Hydrometallurgy 150 (2014) 192–208

Contents lists available at ScienceDirect

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

Review

Extraction of lithium from primary and secondary sources by

pre-treatment, leaching and separation: A comprehensive review
Pratima Meshram a,b, B.D. Pandey a,⁎, T.R. Mankhand b
a
CSIR—National Metallurgical Laboratory, Jamshedpur 831 007, India
b
Dept. of Metallurgical Engineering, IIT, BHU, Varanasi 221 005, India

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

Article history: In this comprehensive review resources of lithium and status of different processes/technologies in vogue or
Received 27 October 2013 being developed for extraction of lithium and associated metals from both primary and secondary resources
Received in revised form 4 October 2014 are summarized. Lithium extraction from primary resources such as ores/minerals (spodumene, petalite and
Accepted 12 October 2014
lepidolite) by acid, alkaline and chlorination processes and from brines by adsorption, precipitation and ion
Available online 23 October 2014
exchange processes, is critically examined. Problems associated with the exploitation of other resources such
Keywords:
as bitterns and seawater are highlighted. As regards the secondary resources, the industrial processes followed
Lithium and the newer developments aiming at the recovery of lithium from lithium ion batteries (LIBs) are described
Primary ores in detail. In particular pre-treatment of the spent LIBs, leaching of metals from the cathode material in different
Brines acids and separation of lithium and other metals from the leach liquors, are discussed. Although spent LIBs are
LIBs currently processed to recover cobalt and other base metals but not lithium, there is a good prospect for the
Hydrometallurgical recovery recovery of lithium in the coming years. Varying compositions of batteries for different applications require
development of a suitable recycling process to recover metals from all types of LIBs.
© 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
2. Resources of lithium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
2.1. Primary resources — minerals/clays and brines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
2.2. Secondary resources — lithium ion batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
3. Extraction of lithium from primary resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
3.1. Lithium extraction from minerals/clays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
3.1.1. Acid process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
3.1.2. Alkaline process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
3.1.3. Chlorination process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
3.1.4. Other processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
3.2. Lithium extraction from brines/sea water/bitterns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
3.2.1. Adsorption process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
3.2.2. Precipitation process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.2.3. Ion exchange/Solvent extraction process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.3. Extraction of lithium from secondary resources — lithium ion batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
3.3.1. Major industrial processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
3.3.2. Recent development in recycling of lithium ion batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206

⁎ Corresponding author.
E-mail address: bd_pandey@yahoo.co.uk (B.D. Pandey).

http://dx.doi.org/10.1016/j.hydromet.2014.10.012
0304-386X/© 2014 Elsevier B.V. All rights reserved.
 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208 193

