanium-based(TBP)[12,13]
in methyl isobutylsieves
lithium-ion ketonehave(MIBK)
and the co-extractant with FeCl 3 have been extensively studied by researchers
attracted the attention of researchers, and precursors include LiMnO2, Li2TiO3, among others. The [14,15]. The membrane
method produces
extraction method ion involves
separation by an
selective electricoffield.
extraction lithiumA with
largeorganic
number of studies
solvents. on ion exchange
The extractant with
membranes
tributyl that can separate
phosphate (TBP) inand concentrate
methyl ions to(MIBK)
isobutyl ketone obtainand lithium-rich brine have
the co-extractant with gradually
FeCl3 have been
been
applied toextensively
the separation studied by researchers
of metal [14,15]. The membrane method produces ion separation by
ions [16,17].
an electricdouble
Layered field. Ahydroxides
large number of studies
(LDHs) are on ion exchange
a kind membranes
of intercalation that canand
material, separate and
the chemical
concentrate II ions to
III obtain lithium-rich
x+ n- brine have gradually been applied
formula is [M 1-x M x (OH)2 ] [A ]x/n ·mH2 O. A typical example is MgAl-layered double hydroxides to the separation of metal
ions [16,17].
(MgAl-LDHs), which have been widely used. The layer is formed by the uniform distribution of MgO6
Layered double hydroxides (LDHs) are a kind of intercalation material, and the chemical
and AlO6 octahedrons, possessing positive charge. The anions are intercalated into the interlayer,
formula is [MII1-x MIIIx(OH)2]x+[An-]x/n·mH2O. A typical example is MgAl-layered double hydroxides
having supramolecular interactions
(MgAl-LDHs), which have been widely with the layers
used. The to balance
layer the positive
is formed by the uniformchargedistribution
of the layers. of The
methods
MgO6 and AlO6 octahedrons, possessing positive charge. The anions are intercalated into the by
for preparing LDHs have been studied. Lee et al. reported the preparation of LDHs
hydration of itshaving
corresponding metal oxides (MgO andtheAllayers 2+ and Al(OH) - obtained
interlayer, supramolecular interactions with 2 O3 ) [18]. The Mg
to balance the positive charge4of the
by hydration
layers. The ofmethods
the metal foroxide wereLDHs
preparing incorporated
have beeninto the MgAl-LDHs
studied. Lee et al. reported structure. In addition,
the preparation of the
LDHs by hydration of its corresponding metal
preparation methods of LDHs were reviewed by Conterosito et al. [19].oxides (MgO and Al 2 O3 ) [18]. The Mg 2+ and Al(OH)4-

obtained
We recentlyby reported
hydrationa new of the metal oxide were
reaction-coupled incorporated
separation into thefor
technology MgAl-LDHs
extracting structure.
lithium from In salt
addition, the preparation methods of LDHs were reviewed by Conterosito
lake brine with a high Mg/Li ratio [20]. The layers of MgAl-LDHs consist of alternatively arranged MO6 et al [19].
We recently reported a new reaction-coupled separation technology for extracting lithium from
(M = Mg or Al) octahedrons. Due to a large distortion angle, Li+ cannot enter the MgAl-LDHs structure.
salt2+lake brine with a high Mg/Li ratio [20]. The layers of MgAl-LDHs consist of alternatively
The Mg and Li+ ions were separated efficiently, and MgAl-LDHs were prepared simultaneously.
arranged MO6 (M = Mg or Al) octahedrons. Due to a large distortion angle, Li+ cannot enter the
The mass ratio of Mg/Li in solution decreased significantly from
MgAl-LDHs structure. The Mg2+ and Li+ ions were separated efficiently, and MgAl-LDHs 12.66 to less than 0.1, and the lithium
were
loss rate was less
prepared than 10%. The
simultaneously. chemical
The mass ratio equations
of Mg/Li inare shown
solution in Equation
decreased (1) on the
significantly fromseparation
12.66 to of
magnesium and lithium from salt lake brine.
less than 0.1, and the lithium loss rate was less than 10%. The chemical equations are shown in
Equation (1) on the separation of magnesium and lithium from salt lake brine.
6Mg2+ +2AlCl3 +2+16NaOH + Na2 CO3 +mH2 O = Mg6 Al2 (OH)16 CO3 ·mH2 O +-6Cl− ++18Na+ (1)
6Mg +2AlCl3 +16NaOH+Na2 CO3 +mH2 O = Mg6 Al2 OH 16 CO3 ·mH2 O+6Cl +18Na (1)
LiAl-layered
LiAl-layered double hydroxides
double hydroxides(LiAl-LDHs)
(LiAl-LDHs) are are aa unique
uniquetype typeofofhydrotalcite.
hydrotalcite.TheThe chemical
chemical
namename(IUPAC)
(IUPAC) is lithium
is lithiumaluminum
aluminumchloride
chloride hydroxide hydrate. TheThe
hydroxide hydrate. general
general formula
formula is is
[LiAl[LiAl
(OH)2(OH)
]X n−
6]Xn−1/n·mH
·mH O,
2O, in
in which
which XXn-n-
is the
is anion,
the e.g.,
anion, CO
e.g., 2-, Cl2-
3CO -, NO3-
, Cl - ,. The
NO 3-
Al(OH)
. The with AlO
3 Al(OH) 6 with
2 6 1/n 2 3 3
AlO6 octahedrons
octahedrons contained ordered
contained vacancies.
ordered The lithium
vacancies. Theions entered
lithium ions theentered
vacancies, thewhich made the
vacancies, which
madelayer positively charged. The anions were intercalated into the interlayer to keep charge balance
the layer positively charged. The anions were intercalated into the interlayer to keep charge
[21–23]. The structural model of chlorine-ion-intercalated LiAl-LDHs is depicted in Scheme 1.
balance [21–23]. The structural model of chlorine-ion-intercalated LiAl-LDHs is depicted in Scheme 1.

