Hydrometallurgy 189 (2019) 105129

Contents lists available at ScienceDirect

Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Recovery of lithium from mineral resources: State-of-the-art and T

perspectives – A review
⁎
Huan Lia, Jacques Eksteena, , Ge Kuangb
a
Western Australian School of Mines: Minerals, Energy and Chemical Engineering, Curtin University, WA 6102, Australia
b
Institute of Chemical Engineering and Technology, Fuzhou University, Fuzhou 350108, China

A R T I C LE I N FO A B S T R A C T

Keywords: Lithium (Li), as a new energy metal, is becoming a “hot” topic in both academia and industry due to the rapid
Lithium vehicle electrification and grid storage. Although brines have been the major Li sources, Li-bearing minerals,
Extraction owing to the wider distribution and more rapid pathway to market, have also attracted much attention in recent
Spodumene years, with a number of new industrial projects launched and various novel methods proposed. The present
Lepidolite
study provides a start-of-the-art review of Li recovery from different mineral resources (i.e. excluding brines),
Zinnwaldite
and gives perspectives and outlook towards various recovery methods. In this study, the major mineral deposits
of Li are summarised and illustrated, which shows its high abundance and wide distribution around the global.
Various methods of Li recovery reported so far are then summarised with flowsheets and discussed by different
type of minerals, covering spodumene, lepidolite, zinnwaldite, amblygonite and clays. It is predicted that spo-
dumene will continue being dominantly used as Li source over other minerals with sulfuric acid (H2SO4) roasting
as a major method of processing. However, other novel methods including direct processing of natural spodu-
mene and the process that favours the direct production of LiOH will be the trends of future research. Fluoride-
based methods can achieve low energy consumption and high extraction efficiency but still need to be further
investigated for a sustainable, economical and safe application. To compete with spodumene, the comprehensive
utilization of all the valuable elements contained in lepidolite and zinnwaldite is crucial. In most of the recovery
processes, more attention should be paid to the treatment of voluminous residue and waste for a safe disposal or
further reuse. In addition, this study not only presents the methods for Li recovery, but also includes various
downstream separation and purification steps to make the process integrated. It is expected that, as a review
specialising in mineral resources of Li, the present study can provide insights for the development of this par-
ticular area.

1. Introduction (LCE), is forecasted to increase by > 200% from 214,000 t/y to

Although lithium (Li) has been discovered for over two centuries, it
has entered mainstream news in recent years as a new energy element
to power electric vehicles (EVs), the next generation of road-based
transportation as well as batteries for grid storage (Cano et al., 2018;
Tarascon, 2010; Wietelmann and Klett, 2018). Up to now, a number of
countries and districts have either announced bans or rapid phase-out
of internal combustion engine vehicles (ICEVs) and are shifting towards
EVs that are almost exclusively driven by Li-ion batteries (LIBs)
(Petroff, 2017). It is reported that the global EV sales have surged
from < 10,000 in 2010 to 2,100,000 in 2018, surpassing 5.4 million
accumulative sales (EV-Volumes, 2019). Driven by the growth of EV
market, the lithium demand, measured as lithium carbonate equivalent
669,000 t/y between 2017 and 2025 (Azevedo et al., 2018).
Apart from EV market, LIBs have been extensively used in portable
electronic devices and increasingly used in electric tools and energy
storage systems in micro and main grids. According to Jaskula (2019),
LIBs account for the largest proportion (56%) of Li market in 2018,
followed by ceramics and glass (23%) that directly use Li minerals as
ore concentrate. In addition, Li has also been used in lubricating
greases, polymer production, continuous casting mould flux powders,
air treatment, etc. with varied proportions.
Before 1980s, all of the Li was mined from mineral resources
(Kavanagh et al., 2018). Due to the low costs of production, brines
gradually became dominant in Li production and resulted in some
closures of Li mineral mines (Helvaci et al., 2003; Kavanagh et al.,

⁎
Corresponding author.
E-mail address: jacques.eksteen@curtin.edu.au (J. Eksteen).

https://doi.org/10.1016/j.hydromet.2019.105129
Received 22 March 2019; Received in revised form 16 June 2019; Accepted 9 August 2019
Available online 11 August 2019
0304-386X/ © 2019 Elsevier B.V. All rights reserved.
H. Li, et al.
Fig. 1. Distribution of major Li mineral deposits (≥0.1 Mt) of the world. Unless specified, scaling is based on the lowest resource estimations reported in the
literature (base map from Wikipedia “Blank maps”, data of Australia from Geology Survey of Western Australia (2018), data outside Australia from Gruber et al.
(2011), Kesler et al. (2012), Liu et al. (2017) and Vikström et al. (2013)).
2018). However, the worldwide distribution of Li brines with eco-
nomical concentrations and size is dramatically uneven, almost ex-
clusively concentrated in South America, including Argentina, Bolivia
and Chile (also known as the “Lithium-Triangle”) (Friedman-Rudovsky,
2011; Kesler et al., 2012). Li has been recognised as a strategic resource
and its supply security has become the top priority for relevant tech-
nology companies in the U.S. and Asia (Jaskula, 2019), which brings
need to exploit the more widely distributed Li-bearing minerals. On the
other hand, the price of lithium carbonate (Li2CO3) has risen sub-
stantially since 2010 and is expected to continue increasing in a short-
to medium- term (Martin et al., 2017b). With the price rising, Li-
bearing minerals that had been considered uneconomical might become
economical for producing Li salts (Economist, 2016; Jaskula, 2016).
As a result, the Li recovery from Li-bearing minerals, e.g. spodu-
mene, lepidolite and zinnwaldite, have attracted much attention in both
industry and academia in recent years. Of that, only spodumene has
been put into a reliable industrial application for the production of Li
salts. Due to the economical, ecological and technical issues, other Li-
bearing minerals still remain challenging. Recently, a number of new
pilot- and industrial- scale projects have been launched to process
spodumene and lepidolite in Australia, Canada, Finland and China
(Beardsmore, 2018; Bulletin, 2017; Argus Media Group, 2018; Jaskula,
2017; People's Government of Yichun, 2017). Western Australia, in
particular, owing to its high quantity and quality of Li deposits, has
been reported as an emerging “Lithium Valley” (Regional Development
Australia, 2018). In academia, a number of advances regarding Li ex-
traction technologies have been updated each year (Barbosa and
González, 2015; Bieseki et al., 2013; Guo et al., 2017; Kuang et al.,
2018; Rosales et al., 2016; Rosales et al., 2014; Tian et al., 2011). Due
to the booming EV market, one can predict that more efforts will be
made to enhance Li recovery from its mineral resources to diversify Li
supply. Hence, there is need to summarise the past and state-of-the-art
2
Hydrometallurgy 189 (2019) 105129
technologies of Li recovery from minerals and to point out the current
barriers and future trends of this particular area.
To date, there have been several reviews published concerning Li
extraction from various resources (Bertau et al., 2017; Choubey et al.,
2016; Meshram et al., 2014; Swain, 2017). Both Meshram et al. (2014)
and Swain (2017) comprehensively summarised Li recovery from pri-
mary and secondary resources, including minerals, brines, sea water,
spent LIBs, etc., while the studies were very broad but lacked detail on
specifics of hard rock processing. Among all these reviews, some novel
processes, especially those proposed in recent three years, are not fully
included. Also, to the best of our knowledge, there is hitherto no review
that specialises in Li recovery from mineral resources only. In this re-
view, the worldwide Li mineral resources are firstly summarised to
contextualise the field and serve as point of reference. Then, various
methods are classified, summarised and discussed by different mineral
type. In addition to Li extraction, the downstream purification and re-
covery of Li and other metals are also included in this study that helps
to form an integrated recovery process. It is worth mentioning that
some important patents, are also reviewed and discussed. Biological
processing approaches are excluded since they are still at an early stage
and studies are still rare. Finally, some perspectives and outlook are
given based on the current status of the area.
2. Mineral resources of lithium: Western Australia under spotlight
Li is dispersed in earth's crust (averagely 0.007%) in different forms,
while the concentrations that can be economically mined are rare
(Sardar and Mubashir, 2012; Swain, 2017). Generally, Li deposits can
be classified into three categories, i.e. brines (and related evaporates),
sedimentary rocks, and pegmatites, representing 66%, 8% and 26% of
world Li resource, respectively (Gruber et al., 2011). According to
Choubey et al. (2016), there are around 131 known minerals of Li. Of
H. Li, et al. Hydrometallurgy 189 (2019) 105129

them, around 7 silicate and phosphate based minerals have an eco-
nomic importance.
Fig. 1 summarises the major Li mineral deposits in the world with a
Li resource of > 0.1 million tons (Mt). It is clear that economically
significant mineral resources of Li are widely distributed across the
global. In particular, the large spodumene deposits (≥0.3 Mt. Li) have
been found in Australia, China, the US and Congo. Furthermore, a large
amount of lepidolite has been discovered in Yichun, Jiangxi province of
China, which is currently obtained as flotation tailings of tantalum (Ta)
and niobium (Nb) (Guo et al., 2019a, 2019b). Jadarite, a unusual Li-
bearing mineral, with an estimated amount of 0.4~Mt., has been dis-
covered in 2004 in Serbia and is currently in pre-feasibility stage of
development by Rio Tinto (Tinto, 2019; Vikström et al., 2013). Hec-
torite, a kind of Li-bearing clay-type mineral, has been found in Kings
Valley/McDermitt of Nevada, USA with an estimated amount of 1~Mt.
(Vikström et al., 2013). Although not presented in Fig. 1, a large
zinnwaldite deposit (~652,000 t Li) has been identified in Europe close
to the German-Czech border (Bertau et al., 2017), which has drawn
attention of German and Czech scientists (Jandová et al., 2009; Martin
et al., 2017a).
Among the states and countries highlighted in Fig. 1, Western
Australia (WA) has particular competitive advantage in Li resources.
According to Jaskula (2019), Australia's Li reserve, mostly located in
WA, has ranked second largest worldwide in 2018. WA has been the
world's largest Li supplier with 41% of global Li produced there as
spodumene concentrate in 2016 (Beardsmore, 2018). It is reported that
up to 50 Li projects are actively ran in WA (Beardsmore, 2018), with the
major ones listed in Table 1. Currently, there are four producing Li
mines, including Greenbushes, Mt. Cattlin, Mt. Marion and Wodgina
(Geology Survey of Western Australia, 2018). Of them, Greenbushes
owns the world's largest hard-rock Li deposit (spodumene) with a Li
resource of 1.64 Mt. (Geology Survey of Western Australia, 2018;
Beardsmore, 2018). Bald Hill and two projects in Pilgangoora are ad-
vanced Li developments. In particular, the potential production of Li
from the pegmatite, containing spodumene and lepidolite, in Pilgan-
goora has been considered a significant Li resources (Aylmore et al.,
2018). With the development of mining and Li recovery technologies, it
is an optimistic hope that more potentials of Li mining and recovery in
WA could be reached.
Table 2 presents the information of typical Li-bearing minerals.
Currently, most of the mineable minerals are in pegmatite environment
which are coarse-grained intrusive igneous rocks formed from the
crystallisation of magma at depth of the crust (Gruber et al., 2011;
London, 2017). It is reported that Li has been extracted from at least 13
pegmatite deposits (Gruber et al., 2011). In addition, some sedimentary
rocks also contain Li minerals, such as Jadarite and Hectorite which
have been massively discovered in Serbia and the US respectively
(Fig. 1). However, most of the research works are currently focused on
pegmatites, mainly including spodumene, lepidolite and zinnwaldite,
due to their higher Li grade, wider distribution and higher abundance.
The representative compositions of their concentrates are listed in
Table 3.
3. Recovery of lithium from spodumene
In nature, spodumene occurs in the form of α-phase and usually
associates with quartz, albite, microcline and micas in pegmatite de-
posits (Aylmore et al., 2018). When it comes to metals extraction,
however, the α-phase spodumene is resistant to the attack of common
industrial chemicals. In the current industry, natural spodumene is first
subjected to a calcination at 1000–1100 °C for up to 2 h to convert it
into β-phase that is more reactive to either acid or alkali due to a more
open crystal lattice (Aylmore et al., 2018; Ellestad and Leute, 1950;
Salakjani et al., 2017). The details of the changes in crystal structure
can be found in Salakjani et al. (2016). However, the calcination for
phase transfer is energy consuming, which adds considerable costs to
the Li recovery process. To avoid the phase transfer, some novel
methods, such as the fluorine- and caustic- based ones, have been ac-
tively investigated to process α-spodumene directly in recent years.
Table 4 summarises the methods reported for the Li recovery from
spodumene, which can be broadly categorised in five approaches: (1)
acid methods; (2) alkali methods; (3) sulphate roasting/autoclaving
method; (4) carbonate roasting/autoclaving method; and (5) chlor-
inating method. As shown in the table, acid method using sulfuric acid
(H2SO4) has only been reported on β-spodumene since there is virtually
no interaction between α-spodumene and H2SO4 (Zeelikman et al.,
1966). However, those involving fluorine, such as hydrofluoric acid
(HF) and fluorite (CaF2), have been shown capability of extracting Li
from α-spodumene directly, due to the intensive reaction between silica
(SiO2)-based materials and HF. Similarly, since strong alkali is capable
of attacking and breaking SieO bond (Wilson et al., 1994), sodium
hydroxide (NaOH) has been used to process α-spodumene at fusion
state or high concentration. In addition, sulphates, carbonates and
chlorides have shown effectiveness to extract Li from both α- and β-
spodumenes by roasting or autoclaving while the direct roasting of α-
spodumene are still rare (Zeelikman et al., 1966). In the following
sections, the methods reported for the Li recovery from α−/β- spodu-
mene will be discussed in details in turn.
3.1. Acid method
3.1.1. Using sulfuric acid for β-spodumene
In 2012, the world's first continuous plant of recovering Li from
spodumene using H2SO4 method was commissioned by Galaxy
Resources in China (Meshram et al., 2014). Currently, this method is
still dominant in the industry of Li extraction from spodumene
(Azevedo et al., 2018; Sardar and Mubashir, 2012). In this method,
ground β-spodumene is roasted by concentrated H2SO4 at a

Table 1
Li projects with resources in Western Australia (Geology Survey of Western Australia, 2018).
Project Company Ore/Mt Average grade/% Li2O/Mt Li/Mt

Greenbushes⁎ a Talison Lithium 157.07 2.25 3.53 1.64

Wodginab Mineral Resources 195.85 1.18 2.32 1.08
Pilgangooraa Pilbara Minerals 150.60 1.24 1.86 0.86
Pilgangooraa Altura Mining 47.50 0.99 0.47 0.22
Mt Holland Earl Grey Kidman Resources/SQM 128.00 1.44 1.84 0.85
Mt Marion Reed Industrial Minerals 77.80 1.37 1.07 0.50
Bald Hilla Tawana Resources/Alliance Mineral Assets 18.90 1.18 0.22 0.1
Mt Cattlina Galaxy Resources 16.42 1.08 0.18 0.08
Lynas Find Pilbara Minerals 5.60 1.57 0.09 0.04
Total 797.74 11.58 5.38

⁎
Updated in September 2015, mined continuously since then.
a
Proven or probable reserves included.
b
Tailings included.