1. Introduction Table 1
Principal commercial lithium minerals with compositiona.

Lithium is the 25th most abundant element (at 20 mg/kg) in the Mineral Formula % Lithium content
earth's crust. Lithium finds an application in rechargeable lithium ion bat- Theoretical Range in commercial
teries (LIBs) because of its very high energy density by weight and high minerals
electrochemical potential (3.045 V). With a present consumption level
Spodumene LiAlSi2O6 or Li2O·Al2O3·4SiO2 3.73 1.9–3.3
of ~22% of the total lithium produced in LIBs, it is expected to reach to Lepidolite LiKAl2F2Si3O9 or 3.56 1.4–1.9
~40% by 2020 (Wang et al., 2012). Besides batteries, at present it has LiF·KF·Al2O3·3SiO2
major applications in glass and ceramics (30%), greases (11%), metallurgi- Amblygonite LiAlFPO4 or 2LiF·Al2O3·P2O5 4.74 3.5–4.2
cal (4%) industries and also in chemicals/pharmaceuticals, rubbers etc. Triphylite LiFePO4 or Li2O·2FeO·P2O5 4.40 2.5–3.8
Petalite LiAlSi4O10 or Li2O·Al2O3·8SiO2 2.27 1.6–2.21
(Garrett, 2004; Holdren, 1971). As per the Madrid Report of July 2010, Bikitaite LiAlSi2O6·H2O 3.28 1.35–1.7
lithium falls in the border-line of low-to-medium in supply and demand, Eucryptite LiAlSiO4 5.53 2.34–3.3
primarily due to scanty resources (Tedjar, 2013). It is also understood that Montebrasite Li2O·Al2O3·2SiO2 3.93 0.9–1.8
the demand for lithium is increasing further due to its application in nu- Jadarite LiNaSiB3O7(OH) 3.39 0.096–0.1
Zinnwaldite LiKFeAl2F2Si3O10 or 1.7 1.21–1.3
clear and strategic areas. As per recent estimates of lithium reserves, out
LiF·KF·FeO·Al2O3·3SiO2
of 103 deposits with more than 1,00,000 t of lithium, each deposit has a Hectorite Na0.3(Mg,Li)3Si4O10(F,OH)2 0.56 0.36
different mineralogical composition and therefore, requires the appropri- Zabuyelite Li2CO3 18.75 –
ate technology to process (Gruber et al., 2011). In view of this, lithium is a
Industrial Minerals and Rocks (2006), Norton and Schlegel (1955), Schaller (1937), and
usually extracted from its mineral that is found in igneous rocks (chiefly Siame and Pascoe (2011).
spodumene) and from lithium chloride salts found in brine pools, while
ignoring other resources including the low-grade ores.
The rising demand for lithium for various applications thus calls for policy about the fate of discarded lithium ion batteries in e-waste that
prospecting and processing all viable resources. Lithium extraction is distributed internationally. Lithium batteries also contain potentially
from ores/minerals utilizes roasting followed by leaching, while its toxic materials including metals, such as copper, nickel and lead, and
extraction from brines includes evaporation, precipitation, adsorption organic chemicals, such as toxic and flammable electrolytes containing
and ion exchange (Garrett, 2004). Lithium can be extracted from LIBs LiClO4, LiBF4, and LiPF6. Defunct Li-ion batteries are classified as hazard-
by leaching followed by precipitation, ion exchange or solvent extrac- ous due to their lead (Pb) (6.29 mg/kg), cobalt (163,544 mg/kg), copper
tion and electrolysis (Shuva and Kurny, 2013). It is estimated that 250 (98,694 mg/kg) and nickel (9525 mg/kg) contents with exceeded limits
t of ore (spodumene) or 750 t of brine or 28 t of lithium ion batteries of chromium, lead, arsenic and thallium (Bernardes et al., 2004; Kang
of mobile phones and laptops or 256 batteries of electric vehicles et al., 2013). Human and environmental exposures to these chemicals
(EVs) are required to produce 1 t of lithium (Tedjar, 2013). Lithium con- are typically regulated during the manufacture of lithium batteries
centrate obtained mainly by the flotation of pegmatites (ore), is pulver- through occupational health and safety laws, and potential fire hazards
ized and leached in hot acid, and lithium is precipitated as lithium associated with their transportation. These findings support the need
carbonate (Tahil, 2010). The processing of pegmatites is expensive as for stronger government policies at the local, national, and
compared to that of the brines due to the heating and dissolution international levels to encourage recovery, recycling, and reuse of lithi-
steps involved, but the higher metal concentration in pegmatites partly um battery materials. In view of the above, efforts must be made to
compensates for the cost. Because of the cost factor in the lithium develop an environmentally benign and economically viable technology
extraction from brine compared to the ores, many deposits of spodu- for recycling spent LIBs.
mene are not currently being mined/processed. Lithium is also present This review focuses on the primary and secondary resources of
in seawater, but the concentration is too low to be economical. As lithium available for exploitation and provides comprehensive details
regards lithium metal, it can be produced by both carbothermic reduc- on the conventional/currently practiced lithium extraction methods
tion and metallothermic reduction of oxide (at times hydroxide) and vis-a-vis the resource type. The resources that are covered include
also by electrolysis of LiCl (Kipouros and Sadoway, 1998). In view ores/minerals/clays and brines/seawater and bitterns, and lithium ion
of the scattered literature on the extraction of lithium from primary batteries for the hydrometallurgical recovery of lithium.
resources viz., ores, minerals and the brines, it is considered worthwhile
to review the details and discuss critically the merits and demerits of 2. Resources of lithium
various processes in vogue or being developed.
With the increasing use of LIBs in mobile phones, laptops, cam- 2.1. Primary resources — minerals/clays and brines
corders, tracking systems, military and medical devices and in large
energy storage systems including that of transportation applications Lithium is produced from a variety of natural sources, e.g., minerals
(None million EVs expected by 2015), there will be a significant pressure such as spodumene, clays such as hectorite, salt lakes, underground
on lithium resources and its supplies (Kuo, 2011). The disposal of spent brine reservoirs etc. Lithium is a minor component of igneous rocks,
batteries may involve landfilling, stabilization, incineration or recycling. primarily granite. The most abundant lithium containing rocks/minerals
In landfills, heavy metals have the potential to leach slowly into the soil, are pegmatites, spodumene and petalite. Other minerals are lepidolite,
groundwater or surface water. amblygonite, zinnwaldite and eucryptite (Ferrell, 1985). Zinnwaldite
The methods for recycling spent LIBs are based mainly on pyro-/ is the impure form of lepidolite with higher content of FeO (up to
hydro-metallurgical processes (Li et al., 2009a). The disadvantage of all 11.5% Fe as FeO) and MnO (3.2%) (Paukov et al., 2010). Pegmatites con-
pyro-recycling processes is that lithium is not recovered. The traditional tain recoverable amounts of lithium, tin, tantalum, niobium, beryllium
pyrometallurgical processes can burn off all the organic electrolyte and and other elements. Table 1 lists the principal commercial lithium min-
binder, and facilitate the leaching of valuable metals. In the hydrometal- erals found in pegmatites along with their composition. The theoretical
lurgical processes, the dismantled electrodes are dissolved in concen- lithium content in these minerals is 3% to 5.53%, but most mineral de-
trated acid and the metal rich leach solutions are treated to recover posits have around 0.5%–2% Li and the pegmatite-bearing ores that are
the individual metal by the different methods mentioned above. These often exploited have b1% Li (Mohr et al., 2010). Spodumene is the pri-
processes may produce wastewater containing fluoride which is difficult mary lithium mineral being mined.
to treat, and can pollute the environment due to the incomplete Among the clay minerals, hectorite, a type of smectite is rich in lith-
recycling of the organic binder and electrolyte. There is an inconsistent ium and magnesium, and generally contains 0.3 to 0.6% Li. The best
194 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208
Table 2
Geographical availability for various lithium resources and their lithium contents.
Resources Li content % (w/w)
Pegmatites
Spodumene 1.9–3.3
Lepidolite 1.53–3.6
Zabuyelite 17–18.75
Petalite 1.6–2.1
Amblygonite 3.5–4.2%
Eucryptite 2.34
Sedimentary rocks
Smectite (hectorite) 0.27–0.7
Lacustrine evaporites 1.8% lithium oxide
Brine
Continental b2700 mg/L (with K, B)
~532 mg/L
Geothermal b400 mg/L (with Mn and Zn)
Oil field b700 mg/L (with Br)
Sea water 0.18 mg/L
Secondary resource
Spent LIBs 2–7%
known hectorite deposit with 0.7% Li is in Hector, California. Flint clays
and other high-alumina clays contain b0.01 to 0.5% Li. Jadarite is a
newly discovered lithium-boron containing mineral found in Serbia
(Mohr et al., 2012). These minerals are often concentrated to around
2%–4% Li for use in the ceramics and glass industry (Garrett, 2004).
Seawater contains about 0.1–0.2 mg/L Li (Bach and Wasson, 1981).
Total amount of metallic lithium in seawater (globally) is estimated to
be ~230 Gt. Brine sources include lithium found in salt water deposits —
lakes, salars, oilfield brines, and geothermal brines. Oilfield brines are
underground brine reservoirs that are located with oil. Geothermal brines
are underground brines naturally heated, e.g., in the Salton Sea California.
Brines containing lithium make up 66% of the world's lithium resources;
pegmatites make up 26% and sedimentary rocks make up 8% (Gruber,
2010; Kesler et al., 2012).
Almost 70% of the global lithium deposits are concentrated in South
America's ABC (Argentina, Bolivia and Chile) region. Table 2 details the
geographical availability of various resources of lithium vis-a-vis lithium
content and their locations. The lithium concentrations in the salars of
Chile, Argentina, and Bolivia are in the range 0.04–0.16%. According to
Yaksic and Tilton (2009) the resource of lithium is estimated to be
64 Mt. Chile has the world's largest resource of brine (7.5 Mt, 1500–
2700 mg/L Li) containing lithium, followed by Bolivia (resource: 9.0 Mt
with 532 mg/L Li) and Argentina (resource: 2.6 Mt, 400–700 mg/L Li)
and these three countries account for almost 80% of the world's brine
reserves (Mohr et al., 2012). Estimates of lithium resources are published
extensively (Clarke and Harben, 2009; Gruber et al., 2011; Ono, 2009;
Evans, 2010a, 2010b; USGS, 1980, 1986, 2005, 2009, 2010, 2011, 2012,
2013).
Lithium rock production began with lithium minerals (1899) in the
USA (Garrett, 2004). Since the first lithium production from brines at
Searles Lake, USA in 1936, brines are exploited largely in South America
and China. The largest producer of lithium in the world is Chile where
lithium is extracted from salar brine at the Atacama Salt Flat. Lithium
production from brines is also at salt lakes in Tibet and Qinghai in
China, besides at Nevada in the United States. Several newer installations
(by 2013) are on various stages of exploration/operation for brine source
which are: one more in China, six in Argentina, three in Chile and one in
Bolivia (Clarke, 2013). Currently 8% of lithium is obtained from salt lake
brines and sea by sedimentation. Significant quantities of lithium com-
pounds and ore concentrates are also produced in Australia, Canada,
Portugal, Russia and Zimbabwe. Currently, Australia produces lithium
concentrate from spodumene at the mines in Mt Catlin, Western
Australia. The 160,000 t/annum concentrate produced in Western
Australia is processed to 16,000 t/annum lithium carbonate in its Chinese
Location of the largest amount References
Australia Industrial Minerals and Rocks (2006), Legers (2008),
Zimbabwe Clarke (2013), AMRA (2013)
China
Zimbabwe
Canada, Brazil, Surinam
Zimbabwe
Hector, California. and Nevada, US Industrial Minerals and Rocks (2006)
Jadar Valley, Serbia
Chile Evans (2008,2009),
Bolivia Legers (2008),
United States Clarke (2013),
United States Mohr et al. (2012)
Chile, Argentina, China and Tibet
– Shuva and Kurny (2013)
plant. Lithium carbonate is mostly produced from both ores and brines
and the production figures are often expressed as lithium carbonate
equivalent (LCE). Other chemicals such as lithium chloride and hydrox-
ide are also produced in varying amounts.
In India small pocket deposits mostly comprising of lepidolite in
pegmatites of mica fields are located. The maximum lithium content
(lepidolite with 2–6% Li2O) is found in Jharkhand followed by that of
Chhattisgarh (2.56% Li2O) and Rajasthan (2.25% Li2O as pegmatites in
Udaipur, Bhilwara, Jodhpur and Ajmer, and zinnwaldite in Dagana).
Others include spodumene in Raichur, Karnataka (Banerjee et al., 1994),
amblygonite in granitic rocks of Paddar (Kashmir) and lepidolite at
Dhir-Bil (Goalpara), Assam. Lithium bearing bauxite has also been identi-
fied in the Salal area, Jammu (Brown and Dey, 1955; Krishnaswamy,
1979; Roonwal et al., 2005).
2.2. Secondary resources — lithium ion batteries
Out of the various secondary resources, spent LIBs are the most prom-
inent secondary source of lithium and other metals. To recycle these
materials, it is desired to understand the construction/composition of
the cells in brief and how they transform during their use.
Lithium ion battery is a term generally used for a battery which has
lithium metal, lithium alloy or material adsorbing lithium ions for its
negative active material. LIB uses carbon as an anode and lithium ions
exist in the carbon material; there is no metallic lithium at any state of
charge during normal usage. Depending on their technical construction
and properties batteries are categorized as either primary or secondary.
From the legislative view point batteries are also categorized as portable
(household) and vehicle or industrial batteries. Primary cells are con-
structed with metallic lithium. The metallic lithium in a non-
rechargeable primary lithium battery is a combustible alkali metal that
self-ignites at 178 °C, and when exposed to water/seawater reacts exo-
thermically and releases hydrogen. Primary batteries are single-use as
irreversible discharge reactions occur in the cells and after use they
are disposed off. Secondary battery cells have a chemistry that allows re-
versing the discharge reaction and are rechargeable. LIBs are of the re-
chargeable secondary type. The functional parts of LIBs are the cathode,
anode, electrolyte and separator, which are housed in a protective
metal casing.
The chemical reaction in the cell expressed below shows the forms
in which lithium and cobalt can be present in the spent LIBs.
LiCoy Oz þ 6C→Lix C6 þ Li1−x Coy Oz : ð1Þ
 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208 195

Table 3
Various components of LIBs, materials used and their meritsa.