Scheme 1. The structural model of chlorine-ion-intercalated LiAl-layered double hydroxides (LDHs)

(a) front view, (b) top view.
Materials 2019, 12, 1968 3 of 13

In this work, LiAl-LDHs were first synthesized from salt lake brine. The chemical composition
of the brine is shown in Table 1. Subsequently, Li+ ions were recovered from the pre-synthesized
LiAl-LDHs into an aqueous solution by mild chemical reaction. Equations (2) and (3) show the
synthesis of chlorine-ion-intercalated LiAl-LDHs and the lithium recovery process. The two successive
steps achieved the efficient extraction of lithium from salt lake brine. The effects of crystallinity of
LiAl-LDHs, slurry concentration, reaction temperature, and reaction time on the lithium recovery
percentage were discussed. Under the optimal conditions, the lithium recovery of LiAl-LDHs-1
prepared from the salt lake brine reached 86.2%, and the concentration of Li+ reached 141.6 mg/L. This
study provides an alternative pathway to efficiently extract and recover lithium from salt lake brine.

Li+ +2AlCl3 +6NaOH + mH2 O = LiAl2 (OH)6 Cl·mH2 O + 5Cl− +6Na+ (2)

LiAl2 (OH)6 Cl·mH2 O = Li+ +Cl− +2Al(OH)3 +mH2 O (3)

Table 1. The chemical composition of the brine after separating Mg2+ ions [24].

Mg2+ Li+ K+ Na+ B2 O3 Cl- SO4 2- CO3 2-

Concentration (g/L) 0.054 0.675 0.84 32.9 1.73 42.87 3.29 8.57

2. Materials and Methods

2.1. Materials
AlCl3 ·6H2 O was purchased from Aladdin Industrial Corporation (Shanghai China). NaOH was
obtained from Beijing Chemical Corporation Ltd. (Beijing China).

2.2. Synthesis
The Mg2+ and Li+ ions are separated from salt lake brine by reaction-coupled separation technology
to obtain the solution, i.e., the brine after separating Mg2+ ions [25]. The method for separating Mg2+
and Li+ is shown in the Supplementary Materials.
Solution A: AlCl3 ·6H2 O had a concentration of 46.96 g/L was dissolved in the brine of 1 L
after separating Mg2+ ions. The molar concentration of the relationship was [Li+ ]:[Al3+ ] = 1:2. By
evaporation and concentration, varied initial Li+ concentrations were obtained. Solution B: NaOH was
dissolved in deionized water to form a clear solution in which the [NaOH] = 2 mol/L. Solution B was
dropped into solution A to keep the pH value at 7 during the reaction in the crystallization reactor.
The deionized water used in the experiment was boiled and cooled to room temperature. Nitrogen gas
was introduced into the reaction process to remove the influence of CO3 2- on the experimental results.
The slurry was aged in a crystallization reactor at 80 ◦ C for 12 h. The solid products obtained were
LiAl-LDHs following filtration, washing, and drying.
LiAl-LDHs were dispersed in deionized water and heated in an oil bath at varied initial Li+
concentrations, slurry concentrations, recovery temperature, and recovery time. The solid product was
recovered by filtration, washing, and drying, and the liquid phase was a lithium-bearing solution.
The lithium recovery from pre-synthesized LiAl-layered double hydroxides is shown in Scheme 2.
Materials 2019, 12, 1968 4 of 13
Materials 2019, 12, x FOR PEER REVIEW 4 of 13

Scheme 2. Flowchart of lithium recovery from pre-synthesized LiAl-layered double hydroxides.

Scheme 2. Flowchart of lithium recovery from pre-synthesized LiAl-layered double hydroxides.
2.2.1. Crystallinity of LiAl-LDHs
2.2.1. Crystallinity of LiAl-LDHs
By evaporation and concentration, the concentration of lithium ions in the brine after separating
By evaporation and concentration, the concentration of lithium ions in the brine after separating
Mg2+ 2+ions reached 6.75 g/L, 3.375 g/L, and 1.6875 g/L. Preparation of LiAl-LDHs under the above
Mg ions reached 6.75 g/L, 3.375 g/L, and 1.6875 g/L. Preparation of LiAl-LDHs under the above
conditions was defined as LiAl-LDHs-1, LiAl-LDHs-2, and LiAl-LDHs-3, respectively. LiAl-LDHs were
conditions was defined as LiAl-LDHs-1, LiAl-LDHs-2, and LiAl-LDHs-3, respectively. LiAl-LDHs
dispersed in water with a slurry concentration (LDHs (g)/water (L) ratio) of 10 g/L. The temperature
were dispersed in water with a slurry concentration (LDHs (g)/water (L) ratio) of 10 g/L. The
and time of the thermal reaction were 85 ◦ C and 90 min, respectively.
temperature and time of the thermal reaction were 85 °C and 90 min, respectively.

2.2.2. Slurry Concentration of LiAl-LDHs-1

Materials 2019, 12, 1968 5 of 13

2.2.2. Slurry Concentration of LiAl-LDHs-1

LiAl-LDHs-1 were dispersed in water at slurry concentrations of 10, 20, 30, or 50 g/L at 85 ◦ C for
90 min.

2.2.3. Lithium Recovery Temperature

LiAl-LDHs-1 were dispersed in water at a slurry concentration of 10 g/L. The temperature of the
thermal reaction was 65, 75, 85, or 95 ◦ C. The reaction time was 90 min.

2.2.4. Lithium Recovery Time

LiAl-LDHs-1 were dispersed in water at a slurry concentration of 10 g/L at 85 ◦ C. The reaction
time was set at 30, 60, 90, or 120 min.