3
H. Li, et al. Hydrometallurgy 189 (2019) 105129

Table 2
Information of typical Li-bearing minerals, adapted from (Vikström et al., 2013).
a
Environment Mineral name General formula Theoretic Li2O content/% Hardness (Mohs scale) Density/g/cm3

Pegmatites Lepidolite K(Li,Al)3(Si,Al)4O10(F,OH)2 7.7 2.5–3 2.8–2.9

Zinnwaldite KLiFe2+Al(AlSi3)O10(F,OH)2 3.42 3.5–4 2.9–3
Spodumene LiAlSi2O6 8.03 6.5–7 3.1–3.2
Eucryptite LiAlSiO4 11.86 6.5 2.6–2.7
Petalite LiAlSi4O10 4.5 6–6.5 2.4–2.5
Amblygonite (Li,Na)Al(PO4)(F,OH) 7.4 5.5–6 3.0–3.1
Sedimentary rocks Jadarite LiNaB3SiO7(OH) 7.28 4–5 2.5
Hectorite Na0.3(Mg,Li)3Si4O10(OH)2 1.17 1–2 2.5

a
general formulas are retrieved from Mineralogy Database at http://webmineral.com.

Table 3
Major compositions of different Li-bearing concentrate.
Concentrate Source Component (wt%) Ref.

Li2O K2 O CaO SiO2 Al2O3 Na2O MgO Fe2O3 TiO2 MnO Rb2O Cs2O F

Spodumene Greenbushes, Australia 6.17 0.92 0.57 63.00 26.38 1.46 0.21 0.61 - - - - - (Kuang et al., 2018)
San Luis, Argentina 7.03 0.14 0.52 68.3 18.6 0.8 0.3 3.2 0.11 - - - - (Rosales et al., 2014)
Lepidolite Yichun, China 3.27 5.91 0.20 60.88 24.96 2.28 - 0.14 - - 1.02 0.08 2.24 (Guo et al., 2019a, 2019b)
Gonçalo, Portugal 4.20 9.27 - 51.8 24.4 0.44 - 0.22 - 0.51 - - 3.58 (Vieceli et al., 2018a)
Gyeongsangbuk-do, Korea 3.85 9.15 1.91 57.7 22.9 0.80 0.47 0.17 - 0.13 0.81 0.25 3.08 (Luong et al., 2014)
Quang Ngai, Vietnam 3.34 8.24 0.99 54.67 25.10 1.56 0.99 0.36 - 0.50 0.88 0.067 2.91 (Hien-Dinh et al., 2015)
Zinnwaldite Zinnwald, Germany 3.0 8.4 - 50.6 17.3 - - 11.5 - 1.1 0.6 - 4.1 (Martin et al., 2017a)

“-”denotes not reported.

temperature of 250 °C, with the reaction represented by Eq. 1 (Kuang
et al., 2018). It has been reported that the reaction mechanism is based
on the ion exchange between H+ and Li+, as the two ions have almost
identical ionic radius (Archambault et al., 1962; Botto, 1985; Xiao
et al., 1997). Xiao et al. (1997) indicated that the crystal structure of β-
spodumene was not destroyed during the roasting, but the crystal lat-
tice locus of former Li+ was filled up by H+ resulting in the formation
of H2O· Al2O3·4SiO2. Fig. 2 gives an example of Li extraction from β-
spodumene using H2SO4 method, followed by purification and recovery
steps. After H2SO4 roasting, the calcine is leached by water to transfer
metal sulphates into soluble forms (Eq. 2), and neutralized by adding
calcium carbonate (CaCO3) to remove residual H2SO4 and some im-
purities. Then, the resulting crude Li2SO4 solution was purified to re-
move Ca, Mg, Al and Fe. Afterwards, most of the Li ions will be pre-
cipitated by introducing sodium carbonate (Na2CO3) into the
concentrated solution, as the reaction shown in Eq. 3, followed by so-
dium sulphate (Na2SO4) and residual Li recoveries. Tian et al. (2011)
investigated the roasting and leaching behaviours of spodumene in
sulfuric acid. The conditions of sulphating roasting for β-spodumene
were optimised to the following conditions: 93% H2SO4 is used at 140%
of stoichiometric demand, using a roasting temperature of 250 °C and
roasting time of 30 min. After water leaching for 15 min at room tem-
perature and using liquid to solid (L/S) ratio of 1.85, a Li extraction
yield of 96.9% can be obtained.
β − Li2 O·Al2 O3 ·4SiO2 (s) + H2 SO4 (conc. ) → H2 O
o
·Al2 O3 ·4SiO2 (s) + Li2 SO4 (s), ΔG250o
C that the extraction of Li was highly dependent on the temperature and
= −151.38 KJ/mol
H2 O
o
Li2 SO4 (s) → Li2 SO4 (aq), ΔG25o = − 10.07 KJ/mol
C
o tions represented by Eqs. 6–8.
Li2 SO4 (aq) + Na2CO3 (aq) → Li2 CO3 (s) + Na2SO4 (aq), ΔG25o
C
1950), the precise control of temperature and energy recovery are
challenging. Furthermore, the precipitated Fe and Al impurities are
quite voluminous that tend to mechanically carry down Li, resulting in
Li losses (Dwyer, 1957). Also, Na2SO4 in solutions after Li precipitation
(Fig. 2) should be recovered, mostly by crystallisation, while the
Na2SO4 market is flooded and sensible approach is required to deal with
it, e.g. caustic regeneration through dual alkaline methods, or NaOH/
H2SO4 generation using electro-electrodialysis. Due to the existence of
these drawbacks, researchers have been actively looking for novel
methods that could be an alternative to H2SO4 method.
3.1.2. Using hydrofluoric acid for α- and β-spodumene
Hydrofluoric acid (HF) is known to be capable of etching silica
(SiO2)-based materials, such as glass and stoneware (Davis, 2000).
Particularly, it has long been used in the digestion of silicate minerals
for analytic purposes (Samchuk and Pilipenko, 1987), and is also used
to liberate diamonds from silicate minerals, e.g. Venetia diamond mine
in South Africa. An early study conducted by Kuang et al. (2012) has
proven the effectiveness of using excessive HF at 40% concentration to
extract Li from α-spodumene at relatively low temperature (127 °C), but
the details are lacking. Recently, Rosales et al. (2014) reported a novel
method (Fig. 3) to leach Li, Al and Si from β-spodumene using HF and
to further recover them from leaching solutions. In their study, 90% Li
could be extracted from β-spodumene by leaching with 7% HF at 1.82%
solid to liquid (S/L) ratio and 75 °C for 20 min, with the reaction pro-
posed as Eq. 4 (Rosales et al., 2014). The same authors also indicated
(1) time (Rosales et al., 2016). The leached Al and Si were then precipitated
as Na3AlF6 and Na2SiF6, respectively, by adding only stoichiometric
amount of sodium hydroxide (NaOH) (Eq. 5). 90% Li remaining in
(2)
solution was finally recovered as Li2CO3 by carbonation, as the reac-

= −17.54 KJ/mol (3) β − LiAlSi2 O6 (s) + 19HF (aq) → LiF (aq) + H3 AlF6 (aq) + 2H2 SiF6 (aq)
+ 6H2 O (4)
However, there are still some drawbacks behind this method. The
roasting using concentrated H2SO4 increases investment for equipment,
H3 AlF6 (aq) + H2 SiF6 (aq) + 5NaOH (aq) → Na3AlF6 (s)
and causes acid gas emissions (Archambault et al., 1962). When the
roasting is usually performed in a rotary kiln (Ellestad and Leute, + Na2SiF6 (s) + 5H2 O (5)

4
H. Li, et al. Hydrometallurgy 189 (2019) 105129

References 1–5: (Archambault et al., 1962; Ellestad and Leute, 1950; Tian et al., 2011; Xiao et al., 1997; Zeelikman et al., 1966); 6–8: (Kuang et al., 2012; Rosales et al., 2016; Rosales et al., 2014); 9–10: (Guo et al., 2017;

1941; Kuang et al., 2018; Zeelikman et al., 1966); 22–26: (Chen et al., 2011; Maurice and Olivier, 1968; Sugyeong, 2018; Tiihonen et al., 2019; Zeelikman et al., 1966); 27: (Barbosa et al., 2014); 28–30: (Barbosa and
Guo et al., 2019a, 2019b); 11–13: (Griffin, 2017; Griffith et al., 2018; Kuang et al., 2012); 14–16: (Martin, 2018; Sugyeong, 2018; Xing et al., 2019); 17: (Kuang et al., 2014); 18: (Mcintosh, 1946); 19–21: (Arne and Johan,
o
2LiOH (aq) + CO2 (g) → Li2 CO3 (s) + H2 O, ΔG25o = − 70.92 KJ/mol

CaCl2/NH4Cl/NaCl

α-s (R), β-s (R, A)

C

(6)
Chlorinating method

o
Li2 CO3 (s) + H2 O + CO2 (g) → 2LiHCO3 (aq), ΔG25o = − 4.50 KJ/mol
C

28–30
R/A
(7)
heating
2LiHCO3 (aq) → o
Li2 CO3 (s) + H2 O + CO2 (g), ΔG95o
Cl2

β-s
27
C
R

= −6.10 KJ/mol (8)

Carbonate roasting/autoclaving method

Compared with sulfuric acid method, this method requires only a

moderate leaching temperature and a short leaching time, which is
much less energy and time consuming. Given that the concentration of
HF used in Rosales et al. (2014) study was relatively low (7%), and the
fluorine (F) was converted into corresponding salts during leaching (Eq.
4) and Al/Si recoveries (Eq. 5), the safety concerns over the use of HF
Na2CO3/CaCO3

will be substantially reduced. However, the very low solid ratio during
α-s (F), β-s (A)

HF leaching (1.82%) and the produced mixed fluoride-salt waste are the
critical drawbacks of this method. Compared with Li2SO4, the LiF ob-
22–26

tained in leaching solution has a low solubility (Ksp = 1.84 × 10−3)

R/A

(Dean, 1999, Table 5), hence a low solid ratio should be maintained to
secure the leaching of Li into solution, which restricts the production
Sulphate roasting/autoclaving method

capacity in industrial practices, and drives concentration costs up. On

the other hand, given that the Al and Si contents in spodumene are
significantly high (Table 3), the amount of the mixed fluoride-salt,
Na3AlF6/Na2SiF6, will accordingly be voluminous. Calculated from the
Al and Si contents in the studied spodumene (Rosales et al., 2014), to
α-s (F), β-s (R, A)

produce one tonne Li2CO3, there will be 16.7 t Na3AlF6/Na2SiF6 mix-

K2SO4/Na2SO4

ture generated stoichiometrically. However, the market capacity for

Na3AlF6/Na2SiF6 mixture is very limited, the disposal of them will be
problematic.
19–21
R/A

3.1.3. Using sulfuric and hydrofluoric acids for α-spodumene

CaO/Ca(OH)2

To overcome the drawback of high energy consumption during

phase transfer of natural spodumene, Guo et al. (2017) used a mixed
acid of HF/H2SO4 to directly dissolve α-spodumene, and investigated
β-s
18

the leaching mechanisms. Under optimised conditions (ore/HF/H2SO4

A

ratio of 1:3:2 (g/mL/mL), 100 °C and 3 h), 96% Li could be mobilised

NaOH+ CaO

into the leachate with a Li concentration of around 1.5 g/L. The overall
leaching reaction was proposed as Eq. 9. The ΔGo of this reaction
e
CTFR

was < 0 between 0 °C (−767.848 KJ) and 125 °C (−882.900 KJ)

Alkali method

β-s
17

F denotes fusion of the major reagent specified during roasting of spodumene.

showing its thermodynamic feasibility (Guo et al., 2017). They also

indicated that the HF molecules were the actual lixiviant to dissolve α-
CTFR denotes digestion in continuous tubular-flow reactor under pressure.
14–16
NaOH

d
F /A

spodumene, and H2SO4 transferred intermediates of fluorides to sul-

α-s
c
The methods reported for the Li recovery from α- and/or β- spodumene.

phates with high solubility (Table 5). For example, the intermediate LiF
Refers to the type of spodumene reported in the specified method.

could be transferred to Li2SO4 as shown in Eq. 10.

CaF2+ H2SO4

2α − LiAlSi2 O6 (s) + 24HF (aq) + 4H2 SO4 → Li2 SO4 (aq)

11–13

González, 2015; Gabra et al., 1975; Zeelikman et al., 1966).

+ Al2 (SO4 )3 (aq) + 4H2 SiF6 (aq) + 12H2 O

α-s
L

The reference numbers applicable to this table only.

o
, ΔG25o = − 786.83 KJ/mol (9)
C
H2SO4 + HF

2LiF + H2 SO4 → Li2 SO4 + 2HF (10)

9–10

This method directly targets α-spodumene to be dissolved or lea-

α-s

A denotes autoclaving under pressure.