Component Wt.% of the total Material Structure Properties/Merits

weight of the battery

Cathode 39.1 ± 1.1 LiCoO2 Layered High structural stability and can be cycled for N500 times with 80–90%
capacity retention
LiMn2O4 Spinel Attractive for ecological and economic reasons; discharges ~3 V
LiNiO2 Layered Cheaper & possesses higher energy density (15% higher by volume, 20% higher
by weight), but less stable & less ordered as compared to LiCoO2
LiFePO4 Olivine Suitable for biomedical applications because of higher safety levels and
Li2FePO4F Olivine lower cost
LiCo1/3Ni1/3Mn1/3O Layered/spinel Possesses high capacity with structural and thermal stability, and safe to use
Li(LiaNixMnyCoz)O2 Layered/spinel
Anode Carbon Graphite Low cost and availability. It has the ability to reversibly absorb and release large
Hard carbon Microspheres quantity of Li (Li:C = 1:6)
Electrolyte Lithium salt like LiPF6, Li[PF3(C2F5)3] Withstands high temperature and possesses high mobility of Li ions
or LiBC4O8 in organic solvents
Plastic case 22.9 ± 0.7 Polyethylene terephthalate layers, a polymer layer and a Hermetically sealed battery body which converts chemical energy to electrical
polypropylene layer, layers of carbonized plastic energy in order to generate current
Outer casing 10.5 ± 1.1 Stainless steel, aluminium
Copper foil 8.9 ± 0.3 Copper ~14 μm thick
Aluminium foil 6.1 ± 0.6 Aluminium ~20 μm thick
Polymer foil & 5.2 ± 0.4 Polyethylene, polypropylene or composite Use of 3–8 μm layers (PP/PE/PP) with 50% porosity
electrolyte polyethylene/polypropylene films
Solvent 4.7 ± 0.2 Ethylene carbonate, dimethyl carbonate Non-aqueous
& diethyl carbonate
Electrical contact 2.0 ± 0.5 Aluminium and copper Conductive
a
Wakihara and Yamamoto (1998), Gaines and Cuenca (2000), Nazri and Pistoia (2004) Paulino et al., (2008) and Fergus (2010).

The active mass (cathode, anode and electrolyte) of LIBs comprises of
almost 40% of the weight whereas ~30% (wt) of these components are
carbon (anode). A number of chemical species in the cathode material
within the lithium-ion family have been reported including the type,
structure of the materials used and their electrochemical properties
which are listed in Table 3. Generally LIBs have a short life of 2–3 years
whether they are used or not. The spent batteries are a good source of
several metals like Li, Co, Ni, Co, Mn etc.
3. Extraction of lithium from primary resources
3.1. Lithium extraction from minerals/clays
Lithium is extracted from its minerals by two processes — acid and
alkaline though chlorination is also attempted in some cases. Averill
and Olson (1978) have reviewed methods and techniques for the
extraction of lithium from ores, brines and clays. Processes followed
for the extraction of lithium from different resources have also been
compiled in detail by Garrett (2004).
In order to process ores/concentrates, acid digestion with H2SO4 may
be followed for decomposition of the silicate structure at 250–400 °C
which is suitable for the processing of lepidolite, amblygonite and
zinnwaldite (Kondás and Jandová, 2006). In the sulfate process lithium
minerals such as lepidolite are decomposed at high temperature in the
presence of potassium and/or sodium sulfate. Alkali digestion is suitable
for the decomposition of spodumene and lepidolite largely by the treat-
ment of potassium carbonate to produce lithium hydroxide. In the alka-
line/gypsum process the mineral is reacted with limestone or a mixture
of calcium sulfate with calcium oxide and/or hydroxide by heating to
convert silicate to soluble lithium aluminate from which LiOH or Li2CO3

Table 4
Lithium extraction from its minerals/clays by acid process.

Raw material % Li Experimental conditions % Li Li2CO3 References

Extraction purity
Pre-treatment Roasting Time Water leaching
(%)
temp. (°C) (h)
L/S ratio Temp. (°C) Time (h)

Lepidolite conc. 2.0 Sulfation roasting 850 0.5 2.5:1 Room temp. 0.5 91.6 – Yan et al.
(RT) (2012a)
Lepidolite conc. 2.0 Salt roasting with 880 0.5 0.8:1 RT 0.5 ~90 N99.5 Yan et al.
Na2SO4 + CaCl2 (2012b)
Lepidolite conc. 2.55 Sulfation roasting 1000 0.5 15:1 85 3 90.4 – Luong et al.
Na2SO4:Li molar (2013)
ratio = 2:1
Lepidolite conc. 1.79 Roasting with iron 850 1.5 1:1 RT 1 85 (open – Luong et al.
sulfate system) (2014)
93 (closed
system)
Zinnwaldite conc. 0.96 Roasting with 850 1 10:1 RT 0.5 N90 N90 Siame and
sodium sulfate Pascoe (2011)
Petalite/Lepidolite 1.9 Calcination 1100 2 7.5/1 50 1 97.3 99 Sitando and
Roasting (H2SO4) 300 1 Crouse (2012)
Spodumene 4.21 Calcination 1100 1 Leaching & – – 90 – Mcketta (1988),
Roasting (H2SO4) 250 0.167 precipitation Tahil (2010)
Spodumene 2.81 Roasting & H2SO4 1050–1090 0.5 1:4 225 1 96 ~99.6 Chen et al.
leaching (2011a, 2011b),
Clarke (2013)
Montmorillonite clay 1.2% Li2O Without roasting – – 5:1 (H2SO4 leach) 250 1.5 90 Li2SO4 Amer (2008)
196 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208

Table 5
Lithium extraction from its minerals/clays by alkali process.

Raw material % Li Pre-treatment Experimental conditions % Li Li2CO3 References

extraction purity (%)
Roasting temp. Water leaching
(°C), time (h)
Time (h) Temp. (°C) (L/S ratio)

Lepidolite 1.4 Defluorination 860, 0.5 h 1 150 4:1; lime: defluor. 98.9 99.9 Yan et al. (2012c)
concentrate lepidolite: 1
Zinnwaldite 1.4 Gypsum roast 950, 1 h 0.167 90 10:1 96 99 Jandová et al.
concentrate (2009)
Zinnwaldite 2.07% Gypsum roast 1050 0.5 85 10:1 84 –
(tailing sample) Li2O
Zinnwaldite 0.19 Roasting with 975 1 90 5:1 93 – Kondás and Jandová
concentrate gypsum & Ca(OH)2 (2006)
Zinnwaldite 1.21 Roasting with CaCO3 825, 1 h 1 90–95 5:1 ~90 99.5 Jandová et al. (2010)
concentrate
Zinnwaldite 1.29 Roasting with CaCO3 825 4 95 10:1 84 – Vu et al. (2013)
concentrate
Montmorillonite 0.3–0.6 Roasting with 750 – RT – 80 99 Lien (1985), Crocker
clay–hectorite CaCO3 900 and Lien (1987)
CaCO3–CaSO4