2.3. Analysis
The X-ray diffraction patterns were obtained from XRD-6000 diffractometer (Shimadzu, Kyoto,
Japan) in which the radiation was Cu Kα radiation at a sweep speed of 10◦ /min from 3◦ to 70◦ .
The Cl and C elements mass percentage were determined by ion chromatography (ICS-5000,
ThermoFisher Scientific, Waltham, MA, USA) and elemental analysis (vario EL CUBE, elementar
Analysensysteme GmbH, Langenselbold, Germany).
The solid sample was dispersed with ethanol and dripped onto a carbon-coated Cu grid, and the
morphology of the sample was observed using transmission electron microscopy (HT7700, Hitachi,
Tokyo, Japan).
Solid-state nuclear magnetic resonance examined the coordination information of 27 Al and 7 Li
using NMR equipment (AV300, Bruker BioSpin GmbH, Rheinstetten, Germany).
The composition and chemical structure of LiAl-LDHs and solid products after lithium recovery
were characterized by X-ray photoelectron spectroscopy (ESCALAB 250, ThermoFisher Scientific,
Waltham, MA, USA).
The concentration of the metal ion to be measured in solid and liquid phase products was
diluted to 0–100 ppm to detect lithium ions and aluminum ions by inductively coupled plasma mass
spectrometry (ICPS-7500 from Shimazduo, Kyoto, Japan). The formulas for Li+ concentration in the
filtrate, lithium recovery percentage, and Al3+ dissolution percentage are shown in the Supplementary
Materials Calculation Section.

3. Results and Discussion

LiAl-LDHs with varied initial Li+ concentrations were prepared from salt lake brine. The chemical
compositions of the prepared LiAl-LDHs are listed in Table 2. The Li/Al molar ratio of LiAl-LDHs-1,
LiAl-LDHs-2, and LiAl-LDHs-3 were 1:2.00, 1:2.02, and 1:2.14, respectively, which are consistent with
stoichiometry. The mass percentage of Cl element was 14.05%, 14.02%, and 13.89%, and the Li/Cl
molar ratio was 1.00. The Cl/C molar ratio of LiAl-LDHs-1, LiAl-LDHs-2, and LiAl-LDHs-3 were
9.90, 9.88, and 9.80, respectively (Table 2), which indicated that the amount of CO3 2- in LiAl-LDHs
was negligible. The XRD pattern (Figure 1) demonstrated that the diffraction line was consistent with
planes (002), (101), (004), (112), (106), (008), (303), and (1010) of [LiAl2 (OH)6 ]Cl·xH2 O (JCPDS Card No.
51-0357) [25,26]. The chlorine-ion-intercalated LiAl-layered double hydroxides were prepared via a
mild solution chemistry process from salt lake brine. The higher the lithium ion concentration, the
sharper the diffraction peak, which indicated that the crystallinity of LiAl-LDHs-1, LiAl-LDHs-2, and
LiAl-LDHs-3 decreased in turn. As shown in Figure 2, the crystal growth of LiAl-LDHs was complete
and displayed a hexagonal sheet morphology, which is characteristic of LDHs, and the crystallization
is consistent with the XRD pattern [27,28]. The 27 Al NMR spectra (Figure S1) of LiAl-LDHs-1 revealed
a chemical shift of 27 Al as 6.39 ppm; that is, the Al environment was six-coordinated Al [29]. This
result was consistent with researchers’ understanding of LiAl-LDHs [26]. The XPS O 1s spectra of
Materials 2019, 12, 1968 6 of 13

LiAl-LDHs-1 (Figure
Materials 2019, 12, S2) were
x FOR PEER divided into three peaks with binding energies of 532.5, 531.9, and6 of
REVIEW 531.3
13
Materials 2019, 12, x FOR PEER REVIEW 6 of 13
eV. These binding energies were attributed to H2 O(Ow ), OH- (Oad ), and O2- (OL ), respectively [30].
Table 2. The chemical compositions of the prepared LiAl-LDHs.
Table 2. The chemical compositions of the prepared LiAl-LDHs.
Table 2. The chemical compositions of the prepared LiAl-LDHs.
LiAl-LDHs-1 LiAl-LDHs-2 LiAl-LDHs-3
Li (wt%) LiAl-LDHs-1
2.75 LiAl-LDHs-2
2.74 LiAl-LDHs-3
2.72
LiAl-LDHs-1 LiAl-LDHs-2 LiAl-LDHs-3
Li
Al (wt%)(wt%) 21.372.75 21.53 2.74 22.63 2.72
Li (wt%) 2.75 2.74 2.72
Al
Cl(wt%) (wt%)
(wt%) 21.37
14.05 14.02 21.53 13.89 22.63
Al 21.37 21.53 22.63
Cl Cl (wt%)
C (wt%)
(wt%) 14.05
0.48
14.05 0.48 14.02
14.02 0.47 13.89
13.89
Li/Al C (wt%)
C molar
(wt%) ratio 0.48
0.48
1:2.00 0.480.48
1:2.02 0.47
0.47
1:2.14
Li/Al
Li/Al molar
molar ratio
Cl/C molar ratio ratio 1:2.00
1:2.00
9.91 1:2.02
1:2.02
9.89 1:2.14
1:2.14
9.80
Cl/C molar
Cl/C ratioratio
molar 9.91 9.89 9.80
Li/Cl molar ratio 1.009.91 1.009.89 1.00 9.80
Li/Cl molar ratio 1.00 1.00 1.00
Li/Cl molar ratio 1.00 1.00 1.00

Figure 1. XRD patterns of LiAl-LDHs prepared from brine at varied initial Li+ concentrations (a) 6.75
Figure XRDg/L,
(b)1.3.375
g/L,Figure patterns1.6875
of LiAl-LDHs prepared from brine at varied initial Li+ concentrations (a) 6.75 g/L,
1. XRD (c)
patterns of g/L.
LiAl-LDHs prepared from brine at varied initial Li+ concentrations (a) 6.75
(b) 3.375 g/L, (c) 1.6875 g/L.
g/L, (b) 3.375 g/L, (c) 1.6875 g/L.