L

ched, which is considered as an important improvement compared with

the methods that needs phase transfer at high temperature
α-sh, β-s

(1000–1100 °C). The introducing of H2SO4 can largely improve Li

6–8
HF
Acid method

b
L

concentration in solution (Table 5), and makes the partial reuse of HF

possible (Eq. 10). Also, H2SO4 media lixiviant benefits the downstream
H2SO4

purification and recovery process owing to its similarity to that in

β-sg
1–5

L denotes leaching.
R denotes roasting.
a
R

conventional H2SO4 method (Section 3.1.1) while F should better be

previously removed to avoid the formation of insoluble metal fluorides
α-spodumene.
β-spodumene.
Spodumene typef

in downstream process. Importantly, the intensive use of HF and the

Major reagent

release of which will accordingly bring significant safety challenges,

and the safe recycle of F released during leaching or remained in re-
Process
Table 4

Ref.i

sidue needs to be further investigated. Also, the recovery of Al in

h
d
b

g
a

e
c

leaching solution and the disposal of H2SiF6 remains outstanding to this

5
H. Li, et al. Hydrometallurgy 189 (2019) 105129

Fig. 2. An example of Li recovery process from β-spodumene by using sulfuric acid method, adapted from Kuang et al. (2018) and Tian et al. (2011).

method. Table 5
Solubilises of different Li salt in water at various temperature, expressed as the
mass percentage of solute (100*mass of solute/(mass of solute + mass of
3.1.4. Using fluoride and sulfuric acid for α-spodumene water)), data from Lide (2005).
HF is well known for its high corrosivity and toxicity, which makes
Formula Temperature (°C)
safe handling challenging. To avoid the direct use of HF, some re-
searchers have employed fluoride to in situ generate HF for the ex- 20 25 30 40 60 80 90 100
traction of Li from spodumene. Kuang et al. (2012) proposed a method
using fluorite (CaF2) and H2SO4 to extract Li from α-spodumene, and Li2SO4 25.6 25.5 25.3 25.0 24.8 24.0 23.8 23.6
LiF 0.131 0.134 - - - - - -
investigated its reaction mechanism. They indicated that, in the reac-
LiCl 45.3 45.8 46.3 47.3 49.8 53.0 55.0 56.3
tion process, in situ produced HF (Eq. 11) first destroyed the basic bonds LiOH 11.0 11.1 11.3 11.7 12.7 14.2 15.1 16.1
of LieO, AleO, SieO and Al-O-Si inside of α-spodumene, with inter- Li2CO3 1.33 1.28 1.24 1.15 0.99 0.85 0.78 0.72
mediates of Li3AlF6, AlF3, SiF4, etc. generated. Afterwards, H2SO4 re-
acted with the intermediates to transfer them into sulphates that can be “-”denotes not reported.
further enriched in aqueous media.
3.2. Alkali method
o
CaF2 (s) + H2 SO4 (l) → CaSO4 (s) + 2HF (g), ΔG25o = − 6.95 KJ/mol
C

(11) 3.2.1. Using sodium hydroxide for α-spodumene

Fluorite is a naturally occurring mineral and has been historically
used (together with conc. H2SO4) for HF production (Meshri, 1986).
The direct use of fluorite seems to be more economical in terms of re-
agent costs compared with HF/H2SO4 system. More importantly, it
decreases the safety requirements, especially making it feasible in de-
veloped countries where strict environmental regulations apply. For
example, Lithium Australia NL has reported a process, termed SiLeach®,
that uses CaF2 and H2SO4 to extract Li from various Li-bearing minerals,
including spodumene (Griffith et al., 2018). This process has been re-
ported to have been called up to pilot scale and has shown potential
application in various low grade Li-bearing minerals (Griffin, 2017).
However, more details of the process have not yet been disclosed.
It is well known that alkali is capable of attacking and breaking
SieO bond to make SiO2 dissolved in solution, and the dissolution in-
creases with the rise of alkalinity and temperature (Leemann et al.,
2011; Wilson et al., 1994). A typical example is the alkali-silica reaction
(ASR) happened in concrete resulting in its durability problems
(Swamy, 2002). The ASR has led some researchers to the using of alkali
for the direct extraction of Li from α-spodumene, a silicate mineral.
Martin (2018) used NaOH to leach Li from α-spodumene in an auto-
clave while the extraction efficiency was limited to around 40% under
optimum conditions, possibly due to the low NaOH concentration.
Another study conducted by Xing et al. (2019) achieved a high Li ex-
traction efficiency of 95.8% when autoclaving α-spodumene with

Fig. 3. A process of Li recovery from β-spodumene by using hydrofluoric acid method, summarised from Rosales et al. (2014).