is obtained. Thus most of the alkaline processes involve either the
heating of lithium minerals with alkali salts or in more advanced hydro-
thermal processes by decomposition in solutions containing Na2CO3,
NaOH, Na2SO4 and/or other alkali salts at elevated temperature and
pressure. Ion-exchange processes are applied for the processing of the
leach liquors obtained from spodumene, petalite and partly from
zinnwaldite. Tables 4–6 summarize recent work on lithium extraction
from its minerals and clays by using different approaches.
3.1.1. Acid process
Sulfation roasting of lepidolite followed by water leaching was
recently reported by Yan et al. (2012a). The lithium extraction effi-
ciency of 91.6% could be achieved at a mass ratio of lepidolite/Na2SO4/
K2SO4/CaO of 1:0.5:0.1:0.1 and roasting at 850 °C (Table 4). Roasting at
880 °C with a mass ratio of lepidolite/Na2SO4/CaCl2 of 1:0.5:0.3 resulted
in improved recovery (~95% Li) of lithium (Yan et al., 2012b). Above
99.5% pure lithium carbonate was obtained by evaporation and precipita-
tion with Na2CO3. Luong et al. (2013) examined the sulfation roasting of a
Korean lepidolite ore with sodium sulfate at 1000 °C, while achieving
extraction of ~ 90.4% Li. Recently, the roasting of lepidolite with iron sul-
fate at 850 °C and water leaching were investigated by Luong et al.
(2014). Leaching of the calcines obtained from the open and closed sys-
tems yielded leach liquors containing ~7.9 g/L Li and ~8.7 g/L Li, corre-
sponding to the extraction of ~85% and ~93% Li, respectively.
Lithium extraction (N90%) by roasting a low grade zinnwaldite
concentrate (0.96% Li) with sodium sulfate followed by water leaching,
was described by Siame and Pascoe (2011). A study by Sitando and
Crouse (2012) showed the extraction of 97.3% Li (~ 5 g/L) by roasting
a Zimbabwean petalite ore concentrate (4.1% Li2O) with concentrated
sulfuric acid at 300 °C followed by water leaching at 50 °C. The leach
liquor was evaporated till lithium was concentrated to N11 g/L and
Li2CO3 of ~ 99% purity was precipitated by the addition of Na2CO3 at
95–100 °C. Amer (2008) reported the extraction of 90% Li from the
Egyptian montmorillonite type clay containing lithium in 90 min of
reaction in sulfuric acid at 250 °C.
In order to process spodumene it is desired to convert α-spodumene
to β-phase by roasting at 1070–1100 °C (Chen et al., 2011b; Clarke,
2013; Tahil, 2010). Tahil (2010) reported the roasting of spodumene
in a kiln at ~ 1100 °C. The calcine was mixed with sulfuric acid and
roasted at 250 °C and then leached in water to yield a solution of lithium
sulfate. Reaction of β‐spodumene with H2SO4 is shown as reaction (2)
(Mcketta, 1988):
Li2 O⋅Al2 O3 ⋅4SiO2ðsÞ þ H2 SO4ðconcÞ →Li2 SO4ðsÞ þ Al2 O3 ⋅4SiO2ðsÞ
þ H2 OðgÞ : ð2Þ
Lithium carbonate can be recovered by the addition of sodium carbon-
ate to the solution after pH adjustment, purification and evaporation
(Reaction (3)).
Li2 SO4ðaqÞ þ Na2 CO3ðaqÞ →Li2 CO3ðsÞ þ Na2 SO4ðaqÞ : ð3Þ
The world's first continuous plant to convert spodumene concentrate
to lithium carbonate by calcination, roasting of calcine with H2SO4 and
water leaching, was commissioned in 2012 by Galaxy Resources in
China (Clarke, 2013).
One of the drawbacks of the sulfuric acid method to treat lepidolite,
petalite and zinnwaldite is the requirement of a high concentration of
acid and complex purification processes, whereas spodumene needs
to be converted to the more leachable β‐phase at higher temperature.

Table 6
Lithium extraction from its minerals/clays by chlorination process.

Raw material Experimental conditions % Li extraction Product References

Roasting temp. (°C) Time (h) Leaching

L/S ratio Temp. (°C) Time (h)

Lepidolite 935 13 – 80 1 ~100 LiCl Löf and Lewis (1942)

Spodumene (3.58% Li) 1000 4 10:1 80 1 58 LiCl Peterson and Gloss (1959)
Lepidolite concentrate (2.0% Li) 880 0.5 2.5:1 60 0.5 92.8 Li2CO3 Yan et al. (2012d)
Spodumene (7.2% Li2O) 1100 2.5 – – – 100 LiCl Barbosa et al. (2014)
Lepidolite ore (3.70% Li2O) With CaCO3 + CaCl2, 950 5 10:1 90 1 80.0 LiCl Vyas et al. (1975)
 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208
3.1.2. Alkaline process
In the alkaline process (Table 5), spodumene or lepidolite ore concen-
trates are ground and calcined with limestone at 825–1050 °C. The
resulting calcine is crushed, milled and treated with water to yield lithi-
um hydroxide which can be converted to chloride by reaction with hy-
drochloric acid. The recovery in this method is approximately 85–90%
(Averill and Olson, 1978). The reaction during calcination of spodumene
with limestone can be represented as :
Li2 O⋅Al2 O3 ⋅4SiO2ðsÞ þ CaCO3 →Li2 OðsÞ þ CaO⋅Al2 O3 ⋅4SiO2ðsÞ
þ CO2ðgÞ : ð4Þ
Lepidolite was pre-roasted at 860 °C under water steam atmosphere
for defluorination followed by pressure leaching of the defluorinated
mass in a lime–milk autoclave at 150 °C. In this process 98.9% lithium
was extracted (Yan et al., 2012c). During the roasting with steam forma-
tion of phases such as lithium aluminium silicate (beta-eucryptite) and
leucite (KAlSi2O6) was noticed (Karstetter, 1971) as per reaction (5)
2LiF⋅KF⋅Al2 O3 ⋅3SiO2 þ 4H2 O→Li2 O⋅Al2 O3 ⋅2SiO2 þ 2KAlSi2 O6
þ 4H2 þ 2F2 : ð5Þ
Extraction of lithium from a zinnwaldite containing waste was inves-
tigated by Jandová et al. (2009). The concentrate (1.40% Li) obtained
from dry magnetic separation of the waste (0.21% Li) was treated by
the gypsum roast method (with CaSO4 and Ca(OH)2). About 96% Li was
leached out from the sinter made at 950 °C. Earlier the concentrate
prepared from this waste by gravity and dry magnetic separation, was
roasted by the gypsum method at 975 °C and water leached to recover
~ 93% Li (Kondás and Jandová, 2006). In another study Jandová et al.
(2010) reported that the roasting of the above concentrate with
CaCO3·Li2CO3 with 99.5% purity was separated from the leach liquors
by either converting the alkaline liquor to the carbonated solution by
CO2 bubbling or by solvent extraction with LIX54 and TOPO as an
extractant followed by stripping with diluted H2SO4; the first method
provided a higher yield. Siame and Pascoe (2011) obtained recovery of
~84% Li from the roasted zinnwaldite concentrate at 1050 °C with lime-
stone, gypsum and sodium sulfate. A similar process was reported by Vu
et al. (2013) from zinnwaldite by sintering with CaCO3 powder at 825 °C,
followed by water leaching and precipitation.
Crocker and Lien (1987) reported the recovery of N85% Li by roasting
montmorillonite type clays (0.3–0.6% Li) with KCl–CaSO4 or CaCO3–
CaSO4 followed by water leaching. Lithium silicate in the clay was con-
verted to Li2SO4 by roasting a pelletized mixture of clay, limestone and
gypsum at 900 °C in a direct gas-fired rotary roaster (Lien, 1985).
Formation of lithium sulfate may be represented by reactions (6) and (7)
1 Medina and El-Naggar (1984) developed an alternate method of
CaSO4  2H2 O þ SiO2 →CaSiO3 þ SO2 þ O2 ð6Þ
2 chlorination to treat spodumene with a recovery of ~87% Li by roasting
1 at 1150 °C with a mixture of 8:1 (wt.) tachyhydrite:spodumene follow-
Li2 Si2 O5 þ SO2 þ O2 →Li2 SO4 þ 2SiO2 : ð7Þ
2 ed by water leaching. Because the production of lithium carbonate from
The initial product obtained from the alkaline process is lithium
hydroxide which can be converted to carbonate or chloride salt.
3.1.3. Chlorination process
A less common method is the chlorination process in which the ore is
roasted in the temperature range 880–1100 °C in the presence of chlorine
gas or HCl depending upon the type of mineral treated (Table 6). For
instance chlorination of lepidolite with HCl can be achieved at lower tem-
perature (935 °C) while giving a high yield (~100%) of lithium during
leaching as compared to the roasting of spodumene (Löf and Lewis,
1942). Lithium in spodumene can be converted to LiCl almost quantita-
tively at higher temperature (1100 °C) in 2.5 h with Cl2 gas (Barbosa
et al., 2014); the recovery is found to be quite low (58%) at the lower
temperature (1000 °C) (Peterson and Gloss, 1959). In the chlorination
process, when the ore is sintered with NH4Cl and CaCl2 in a furnace at
197
750 °C, ~98% of the lithium contained in spodumene is converted to its
chloride which can be water leached (Zelikman et al., 1996). Vyas
et al. (1975) reported a similar process using CaCO3 and CaCl2 to roast
Indian lepidolite at 950 °C by which 80% Li was recovered as LiCl. The
chlorination process with calcium chloride and/or sodium chloride
with lepidolite (M = Li, K, Rb, Cs) may be represented as:
2NaCl þ 6SiO2 þ M2 O þ Al2 O3 →2NaAlSi3 O8 þ 2MCl ð8Þ
CaCl2 þ SiO2 þ M2 O→CaSiO3 þ 2MCl ð9Þ
CaCl2 þ 2SiO2 þ Al2 O3 þ M2 O→CaAlSi2 O8 þ 2MCl: ð10Þ
Chlorination roasting with a mixture of CaCl2 and NaCl gives a better
lithium extraction yield because of its lower melting point than either
of the agents, which increases the fluidity of chloride melt. This allows
diffusion of the chlorinating agent to the surface of the lepidolite facili-
tating the lithium extraction selectively and yielding a pure product.
Crocker and Lien (1987) also reported a process for selective chlorina-
tion of hectorite (0.3–0.65% Li) in clays with limestone at 750 °C using
20 wt.% HCl.
3.1.4. Other processes
Chlorination roasting of ores requires corrosion-resistant equip-
ment. To overcome this drawback the autoclave method is used. Chen
et al. (2011b) reported a process to treat β-spodumene obtained in
the calcination of α-spodumene, by sodium carbonate solution in an au-
toclave at a liquid/solid ratio of 4 and Na/Li of 1.25 at 225 °C. During
pressure leaching lithium carbonate and analcime slurry are formed
according to reaction (11).
β−Li2 O⋅Al2 O3 ⋅4SiO2 þ Na2 CO3 þ nH2 O→Li2 CO3
þ Na2 O⋅Al2 O3 ⋅4SiO2 ⋅nH2 O: ð11Þ
The slurry was leached in carbon dioxide to form lithium bicarbonate
which on heating produced lithium carbonate of 99.6% purity as per
reactions (12) and (13).
Li2 CO3 þ CO2 þ H2 O→2LiHCO3 ð12Þ
2LiHCO3 →Li2 CO3 þ CO2 þ H2 O: ð13Þ
spodumene is energy intensive and expensive, lithium carbonate is
mostly produced from the brines.
3.2. Lithium extraction from brines/sea water/bitterns
In order to meet the growing demand of lithium, brines and bitterns
have received increasing attention. Tables 7 and 8 elaborate the summa-
ry of work carried out recently for the extraction of lithium from sea
water/brines/bitterns. Production process for brine-water lithium costs
30% to 50% less than that of the mined ores (Abe, 2010). As mentioned
earlier, lithium carbonate is produced from brines by an evaporative con-
centration and refining method. Firstly, brine is concentrated by solar
evaporation over a year in a pond to crystallize sodium, potassium and
magnesium chlorides. During the refining process calcium carbonate
is roasted and then added to the solution of LiCl for the removal of
198 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208