Figure2.2.TEM
Figure TEMmicrographs
micrographsofofLiAl-LDHs
LiAl-LDHsatatvaried
varied Li+Liconcentrations
initial
initial + concentrations (a) 6.75 g/L, (b) 3.375
(a) 6.75 g/L, (b) 3.375 g/L,
g/L, (c) 1.6875
(c) 1.6875 g/L. g/L.
Figure 2. TEM micrographs of LiAl-LDHs at varied initial Li+ concentrations (a) 6.75 g/L, (b) 3.375
3.1. g/L, (c) 1.6875
3.1. Crystallinity
Crystallinity of g/L.
of LiAl-LDHs
LiAl-LDHs
The
The
3.1. effect
effectof
ofthe
Crystallinity of thermal
the thermal reaction
LiAl-LDHs reaction of LiAl-LDHs
LiAl-LDHs with with different
different crystallinity
crystallinityon onlithium
lithiumrecovery
recovery
was studied. Figure 3
was studied. Figure 3 showsshows the XRD pattern of solid products after lithium recovery by
of solid products after lithium recovery by the thermal the thermal
reaction. The effect of the thermal reaction of LiAl-LDHs with different crystallinity on lithium recovery
reaction.The
Theposition
positionofofthethediffraction
diffractionpeak
peakofof
thethethermally
thermally reacted
reactedsolid product
solid productof LiAl-LDHs
of LiAl-LDHs was
was studied.
consistent Figure
with with
Al(OH) 3 shows the XRD pattern of solid products after lithium recovery by the
Li thermal
+
was consistent 3 as a3 gibbsite
Al(OH) phase
as a gibbsite (JCPDS
phase CardCard
(JCPDS No. 33-0018)
No. 33-0018)[31],[31],
indicating thatthat
indicating was
Li+
reaction.
released The position of the diffraction peak of the thermally reacted solid
◦ and
was released from the solid product. The diffraction peaks are different at 2theta 36° and 63° inas
from the solid product. The diffraction peaks are different at 2theta 36 product
63 of LiAl-LDHs
◦ in Figure 3,
was 3,
Figure consistent withcannot
as such they Al(OH) as a as
be3used gibbsite phase
evidence (JCPDS Card
for identifying No. 33-0018)
substances because[31], indicating
they that Li+
are weaker
was released
diffraction from
signals. In the
ordersolid
to product. The diffraction
further discuss peaks arebetween
the relationship differentlithium
at 2theta 36° and
recovery and63° in
Figure 3, as such they cannot be used as evidence for identifying substances because they are weaker
diffraction signals. In order to further discuss the relationship between lithium recovery and
Materials 2019, 12, 1968 7 of 13

Materials 2019, 12, x FOR PEER REVIEW 7 of 13

such they cannot be used as evidence for identifying substances because they are weaker diffraction
signals. In order
crystallinity, to further
we studied thediscuss
changesthe
in relationship between
Li+ concentration lithium
in the recovery
filtrate, and crystallinity,
the chemical we
shift of 27Al,
studied the changes 27
and binding energy. in Li+ concentration in the filtrate, the chemical shift of Al, and binding energy.

Figure 3. XRD patterns of solid products after lithium recovery from LiAl-LDHs at varied initial Li+
Figure 3. XRD patterns of solid products after lithium recovery from LiAl-LDHs at varied initial Li+
concentrations (a) 6.75 g/L, (b) 3.375 g/L, (c) 1.6875 g/L (N Al(OH)3 ).
concentrations (a) 6.75 g/L, (b) 3.375 g/L, (c) 1.6875 g/L (▲ Al(OH)3).
The concentration of Li+ in the filtrate decreased with the decreasing of crystallinity because
The concentration of Li+ in the filtrate decreased with the decreasing of crystallinity because the
the amount of Li+ extracted decreased from LiAl-LDHs (Table 3). Because of the low crystallinity,
amount of Li extracted decreased from LiAl-LDHs (Table 3). Because of the low crystallinity, the
+
the distortion of AlO6 octahedrons occurred. The Al-O chemical bonds were broken under the mild
distortion of AlO6 octahedrons occurred. The Al-O chemical bonds were broken under the mild
chemistry process, allowing a small amount of Al3+ to be dissolved in the solution.
chemistry process, allowing a small amount of Al3+ to be dissolved in the solution.
Table 3. Analyses on the solution after lithium recovery from LiAl-LDHs at varied initial
Table 3. Analyses on the solution after lithium recovery from LiAl-LDHs at varied initial Li+
Li+ concentrations.
concentrations.
Lithium Recovery Li+ Concentration Al3+ Dissolution
Sample Lithium Recovery Li + Concentration Al 3+ Dissolution
Sample Percentage (%) in Filtrate (mg/L) Percentage (%)
Percentage (%) in Filtrate (mg/L) Percentage (%)
LiAl-LDHs-1 86.2 141.6 -
LiAl-LDHs-1
LiAl-LDHs-2 86.2
66.6 141.6
127.4 - -
LiAl-LDHs-2
LiAl-LDHs-3 66.6
56.2 127.4
107.4 - 0.32
LiAl-LDHs-3 56.2 107.4 0.32
The weight of LiAl-LDHs is 1 g. The volume of the solution after
The weight of LiAl-LDHs is 1 g. The volume of the solution after the experiment the experiment is 167is mL,
167 143
mL,
mL, and 142 mL for LiAl-LDHs-1, LiAl-LDHs-2, and LiAl-LDHs-3,
143 mL, and 142 mL for LiAl-LDHs-1, LiAl-LDHs-2, and LiAl-LDHs-3, respectively. respectively.
The
The dissolution
dissolution of of Li
Li+ with
+
with Cl Cl- from
-
from LiAl-LDHs
LiAl-LDHs intointo aqueous
aqueous solution
solution changes
changes thethe Al-O
Al-O
coordination environment of solid products after lithium recovery. The recovery
coordination environment of solid products after lithium recovery. The recovery rate of lithium rate of lithium from
LiAl-LDHs-1
from LiAl-LDHs-1reached 86.2%86.2%
reached to deform the Al-O
to deform octahedron
the Al-O [32], and
octahedron [32],the
andchemical shift shift
the chemical of 27Al
of was
27 Al
shifted from 6.39 ppm (27Al27 chemical shift of LiAl-LDHs-1, Figure S1) to the low-field
was shifted from 6.39 ppm ( Al chemical shift of LiAl-LDHs-1, Figure S1) to the low-field by 0.32 ppm by 0.32 ppm
(Figure 4). Moreover,
(Figure 4). Moreover,the the chemical
chemical shifts
shifts of LiAl-LDHs-2
of LiAl-LDHs-2 and LiAl-LDHs-3
and LiAl-LDHs-3 were to
were shifted shifted to the
the low-field
low-field by 0.24 and 0.09 ppm, respectively. The chemical
27 shift of 27Al was shifted towards the
by 0.24 and 0.09 ppm, respectively. The chemical shift of Al was shifted towards the low-field with
low-field
increasingwith increasing
crystallinity crystallinity Larger
of LiAl-LDHs. of LiAl-LDHs. Larger lithium
lithium recovery recovery
percentage lead topercentage lead toon
a greater impact a
greater
aluminumimpact on aluminum coordination.
coordination.
Materials 2019, 12, 1968 8 of 13
Materials 2019, 12, x FOR PEER REVIEW 8 of 13
Materials 2019, 12, x FOR PEER REVIEW 8 of 13