6
H. Li, et al.
Fig. 4. A process of Li recovery from α-spodumene by using NaOH, summarised from (Xing et al., 2019).
600 g/L (15 M) NaOH at L/S ratio of 5 and 250 °C for 2 h, with the
reaction predicted as Eq.12. Fig. 4 gives a flow chart of the Li extraction
and the further recovery reported in the study. The generated hydro-
xysodalite (Na4Al3Si3O12(OH)) with an impurity of zeolite
(1.2Na2O·0.8CaO·Al2O3·2SiO2·H2O) is a by-product that possesses ap-
plications in small-molecule separation, hydrogen storage, catalysis, etc.
After leaching, the silicon (Si) in the leaching solution was precipitated
as Ca2SiO4 by adding CaO, namely desilication. Subsequently, the Li
remaining in solution was enriched and further precipitated as Li2CO3.
6α − LiAlSi2 O6 + 14NaOH → 2Na 4 Al3Si3 O12 (OH) + 3Li2 SiO3 + 3Na2
SiO3 + 6H2 O (12)
By using NaOH to directly process α-spodumene, the phase transfer
at high temperature is avoided, and a high Li extraction efficiency has
been reached (Xing et al., 2019). In particular, the production of by-
product, hydroxysodalite, could increase profitability of the process and
significantly reduce the amount of solid waste generated. However, this
method often accompanies with high caustic consumption due to the
nature of ASR. In Xing et al.'s (2019) study, the NaOH amount used
under optimum conditions was as high as 0.6 ton/ton ore. Hence the
highly anti-corrosive equipment is required, and the operational safety
should be concerned.
3.2.2. Using sodium/calcium hydroxide for β-spodumene
In addition to the direct processing of α-spodumene, alkali has also
been reported to treat β-spodumene. Mcintosh (1946) published a US
patent, in which lime was used as a main extracting agent to digest β-
spodumene in an autoclave. In this method, lime and water were pre-
mixed as milk lime (Ca(OH)2), and then reacted with β-spodumene at
100–250 °C, with the overall reaction shown in Eq. 13 (Zeelikman et al.,
1966). In this way, Li was leached as LiOH and most of the impurities
(Fe, Al and Mg) reported to residue. After evaporation, the leaching
solution was supplied with CO2 to precipitate Li2CO3 product, and a
purity of 97.8% was obtained (Choubey et al., 2016; Mcintosh, 1946).
β − Li2 O·Al2 O3 ·4SiO2 + 4CaO + 4H2 O → 2LiOH + 4CaSiO3 + 2Al
(OH)3 (13)
Recently, a China (CN) patent was published by Kuang et al. (2014)
to produce LiOH from β-spodumene. In this disclosure, lime and NaOH
were used to digest β-spodumene in a CTFR at 0.1–1.5 MPa and
90–250 °C. The β-spodumene/NaOH/lime/water mass ratio was kept at
1/(0.05–0.35)/(0–0.3)/(1.5–6), and the flow rate in CTFR was
0.08–0.8 m/s. After CTFR digestion, a solution containing LiOH was
obtained. The solution was then concentrated, purified and further
subjected to crystallisation to produce LiOH∙H2O product.
Compared with the direct processing of α-spodumene (Section
3.2.1), using alkali to treat β-spodumene seems to come with lower
alkali consumption and leaves Si in residue. In this way, the step for
7
Hydrometallurgy 189 (2019) 105129
desilication could be avoided. Generally, LiOH has higher value than
Li2CO3 and is currently the preferred form of Li salt for the longest-
range EV batteries (Alibaba Group, 2019; Azevedo et al., 2018). Using
hydroxide to extract Li from β-spodumene can also favour the down-
stream LiOH production, since Li will exist in leaching solution as LiOH
that can be further crystallised. This is considered an important ad-
vantage when it comes to the production of LiOH, compared with using
other salt, like sulphate and carbonate.
3.3. Sulphate roasting/autoclaving method for α- and β-spodumene
Arne and Johan (1941) published a US patent employing molten
alkali sulphate, including Na2SO4, to extract Li from silicate. The ex-
traction was conducted at a temperature higher than the melting point
of alkali sulphate (~850 °C), but lower than the temperature at which
the silica skeleton is destroyed. In this method, 90% Li could be ex-
tracted from α-spodumene grains at 1000 °C in only 10 min. In 1966,
Zeelikman et al. (1966) reported the process of roasting α-spodumene
with potassium sulphate (K2SO4). Although it has been indicated that
the reaction between spodumene and K2SO4 starts at ~700 °C, in
practice, the roasting was usually conducted at 920–1150 °C during
which α-spodumene was firstly converted into its β-phase and then
enters a substitution reaction with K2SO4 (Zeelikman et al., 1966). Also,
since the reaction is reversible, a large excess of K2SO4 was required in
practice to secure an effective extraction of Li as LiSO4 (Zeelikman
et al., 1966). Recently, Kuang et al. (2018) reported an autoclaving
method to extract Li from β-spodumene using Na2SO4 with the addition
of calcium oxide (CaO) or NaOH. The results reveal that the highest Li
extraction, i.e. 93.30% for CaO and 90.70% for NaOH, were achieved
under following conditions: Na2SO4/additive (CaO or NaOH)/ore mass
ratio of 9:0.4:20, temperature of 230 °C, L/S ratio of 7.5 mL/g, particle
size (D90) of 39 μm, autoclaving pressure of 2.7 ± 0.1 MPa, and time of
3 h. The XRD analysis of residue verified that the extraction mechanism
was based on the ion exchange between Li+ and Na+.
Compared with acid methods, the sulphate method through roasting
or autoclaving can reduce the dissolution of Al and Fe considerably,
which simplifies the downstream purification process and decreases the
potential Li losses. The direct roasting of α-spodumene with sulphate
seems to be more straightforward than the process wherein phase
transfer is done separately prior to sulphate roasting, whereas more
detailed investigations are needed to prove its applicability. Notably,
the use of Na2SO4 can largely decrease the reagent costs, because of its
cheap price and high recyclability. However, it should be noted that the
particle size (39 μm at optimal) used in Kuang et al.'s (2018) study was
very small, which requires expensive grinding costs.
3.4. Carbonate roasting/autoclaving method for α- and β-spodumene
Similar with sulphate method, the Li extraction with carbonate
H. Li, et al.
Fig. 5. A process of Li recovery from β-spodumene by carbonate autoclaving method, adapted from Chen et al. (2011).
method is also based on the ion exchange between Li+ and the metal
ion from carbonate, mostly Na+. The reaction between β-spodumene
and sodium carbonate (Na2CO3) can be represented as Eq. 14 (Chen
et al., 2011). This reaction has been achieved by roasting at 450–750 °C
(through solid-solid reaction) (Maurice and Olivier, 1968) or auto-
claving at around 225 °C (Chen et al., 2011). As a result, Li2CO3 and
analcime will be formed. Since Li2CO3 has a low solubility
(Ksp = 2.5 × 10−2), especially at higher temperature (Dean, 1999), it
may report to residue after roasting or autoclaving. To render soluble
and separable with residue (e.g. analcime), a carbonation step is usually
employed to convert Li2CO3 into lithium bicarbonate (LiHCO3) (Eq. 7),
to be separated with residue by filtration. Afterwards, high-purity
Li2CO3 can be obtained by heating the LiHCO3 rich filtrate (Eq. 8).
β − Li2 O·Al2 O3 ·4SiO2 + Na2CO3 + nH2 O
→ Li2 CO3 + Na2O·Al2O3 ·4SiO2 ·nH2 O (14)
In Chen et al.'s (2011) research, as summarised in Fig. 5, ~94% Li
was extracted from β-spodumene by autoclaving with Na2CO3 at L/S
ratio 4 mL/g, Na/Li ratio 1.25 and 225 °C for 60 min, and around 70%
Li2CO3 was recovered from LiHCO3 solution by heating at 90 °C for 1 h,
with a purity of 99.6%. However, it should be noted that the formed
Li2CO3 in Eq. 14 may cause reaction blockage by wrapping the β-spo-
dumene particles. To solve this, Chen et al. (2011) has added steel balls
(ø10 mm × 20) into autoclave.
A different process employing Na2CO3 to autoclave β-spodumene
has been newly reported in a bench scale (Tiihonen et al., 2019). In this
study, as shown in Fig. 6, an additional leaching step, namely conver-
sion leaching, was used to convert Li2CO3 into soluble LiOH (Eq. 15)
that is further crystallised as LiOH∙H2O following impurity removal by
ion exchange. It is reported that the Li extraction reached up to 94%
and the purity of product obtained in one crystallisation stage was as
high as > 56.5% LiOH which is of battery grade (Tiihonen et al., 2019).
This process gives another option of downstream treatment, following
the carbonate autoclaving of β-spodumene, which can directly produce
LiOH product instead of Li2CO3. The conversion leaching at alkaline
environment could significantly remove impurities of Al, Ca, Mg, Fe
and P, which shows advantage compared with the relatively non-se-
lective acid leaching (Section 3.1). However, the mixed residue ob-
tained in this process contains Na, Al, Si and Ca, further treatment is
required for the recovery of them, Al in particular. Moreover, given that
there is already direct autoclaving of β-spodumene with Ca(OH)2,
Fig. 6. A process of Li recovery from β-spodumene by carbonate autoclaving, followed by conversion leaching, adapted from (Tiihonen et al., 2019).
8
Hydrometallurgy 189 (2019) 105129
which is also capable of producing LiOH (Section 3.2.2), if it is
worthwhile to add a carbonate autoclaving step is concerned although
this process seems to reduce residue amount by around 10% by cal-
culation (Eqs. 13–15).
Li2 CO3 (s) + Ca(OH)2 (s) → 2LiOH (aq) + CaCO3 (s) (15)
In addition, Na2CO3 has also been used to roast α-spodumene di-
rectly for the extraction of Li. Sugyeong (2018) reported a process
wherein fused Na2CO3 was employed to roast α-spodumene at Na2CO3/
spodumene mass ratio of 1 and 850 °C for 60 min, followed by acid
leaching with 1.5 M H2SO4 for 5 h. The results reveal that Li was almost
completely extracted (99.98%) from α-spodumene together with all the
Si and 75% Al (Sugyeong, 2018). This method requires lower energy
input since no phase transfer is needed and has high Li extraction ef-
ficiency. However, the Na2CO3 consumption was quite high and large
amount of unprofitable Na2SO4 by-product will be generated after acid
leaching.
3.5. Chlorinating method
Extraction of Li from spodumene using chlorination has been proven
effective due to the high reactivity and strong affinity of chlorine and
the formation of lithium chloride (LiCl) that can be easily dissolved in
water (Barbosa et al., 2013, Table 5). To date, chlorine gas (Cl2) and
chloride have been used as chlorinating agents. No matter what kind of
reagents is used, the basis is converting Li in spodumene into water-
soluble LiCl, which can be further leached in water.
3.5.1. Using chlorine gas for β-spodumene
Barbosa et al. (2014) used pure Cl2 to extract Li from β-spodumene
obtained from phase transfer of α-spodumene (100% < 50 um). The
tests were conducted in a furnace at ≥1000 °C with 100 mL/min Cl2
supply, and the complete extraction of Li as LiCl was achieved at
1100 °C for 150 min. The reaction between spodumene and Cl2 is re-
ported as Eq. 16, which is non-catalytic and gas-solid in nature (Barbosa
et al., 2013).
12β − LiAlSi2 O6 (s) + 6Cl2 (g) → 3O2 (g) + 12LiCl (l) + 2Al 6Si2 O13
o
(mullite) + 20SiO2 (cristobalite), ΔG1100o
C
= −707.88 KJ/mol (16)
H. Li, et al.
This method could be possible where the Li plant is close to a chlor-
alkali industry, such as in the industrial hub of Kwinana (Western
Australia), where Cl2 is also used for TiCl4 production. It was found that
LiCl product and other formed chlorides by impurities (e.g. FeCl3,
CaCl2) will volatilize together during the extraction, resulting in con-
tamination of product that needs to be further treated (Barbosa et al.,
2014). The direct use of Cl2 at high temperature has significant safety
risks, and requires expensive materials of construction, which makes
the process challenging. Furthermore, the high temperature (≥1000 °C)
roasting is much more energy consuming compared with acid methods
(Section 3.1), especially when a phase transfer roasting (1180 °C, 2 h)
already exists. Additionally, given that the roasting happened at a
temperature (1100 °C) also suitable for phase transfer, this method,
given the aggressive nature of Cl2, may also be feasible for the direct
processing of α-spodumene while experiment is needed to prove this
presumption.
3.5.2. Using chloride routes for α- and β-spodumene
Another chlorinating agent, calcium chloride (CaCl2), has been re-
ported by Barbosa and González, 2015 to extract Li from β-spodumene.
Compared with Cl2, CaCl2 can react with β-spodumene at lower tem-
perature, starting at 700 °C, and is non-toxic and less corrosive. Under
the optimised conditions, i.e. 900 °C, 2 h and ore/CaCl2 molar ratio 0.5,
the extent of Li conversion reached 90.2%. The results also indicate that
β-spodumene was decomposed and converted to LiCl, SiO2, and
CaAl2Si2O8 (further decomposed to CaSiO3) during the chlorinating
roasting.
Gabra et al. (1975) used sodium chloride (NaCl), a cheap and easily
obtained chemical, as chlorinating agent to extract Li from β-spodu-
mene under pressure and at alkaline environment (adjusted by Ca
(OH)2). The reaction is shown in Eq. 17, and the process flow chart is
summarised in Fig. 7. In their study, various parameters, including NaCl
and Ca(OH)2 concentrations, temperature, pulp density, time and ore
size, were investigated, and an almost complete extraction of Li was
obtained in around 3.5 h of leaching (ore size 100% < 42 um). The
direct crystallisation of leaching solution obtained from autoclaving
was also conducted to prepare LiCl with 91% purity. This seems to be a
simple way of producing LiCl product when the high purity is not re-
quired. Further, by solvent extraction using n-butanol as solvent and DI
water as stripping agent, the crystalized LiCl reached a purity as high as
99.9% (Gabra et al., 1975).
β − Li2 O·Al2 O3 ·4SiO2 + 2NaCl + 2H2 O → 2LiCl + Na2O·Al2 O3 ·4SiO2 ·
2H2 O (17)
In addition, there has been report, although not common, using
NH4Cl to roast α-spodumene directly for Li extraction. It is reported
that when α-spodumene was sintered with CaCO3 and NH4Cl at 1/3/1
ratio and 750 °C, around 97% Li could be converted to LiCl according to
Eq. 18 (Medina and El-Naggar, 1984; Zeelikman et al., 1966).
α − Li2 O·Al2O3 ·4SiO2 + 4CaCO3 + 2NH 4 Cl
→ 2LiCl + 4CaSiO3 + Al2 O3 + 4CO2 + 2NH3 + H2 O (18)
Fig. 7. A process of Li recovery from β-spodumene by chlorinating method with NaCl as chlorinating agent, adapted and simplified from Gabra et al. (1975).
9
Hydrometallurgy 189 (2019) 105129
4. Recovery of lithium from lepidolite
In contrast to spodumene, lepidolite, with a general formula of K
(Li,Al)3(Si,Al)4O10(F,OH)2, is a low-grade Li-bearing ore, belonging to
mica group. The concentrate of lepidolite contains only ~4.5% Li2O,
which is much lower than that of spodumene (Table 3). Furthermore,
unlike spodumene, lepidolite contains F (theoretically 4.89%), a re-
active and harmful element that brings complexity by forming HF or
fluorides during the recovery of Li. In addition, the intrinsic structure of
lepidolite has made it often associate with rare metals, Rubidium (Rb)
and Caesium (Cs) (Table 3) (Guo et al., 2019a, 2019b). For an eco-
nomically feasible industrial practice, the valuable Rb and Cs, as well as
K and Al, should also be recovered as by-products to increase profit-
ability (Kuang et al., 2015). To date, a number of methods of Li re-
covery from lepidolite, including downstream purification processes,
have been reported in both lab- and pilot- scales that are summarised in
below sections.
4.1. Acidic method
4.1.1. Using sulfuric acid
In sulfuric acid method, like the one for spodumene (Section 3.1.1),
lepidolite is treated by H2SO4 at elevated temperature to replace Li+
with H+ resulting in the formation of water-soluble LiSO4. Other me-
tals, such as potassium (K), Al, Rb and Cs, could also be extracted and
report to solution as corresponding sulphates that mostly need to be
separated prior to the precipitation of Li salt.
A Chinese patent published by Li et al. (2006) illustrates a method
to make pregnant Li2SO4 solution (Fig. 8) and further produce Li salts
from lepidolite. As can be seen from Fig. 8, after H2SO4 leaching, K, Rb
and Cs reported to solution together with the extracted Li. Subse-
quently, K, Rb, Cs and partial Al were crystallised as corresponding
alums according to Eq. 19. After further purification steps for the re-
movals of acid, Al, Fe, Mn, Mg and Ca, dilute Li2SO4 solution was ob-
tained that was to be treated for Li2CO3 or LiF production.
M2 SO4 + Al2 (SO4 )3 + 24H2 O → 2MAl(SO4 )2 ·12H2 O (with cooling)
(19)
where M stands for K, Rb and Cs.
To improve Li recovery, Vieceli et al. (2017a) reported a method to
extract Li from lepidolite by mechanical activation, acid digestion, and
water leaching. The mechanical activation was performed by milling
lepidolite in a disc mill to increase its reactivity. When lepidolite was
milled for 30 min, followed by H2SO4 (98%) digestion (650 g acid/Kg
lepidolite, 165 °C and 4 h) and water leaching (S/L 1:10 (w/v), 80 °C
and 4 h), around 87% Li was extracted from lepidolite. This figure was
elevated to over 90% under different conditions in another study
(Vieceli et al., 2018b). However, the ultrafine grinding for the me-
chanical activation is quite energy intensive.
Recently, Liu et al. (2019) used H2SO4 solution to leach lepidolite
(100% < 180 μm) and investigated the leaching kinetics. The results
show that 94.18% Li, 93.70% K, 91.81% Rb and 89.22% Cs were lea-
ched into solution at concentrate/H2SO4 mass ratio of 1.2, L/S ratio of
2.5 and 138 °C for 10 h. The kinetics analysis indicates that the leaching
process was controlled by diffusion through the insoluble layer of as-
sociated minerals (Liu et al., 2019). In another recent study (Zhang
H. Li, et al.
Fig. 8. A process of Li recovery from lepidolite by sulfuric acid method, summarised from Li et al. (2006).
et al., 2019), higher extraction efficiencies, i.e. 97.1% for Li, 96.0% for
Rb and 95.1% for Cs, were obtained by baking lepidolite with 85%
H2SO4 at acid/concentrate (88% < 74 μm) ratio of 1.7 and 200 °C for
4 h, and then leaching with water at 85 °C. They indicated that the F
contained in lepidolite was partially volatilised as HF and SiF4 during
the baking. The baking reactions were proposed as Eqs. 20–21 (Zhang
et al., 2019).
KLi1.6Al2.2Si3.2 O10 FOH + 4H2 SO4 + 2. 6H2 O → KAl
(SO4 )2 + 0. 8Li2 SO4 + 1
. 2Al(SO4 )OH·5H2 O + 3. 2SiO2 + HF (g)
KLi1.6Al2.2Si3.2 O10 FOH + 4H2 SO4 + 2. 1H2 O → KAl
(SO4 )2 + 0. 8Li2 SO4 + 1
. 2Al(SO4 )OH·5H2 O + 2.95SiO2 + 0.25
SiF4 (g)
Johnson et al. (2017) has a pending patent under Patent Coopera-
tion Treaty (PCT) to produce Li2CO3 and by-products from lepidolite by
using H2SO4 method (termed L-Max®), in which a process for the re-
covery of F was also reported. As summarised in Fig. 9, the solution
containing F obtained after crystallisation of alums was subjected to
another crystallisation to separate khademite (Al(SO4)F∙5H2O) with
Li2SO4 solution. Afterwards, khademite was re-dissolved to precipitate
aluminium hydroxyl fluoride using Al(OH)3, followed by calcination to
obtain AlF3/Al2O3.
Based on the above mentioned reports, H2SO4 method can effec-
tively extract Li from lepidolite with a satisfactory extraction percen-
tage. However, the downstream separation and purification process is
relatively complicated (Figs. 8-9), since multi-elements (K, Rb, Cs, Al,
Fe, F, etc.) exist in leaching solutions, which seems to be inevitable. The
Fig. 9. A process for the recovery of F and Al from solutions obtained from lepidolite processing, summarised from Johnson et al. (2017).
Hydrometallurgy 189 (2019) 105129
separation process can also cause considerable Li losses by adsorption
or entrainment. For example, in a study reported by Kuang et al.
(2015), the Li content in gypsum residue obtained during separation
was as high as 0.95%, requiring additional steps for its recovery. The
separation of K, Rb and/or Cs by crystallizing as mixed alums has been
proven effective by some researchers (Guo et al., 2016; Li et al., 2016;
Vieceli et al., 2018b). However, the further recovery of these metals
should be given with more details in future research.
4.1.2. Using hydrofluoric acid
Owing to the capability of destroying SieO bond, HF has also been
(20) used to extract Li from lepidolite. Rosales et al. (2017) proposed a
process to recover Li, Al and Si from lepidolite, in which HF was used as
lixiviant. The leaching reaction is represented by Eq. 22 (Rosales et al.,
2017). As shown in Fig. 10, the process involves acid leaching of lepi-
dolite, followed by the addition of stoichiometric KOH and NaOH to
precipitate the by-products, K2SiF6 and Na3AlF6, respectively (Eqs.
(21) 23–24). Li remaining in solution was finally recovered as LiF by eva-
poration. The results indicate that above 90% Li was leached from le-
pidolite by using 7% HF at 1.82% solid and 123 °C for 120 min, and
92% Li in solution was precipitated as LiF with a purity of 99.1%.
KLi2 AlSi 4 O10 F(OH) (s) + 32HF(aq) → 2LiF(aq) + H3 AlF6 (aq) + 4H2
SiF6 (aq) + KF (aq) + 11H2 O (22)
o
2KOH (aq) + H2 SiF6 (aq) → K2SiF6 (s) + 2 H2 O, ΔG25o
C
= −131.07 KJ/mol (23)
3NaOH (aq) + H3 AlF6 (aq) → Na3AlF6 (s) + 3H2 O (24)
Compared with H2SO4 method, HF method employs a lower
leaching temperature and shorter leaching time, which is less energy
consuming and more efficient. Like using HF for spodumene (Section
10
H. Li, et al.
Fig. 10. A process for the recovery of Li, Al and Si from lepidolite by HF method, adapted from Rosales et al. (2017).
3.1.2), the conversion of F into its salts reduces safety concerns, while
the operational capacity is still restricted by the low solubility of LiF
(Table 5). For example, the solid ratio used by Rosales et al. (2017) was
as low as 1.82% that is too low for a practical use. It is worth high-
lighting that Al and Si were recovered as K2SiF6 and Na3AlF6 separately
in this study, rather than a mixture of both, by controlling the alkali
added at a stoichiometric amount (Rosales et al., 2017).
4.1.3. Using sulfuric and hydrofluoric acids
More recently, Guo et al. (2019a, 2019b) reported a fluorine-based
method to extract Li from lepidolite, and investigated the extraction
mechanism in depth. In the method, a mixed acid of H2SO4 and HF was
used to digest lepidolite with the reaction proposed as Eq. 25 (Guo
et al., 2019a, 2019b). The results reveal that 98% Li, and 90% of Rb and
Cs were extracted as sulphates at ore/HF/H2SO4 ratio of 1:2:3.5 (g/mL/
mL) and 85 °C for 3 h. During the extraction, HF played a dominant
role, while H2SO4 reduced the consumption of HF but only accelerated
the leaching slightly. F and the extracted Al in leachate mainly existed
as HF/F− and Al3+, respectively, as well as a small amount of [AlFn]3-n.
In addition, the authors found that the leaching percentage of Si (66%)
was much lower than Li (98%), owing to the preferential dissolution of
lepidolite over quartz, which favours the downstream separation and
purification of leachate.
KLi1.5Al1.5AlSi3O10 F2 + 16HF + 5H2 SO4 → 0.75
Li2 SO4 + 1.25Al2 (SO4 )3 + 3H2 SiF6 + 0
o
. 5K2SO4 + 10H2 O, ΔG25o
C
= −1061.39 ± 18 KJ/ Mol (25)
Not surprisingly, through using both H2SO4 and HF, the separation
of Al, K, Rb and Cs from leachate can also be implemented by alum
crystallisation, which is similar with that in H2SO4 method (Section
4.1.1). A fundamental study conducted by Guo et al. (2016) indicates
that Al3+ in the solution from HF/H2SO4 leaching of lepidolite could be
removed as potassium alum (KAl(SO4)2·12H2O) with K2SO4 added,
during which Li alum or other double salts between Li2SO4 and
Al2(SO4)3 were not found. It was shown that K/Al molar ratio (m (K/
Al)) affected the Al removal % greatly at pH of 2 and 5 °C, with the
percentage increasing from 43.56% by direct crystallisation of leaching
solution (m (K/Al) = 0.4) to 78.81% by adding K2SO4 to a m (K/Al) of
0.9.
However, the possible interference of alum crystallisation brought
by the F remaining in water-leaching solution was not reported in de-
tails so far. Furthermore, the safety concerns existing in using H2SO4
and HF for spodumene also exist here. More studies focusing on the F
recycle will supplement this method. In addition the use of fluoride
(CaF2) and H2SO4 or H2SiF6 and H2SO4 to in situ generate HF could be
feasible as reported by Griffith et al. (2018) and Li et al. (2016) re-
spectively, while the detailed data has not yet been reported.
4.2. Sulphate roasting method
Several sulphates, such as Na2SO4, K2SO4, FeSO4 and CaSO4, have
been used to extract Li from lepidolite. Table 6 lists the conditions and
Li extractions (%) by using sulphate roasting method reported in recent
years. Yan et al. (2012b) used Na2SO4 together with CaCl2 to roast le-
pidolite, followed by water leaching, and > 90% Li, Rb and Cs were
11
Hydrometallurgy 189 (2019) 105129
extracted at ore/Na2SO4/CaCl2 mass ratio 1/0.5/0.3 and 880 °C for
0.5 h. As shown in Fig. 11, following the roasting, Na2CO3 and NaOH
were introduced to precipitate impurities of Ca, Fe, Mn and Al while the
losses of Li, K, Rb and Cs were < 1%. To avoid the precipitation of
KLiSO4, a desalination step was performed to remove SO42− prior to
precipitating Li2CO3, during which the losses of Li, K, Rb and Cs were
also < 1%. By evaporation and precipitation at 95–100 °C with 5 M
Na2CO3, ~86% Li was precipitated as Li2CO3 with a purity of 99.5%. Rb
and Cs remained in the mother solution and can be further recovered.
Another method reported by the authors uses Na2SO4 with the ad-
dition of K2SO4 and CaO to roast lepidolite, followed by water leaching
(Table 6) (Yan et al., 2012c). The XRD analysis of residue indicates that
the roasting made the ore decompose to NaSi3AlO8, KAlSi2O6 and
CaAl2Si2O8. Due to the addition of CaO, some F-containing compounds
(CaF2, Ca4Si2O7F2) were formed and reported to residue. In this way,
the interference to downstream metals recovery brought by forming
insoluble metal fluorides may be reduced. In addition, > 90% Li ex-
tractions were also obtained by using FeSO4 or Na2SO4 (with additive)
to roast lepidolite at 850–1000 °C for 0.5–1.5 h (Table 6) (Luong et al.,
2014; Luong et al., 2013; Vieceli et al., 2017b).
Compared with acid method, sulphate roasting is more energy
consuming since it requires roasting at high temperature
(850–1000 °C), while it is also more selective to Li making some K, Al,
Si, and/or F remain in residue. The elements in residue (e.g. K, Al)
should also be further recovered to increase the profitability of the
process that may compensate for the low Li content in lepidolite.
4.3. Sulphide roasting/grinding method
Sulphides, such as Na2S and FeS, have been reported to be effective
for Li extraction from lepidolite through the process of roasting or
grinding, followed by water leaching. Lee (2015) tested the grinding of
lepidolite with Na2S in a planetary ball mill, resulting in considerable
increase of the ore's leachability. It was found that only 4.53% of Li was
extracted without Na2S added during 12 h of grinding. However, 93%
Li extraction was recorded when lepidolite was ground at an ore/Na2S
mass ratio of 1/3 for 12 h, although the long-time grinding is relatively
energy and time consuming. By contrast, a sulphide roasting method
reported by Hien-Dinh et al. (2015) reveals lower Li extractions, in
which FeS together with CaO was used. The results indicate that only
81% Li could be extracted by roasting at FeS/Li and Ca/F molar ratios
of 5:1 and 1:1, respectively, and 750 °C for 1.5 h, and leaching with
water at L/S mass ratio > 5/1 and 50 °C. This was explained by the
significant loss of Sulphur (S) (71.5%) into atmosphere as SO2/SO3
during the roasting.
4.4. Carbonate roasting method
There have been patents, although quite rare, that have disclosed
the method of carbonate roasting, followed by water leaching, to ex-
tract Li from Li-bearing minerals, including lepidolite (Harold et al.,
1960; Walter and Bichowsky, 1935). In a method reported by Harold
et al. (1960), lepidolite is roasted with CaCO3 (limestone) at
800–1000 °C for 1–3 h. In the roasted materials, half of the silica was
present as spurrite (4CaO∙2SiO∙2CaCO3), and all the Al was present as
calcium aluminates that were to be separated by filtration. Then, the
roasted materials were quenched, ground and leached to obtain a
H. Li, et al. Hydrometallurgy 189 (2019) 105129