Table 7
Adsorption process for lithium extraction with product synthesized from seawater, brines and bitterns.

Source/Raw material Adsorbent used Conditions Adsorption/Remarks Product References

Seawater H1.6Mn1.6O4 Adsorbent: 200 mg, sea water: 50 L, Max. uptake: 40 mg Li/g adsorbent – Chitrakar et al.
4 weeks; desorption by 0.5 M HCl, 1 day (2001)
Seawater (Li 0.17 mg/L) Spinel type Mn-oxide 30 °C, 15 days b90% Li, LiCl Umeno et al.
Li uptake: 10.6 mg/g adsorbent (2002)
Seawater (Li 0.15 mg/L) λ-MnO2 (granulated) 150 days Recovery—264 g LiCl in 791 g dried LiCl Yoshizuka
precipitated salt (816 m3 seawater) et al. (2006)
Artificial seawater Ion-sieve type Mn-oxide Adsorption at 0.4 M HCl, 5 days Adsorption: 88% Li by adsorbent I and 89% Li LiCl Chung et al.
(Li 0.2 mg/L, 8.01 pH) spinels: HMg0.5Mn1.5O4(I) by adsorbent II. (2004, 2008)
HZn0.5Mn1.5O4 (II) Equil. sorption: 30.3 mg/g (I) and
33.1 mg/g (II).
Seawater (1 mmol/L Li) HMn2O4 60 °C, 24 h Loading capacity: 1.53 mmol/g sorbent Li salt Wajima et al.
(2012)
Brine (Salars de Uyuni, LimMgxMnIIIyMnIVzO4 24 h, pH 6.5 Adsorption capacity: 23–25 mg/g Li2CO3 Chitrakar et al.
Bolivia) (0 b x ≤ 0.5) adsorbent (2013)
Seawater (Li Surface deposition on 30 °C, 10 days 34% Li – Takeuchi
0.192 mg/L) corrosion product of Al (1980)
Salt lake bitterns Hydrated alumina: pH 5.8 Adsorption:0.6–0.9 mg/g sorbent – Dong et al.
LiOH = 2 M ratio (2007)
Egyptian bitterns Al(OH)3 30 °C, pH 9 Adsorption capacity: 123 mg/g adsorbent LiAlO2 Hawash et al.
(19.5, 5.5, 8.8 mg/L) (2010)
Brine (Salar de Hombre Hydrated alumina LiCl solution— Adsorbed Li eluted by acid and Li2CO3 Clarke (2013)
Muerto, Argentina) 1% Li (20 times conc.) by solar evaporation. precipitated by sodium carbonate

Mg(OH)2. A general flowsheet of Li2CO3 production from brine water is
shown in Fig. 1.
The basic approaches for the separation of mineral products (K, Mg,
Na, Ca, Li) from the seawater comprises of flotation (using anionic col-
lectors), sorption, ion exchange, solvent extraction etc. as described by
Koyanaka and Yasuda (1977). The existing evaporation process for lith-
ium recovery from brine lakes is time consuming and suffers from low
recovery efficiency. Besides, tremendous burden is posed on the envi-
ronment due to waste generation and substantial water consumption.
3.2.1. Adsorption process
Various types of adsorbents have been used for selective lithium
recovery from seawater and brines. In the adsorption method certain
inorganic ion-exchangers such as the spinel-type manganese oxide
show extremely high selectivity for lithium from seawater (Kitajou
et al., 2003; Ooi et al., 1989, 1991; Umeno et al., 2002; Yoshizuka et al.,
2002, 2006). Such materials exhibit high adsorption capacities in alkaline
medium (pH of seawater being ~8) for Li+ in the presence of alkali and
alkaline earth ions. For instance Kitajou et al. (2003) reported the separa-
tion of Li+ from a large amount of Na+ by the spinel-type λ-MnO2
whereby Li+ was concentrated 400 times leaving most Na+ in the sea-
water. Extraction/separation of lithium from brines and such resources
is summarized in Table 7.
The manganese oxide (H1.6Mn1.6O4) prepared from the precursor,
Li1.6Mn1.6O4 by hydrothermal and reflux methods, showed the maxi-
mum uptake of 40 mg Li/g of adsorbent from the seawater, the highest
among the inorganic adsorbents (Chitrakar et al., 2001). The very fine
size (nano-size range) of the synthesized manganese oxide was found
to be responsible for its high adsorption capacity towards lithium as
compared to other adsorbents. Adsorption of lithium from seawater by
a spinel type λ-MnO2 produced low purity (~33%) Li+ ions contaminat-
ed with Na+ (Yoshizuka et al., 2006). Chung et al. (2004) synthesized
nano-manganese oxide (Li1.33Mn1.67O4) through a gel process. The ion
sieve-type adsorbent containing magnesium after acid treatment was

Table 8
Precipitation and other processes for lithium extraction from seawater and brines.

Source/Raw material Process Conditions Recovery (%)/Remarks Product References

(% purity)