Figure
Figure 4.4.27
4. 27AlAl
27 NMR
AlNMR spectra
NMRspectra of
of the
spectra of the solid
solid products afterlithium
products after lithiumrecovery
recoveryfrom
fromLiAl-LDHs
LiAl-LDHs
at at
LiAl-LDHs varied
varied
varied
initial +
LiLiconcentrations
initial + +concentrations (a)
concentrations(a) 6.75
(a)6.75 g/L,
6.75 g/L,
g/L, (b)
(b) 3.375 g/L, (c)
3.375 g/L, (c)1.6875
1.6875g/L.
g/L.

As
AsAs the
the thermal
thethermal reaction
thermalreaction proceeded,
reactionproceeded,
proceeded, the thebinding
bindingenergy
binding energy
energy ofofof
OO1sO1schanged
1schanged
changed duedue due
to to
theto
the the conversion
conversion
conversion of of
of solids
solids
solidsfrom from
from LiAl-LDHs
LiAl-LDHs
LiAl-LDHs to Al(OH)
totoAl(OH)
Al(OH) 33.. The
The3 . XPS
TheO OXPS O 1s spectra
1s spectra
1s spectra ofofthe
thesolidof the
solid solid after
products
products products
after after
lithium
lithium lithium
recovery
recovery
recovery
(Figure5)(Figure
(Figure 5)was 5) wasinto
wasdivided
divided divided
threeinto
into three three
peaks
peaks with
withpeaks withenergies
binding
binding bindingofof
energies energies
533.2(O
533.2(O Wof 533.2(O
),W),531.8(O
531.8(O W
ad ),and
),ad),531.8(O
531.3
and ad ),
531.3
and
eV(O 531.3
eV(OL) L) eV(O
[33].
[33]. L ) [33].
Since
Since the Since
the the Ow was
OOww intensity
intensity intensity was
greatly
greatly greatlyby
affected
affected affected
by the by the
thedrying
drying drying condition,
condition,
condition, it it
will itbe
notnot
will will
be
not be discussed
discussed here. here.
Compared Compared
with with
LiAl-LDHs-1 LiAl-LDHs-1
(Figure (Figure
S2), the OS2), the
peak
discussed here. Compared with LiAl-LDHs-1 (Figure S2), the Oad peak intensity of the solid product
ad O peak
intensity
ad ofintensity
the solid of the
product solid
after
product
after lithium
lithium recoveryrecovery
after recovery
lithium increased,
increased, and the
increased,
and the OO L peak
and the intensity
L peak OL peakdecreased,
intensity which
whichmeant
intensity decreased,
decreased, meant that
which the
that metal
meant
the that
metal
thehydroxides or
metal hydroxides
hydroxides the hydroxyl
or the hydroxyl group
or the group
hydroxyl gradually increased
group gradually
gradually and the
increased increased metal–oxygen–metal
and the metal–oxygen–metal
and the metal–oxygen–metal bond gradually
bond gradually bond
broke.
gradually This result
broke. is
This consistent
result is with the
consistent process
with of
the forming
process Al(OH)
of 3 fromAl(OH)
forming
broke. This result is consistent with the process of forming Al(OH)3 from LiAl-LDHs. In Figure 5, the LiAl-LDHs. 3 from In Figure
LiAl-LDHs.5, the In
solid5,product
Figure the solid after lithium
product after recovery
lithium tends to tends
recovery form toAl(OH)
form 3 when the
Al(OH) when crystallinity
the degree
crystallinity of
degree
solid product after lithium recovery tends to form Al(OH)3 when 3 the crystallinity degree of
of LiAl-LDHs
LiAl-LDHs increased.
increased.
LiAl-LDHs increased.