Table 6
Various reports regarding Li extraction from lepidolite using sulphate roasting method, conditions and results are the optimal.
Li2O in lepidolite/% Sulphate roasting Water leaching Li extraction/% Ref.

a o o
Amounts of reagent T/ C t/h L/S ratio T/ C t/h

b
4.30 ore/Na2SO4/CaCl2 = 1/0.5/0.3 880 0.5 0.8/1 RT 0.5 > 90 (Yan et al., 2012b)
4.30 ore/Na2SO4/K2SO4/CaO = 1/0.5/0.1/0.1 850 0.5 2.5/1 RT 0.5 91.61 (Yan et al., 2012c)
5.49 Na2SO4/Li = 2/1 1000 0.5 15/1 (w/w) 85 3 90.4 (Luong et al., 2013)
3.85 FeSO4/Li = 3/1, CaO/F = 1:1 (both are molar ratios) 850 1.5 1/1 (w/w) RT 1 ~93 (Luong et al., 2014)
4.20 ore/(Na2SO4 + CaSO4∙2H2O) = 1/0.60 875 1 10/1 80 4 > 90 (Vieceli et al., 2017b)
Na2SO4/CaSO4∙2H2O = 1/3

a b
In mass ratio, unless specified. denotes room temperature.

Fig. 11. A process for Li recovery from lepidolite by Na2SO4 roasting method, summarised from Yan et al. (2012b).

leaching solution containing alkali metal hydroxide and LiF which were
then separated based on their deference in solubility. The obtained LiF
could be converted to LiOH by causticizing its solution with lime. Fi-
nally LiOH∙H2O product was crystallised from solution by evaporation
and cooling.
4.5. Chlorinating method
Chlorinating method, involving the use of chloride or Cl2, has been
reported to extract Li from lepidolite. In particular, several studies of
chlorination have been carried out to treat lepidolite produced in
Yichun, China, where huge amount of lepidolite deposit is located (Wu
et al., 2012; Xu and Wang, 1993; Yan et al., 2012a). Xu and Wang
(1993) used ammonium chloride (NH4Cl) and NaCl to digest lepidolite
in an autoclave with stirring enhanced by steel/alloy balls, followed by
water washing. The results show that 91% Li was extracted when le-
pidolite was digested at ∑(M2O)/NH4Cl/NaCl molar ratio 1/3.5/1, L/S
ratio 4.0 and 230 °C for 2.5 h, where M stands for Li, Na, K, Rb, Cs and
Al. Another study carried out by Yan et al. (2012a) used NaCl and CaCl2
as chlorinating agents to roast lepidolite, followed by water leaching. In
this study, 92.86% Li together with 88.49% K, 93.60% Rb, and 93.01%
Cs were extracted at ore/NaCl/CaCl2 mass ratio 1/0.6/0.4 and 880 °C
for 30 min. The XRD analysis of leaching residue reveals that the major
products after roasting were CaAl2Si2O8, NaAlSi3O8, SiO2, CaF2, KCl,
CaSiO3 and NaCl. In addition, Wu et al. (2012) used Cl2 to roast lepi-
dolite, and 92.49% Li and 71.06% K extractions were achieved at
850 °C during 3 h. Likewise, the XRD analysis indicates that the roasting
products included LiAl(SiO3)2, SiO2, KCl, NaCl, K(Si3Al)O8. However,
the use of Cl2 will bring operational risks, and require expensive ma-
terials of construction.
4.6. Alkaline autoclaving method
To lower the temperature and pressure in the case of autoclaving
(Xu and Wang, 1993), Yan et al. (2012d) proposed a novel method that
employs a pre-treatment of de-fluorination before lepidolite was auto-
claved. When the ore was roasted in water steam atmosphere under
optimised conditions (860 °C and 30 min), 42.3% F was removed by
forming HF between H+ (derived from water) and F−. The XRD ana-
lysis of de-fluorinated residue shows that lepidolite was decomposed
into aluminium silicate (LiAl(SiO3)2) and leucite (KAlSi2O6), which
favoured Li extraction. After grinding the de-fluorinated lepidolite, an
autoclaving leaching using lime milk (Ca(OH)2) was performed at ore/
lime ratio 1/1, L/S ratio 4/1 and 150 °C for 60 min, with Li extraction of
98.9% reached. Finally, Li2CO3 was prepared from leaching solution
with a purity of as high as 99.9%.
5. Recovery of lithium from zinnwaldite
Like lepidolite, zinnwaldite also belongs to mica mineral group but
has significantly lower Li content (Table 3) (Botula et al., 2005).
Zinnwaldite has a general formula of KLiFeAl(AlSi3)O10(F,OH)2, in-
dicating considerable amounts of Fe (~12.78%) and F (~6.52%) con-
tained which are both much higher than that contained in lepidolite.
These differences have made the Li recovery from zinnwaldite chal-
lenging in a large scale and required a recovery process that should be
different from the one for lepidolite (Martin et al., 2017a). So far,
several methods have been proposed and investigated for Li recovery
from zinnwaldite, which will be discussed in the following sections.
5.1. Acid method
Recently, a novel method of Li recovery from zinnwaldite using HCl
as lixiviant has been proposed by (Martin et al., 2017a). The integrated
process is summarised in Fig. 12. When zinnwaldite concentrate
(Zinnwald, Germany) was digested by 29% HCl under reflux (ap-
prox.110 °C) and atmospheric pressure for 7 h, the highest Li extraction
of 94% was achieved. Importantly, the authors indicated that no HF/
SiF4 was formed during HCl digestion, which is advantageous compared
with conventional H2SO4 digestion (with pronounced HF release). The
excess HCl was recycled for reuse by distillation, which reduced HCl
usage considerably. The Fe contained in digestion solution was re-
moved by adding sodium hexacyanoferrate (Na4FeII(CN)6) to form
Prussian blue (FeIII[FeIIIFeII(CN)6]3), with the reaction represented by
Eq. 26. The Prussian blue was further converted to goethite (α-FeO
(OH)) as by-product by adding NaOH, while Na4FeII(CN)6 was re-
generated for reuse (Eq. 27). Al, K and F remaining in solution were
removed as sodium/potassium cryolite ((Na2.6K0.4)AlF6) by adjusting
pH to 3.0 and introducing stoichiometric NaF. The obtained by-product,
(Na2.6K0.4)AlF6, could be used in the known aluminium production