Synthetic solution,
Geothermal water
(Li = 10 mg/L)
Synthetic solution (2.5 M
LiCl, 0.3 M CaCl2 and 0.15 M
MgCl2)
Seawater (0.12–0.16 mg/L Li)
Seawater (0.18–0.20 mg/L Li)
Uyuni Salar brine, Bolivia,
15–18 g/L Mg,
0.7–0.9 g/L Li
Brine from Salar de Hombre
Muerto, Argentina
Brine (high Mg/Li ratio)
Precipitation pH 12.5 for [Al]: 50–1000 mg/L 70% Li – Yoshinaga et al.
(1986)
Precipitation followed by IX using Poly BD® Precipitation with 1.8 M Na2CO3 Good usable volume cap. Li salt Bukowsky et al.
R45HTLO (MC50), Lewatit® (TP 207), at 80 °C. of resin TP207: solution (1991)
Dowex®(Y80) IX—50 °C, 30 min 56.4 g/L
Integrated ion-exchange method 1st stage: sorption on λ-MnO2, 56% yield Li2CO3 Nishihama et al.
150 days (N99.9) (2011), Onishi et al.
(264 g LiCl in 816 m3 seawater); (2010)
2nd stage: Sep. of Mg(II), Ca(II),
Sr(II) and Mn(II) with SK110 resin
(pH 9)
Two stage precipitation 1st stage pH : 11.5–12.5; Recovery of pure Li2CO3 (99.4) Um and Hirato
2nd stage: Na2CO3 at 100 °C lithium carbonate (2012)
Two stage precipitation with lime 1st stage pH: 11.3, Precipitation as Li2CO3 LiCO3 (99.55) An et al. (2012),
& Na-oxalate 2nd stage: sodium oxalate, Tran et al. (2013)
80–90 °C
Precipitation (2.5 g/L LiCl from solar pond) Separation of Mg as hydroxide and LiCl salt feed for Li extr. LiCl Clarke (2013)
with lime and Na2SO4 Ca as sulfate in a chemical plant
Electrochemical Electrolyte: 0.5 M NaCl, 10 h ~94% Li; – Zhao et al. (2013)
Li sorption: 28.65 mg/g
LiFePO4
 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208
Brine
Evaporation concentration
Concentrated brine
Lime milk
Magnesium removal
Magnesium
Filtration /Washing
hydroxide
Calcium-lithium-salt solution
Lithium Calcium removal
carbonate
Filtration Calcium carbonate
Lithium salt solution
Roasting
Na2CO3 Evaporation
Precipitation crystallization
Hydration
Filtration/Washing
Lithium carbonate
Fig. 1. A flowsheet for Li2CO3 production from brine.
then generated which selectively adsorbed lithium (~30.3 mg/g adsor-
bent) from seawater. When a polymeric membrane reservoir containing
an inorganic ion-exchange adsorbent inside it with zinc was used, lithi-
um recovery from seawater was very effective and kinetically favored
with adsorption of 33.1 mg Li/g sorbent (Chung et al., 2008). This adsor-
bent had excellent lithium adsorption of 89% of 400 mg Li in a day only;
the desorption efficiency being 92.88% by dipping in 4 L of 0.5 M HCl so-
lution in a day. By using Mg-doped manganese oxide, Chitrakar et al.
(2013) also observed very fast adsorption equilibrium (within 24 h) for
effective recovery of lithium from salar brine (Table 7).
Recently Wajima et al. (2012) prepared HMn2O4 by elution of spinel-
type lithium di-manganese-tetra-oxide (LiMn2O4) and examined the
kinetics of lithium adsorption. The intermediate, LiMn2O4, was also syn-
thesized from LiOH·H2O and Mn3O4 by acid treatment. Lithium recovery
from seawater reached ~100% at 60 °C using both products.
Aluminium foil immersed in sea water forms a corrosion product on
its surface which extracts lithium selectively from sea water at the same
time, at the optimum temperature of ~ 30 °C (Takeuchi, 1980). Dong
et al. (2007) prepared an aluminium salt adsorbent using Al(OH)3 and
LiOH at pH 5.8, and a molar ratio of 2, and investigated the recovery of
lithium from a salt lake bittern by this adsorbent. The adsorbent showed
high adsorption and uptake of 0.6–0.9 mg Li/g rather than the other
alkali or alkaline metals of bitterns. Use of hydrated alumina for adsorp-
tion of lithium was also reported from Egyptian bitterns (Hawash et al.,
2010) and salar brines of Argentina (Clarke, 2013).
The Institute of Ocean Energy at Saga University began operating the
world's first — but small — lab aiming for practical lithium production
from seawater and succeeded in acquiring about 30 g of lithium chloride
from 140,000 L of seawater in one month. Similarly in early 2010, POSCO
199
and the Korea Institute of Geoscience and Mineral Resources, Korea had
joined hands to build a pilot plant for the commercial production of
lithium carbonate from sea water based on the adsorption process
(USGS, 2009), the outcome of which remains uncertain presently.
3.2.2. Precipitation process
Some of the precipitation and other processes used for lithium recov-
ery from seawaters/brines are summarized in Table 8. Among various co-
precipitating agents used, aluminium salts show the best performance
for lithium recovery from geothermal water. The appropriate pH for
lithium recovery is 10–13 and use of NaAlO 2 seems better than
AlCl3. With a high purity NaAlO2 solution as co-precipitating agent,
about 98–99% Li recovery was achieved at pH 11.5 from Ca- and
SiO2-free geothermal water (Yoshinaga et al., 1986).
Despite being the richest lithium resource (10.2 Mt) Uyuni salar
brine containing a high magnesium concentration (Mg/Li mass ratio
~21.2:1) causes difficulties in lithium production. The high magnesium
content represents a significant metal value which should be recovered
with lithium. Consequently, calcium and magnesium had to be removed
from the brine by using oxalic acid before the production of lithium. The
Mg-oxalate produced was suitable for use as a precursor for the produc-
tion of MgO by roasting (Tran et al., 2013). An et al. (2012) developed a
hydrometallurgical process to recover lithium from Uyuni salar brine
containing 15–18 g/L Mg and 0.7–0.9 g/L Li saturated with sodium, chlo-
ride and sulfate. In a 2-stage precipitation process, magnesium and
sulfate were removed as Mg(OH)2 and gypsum (CaSO4·2H2O) at
pH 11.3 by lime in the first stage. Residual magnesium after lime precip-
itation and almost all soluble calcium were then removed by the addi-
tion of sodium oxalate. In the second stage 99.6% lithium carbonate
was precipitated at 80–90 °C using sodium carbonate. Residual Li+
from the solution was quantitatively extracted in the presence of
other alkali metals by a mixture of commercial β-diketones (LIX-51)
and TBP (Miyai et al., 1988). A 2-stage lime precipitation process to
treat seawater was reported by Um and Hirato (2012) to separate
lithium from calcium and magnesium, whereas Clarke (2013) men-
tioned the use of precipitation method to remove the two metals (mag-
nesium and calcium) from the salar brine of Argentina to produce LiCl
which was further processed to recover lithium.
3.2.3. Ion exchange/Solvent extraction process
For high magnesium and calcium containing bitterns or brines solvent
extraction or ion exchange can be used. After selective stripping/elution
lithium can be precipitated out. A combined process consisting of solar
evaporation and ion exchange for the extraction of lithium was proposed
by Steinberg and Dang (1975, 1976). The Dowex resin was used for selec-
tive exchange of its H+ with the cations present in sea water in the order:
K+, Na+, Li+ and Mg2+. Lithium ions were eluted using 0.2–0.5 M HCl
and eluted LiCl was transferred into an electrolyser to produce lithium.
Strelow et al. (1974) separated lithium from sodium, beryllium and
many other elements by eluting lithium with 1 M HNO3 in 80% methanol
from a column of AG50W-XS, a sulfonated polystyrene cation-exchange
resin. Samples were loaded onto a 20 cm3 AG50W-XS (200–400 mesh)
resin column and then eluted with a mixed acid–methanol solution
(1 M HNO3 and 80% methanol) which ensured an extremely good separa-
tion of lithium from sodium in a single column pass.
Earlier studies showed that organic ion-exchange resins exhibited low
selectivity for lithium ions (Abe and Hayashi, 1984; Alberti and Massucci,
1970; Ho et al., 1978). However, Bukowsky et al. (1991) demonstrated
that precipitation followed by ion exchange can be effectively used for
separation and recovery of lithium from a synthetic solution of calcium
and magnesium chlorides. Recently Nishihama et al. (2011) applied
SK110 resin (sulfonated type) from a concentrated solution to remove
divalent metal ions (Mg 2 + , Ca 2 + , Sr 2 + and Mn 2 + ) due to their
higher sorption capacity compared to that of mono-valent ions.
The separation of Li+ from the resultant solution with Na+ and K+
was achieved in a packed column of impregnated resin containing
200 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208

1-phenyl-1,3-tetradecanedione (C11phβDK)/tri-n-octylphophine oxide Spent lithium ion batteries