Figure
Figure XPS
5. 5. OO
XPS 1s 1s
spectra of the
spectra solid
of the products
solid after
products lithium
after recovery
lithium from
recovery LiAl-LDHs
from at varied
LiAl-LDHs initial
at varied
Li+initial
concentrations (a) 6.75 g/L, (b) 3.375 g/L, (c) 1.6875 g/L.
Li concentrations (a) 6.75 g/L, (b) 3.375 g/L, (c) 1.6875 g/L.
+

Figure 5. XPS O 1s spectra of the solid products after lithium recovery from LiAl-LDHs at varied
initial Li+ concentrations (a) 6.75 g/L, (b) 3.375 g/L, (c) 1.6875 g/L.
Materials 2019, 12, 1968 9 of 13
Materials 2019, 12, x FOR PEER REVIEW 9 of 13

3.2.
3.2.Slurry
SlurryConcentration
ConcentrationofofLiAl-LDHs-1
LiAl-LDHs-1
Lithium
Lithiumions ionswere
were extracted
extractedfrom
from LiAl-LDHs-1
LiAl-LDHs-1at atdifferent
different slurry
slurry concentrations
concentrations ranging rangingfrom
from
10
10 g/L
g/L to
to 50
50 g/L.
g/L. AtAt 10
10 g/L, the diffraction line can be indexed indexed to to the
the planes
planes (002),
(002), (110),
(110), (022),
(022), and
and
(324)
(324) of
of Al(OH)
Al(OH)33 (JCPDS
(JCPDSCard Card No.
No. 33-0018)
33-0018)in inthe
the XRD
XRD patterns
patterns [34,35].
[34,35]. As Asthe
the slurry
slurry concentration
concentration
increased,
increased, thethe dissolution
dissolution of Li++from
of Li fromthetheLiAl-LDHs-1
LiAl-LDHs-1became
becamemore moreincomplete,
incomplete,as as the
the LiAl-LDHs
LiAl-LDHs
phase
phase existed
existed at at 2theta 11.59◦ , 23.21°,
2theta 11.59°, 23.21◦ ,35.74°,
35.74◦ ,63.20°,
63.20◦ ,and 64.43◦(Figure
and64.43° (FigureS3).S3).
Figure
Figure 66 shows
shows the the effects
effects of
of slurry
slurry concentration
concentration on on the
the lithium
lithium recovery
recovery percentage
percentage and and Li++
concentration
concentration in inthethe filtrate,
filtrate, which which is consistent
is consistent with XRD with
data.XRDWithdata. Withslurry
increasing increasing slurry
concentration,
concentration, the lithium
the lithium recovery recovery
percentage percentage
decreased, on thedecreased, Li+the
contrary, on contrary, Liin
concentration + concentration in the
the filtrate increased
filtrate increased
gradually. gradually.
The lithium The lithium
recovery recovery
percentage waspercentage
86.2%, andwas the86.2%, +
and the concentration
concentration of Li in the liquidof Li+
in the liquid
phase phase
was 141.6 waswhen
mg/L 141.6the
mg/L when
slurry the slurry concentration
concentration was 10 g/L.toContinuing
was 10 g/L. Continuing increase thetoamount
increase of
the amount
reactants (50ofg/L)
reactants
caused(50 theg/L) caused
lithium the lithium
recovery recovery
percentage to bepercentage
only 35.4%,tobut be the
only +
Li35.4%, but the Liin
concentration +

concentration in the318.3
the filtrate reached filtrate reached
mg/L. 318.3 mg/L.
According According
to Equation to increase
(3), the Equationof(3), the increase
product of product
concentration will
concentration
affect the balancewillofaffect the balance
reaction, and the of reaction,
amount and thedissolved
of lithium amount of lithium
from dissolved
the solid phase from the solid
decreases, thus
phase decreases,
the lithium recovery thus the lithium
percentage recovery
decreased. Al3+
percentage decreased.
was not detected in theAldetection
3+ was not detected
limit by ICP,insothe
the
detection
lithium ion limit by ICP,
solution so theimpure
without lithiumions
ionwas solution without
obtained, whichimpure
led toions was obtained,
the extraction which led to
and enrichment of
the extraction
lithium andlake
from salt enrichment
brine. of lithium from salt lake brine.

.
Figure 6. Lithium recovery percentage (round symbol) and Li+
concentration in the filtrate (triangle
symbol) from LiAl-LDHs-1 slurry at varying concentrations of 10 g/L, 20 g/L, 30
Figure 6. Lithium recovery percentage (round symbol) and Li concentration
+ in g/L, 50 g/L. (triangle
the filtrate
symbol) from LiAl-LDHs-1 slurry at varying concentrations of 10 g/L, 20 g/L, 30 g/L, 50 g/L.
The chemical shift of 27 Al varies with the slurry concentration according to NMR. The chemical
shiftThe
waschemical
6.07, 6.30,shift
6.32,ofand 6.38
27Al ppmwith
varies at 10the
g/L, 20 g/L,
slurry 30 g/L, and 50
concentration g/L, respectively
according to NMR.(Figure S4) [36].
The chemical
This change was affected by the lithium recovery percentage, which was the same trend
shift was 6.07, 6.30, 6.32, and 6.38 ppm at 10 g/L, 20 g/L, 30 g/L, and 50 g/L, respectively (Figure S4)as shown in
Figure 4. The chemical shift was clearly more biased toward the low-field with the
[36]. This change was affected by the lithium recovery percentage, which was the same trend as increase in lithium
recovery
shown percentage
in Figure 4. The(i.e., decreased
chemical shift slurry concentration),
was clearly more biasedwhich meant
toward that the LiAl-LDHs
the low-field phase
with the increase
converted more to the Al(OH)
in lithium recovery percentage 3 phase.
(i.e., decreased slurry concentration), which meant that the
LiAl-LDHs phase converted more to the Al(OH)3 phase.
3.3. Lithium Recovery Temperature
3.3. Lithium Recovery
Lithium-ion Temperature
extraction at different reaction temperatures was investigated. With increasing
reaction temperature, the LiAl-LDHs phase gradually disappeared, showing the Al(OH)3 phase
Lithium-ion extraction at different reaction temperatures was investigated. With increasing
(Figure S5). No other phase was detected at 85 ◦ C and 95 ◦ C.
reaction temperature, the LiAl-LDHs phase gradually disappeared, showing the Al(OH)3 phase
The temperature dependence of the lithium recovery percentage was investigated over the range
(Figure S5). No other phase was detected at 85 °C and 95 °C.
of 65 ◦ C to 95 ◦ C (Figure 7). At lower temperatures (65–75 ◦ C), the lithium recovery percentage is more
The temperature dependence of the lithium recovery percentage was investigated over the
sensitive to temperature, so the lithium recovery percentage increased rapidly as the temperature rose.
range of 65 °C to 95 °C (Figure 7). At lower temperatures (65–75 °C), the lithium recovery percentage
At 95 ◦ C, the chemical reaction reached equilibrium, that is, the amount of lithium dissolved from the
is more sensitive to temperature, so the lithium recovery percentage increased rapidly as the
temperature rose. At 95 °C, the chemical reaction reached equilibrium, that is, the amount of lithium
Materials
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2019, 12,
12, x1968
FOR PEER REVIEW 10
10 of
of 13
13