12
H. Li, et al.
Fig. 12. An integrated process for Li recovery from zinnwaldite, adapted from
Martin et al. (2017a).
process (Hall-Héroult process) (Bertau et al., 2017). After electro-
dialysis for impurity removal and evaporation for concentration, Li
precipitation was carried out by adding Na2CO3 (Eq. 28), and a main
product of Li2CO3 (purity ≥98.0%) was obtained.
4FeCl3 (aq) + 3Na 4 FeII (CN)6 (aq) → FeIII [FeIIIFeII (CN)6 ]3
(s) + 12NaCl (aq)
FeIII [FeIIIFeII (CN)6 ]3 (s) + 12NaOH (aq) → 3Na 4 FeII (CN)6
(aq) + 4FeO(OH) (s) + 4H2 O
o
Na2CO3 (aq) + 2LiCl (aq) → 2NaCl (aq) + Li2 CO3 (s), ΔG25o
C Li2CO3 was stepwise crystallised by evaporating solution in three steps
= −24.62 KJ/mol
5.2. Sulphate roasting method
A sulphate roasting method, also called gypsum method, has been
reported by Czech scientists to recover Li from zinnwaldite (Cínovec,
Czech Republic) (Jandová et al., 2009). In the method, zinnwaldite was
sintered with CaSO4 and Ca(OH)2, followed by water leaching. The
highest Li extraction of 96% was reached when the concentrate was
sintering at concentrate/CaSO4/Ca(OH)2 ratio 6/4.2/2 and 950 °C for
60 min, and water-leached at 90 °C for 10 min. By analysis of the sin-
ters, it was found that the zinnwaldite was decomposed into
Ca3Fe2(SiO4)3, Ca(Al2Si2O8), Ca4Si2O7F2, traces of CaF2, and leachable
LiKSO4. F was hence prevented from reporting to leaching solution by
the formation of F-containing compounds (Martin et al., 2017a). Most
of the Ca2+ contained in leaching solution was then removed by adding
K2CO3, and the rest was removed during condensation of leaching so-
lution. After condensation, K2CO3 was added again to precipitate Li as
crude Li2CO3 (purity 96%) at 90 °C. Finally, a Li2CO3 product with a
purity of 99% was obtained after water washing of the crude one.
In addition, Siame and Pascoe (2011) used CaSO4 to roast para-
magnetic mica concentrate containing zinnwaldite up to 85%, followed
by pulverization and water leaching. The results indicate that a max-
imum Li extraction of 84% was achieved by roasting at concentrate/
CaSO4 mass ratio 2/1 at 1050 °C for 60 min. Meanwhile, the Rb ex-
traction was only 14%. It is worth highlighting that Fe content in
leaching solution was less than detection limit under all experimental
Hydrometallurgy 189 (2019) 105129
conditions. The XRD analysis of roasting residue shows that KLiSO4,
Ca3(Cr0.85Al0.15)2(SiO4)3 and Ca4Si2O7F2/3CaO·2SiO2·CaF2) were
formed during the roasting.
5.3. Carbonate roasting method
A carbonate roasting method has been employed in the Li and Rb
recoveries from zinnwaldite (Jandová et al., 2010; Siame and Pascoe,
2011; Vu et al., 2013). Vu et al. (2013) used CaCO3 to sinter zinnwal-
dite concentrate at concentrate/CaCO3 mass ratio 1/5 for 1 h, followed
by water leaching at L/S ratio 10/1. The optimal extractions of 84% for
Li and 91% for Rb were reached at sintering temperature of 825 °C and
leaching temperature of 95 °C. An investigation of sintering mechanism
indicates that the process happened through the following three partly
overlapping stages (Vu et al., 2013):
(1). At ~800 °C, zinnwaldite decomposed gradually and transformed to
polylithionite, during which Fe2O3 was formed.
(2). At 750–835 °C, new phases were formed as a result of Ca diffusing
inward, and K, Rb and Si diffusing outward. As the temperature
rising up to 835 °C, the extraction of Li stayed at 84% and that of
Rb slightly increased to 92%.
(3). At ~835 °C, glass phase was formed, accounting for the decrease of
Li extraction. However, no effect occurred on Rb extraction due to
its outward diffusion behaviour.
Following CaCO3 sintering/roasting and water leaching, Jandová
et al. (2010) focused on the downstream purification and Li2CO3 pre-
paration from leaching solution. In their study, two recovery routes
were proposed in details, i.e. carbonation-crystallisation route, and
solvent extraction-precipitation route (Jandová et al., 2010). In the first
route, CO2 was bubbled into the original alkaline leaching solution (pH
(26) ~13) with a final pH of 6.8 (Eq. 6–7), accompanying with Al, Ca and Si
precipitation. Then, the resulting solution was refined by evaporation at
90 °C with 75% H2O removed, during which about 80% Ca was pre-
(27) cipitated. Before the crystallisation of Li2CO3, > 99% Al and Si, and
90% Ca were removed, and the Li loss was around 6%. Afterwards,
(28) (Eq. 8), with a final pH of 9.94. The purity of Li2CO3 product obtained
after water washing in this route was ≥99.5%. In the second route, Li
from the original alkaline leaching solution was extracted by 0.218 M
LIX54 and 0.075 M TOPO, and stripped by 0.2 M H2SO4 to obtain
Li2SO4 solution. By solvent extraction, 97% Li was extracted in one
step, whilst Rb together with most of K, Na, Na, Al and Si remained in
aqueous phase. Subsequently, Li2SO4 was crystallised from striping
solution by two-step evaporation, with most of Ca removed in the first
step. Li2CO3 product, with a purity of 99.5%, was finally obtained by re-
dissolving Li2SO4 crystal in water, followed by known precipitation and
water washing. However, the Li2CO3 precipitation (%) was lower than
71% related to the Li2SO4 striping solution, due to high Li losses and
low precipitation efficiency, which made the first route superior.
5.4. Direct carbonation method
Direct carbonation of calcined zinnwaldite has been used to extract
Li from such mineral (Martin et al., 2017c; Schneider et al., 2017). As
summarised in Fig. 13, crushed zinnwaldite concentrate was calcined at
950 °C for 3 h, decomposing the concentrate. After milling, the calcined
concentrate was directly carbonated in an autoclave by adding super-
critical CO2 (10 MPa, 230 °C) for 3 h, transferring > 70% Li into solu-
tion as soluble LiHCO3. Subsequently, electrodialysis with monovalent
cation exchange membranes was used to concentrate and purify LiHCO3
solution, resulting in the enrichments of Li, K and Rb, separated with
higher valent species like Ca2+. Li2CO3 precipitate (purity ≥99.0%)
was finally obtained by using common method of evaporation (Eq. 8)
(Martin et al., 2017c).
13
H. Li, et al.
Fig. 13. A process for Li recovery from zinnwaldite by direct carbonation,
adapted from Martin et al. (2017c).
It is interesting that Schneider et al. (2017) has found that during
the calcination of zinnwaldite at a temperature higher than 900 °C, the
decomposed products were mainly β-spodumene, silicates leucite, he-
matite and magnetite. This result indicates that the methods applied to
β-spodumene (Section 3) may also be potentially used for the calcined
zinnwaldite.
6. Recovery of lithium from other mineral resources
6.1. Recovery of lithium from amblygonite
Amblygonite, with a general formula of (Li,Na)Al(PO4)(F,OH)
(Table 2), is a kind of fluorophosphate mineral. It geologically occurs in
granite pegmatite and is found in fluorine-rich topaz-bearing granites
(Choubey et al., 2016). As can be calculated from the formula, am-
blygonite has high theoretical contents of phosphorus (P, 20.46%) and
F (9.41%), which represents different materials compared with silicate-
based pegmatite minerals. So far, Li extraction from amblygonite is not
actively studied with only a few reports published in the last century.
A US patent published by Hans and Oskar (1936) reports an acid
(H2SO4) method to extract Li from amblygonite. In the method, two-
step heating with H2SO4 was proposed. Firstly, amblygonite was heated
in H2SO4 at 100–200 °C until the mass becomes pulpy. In this step, Li, Al
and Fe transferred into corresponding sulphates and free phosphoric
acid (H3PO4) was formed. The pulp was then heated at 800–850 °C,
until the mass ceases to generate appreciable fumes, during which Al
and Fe sulphates converted into their phosphates and oxides by the
more refractory H3PO4, with SO3, or SO2 and O2 liberated. Meanwhile,
Li still remained as Li2SO4. By water leaching, Li2SO4 was mobilised to
solution with a Li yield of ~95%. Another US patent indicates an al-
ternative method that uses SO3 gas to treat amblygonite at 600–900 °C
to transfer Li to Li2SO4, followed by water leaching (Frevel and
Kressley, 1962). However, the Li yield seems not to be satisfactory
(Frevel and Kressley, 1962).
In addition, an alkali (NaOH) method reported in a US patent was
used to extract Li from amblygonite (Harry and Jaffa, 1935). By di-
gesting with NaOH, Al in amblygonite was dissolved while Li still re-
mained as insoluble form. In this way, Al was separated into solution
and a Li-rich residue was obtained. The residue was then washed by
NaH2PO4 or H3PO4 to partially remove P2O5, followed by leaching with
dilute acid to dissolve Li compound. The impurities, such as Fe, Al, Ca
and/or Mn, were precipitated from the acid-leaching solution by adding
lime or soda ash. The purified Li-rich solution was concentrated and
finally treated to precipitate Li2CO3 product (Eq. 3) (Harry and Jaffa,
14
Hydrometallurgy 189 (2019) 105129
1935).
6.2. Recovery of lithium from clays
Some Li-bearing clays have been seen as a kind of unusual and often
uneconomic Li sources, from which several minerals have attracted
attention for Li recovery. Amer (2008) used H2SO4 to digest mon-
tmorillonite-type clay in a ball-mill autoclave. The clay is native to El-
Fayoum and Cairo-Alexandria Desert in Egypt, with Li existing as
hectorite. The results indicate that approximately 90% Li was extracted
by digesting with 7 M H2SO4 at L/S ratio 1/5 (w/w) and 250 °C for
90 min. Barzegari et al. (2016) used CaCO3 and CaSO4 to roast low-
grade gypsiferous clay (Khorasan Razavi, Iran), followed by water
leaching. Li existing in the samples was considered as hectorite and
jadarite, with a content of 400 ppm (0.04%). By roasting at feed/
CaCO3/CaSO4 ratio 5/1/1 and 1100 °C for 5 h, the highest Li extraction
of 75.65% was reached. No Mg was detected in the leaching solution
and the concentration of Ca was lowered to 0.1%, which favours the
downstream purification process. Another study reveals that it seems to
be economical to extract Li from boron clays (0.2% Li, Bigadic, Turkey)
by using natural limestone-clay materials and waste of boric acid pro-
duction as a source of gypsum (Büyükburç et al., 2006).
Unlike pegmatite ore, Li-bearing clays often have a very low Li
content and sometimes they are difficult to be beneficiated due to the
great dissemination of Li (Amer, 2008). Using the common methods,
such as H2SO4, sulphate or carbonate roasting/autoclaving, will usually
cause high reagent consumption and energy costs that makes the pro-
cess uneconomical. Given that pegmatite ores have wide distribution,
high abundance (Fig. 1) and Li content (Table 2), it is predicted that Li-
bearing clays will still remain as an unusual and additional mineral
resources for Li recovery in the near future.
7. Perspectives and outlook
With the development of new energy technologies, EVs in parti-
cular, Li has attracted much attention in recent years. Although Li
production from brines incurs lower costs, the mineral resources will
still play an important and indispensable role in Li-salt industry due to
their wider distribution and technological advancements. Below the
perspectives and outlook are presented based on the foregoing state-of-
the-art review.
7.1. Spodumene: the main mineral source of Li
Compared with other Li-bearing minerals, spodumene has higher Li
grade, simpler composition, and less impurities. In 2011, 85% of world
Li production from ores came from a spodumene deposit in
Greenbushes, Western Australia (Tadesse et al., 2019). It can be fore-
seen that spodumene will continue to be the preferred source of Li in
the near future. The research works regarding Li recovery from spo-
dumene will be targeting a process that has less energy consumption
and higher efficiency, compared with the already industrialised H2SO4
method. To achieve this, the direct treatment of α-spodumene at low
temperature (e.g. ≤250 °C) that avoids the energy-intensive phase
transfer could be a promising direction. So far, alkali digestion and
fluorine-based method have been used to directly extract Li from α-
spodumene (Section 3.1.2). It is expected that more efforts about re-
action mechanism, process optimisation and the design of highly anti-
corrosive equipment for the direct processing of α-spodumene will be
made in the future researches.
Currently, there are a number of forms of Li salt have been prepared
from spodumene, including Li2CO3, LiOH, LiCl and LiF. Among them,
Li2CO3 has been most widely reported as a final product of Li recovery
from spodumene in the literature. However, LiOH has been seen as a
preferred form of Li salt for the EV batteries with high energy density
and its demand growth has been expected to exceed the demand growth
H. Li, et al.
of Li2CO3 in the next few years (Tiihonen et al., 2019). With the in-
creasing demand for LiOH, more researches on the direct production of
LiOH from spodumene are expected in the future. The basic process to
produce LiOH at present is via a reaction between Li2CO3 and Ca(OH)2
(Jiang et al., 2014), which is referred as indirect method. By compar-
ison, the direct production of LiOH from spodumene is considered as a
more straightforward and cheap method. To achieve this, using hy-
droxides to process α/β-spodumene (Section 3.2) or to treat the inter-
mediate Li-containing residue (Section 3.4) seems to be more feasible
than other methods since Li can be converted as LiOH and can be fur-
ther crystallised. It is worth mentioning that the hydroxide processing
of spodumene also has the advantage of less impurities in pregnant
leaching solution (PLS) due to the precipitation of Fe, Al, Ca and Mg at
alkaline environment, which favours the production of high-purity
LiOH.
By contrast, Li recovery from lepidolite, zinnwaldite, as well as
other additional mineral resources, still needs to be further investigated
in order to work out an integrated process that is technically, eco-
nomically, and environmentally feasible. Since lepidolite and zinn-
waldite have much lower Li grade and more complicated components,