(TOPO). Li2CO3 was precipitated from the concentrated Li+ solution by
a (NH4)2CO3 solution with an overall yield of 56% and a purity of
Dry N2 gas Cut up
N99.9%. Earlier this group reported selective adsorption of Li+ in aqueous
o
chloride media using a novel synergistic solvent impregnated resin (SIR) 50 C Steel
containing both 1-phenyl-1,3-tetradecanedione (C11phβDK) and TOPO Acetonitrile Dissolution of electrolyte
(Onishi et al., 2010). About 94% Li+ was adsorbed by SIR containing
0.66 mmol/g of each extractant at pH 12. Almost 96.9% Li+ was eluted 50-60 oC
with a 1.0 mol/L HCl solution with 99.8% purity at a bed volume (BV) Acetonitrile Solvent evaporation
of 2.7.
Nelli and Arthur (1970) patented a selective liquid extraction process
for lithium from bitterns of high magnesium content. In the presence of
Electrolyte stored
strong chloride and HCl, lithium was converted into stable lithium tetra
chloroferrate (Cl4FeLi2), which can be extracted by a number of solvents.
About 90% Li was extracted with a mixture of 20% TBP and 80% diisobutyl 50 oC Dissolution of binder
NMP
ketone in 7 counter current stages. Any co-extracted magnesium was
recycled back to the initial extraction step by washing with water in 4
stages. Finally lithium tetra chloroferrate was stripped in 5 counter
current stages. The strip water with ~2 M NaCl was contacted with a mix-
ture of solvent (20% D2EHPA and 30% TBP in benzene) in 6 stages to Filtration Sorting of solids
remove FeCl3. The raffinate in this step is the product containing
~ 0.36% Li, 200 mg/L Mg and 20 mg/L Fe. The second solvent is then 90 oC
stripped of its FeCl3 with about 0.3 parts of water in 6 stages. NMP Solvent evaporation Cu Al Plastics
Separation of lithium and magnesium is difficult because they exhibit
many chemical similarities. However, by utilizing the high charge density
of Mg2+ which is twice that of Li+ with almost the same ionic radius and Water + LiOH Electrolysis
its easy hydrated properties, Zhao et al. (2013) reported a separation
method using LiFePO4/FePO4 as electrodes (Table 8). Lithium exhibits
good reversibility in LiFePO4/FePO4 structures, and the redox peak separa- LiOH solution Decantation
tion is 0.592 V compared to 1.403 V for Mg2+ indicating its higher polar-
ization. At a voltage of 1.0 V in pure lithium solution, the inserted capacity
CoO
Washing
of lithium can reach 41.26 mg/g LiFePO4, which is 93.78% of its theoretical
value (44 mg). The subsequent extracted capacity of lithium can be
CoO
attained to 38.93 mg/g LiFePO4, which is 94.3% of its inserted capacity,
while the extraction capacity of Mg2+ from a solution containing magne-
Fig. 2. Process flowsheet of AEA technology.
sium is only 5.5 mg/g LiFePO4. The lower voltage is found to be beneficial
for separating Mg and Li and the method also works for brine to reduce
the Mg/Li ratio to 0.45 from 60.

3.3. Extraction of lithium from secondary resources — lithium ion batteries
Secondary resources like spent batteries have lithium compounds
coupled with valuable metals such as cobalt, nickel, manganese etc.
which can be economically viable to recycle, whereas low value elements
such as iron and phosphorous will be a greater challenge to create a prof-
itable recycling program. World over several companies viz., Toxco, OnTo,
Sony, Accurec etc. are currently performing and improving battery
recycling processes. Though Toxco and Sony were the first to recycle
LIBs which they still continue, several others also started processing
such materials recently (Espinosa et al., 2004; Gaines and Cuenca,
2000; Li et al., 2009a). The Toxco process is designed for all types of lith-
ium containing wastes. The main product is targeted as appropriate
(cobalt/other base metals) and the other component being the lithium
hydroxide. Sony uses incineration which is followed by hydrometallurgi-
cal techniques. The industrial processes in vogue/developed for recycling
LIBs are described in brief.
3.3.1. Major industrial processes
3.3.1.1. AEA technology. A patented process developed in the UK aims at
the recovery of all battery materials (Lain, 2002). The casing of the bat-
tery is first removed in N2 and cells are cut mechanically to remove
other components wound into a spiral. The anode, cathode and separa-
tors are shredded (~1 cm2 size) to leach the electrolyte and the solvent
in acetonitrile at 50 °C. The electrolyte and the solvent are recovered by
evaporation of the leach liquor and acetonitrile is recycled back. The
binder-PVDF is dissolved in NMP (N-methyl-2-pyrrolidone) and filtered
to separate it from electrode material (Al, Cu, steel and plastics). The NMP
is evaporated from the filtrate and recycled back. Residue is back-washed
and the suspended particulate (LiCoO2 and carbon) is electrolysed with
LiOH as electrolyte. LiCoO2 is reduced adjacent to the cathode to form
CoO while increasing the concentration of LiOH (Fig. 2) which is recov-
ered by decantation. The reaction can be represented as:
− þ −
e þ H2 O þ LiCoðIIIÞO2 →CoðIIÞO þ Li þ 2OH : ð14Þ
3.3.1.2. Toxco process (Canada). A variety of batteries is processed in cryo-
genic conditions (in liquid nitrogen) to reduce the reactivity and mechan-
ical and hydrometallurgical approaches are utilized to recover metal
values (McLaughlin and Adams, 1998). The process flow-diagram is
shown in Fig. 3. Large batteries are sheared into three pieces in a caustic
bath, which neutralizes any acidic components and dissolves the lithium
salts. The salts precipitated and dewatered in filter press, are used to pro-
duce lithium carbonate. Besides organics, H2 formed by reaction with lith-
ium, burns off at the surface of the process bath. Sludge from LIBs is sent to
recover cobalt. The large pieces are mechanically treated while the batte-
ries are submerged in a process solution of lithium brine, after which
ferrous and nonferrous metals are recovered. Li-ion fluff (mixture of
steel and plastics) can then be separated from the rest of the materials
(Cu–Co and slurry). Copper is extracted in the next step and lithium
brine is treated with Na2CO3 to obtain Li2CO3. Plastics and paper floating
at the top are recovered for disposal or recycling. The filtered carbon
 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208 201

Spent lithium ion batteries Spent lithium ion batteries

Conveyor
Mechanical pre-treatment Electronics, plastic casing
o
Disposal/ steel 250 C
Hammer mill Li-ion fluff
recovery Electrolyte, solvent,
Vacuum thermal treatment
conductive salt
Water spray Copper -cobalt
Shaker table
product
Mechanical crushing
Slurry

Primary metal
Sieving, magnetic,
Lithium brine Mixing & Holding production or other Al, steel, Cu, plastics
tank applications air separation

< 0.2 mm electrode material

Cobalt filter
Filter press
cake Binder Agglomeration

Lithium brine
Slag former Reducing meltdown Cobalt manganese
Na2CO3 Mixing tank alloy

Spent brine Acid Leaching Residue

Product filter
to disposal
Precipitant
Washing Precipitation Filtration

Drying Lithium chloride

Li2CO3(s) Fig. 4. Flow-sheet of Accurec recycling process.

Fig. 3. Toxco's hydrometallurgical recycling process for LIBs.

cake from the sludge is un-economical to reuse or even to burn off. Cobalt performed under an inert atmosphere to reduce the reactivity of lithi-
in the spent LIBs presents higher economic worth. um. Plastics, steel and copper are then separated by physical treatment.
The fine powder obtained by screening is suspended in stirred water for
3.3.1.3. Accurec GmbH (Germany) process. The process involves mechan- subsequent leaching and hydrolysis step. Filtering the hydrolyzed solu-
ical treatment to separate the electrode material which is treated by tion produces an alkaline solution of lithium salt and a suspension of
pyro-metallurgy to recover the Co–Mn alloy and lithium chloride
(Sojka, 1998). Electronics and plastic casings are removed followed by
vacuum thermal treatment and pyrolysis to take care of the electrolyte Spent lithium ion batteries
and solvent including conductive salts (Fig. 4). The batteries are then
crushed and by employing sieving, magnetic as well as air separator,
Mechanical treatment CO2 & inert gas mixture
aluminium, copper and steel are removed. The remaining electrode
material is agglomerated with the addition of a binder and pressed to
briquettes, which are smelted (reduction) in a furnace to obtain two Physical treatment Steel, copper, plastics
fractions, the metallic Co–Mn alloy and lithium containing slag. By
acid leaching of the slag lithium can be extracted as lithium chloride/ pH > 12
carbonate. LiOH(aq) Leaching of fines Li(aq)
Precipitation
Soluble lithium
3.3.1.4. Sony/Sumitomo (Japan) process. In this process untreated LIBs are
calcined at 1000 °C by which the cells open and inflammable compo- Mixed oxides +
nents such as the plastic casing and organic solvent burn off. The residue Precipitation inserted Li + Carbon Li2CO3(s)
consisting of metallic and metal pieces of iron, copper and aluminium
can be magnetically separated. The remaining fraction is mainly carbon Lithium phosphate Leaching H2SO4
powder and active cathode material (LiCoO2 and/or LiCoxNi(1−x)O2).
The powder is treated at the Sumitomo plant by hydrometallurgical Cu and other
methods to recover cobalt; lithium is not targeted. Cobalt oxide of Purification Soda
impurities
high quality is recovered to use directly in the fabrication of new LIBs
and the metallic scraps such as copper and stainless steel can be used
as the by-products. Large batteries can also be handled but needs to NaClO Oxidation Li2SO4(aq)
be punctured prior to introduction to the furnace (Gaines and Cuenca,
2000; Lupi et al., 2005).
Cobalt(III) hydroxide
3.3.1.5. Recupyl process (France). This is also called as the Valibat process
for recycling LIBs. Mechanical preparation of the spent batteries is Fig. 5. Recupyl process for LIBs recycling.
202 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208

Spent lithium batteries 3.3.1.7. OnTo Technology (USA). Spent batteries are discharged before
dismantling. Batteries are cleaned and then placed in a high pressure
Protective extraction container filled with liquid CO2 and some additives like alkyl
CO2
atmosphere ethers, ammonia etc. The CO2 is transformed into a supercritical fluid by
increasing the pressure and temperature in the container. With an
increase in pressure, the battery casings are breached by fluid. When
Feeder &
CO2 the desired pressure and temperature are reached the electrolyte extrac-
Shredder
tion can either be carried out by circulating CO2 through the system or by
soaking the batteries in the supercritical fluid. Batteries without function-
Moist air Neutralization al potential are subsequently recycled through pulverization and the var-
ious materials separated and recovered based on the physical properties.