dissolved from the solid phase was balanced with the amount of lithium entering the vacancy of
solid phase
Al(OH) was
3. The balanced
lithium with the
recovery amount ofand
percentage lithium entering the vacancy
Li+ concentration in the of Al(OH)
filtrate 3 . The
were no lithium
longer
recovery percentage and Li+ concentration in the filtrate were no longer increased.
increased.

.
Figure 7. Lithium recovery percentage (round symbol) and Li+
concentration in the filtrate (triangle
symbol) from LiAl-LDHs-1 at varied recovery temperatures of 65 ◦ C, 75 ◦ C, 85 ◦ C, 95 ◦ C.
Figure 7. Lithium recovery percentage (round symbol) and Li concentration
+ in the filtrate (triangle
symbol) from LiAl-LDHs-1 at varied recovery temperatures of 65 °C, 75 °C, 85 °C, 95 °C.
In the NMR spectra (Figure S6A), the peaks corresponding to the chemical shift of 27 Al in the solid
productIn theafter
NMRlithium
spectrarecovery
(Figurewere
S6A),6.35,
the6.19, 6.07 ppm at 65to◦ C,
andcorresponding
peaks
◦ C, and 85 ◦ C, respectively.
the75chemical shift of 27Al in the
The main peakafter
of the 27 Al NMR spectra was6.35,
6 ppm at 95 ◦
solid product lithium recovery were 6.19, andC,6.07
andppm
a peakat appeared
65 °C, 75 with a relatively
°C, and 85 °C,
broad low-frequency shoulder at 1.29 ppm (Figure S6B) [37]. This phenomenon
respectively. The main peak of the Al NMR spectra was 6 ppm at 95 °C, and a peak appeared with
27 was consistent with
a
the literature where Al(OH)
relatively broad low-frequency 3 as gibbsite phase had a shoulder peak [38]. With increasing
shoulder at 1.29 ppm (Figure S6B) [37]. This phenomenon was temperature,
the solid product
consistent with the was transformed
literature whereto Al(OH)
the Al(OH) phase, where the amount of Li+ dissolved with
3 as 3gibbsite phase had a shoulder peak [38]. With
-
Cl from LiAl-LDHs-1
increasing temperature,increased;
the solid in other words,
product the lithiumtorecovery
was transformed percentage
the Al(OH) increased. Through
3 phase, where the amount
the lithium recovery percentage, the requirements of lithium recovery
of Li+ dissolved with Cl- from LiAl-LDHs-1 increased; in other words, the lithium could be met at a temperature
recovery
of 85 ◦ C and 95 ◦ C. Obviously, nearly the same effect was achieved at 95 ◦ C and reduced energy
percentage increased. Through the lithium recovery percentage, the requirements of lithium
consumption was achieved at 85 ◦ C.
recovery could be met at a temperature of 85 °C and 95 °C. Obviously, nearly the same effect was
achieved at 95 °C and reduced energy consumption was achieved at 85 °C.
3.4. Lithium Recovery Time
3.4. Lithium Recovery
The reaction Time
time determines the degree of the reaction. The XRD patterns (Figure S7) show that
the LiAl-LDHs phase gradually disappears with increasing reaction time from 30 min to 120 min.
The reaction time determines the degree of the reaction. The XRD patterns (Figure S7) show that
After 90 min of reaction, a sharp and high-intensity Al(OH) characteristic diffraction peak appeared
the LiAl-LDHs phase gradually disappears with increasing3 reaction time from 30 min to 120 min.
with planes of (002), (110), (022), and (324). The effect of time on the lithium recovery percentage was
After 90 min of reaction, a sharp and high-intensity Al(OH)3 characteristic diffraction peak appeared
consistent with the temperature, as lithium recovery percentage increases with increasing reaction
with planes of (002), (110), (022), and (324). The effect of time on the lithium recovery percentage was
time. The reaction was essentially complete after 90 min because the lithium recovery percentage no
consistent with the temperature, as lithium recovery percentage increases with increasing reaction
longer increased (Figure 8). The Li+ concentration was 141.6 mg/L and 142.0 mg/L in the liquid phase
time. The reaction was essentially complete after 90 min because the lithium recovery percentage no
at 90 min and 120 min, respectively. No Al3+ dissolution was observed within the detection limit.
longer increased (Figure 8). The Li+ concentration was 141.6 mg/L and 142.0 mg/L in the liquid phase
Within the range of error, we consider that the Li+ concentration in the filtrate is the same with reaction
at 90 min and 120 min, respectively. No Al3+ dissolution was observed within the detection limit.
times of 90 min and 120 min.
Within the range of error, we consider that the Li+ concentration in the filtrate is the same with
reaction times of 90 min and 120 min.
Materials 2019, 12, 1968 11 of 13
Materials 2019, 12, x FOR PEER REVIEW 11 of 13