they are still hard to be competitive with spodumene at current stage
and will remain as alternative mineral sources of Li. Given that an
abundance of lepidolite and zinnwaldite have been found in particular
areas in China and Europe respectively (Fig. 2) (Bertau et al., 2017), the
Li recovery from these minerals will still be of interest of researchers,
which could be a way to diverse Li market and secure Li supply do-
mestically.
7.2. The fluorine-based method
As reviewed in the foregoing sections, fluorine-based methods have
been actively reported in recent years, which brings them into high-
light. The methods can be divided into: (1) using HF only (Sections
3.1.2 and 4.1.2); (2) using HF/H2SO4 mixture (Sections 3.1.3 and
4.1.3); (3) using CaF2 and H2SO4 to in situ generate HF (Section 3.1.4);
and (4) using H2SiF6 and H2SO4 to in situ generate HF (no data disclosed
yet). No matter what kind of method is used, the mechanism is essen-
tially based on HF molecules' powerful ability of attacking SieO bond in
silicate minerals (Guo et al., 2019a, 2019b). As summarised in Table 7,
fluorine-based methods with direct use of HF can achieve a high ex-
traction efficiency at moderate temperature. It is shown that 90% Li can
be extracted from β-spodumene by using HF at 75 °C for only 20 min
(Rosales et al., 2014), and 96% was achieved for α-spodumene that was
even not yet undergone a phase transfer (Guo et al., 2017). Compared
with the H2SO4 method (~250 °C), roasting method (~1200 °C) and
autoclaving method (~250 °C, under pressure), fluorine-based methods
show advantages on energy consumption. In addition, the required
energy can also be partially from the dehydration effect of concentrated
H2SO4, which could further reduce the energy costs.
However, the major concern behind the methods is the operational
Table 7
Fluorine-based methods for Li extraction from reported minerals.
Extracting agent(s) Mineral studied Use of HF Conditionsc
HF β-s , L
a b
Direct β-s: 75 °C, 20 min
L: 123 °C, 120 min
HF + H2SO4 α-sd, L Direct α-s: 100 °C, 3 h
L: 85 °C, 3 h
CaF2 + H2SO4 α-s Indirect - -
H2SiF6 + H2SO4 L Indirect - -
“-” denotes not reported.
a
β-spodumene.
b
Lepidolite.
c
Conditions and extractions given at optimal.
d
α-spodumene.
15
Hydrometallurgy 189 (2019) 105129
safety and environmental risks particularly when HF is directly used. In
the case of using HF only, researchers have reduced the HF con-
centration to 7% and F converted into by-products during leaching and
purification (Rosales et al., 2017; Rosales et al., 2014), so that the re-
lease of free-HF can be reduced. Nevertheless, due to the low solubility
of LiF (Ksp = 1.84 × 10−3, Table 5), a low solid ratio during leaching
of the minerals should be maintained to secure the dissolution of Li,
which will limit the production capacity and bring high costs of con-
centration. By introducing H2SO4, the fluorides can be converted to
corresponding sulphates that have high solubility (Table 5), while this
will also bring the release of free-HF and SiF4 gas (Guo et al., 2019a,
2019b). For safety, environment, and economy considerations, the re-
lease of F must be controlled, and the F should be recycled for reuse.
Moreover, the removal and recycling of F should better happen before
the separation and purification of water-leaching solution, such as
alums crystallisation, to avoid the interference from the formation of
insoluble metal fluorides (LiF, AlF3, etc.). However, the recycling of F
has not been well reported so far. On the other hand, to avoid the direct
use of HF, the combination of CaF2/H2SO4, as well as H2SiF6/H2SO4,
has been reported or mentioned recently, to in situ generate HF during
the extraction of Li (Griffith et al., 2018; Li et al., 2016), while still not
many details are reported. Therefore, the future research can be focused
on the F recycling and the indirect use of HF. Another problem behind
the fluorine-based methods is the generation of F-containing waste.
Both spodumene and lepidolite have high contents of Al (18–27%
Al2O3) and Si (50–70% SiO2), hence large amount of fluoride salts, such
as Na3AlF6 and Na2SiF6, could be generated that have limited market
capacity and need to be disposed properly. In addition, based on the
mechanism investigation (Guo et al., 2019a, 2019b), one may hope that
the fluorine-based methods may also be applicable for the metal ex-
traction from other silicate minerals, such as zinnwaldite and feldspars.
7.3. Towards comprehensive utilization
Although Li salt is the main product from the processing of Li-
bearing minerals, it should be realised that Li2O only accounts for ~8%
of the total mass of both Li-bearing ores and concentrates. The com-
prehensive utilization of the rest 92~% will determine if a process is
successful in its economic and environmental aspects. In particular,
many other valuable metals, such as K, Al, Rb and Cs, are also present in
the mineral (Table 3). Given that the Li grade in lepidolite, zinnwaldite
and some additional mineral resources is much lower than spodumene,
those valuable metals are not just impurities, but also potential by-
products that can make the process economically feasible and compe-
titive. In addition, the problem brought by the generation of large
amount of residue should be concerned. Particularly, when the Li ex-
traction is based on ion exchange (e.g. Na2SO4/Na2CO3/NaCl roasting/
autoclaving,), considerable amount of Al/Si-based residue will be pro-
duced that needs to be further treated for disposal or recovery. How-
ever, the processing of residue is often neglected in most studies. One
Extractionc/% Ref.
β-s: 90 (Rosales et al., 2017; Rosales et al., 2014)
L: > 90
α-s: 96 (Guo et al., 2019a, 2019b; Guo et al., 2017)
L: 98
(Kuang et al., 2012)
(Li et al., 2016)
H. Li, et al.
promising way to solve residue problem is the conversion of Al and Si
into by-products with added value, such as hydroxysodalite (Xing et al.,
2019). It is worth mentioning that F originally contained in the mi-
nerals (e.g. lepidolite, zinnwaldite) must be recovered for environ-
mental considerations. Hence, an industrially viable process should be
integrated from various recovery modules that achieve a comprehen-
sive utilization of all the profitable elements and a proper treatment of
residue and waste.
Finally, a comprehensive economic assessment of the integrated
process, with regard to transportation costs (international/domestic),
energy consumption, production efficiency etc., needs to be done to
prove its economic feasibility.
8. Conclusions
The present work reviews the up-to-date status of Li recovery from
mineral resources, and gives discussions and perspectives regarding
various recovery methods. The general conclusions drawn from this
review are listed below.
• Conventional H SO 2 4 method has the advantages of high extraction
efficiency, relatively lower costs, and mature technology, which will
continue being dominantly used for spodumene, the main mineral
source of Li in the near future.
• Alkali- and fluorine- based method can process natural spodumene
directly and reduce energy consumption, and the fluorine-based one
can extract Li from both spodumene and lepidolite efficiently while
more efforts still need to be done regarding their reaction me-
chanism, process optimisation, anti-corrosive equipment design,
reagent recycling, and safety control.
• Roasting or autoclaving with sulphates, carbonates, chlorides, hy-
droxides, etc. is energy intensive, but can reduce the amount of
impurities in PLS. Using hydroxides could favour the direct pro-
duction of high-purity LiOH to meet the future EV market, while
using chlorinating method requires anti-corrosive equipment.
• Considerable amount of residues and wastes, such as Al/Si-based
residue after ion exchange and F-containing waste from fluorine-
based methods, should be treated properly for disposal or recovery.
Acknowledgements
Mr. Huan Li gratefully acknowledges the financial sponsorship by
Curtin University and China Scholarship Council (CSC). The authors
thank Miss Hui Guo at Central South University (China) for reading and
commenting on this study.
References
Alibaba Group, 2019. Chemicals average prices Jan 2019. http://www.alibaba.com/.
Amer, A.M., 2008. The hydrometallurgical extraction of lithium from Egyptian mon-
tmorillonite-type clay. JOM 60 (10), 55–57.
Archambault, M., Macewan, J.U. and Olivier, C.A., 1962. Method of producing lithium
carbonate from spodumene. US Patent 3017243.
Argus Media Group, 2018. Argus white paper - Lithium pricing at a crossroads. Retrieved
from. https://www.argusmedia.com/-/media/Files/white-papers/argus-white-
paper-lithium-pricing-at-a-crossroads.ashx, Accessed date: 5 January 2019.
Arne, S.K. and Johan, W.S., 1941. Method of recovering lithium salts from lithium-con-
taining minerals. US Patent 2230167.
Aylmore, M.G., Merigot, K., Rickard, W.D.A., Evans, N.J., McDonald, B.J., Catovic, E.,
Spitalny, P., 2018. Assessment of a spodumene ore by advanced analytical and mass
spectrometry techniques to determine its amenability to processing for the extraction
of lithium. Miner. Eng. 119, 137–148.
Azevedo, M., Campagnol, N., Hagenbruch, T., Hoffman, K., Lala, A., Ramsbottom, O.,
2018. Lithium and Cobalt - a Tale of Two Commodities. McKinsey & Company Jun
2018, Retrieved from. https://www.mckinsey.com/~/media/mckinsey/industries/
metals%20and%20mining/our%20insights/lithium%20and%20cobalt%20a%20tale
%20of%20two%20commodities/lithium-and-cobalt-a-tale-of-two-commodities.ashx,
Accessed date: 12 December 2018.
Barbosa, L.I., González, J.A., Ruiz, M.D.C., 2015. Extraction of lithium from β-spodumene
using chlorination roasting with calcium chloride. Thermochim. Acta 605, 63–67.
Barbosa, L.I., Valente, N.G., Gonzalez, J.A., 2013. Kinetic study on the chlorination of β-
spodumene for lithium extraction with Cl2 gas. Thermochim. Acta 557, 61–67.
16
Hydrometallurgy 189 (2019) 105129
Barbosa, L., Valente, G., Orosco, R., González, J., 2014. Lithium extraction from β-spo-
dumene through chlorination with chlorine gas. Miner. Eng. 56, 29–34.
Barzegari, M.R., Ghorbankarimi, G., Saadati, H., Torshizian, H., 2016. Selective extrac-
tion of lithium from low-grade gypsiferous clays by reduction of calcium and mag-
nesium content in the pregnant leach solution (PLS). Int. Acad. J. Sci. Eng. 3 (4),
70–79.
Beardsmore, T., 2018. Western Australia: a battery metal powerhouse, Western Australia,
Feb 13, 2018. Retrieved from. http://dmpbookshop.eruditetechnologies.com.au/
product/western-australia-a-battery-metal-powerhouse.do, Accessed date: 18
January 2019.
Bertau, M., Voigt, W., Schneider, A., Martin, G., 2017. Lithium recovery from challenging
deposits: Zinnwaldite and magnesium-rich salt Lake brines. ChemBioEng Reviews 4
(6), 360–376.
Bieseki, L., Melo, V.V., Sobrinho, E., Melo, D., Pergher, S., 2013. Extraction of lithium
from β-spodumene sample. Cerâmica 59 (352), 557–562.
Botto, I.L., 1985. Structural and spectroscopic properties of leached spodumene in the
acid roast processing. Mater. Chem. Phys. 13 (5), 423–436.
Botula, J., Rucký, P., Řepka, V., 2005. Extraction of zinnwaldite from mining and pro-
cessing wastes. Min. Geol. Ser. 2, 9–16.
Bulletin, M., 2017. Chinese EV boom to spur lithium capacity growth in 2018. Retrieved
from. https://www.metalbulletin.com/Article/3775671/Chinese-EV-boom-to-spur-
lithium-capacity-growth-in-2018.html, Accessed date: 18 January 2019.
Büyükburç, A., Maraşlıoğlu, D., Bilici, M.S.U., Köksal, G., 2006. Extraction of lithium
from boron clays by using natural and waste materials and statistical modelling to
achieve cost reduction. Miner. Eng. 19 (5), 515–517.
Cano, Z.P., Banham, D., Ye, S., Hintennach, A., Lu, J., Fowler, M., Chen, Z., 2018.
Batteries and fuel cells for emerging electric vehicle markets. Nat. Energy 3 (4),
279–289.
Chen, Y., Tian, Q., Chen, B., Shi, X., Liao, T., 2011. Preparation of lithium carbonate from
spodumene by a sodium carbonate autoclave process. Hydrometallurgy 109 (1–2),
43–46.
Choubey, P.K., Kim, M.-S., Srivastava, R.R., Lee, J.-C., Lee, J.-Y., 2016. Advance review
on the exploitation of the prominent energy-storage element: Lithium. Part I: from
mineral and brine resources. Miner. Eng. 89 (Supplement C), 119–137.
Davis, J.R., 2000. Corrosion: Understanding the Basics. ASM International.
Dean, J.A., 1999. Lange's Handbook of Chemistry (15th Edition). McGraw-Hill Inc.
Dwyer, T.E., 1957. Recovery of lithium from spodumene ores. US Patent 2801153.
Economist, 2016. An Increasingly Precious Metal. The Economist, New York Jan 14,
2016, Retrieved from. https://www.economist.com/business/2016/01/14/an-
increasingly-precious-metal, Accessed date: 12 June 2018.
Ellestad, R.B. and Leute, K.M., 1950. Method of extracting lithium values from spodu-
mene ores. US Patent 2516109.
EV-Volumes, 2019. Global plug-in vehicle sales for 2018 - final results. Retrieved from.
http://www.ev-volumes.com/country/total-world-plug-in-vehicle-volumes,
Accessed date: 12 March 2019.
Frevel, L.K. and Kressley, L.J., 1962. Separation of lithium from lithium bearing micas
and amblygonite. US Patent 3032389.
Friedman-Rudovsky, J., 2011. Dreams of a Lithium empire. Science 334 (6058), 896–897.
Gabra, G., Torma, A., Olivier, C., 1975. Pressure leaching of beta-spodumene by sodium
chloride. Can. Metall. Q. 14 (4), 355–359.
Geology Survey of Western Australia, 2018. Lithium: Investment Opportunities, Western
Australia, Jan 2018. Retrieved from. http://geodocs.dmp.wa.gov.au/viewer/
multipageViewerAction.do?documentId=642478&viewMarkId=0&ct=true&at=
none&btv=true&atv=false&vmtv=false&ac=ff0000&cabinetId=-1&pg=0&scl=
64&bds=0|0|2560|3584, Accessed date: 18 January 2019.
Griffin, A., 2017. Hydrometallurgical Processes for the Recovery of Lithium from
Silicates. Proceeding of ALTA, Perth, Australia 20–27 May.
Griffith, C.S., Griffin, A.C., Roper, A., Skalski, A., 2018. Development of SiLeach®
Technology for the Extraction of Lithium Silicate Minerals. Extraction 2018. Springer
International Publishing, Cham, pp. 2235–2245.
Gruber, P.W., Medina, P.A., Keoleian, G.A., Kesler, S.E., Everson, M.P., Wallington, T.J.,
2011. Global lithium availability: a constraint for electric vehicles? J. Ind. Ecol. 15
(5), 760–775.
Guo, H., Kuang, G., Yang, J.-X., Hu, S., 2016. Fundamental research on a new process to
remove Al3+ as potassium alum during Lithium extraction from Lepidolite. Metall.
Mater. Trans. B 47 (6), 3557–3564.
Guo, H., Kuang, G., Wang, H., Yu, H., Zhao, X., 2017. Investigation of enhanced leaching
of Lithium from α-Spodumene using hydrofluoric and sulfuric acid. Minerals 7 (11),
205.
Guo, H., Kuang, G., Wan, H., Yang, Y., Yu, H., Wang, H., 2019a. Enhanced acid treatment
to extract lithium from lepidolite with a fluorine-based chemical method.
Hydrometallurgy 183, 9–19.
Guo, H., Yu, H., Zhou, A., Lu, M., Wang, Q., Kuang, G., Wang, H., 2019b. Kinetics of
leaching lithium from α-spodumene in enhanced acid treatment using HF/H2SO4 as
medium. Trans. Nonferrous Metals Soc. China 29 (2), 407–415.
Hans, S. and Oskar, R., 1936. Process for the production of lithium salts. US Patent
2040573.
Harold, M., Cohen, S.L. and Schafer, G.H., 1960. Process for recovering alkali metal va-
lues from lepidolite. US Patent 2940820.
Harry, C.J. and Jaffa, N.E., 1935. Recovering lithium compounds. US Patent 2024026.
Helvaci, C., Mordogan, H., Çolak, M., Gündogan, I., 2003. Presence and distribution of
Lithium in borate deposits and some recent Lake waters of west-Central Turkey. Int.
Geol. Rev. 46 (2), 177–190.
Hien-Dinh, T.T., Luong, V.T., Gieré, R., Tran, T., 2015. Extraction of lithium from lepi-
dolite via iron sulphide roasting and water leaching. Hydrometallurgy 153, 154–159.
Jandová, J., Vu, H.N., Belkova, T., Dvorák, P., Kondás, J., 2009. Obtaining Li2CO3 from
zinnwaldite wastes. Ceramics-Silikáty 53 (2), 108–112.
Jandová, J., Dvořák, P., Vu, H.N., 2010. Processing of zinnwaldite waste to obtain Li2CO3.
Hydrometallurgy 103 (1), 12–18.
Jaskula, B.W., 2016. Lithium. In: Minerals Yearbook - 2014, Retrieved from. https://
H. Li, et al.
minerals.usgs.gov/minerals/pubs/commodity/lithium/myb1-2014-lithi.pdf,
Accessed date: 8 June 2018.
Jaskula, B.W., 2017. Lithium. In: Minerals Yearbook - 2015, Retrieved from. https://
minerals.usgs.gov/minerals/pubs/commodity/lithium/myb1-2015-lithi.pdf,
Accessed date: 12 December 2018.
Jaskula, B.W., 2019. Lithium. In: Mineral Commodity Summaries, Retrieved from.
https://minerals.usgs.gov/minerals/pubs/commodity/lithium/mcs-2019-lithi.pdf,
Accessed date: 6 March 2019.
Jiang, C., Wang, Y., Wang, Q., Feng, H., Xu, T., 2014. Production of lithium hydroxide
from lake brines through electro–electrodialysis with bipolar membranes (EEDBM).
Ind. Eng. Chem. Res. 53 (14), 6103–6112.
Johnson, G.D., Urbani, M.D. and Vines, N.J., 2017. Recovery process. WO Patent 2016/
054683 Al.
Kavanagh, L., Keohane, J., Garcia Cabellos, G., Lloyd, A., Cleary, J., 2018. Global Lithium
sources—industrial use and future in the electric vehicle industry: a review.
Resources 7 (3), 57.
Kesler, S.E., Gruber, P.W., Medina, P.A., Keoleian, G.A., Everson, M.P., Wallington, T.J.,
2012. Global lithium resources: relative importance of pegmatite, brine and other
deposits. Ore Geol. Rev. 48, 55–69.
Kuang, G., Chen, Z.B., Guo, H., Li, M.H., 2012. Lithium extraction mechanism from α-
Spodumene by fluorine chemical method. Adv. Mater. Res. 524-527, 2011–2016.
Kuang, G., Sun, J., Yang, J. and Jin, R., 2014. A method for the production of lithium
hydroxide from spodumene using pipe reactor. CN Patent 104003428 A.
Kuang, G., Li, H., Hu, S., Jin, R., Liu, S., Guo, H., 2015. Recovery of aluminium and
lithium from gypsum residue obtained in the process of lithium extraction from le-
pidolite. Hydrometallurgy 157, 214–218.
Kuang, G., Liu, Y., Li, H., Xing, S., Li, F., Guo, H., 2018. Extraction of lithium from β-
spodumene using sodium sulfate solution. Hydrometallurgy 177, 49–56.
Lee, J., 2015. Extraction of lithium from lepidolite using mixed grinding with sodium
sulfide followed by water leaching. Minerals 5 (4), 737–743.
Leemann, A., Le Saout, G., Winnefeld, F., Rentsch, D., Lothenbach, B., 2011. Alkali–silica
reaction: the influence of calcium on silica dissolution and the formation of reaction
products. J. Am. Ceram. Soc. 94 (4), 1243–1249.
Li, L., Hu, N., Huang, X., Xiong, X., Zeng, X. and Luo, S., 2006. Method for producing
refined lithium sulfate solution used in lepidolite lithium-extracting technique by
sulfuric acid process. CN Patent 100503849C.
Li, H., Kuang, G., Hu, S., Guo, H., Jin, R., Vekariya, R.L., 2016. Removal of aluminum
from leaching solution of lepidolite by adding ammonium. JOM 68 (10), 2653–2658.
Lide, R.D., 2005. CRC Handbook of Chemistry and Physics. CRC Press, Boca Raton, FL.
Liu, L., Wang, D., Liu, X., Li, J., Dai, H., Yan, W., 2017. The main types, distribution
features and present situation of exploration and development for domestic and
foreign lithium mine. Geol. China (in Chinese) 44 (2), 263–278.
Liu, J.-L., Yin, Z.-L., Li, X.-H., Hu, Q.-Y., Liu, W., 2019. Recovery of valuable metals from
lepidolite by atmosphere leaching and kinetics on dissolution of lithium. Trans.
Nonferrous Metals Soc. China 29 (3), 641–649.
London, D., 2017. Reading pegmatites: part 3—what Lithium minerals say. Rocks Miner.
92 (2), 144–157.
Luong, V.T., Kang, D.J., An, J.W., Kim, M.J., Tran, T., 2013. Factors affecting the ex-
traction of lithium from lepidolite. Hydrometallurgy 134-135, 54–61.
Luong, V.T., Kang, D.J., An, J.W., Dao, D.A., Kim, M.J., Tran, T., 2014. Iron sulphate
roasting for extraction of lithium from lepidolite. Hydrometallurgy 141 (2), 8–16.
Martin, A.B., 2018. The Leaching of α-Spodumene. Murdoch University Retrieved from.
https://researchrepository.murdoch.edu.au/id/eprint/44868/1/Albertani2018.pdf,
Accessed date: 25 May 2019.
Martin, G., Pätzold, C., Bertau, M., 2017a. Integrated process for lithium recovery from
zinnwaldite. Int. J. Miner. Process. 160, 8–15.
Martin, G., Rentsch, L., Hoeck, M., Bertau, M., 2017b. Lithium market research - global
supply, future demand and price development. Energy Storage Mater. 6, 171–179.
Martin, G., Schneider, A., Voigt, W., Bertau, M., 2017c. Lithium extraction from the
mineral zinnwaldite: part II: Lithium carbonate recovery by direct carbonation of
sintered zinnwaldite concentrate. Miner. Eng. 110, 75–81.
Maurice, A. and Olivier, C.A., 1968. Carbonatizing roast of lithium bearing ores. US
Patent 3380802.
Mcintosh, N.C., 1946. Production of lithium compounds. US Patent 2413644.
Medina, L.F., El-Naggar, M.M.A.A., 1984. An alternative method for the recovery of li-
thium from spodumene. Metallurgical Transactions B 15 (4), 725–726. https://doi.
org/10.1007/BF02657295.
Meshram, P., Pandey, B.D., Mankhand, T.R., 2014. Extraction of lithium from primary
and secondary sources by pre-treatment, leaching and separation: a comprehensive
review. Hydrometallurgy 150, 192–208.
Meshri, D.T., 1986. The modern inorganic fluorochemical industry. J. Fluor. Chem. 33
(1), 195–226.
People's Government of Yichun, 2017. Opinions of the People's Government of Yichun on
accelerating the development of lithium new energy industry. Available at. http://
www.yichun.gov.cn/zwgk/fgwj/gfxwj/201702/t20170207_491956.html (accessed
on Dec 12, 2018, in Chinese).
Petroff, A., 2017. These Countries want to Ban Gas and Diesel Cars. CNN Business Sep 11,
2017, available at. https://money.cnn.com/2017/09/11/autos/countries-banning-
diesel-gas-cars/index.html, Accessed date: 12 December 2018.
Regional Development Australia, 2018. Lithium valley - Establishing the case for energy
metals and battery manufacturing in Western Australia. Western Australia. available
at. https://www.rdaperth.org/wp-content/uploads/2018/05/RDA4491-LITHIUM-
REPORT-2018_LOWRES.pdf, Accessed date: 18 January 2019.
Rosales, G.D., Ruiz, M.D.C., Rodriguez, M.H., 2014. Novel process for the extraction of
lithium from β-spodumene by leaching with HF. Hydrometallurgy 147, 1–6.
Rosales, G.D., Ruiz, M.C., Rodriguez, M.H., 2016. Study of the extraction kinetics of
17
Hydrometallurgy 189 (2019) 105129
Lithium by leaching β-Spodumene with hydrofluoric acid. Minerals 6 (4), 98.
Rosales, G.D., Pinna, E.G., Suarez, D.S., Rodriguez, M.H., 2017. Recovery process of Li, Al
and Si from Lepidolite by leaching with HF. Minerals 7 (3), 36.
Salakjani, N.K., Singh, P., Nikoloski, A.N., 2016. Mineralogical transformations of spo-
dumene concentrate from Greenbushes, Western Australia. Part 1: conventional
heating. Miner. Eng. 98, 71–79.
Salakjani, N.K., Nikoloski, A.N., Singh, P., 2017. Mineralogical transformations of spo-
dumene concentrate from Greenbushes, Western Australia. Part 2: microwave
heating. Miner. Eng. 100, 191–199.
Samchuk, A.I., Pilipenko, A.T.E., 1987. Analytical Chemistry of Minerals. (VSP.).
Sardar, A., Mubashir, S., 2012. Evolution of EV battery: role of materials availability.
Auto Tech Rev. 1 (5), 20–25.
Schneider, A., Schmidt, H., Meven, M., Brendler, E., Kirchner, J., Martin, G., Bertau, M.,
Voigt, W., 2017. Lithium extraction from the mineral zinnwaldite: part I: effect of
thermal treatment on properties and structure of zinnwaldite. Miner. Eng. 111,
55–67.
Siame, E., Pascoe, R.D., 2011. Extraction of lithium from micaceous waste from China
clay production. Miner. Eng. 24 (14), 1595–1602.
Sugyeong, L., 2018. Extraction of Lithium from Spodumene by Alkali Fusion. Seoul
National University Retrieved from. http://s-space.snu.ac.kr/bitstream/10371/
143846/1/000000152139.pdf, Accessed date: 2 June 2019.
Swain, B., 2017. Recovery and recycling of lithium: a review. Sep. Purif. Technol. 172,
388–403.
Swamy, R.N., 2002. The Alkali-Silica Reaction in Concrete. CRC Press.
Tadesse, B., Makuei, F., Albijanic, B., Dyer, L., 2019. The beneficiation of lithium minerals
from hard rock ores: a review. Miner. Eng. 131, 170–184.
Tarascon, J.-M., 2010. Is lithium the new gold? Nat. Chem. 2 (6), 510.
Tian, Q., Chen, B., Chen, Y., Ma, L., Shi, X., 2011. Roasting and leaching behavior of
spodumene in sulphuric acid process. Chin. J. Rare Metals (in Chinese) 1, 025.
Tiihonen, M., Haavanlammi, L., Kinnunen, S., Kolehmainen, E., 2019. Outotec lithium
hydroxide process - a novel direct leach process for the production of battery grade
lithium hydroxide monohydrate from calcined spodumene. In: Proceedings of ALTA
2019. ALTA Metallurgical Services, Perth, Australia.
Tinto, Rio, 2019. Jadar project. Available at. https://www.riotinto.com/
energyandminerals/jadar-4643.aspx, Accessed date: 18 January 2019.
Vieceli, N., Nogueira, C.A., Pereira, M.F.C., Dias, A.P.S., Durão, F.O., Guimarães, C.,
Margarido, F., 2017a. Effects of mechanical activation on lithium extraction from a
lepidolite ore concentrate. Miner. Eng. 102, 1–14.
Vieceli, N., Nogueira, C.A., Pereira, M.F.C., Durão, F.O., Guimarães, C., Margarido, F.,
2017b. Optimization of lithium extraction from lepidolite by roasting using sodium
and calcium sulfates. Miner. Process. Extr. Metall. Rev. 38 (1), 62–72.
Vieceli, N., Nogueira, C.A., Pereira, M.F.C., Durão, F.O., Guimarães, C., Margarido, F.,
2018a. Optimization of an innovative approach involving mechanical activation and
acid digestion for the extraction of lithium from lepidolite. Int. J. Miner. Metall.
Mater. 25 (1), 11–19.
Vieceli, N., Nogueira, C.A., Pereira, M.F.C., Durão, F.O., Guimarães, C., Margarido, F.,
2018b. Recovery of lithium carbonate by acid digestion and hydrometallurgical
processing from mechanically activated lepidolite. Hydrometallurgy 175, 1–10.
Vikström, H., Davidsson, S., Höök, M., 2013. Lithium availability and future production
outlooks. Appl. Energy 110, 252–266.
Vu, H., Bernardi, J., Jandová, J., Vaculíková, L., Goliáš, V., 2013. Lithium and rubidium
extraction from zinnwaldite by alkali digestion process: sintering mechanism and
leaching kinetics. Int. J. Miner. Process. 123, 9–17.
Walter, R. and Bichowsky, F.R., 1935. Method of recovering lithium from its ores. US
Patent 2020854.
Wietelmann, U., Klett, J., 2018. 200 years of Lithium and 100 years of Organolithium
chemistry. Z. Anorg. Allg. Chem. 644 (4), 194–204.
Wilson, M., Cabrera, J.G., Zou, Y., 1994. The process and mechanism of alkali - silica
reaction using fused silica as the reactive aggregate. Adv. Cem. Res. 6 (23), 117–125.
Wu, X., Yi, Z., Li, X., Wang, Z., Guo, H., 2012. Extraction of lithium and potassium from
Yichun lepidolite by chloridizing roasting. Mining Metallurg. Engg. (in Chinese) 32
(03), 95–98.
Xiao, M., Wang, S., Zhang, Q., Zhang, J., 1997. Leaching mechanism of the spodumene
sulphuric acid process. Rare Metals 16 (01), 37–45.
Xing, P., Wang, C., Zeng, L., Ma, B., Wang, L., Chen, Y., Yang, C., 2019. Lithium extraction
and hydroxysodalite zeolite synthesis by hydrothermal conversion of α-spodumene.
ACS Sustain. Chem. Eng. 7, 9498–9505.
Xu, S., Wang, X., 1993. Study on pressure leaching process for the calcine of lepidolite by
ammonium chloride. Rare Metals and Cemented Carbides (in Chinese) 4, 22–27.
Yan, Q., Li, X., Wang, Z., Wang, J., Guo, H., Hu, Q., Peng, W., Wu, X., 2012a. Extraction of
lithium from lepidolite using chlorination roasting–water leaching process. Trans.
Nonferrous Metals Soc. China 22 (7), 1753–1759.
Yan, Q., Li, X., Wang, Z., Wu, X., Guo, H., Hu, Q., Peng, W., Wang, J., 2012b. Extraction of
valuable metals from lepidolite. Hydrometallurgy 117–118 (0), 116–118.
Yan, Q., Li, X., Wang, Z., Wu, X., Wang, J., Guo, H., Hu, Q., Peng, W., 2012c. Extraction of
lithium from lepidolite by sulfation roasting and water leaching. Int. J. Miner.
Process. 110-111, 1–5.
Yan, Q., Li, X., Yin, Z., Wang, Z., Guo, H., Peng, W., Hu, Q., 2012d. A novel process for
extracting lithium from lepidolite. Hydrometallurgy 121-124, 54–59.
Zeelikman, A.N., Krein, O.E., Samsonov, G.V., 1966. Metallurgy of Rare Metals. Israel
Program for Scientific Translations, Jerusalem.
Zhang, X., Tan, X., Li, C., Yi, Y., Liu, W., Zhang, L., 2019. Energy-efficient and simulta-
neous extraction of lithium, rubidium and caesium from lepidolite concentrate via
sulfuric acid baking and water leaching. In: Hydrometallurgy. In Press, Retrieved
from. https://doi.org/10.1016/j.hydromet.2019.02.011.