.
Figure 8. Lithium recovery percentage (round symbol) and Li+
concentration in the filtrate (triangle
symbol) from LiAl-LDHs-1 at varied recovery times of 30 min, 60 min, 90 min, in
Figure 8. Lithium recovery percentage (round symbol) and Li concentration
+ 120 min.
the filtrate (triangle
symbol) from LiAl-LDHs-1 at varied recovery times of 30 min, 60 min, 90 min, 120 min.
We repeated the experiments and analyzed the data under the varying concentrations, recovery
temperatures, andthe
We repeated recovery times (Tables
experiments S1–S3).the
and analyzed Thedata
results arethe
under repeatable.
varying concentrations, recovery
temperatures, and recovery times (Tables S1–S3). The results are repeatable.
4. Conclusions
Lithium was extracted from LiAl-LDHs prepared from salt lake brine using reaction-coupled
4. Conclusions
separation technology. Lithium was released from the lattice vacancies of the ordered AlO6 octahedrons
Lithium was extracted from LiAl-LDHs prepared from salt lake brine using reaction-coupled
in pre-synthesized LiAl-Cl-LDHs. Lithium and aluminum were effectively separated to obtain a pure
separation technology. Lithium was released from the lattice vacancies of the ordered AlO6
lithium salt solution, which can be used in industrial production. As the crystallinity of LiAl-LDHs
octahedrons in pre-synthesized LiAl-Cl-LDHs. Lithium and aluminum were effectively separated to
decreased, the lithium recovery percentage decreased. Al3+ was detected to be dissolved in the
obtain a pure lithium salt solution, which can be used in industrial production. As the crystallinity of
liquid phase due to the Al-O bonds being more easily broken during the thermal reaction with low
LiAl-LDHs decreased, the lithium recovery percentage decreased. Al3+ was detected to be dissolved
crystallinity LiAl-LDHs. The slurry concentration had an opposite effect on the lithium recovery
in the liquid phase due+to the Al-O bonds being more easily broken during the thermal reaction with
percentage and the Li concentration in the filtrate. The lithium recovery percentage decreased
low crystallinity LiAl-LDHs. The slurry concentration had an opposite effect on the lithium recovery
as the slurry concentration increased because the lithium-ion extraction rate was suppressed. The
percentage and the Li+ concentration in the filtrate. The lithium recovery percentage decreased as the
dissolution of Li+ from LiAl-LDHs affected the chemical environment of aluminum, where the 27 Al
slurry concentration increased because the lithium-ion extraction rate was suppressed. The
chemical peak shifted to the low-field and a peak with a broad low-frequency shoulder appeared.
dissolution of Li+ from LiAl-LDHs affected the chemical environment of aluminum, where the 27Al
The Al-OH bond gradually formed and the metal-oxygen-metal bond was gradually broken with the
chemical peak shifted to the low-field and a peak with a broad low-frequency shoulder appeared.
increase of lithium recovery percentage, and the solid phase product was converted to Al(OH)3 when
The Al-OH bond gradually formed and the metal-oxygen-metal bond was gradually broken with
LiAl-LDHs disappeared. When the slurry concentration was 10 g/L, the lithium recovery percentage of
the increase of lithium recovery percentage, and the solid phase product was converted to Al(OH) 3
LiAl-LDHs-1 was 86.2% at 85 ◦ C for 90 min, and the Li+ concentration in the filtrate was 141.6 mg/L.
when LiAl-LDHs disappeared. When the slurry concentration was 10 g/L, the lithium recovery
Al3+ was hardly detected in the solution under various reaction conditions. This work provides a
percentage of LiAl-LDHs-1 was 86.2% at 85 °C for 90 min, and the Li+ concentration in the filtrate
method for extracting lithium ions from salt lake brine and for obtaining a lithium-bearing solution,
was 141.6 mg/L. Al3+ was hardly detected in the solution under various reaction conditions. This
which is capable of directly producing lithium salts, such as Li2 CO3 and LiOH.
work provides a method for extracting lithium ions from salt lake brine and for obtaining a
lithium-bearing solution,The
Supplementary Materials: which is capable
following of directly
are available onlineproducing lithium salts, such as Li2CO3 and
at http://www.mdpi.com/1996-1944/12/12/1968/s1,
LiOH.
the content of elements in LiAl-LDHs; additional NMR spectra, XPS O 1s spectra, XRD patterns.
Author Contributions: X.X. proposed the idea and designed the experiments. Y.S. carried out the experiments.
Supplementary Materials:
X.X. and Y.S. analyzed The
the data following
and wrote theare available X.X.,
manuscript. online
Y.S.,atR.Y.,
www.mdpi.com/xxx/s1,
Y.Z., M.P. discussed thethe content of
results.
elements in LiAl-LDHs; additional NMR spectra, XPS O 1s spectra, XRD patterns.
Funding: This work was supported by the National Natural Science Foundation of China (Grant U1507202,
U1707603,
Author 21521005), the
Contributions: Key
X.X. R&D Program
proposed the ideaofand
Qinghai Province
designed (Grant 2017-GX-144)
the experiments. Y.S. carriedand
outthe
theFundamental
experiments.
Research Funds for the Central Universities (XK1803-05, XK1802-6, 12060093063).
X.X. and Y.S. analyzed the data and wrote the manuscript. X.X., Y.S., R.Y., Y.Z., M.P. discussed the results.
Conflicts of Interest: The authors declare no conflict of interest.
Funding: This work was supported by the National Natural Science Foundation of China (Grant U1507202,
U1707603, 21521005), the Key R&D Program of Qinghai Province (Grant 2017-GX-144) and the Fundamental
Research Funds for the Central Universities (XK1803-05, XK1802-6, 12060093063).

Conflicts of Interest: The authors declare no conflicts of interest.

Materials 2019, 12, 1968 12 of 13

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