Release of protective 3.3.1.8. Umicore process (Belgium and Sweden). Also called as the ValÉas
Gases
atmosphere
process, this is a combined pyro-and-hydro-metallurgical process to
separate nickel and cobalt without recovering lithium. The spent batte-
Acidified Gas Scrubber
Leaching & washing ries are smelted in a furnace. Plastic, solvent and graphite are burnt off
aqueous liquid while the metals are reduced and collected in a melt. The process is
SO2(aq), Cl2(aq) operated in Sweden while the molten metal consisting of Ni, Co, Cu
Leach liquor and Fe is cooled and processed in Belgium by sulfuric acid leaching
Metal fractions
& plastics and solvent extraction. NiSO4 and CoCl2 are separated from the solution
Hydrometallurgical from which cobalt oxide and Ni(OH)2 are obtained.
processing Residue A disadvantage of pyrometallurgical recycling processes including
(SX/Precipitation) that of Umicore is that lithium recovery is not targeted and for which
a combination of pyrometallurgical and hydrometallurgical processing
Recovered chemical steps are necessary. The Umicore process has another drawback of
substances losing base metals which are slagged off, besides the loss of organic
materials as well as carbon.
Fig. 6. Batrec Industrie AG process flowsheet.
3.3.2. Recent development in recycling of lithium ion batteries
metal oxides and carbon. Lithium is precipitated as Li2CO3 using the Spent LIBs containing lithium and other metals are mostly treated
CO2 obtained from the mechanical treatment. The suspension of metal by the hydrometallurgical process which is used at times in combi-
oxides is dissolved in H2SO4. Copper is cemented out by the steel nation with pyrometallurgical treatment. This may have integrated
shots (Tedjar and Foudraz, 2007). The purified solution is oxidized by pre-treatment steps like pyrolysis or mechanical processing, i.e. crushing
NaClO to precipitate cobalt(III) hydroxide (Fig. 5) and cobalt is separat- and material separation. In order to investigate the extraction of cobalt,
ed by electrolysis. The remaining lithium in the solution is precipitated nickel, manganese etc. from LIBs by such processes thermodynamic as-
with CO2 gas. pects particularly the stability regions of different phases in aqueous solu-
tion under redox conditions may be examined. For this standard Eh–pH
3.3.1.6. Batrec Industrie AG process (Switzerland). The company Batrec diagrams of Li–H2O, Co–H2O, Mn–H2O and Ni–H2O systems can be re-
mainly runs a mechanical processing plant for LIBs. In this process ferred from literature (Pourbaix, 1966; Schweitzer and Pesterfield, 2010).
batteries are crushed in CO2 gas atmosphere and the released lithium Leaching of LIBs are carried out with different acids like HCl
is neutralized. With the completion of the neutralization step, the (Contestabile et al., 2001; Zhang et al., 1998), H2SO4 (Aktas et al., 2006;
protective environment is released and subsequently treated in a gas Dorella and Mansur, 2007; Kang et al., 2010a,b; Nan et al., 2005; Shin
scrubber to reduce the emission during the process. Scrap material is et al., 2005; Swain et al., 2007), HNO3 (Lee and Rhee, 2002, 2003), and a
leached and washed in acidified aqueous liquid and leach liquor is few organic acids like DL-malic acid (Li et al., 2010a), citric acid (Li et al.,
further processed for the recovery of different chemical substances. 2010b) etc. The binder (PVDF) which links the cathode material, LiCoO2
Metal containing a solid fraction can be separated from liquid and treat- with aluminium foils does not dissolve easily in the organic reagents
ed to remove impurities. The flowsheet of the process is presented in such as fatty hydrocarbon or alcohol at room temperature making the
Fig. 6. leaching reactions more difficult to proceed. The important developments

Table 9
Extraction and recovery of metals from spent LIBs in hydrochloric acid system.

Material Leaching conditions Extraction/Separation—parameters Highlights (with References

merits/demerits)
Acid concentration Temp. Time Pulp density
(M) (°C) (h) (g/L)

Cylindrical- 4 80 1 100 SX with 0.29 M D2EHPA and 0.90 M PC-88A SX: N99.9 Co and 12.6% Li with Zhang et al.
shaped LIBs 0.9 M PC-88A. (1998)
Higher selectivity with PC 88A.
Spent LIBs 4 80 1 100 Precipitation: pH 6–8 with 4 M NaOH. Co(OH)2 separated easily. Contestabile
Synthesis of precursor material by NixCoyMnz a precursor to cathode et al. (2001)
co-precipitation. material
LIBs 4 80 1 20 Precipitation: pH 2 with KMnO4 for Mn(II), Purity (%): 96.9 Li, 98.23 Mn, Wang et al.
pH 9 for Co by DMG and Li2CO3 96.94 Co and 97.43 Ni (2009)
LIBs 3 M acid + 3.5% 80 1 50 Precipitation: pH 11–12 with NaOH for Co; Recovery (%): 95 Co and 93 Li in Shuva and
H2O2 Na2CO3 at 100 °C for Li precipitate Kurny (2013)
Ash from LIBs 4 90 18 50 Precipitation by NaClO at pH 3 and base Recovery (%): 100 Co and 99.99 Ni. Joulié et al.
addition at pH 11 HCl gives higher leaching efficiency. (2014)
 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208 203

Table 10
Extraction and recovery of metals from spent LIBs in sulfuric acid system.

Material Leaching conditions Extraction/Separation— Highlights (with References

parameters merits/demerits)
Acid concentration Temp. Time Pulp density
(°C) (h) (g/L)

LIBs waste 2 M acid + 15 vol.% 75 0.167 50 – Leaching (%): 95 Co Shin et al.

H2O2 and 100 Li. (2005)
Harmful gas—SOx
generated.
Square-shaped LIBs 3 M acid 70 4 200 Precipitation & SX using Acorga M5640 Precipitation: 90% Co Nan et al. (2005)
and Cyanex 272 SX: ~97% Cu by Acorga
M5640, 97% Co by Cyanex
272
LIBs 6% acid + 1% H2O2 65 33.3 Precipitation with NH3 at pH 5. Leaching (%): ~55 Al, 80 Dorella and
Co/Li separation by diluted (0.72 M) Co and 95 Li. Mansur (2007)
Cyanex 272 Extraction (%):~85 Co by
Cyanex 272.
LIB wastes 2 M acid + 5% H2O2 75 0.5 100 SX by 0.5 M Cyanex 272, pH 5.35 Leaching (%): 93 Co Swain et al.
and O/A = 1 in 1-stage and 94 Li. (2007)
CoSO4 solution: 99.99%
pure.
Spent LIBs 4 M acid + H2O2 80 4 Precipitation using ethanol, ethanol/ Co recovery: 92% as Aktas et al.
solution = 3:1; 15 min, room CoSO4 and (2006)
temperature 8% Co as Co(OH)2 by
adding Li(OH)2 at pH 10.
Synthetic solution (10 mol/L – – – – SX by Cyanex 272 and DP-8R Separation factor (Co/Li): Swain et al.
Co(II) and 20 mol/L Li2SO4) 497 at pH 5 (2010)
Spent LIBs 2 M acid + 6% H2O2 60 1 100 Precipitation at pH 6.5 for Cu, Fe and Al Leaching (%): N99 Co, Kang et al.
SX by 50% saponified 0.4 M Cyanex 272, SX: 99.9% Co in 2 stages. (2010a, 2010b)
pH 6, O/A = 2 Separation factor 750
(Co/Li) and Co/Ni at
pH 6.
Spent LIBs 1 M acid + 30% 80 2 714 Precipitation by 1 M citric acid, 2 h, Max. Co leaching (%): 88.3. Li and Zeng
H2O2 65 °C; calcined at 450 °C, 4 h Crystalline LiCoO2 (2011)
synthesized
Spent LIBs 4 M acid + 10% 85 2 100 SX by 25% P507 SX: 98% Co and removal Chen et al.
H2O2 Precipitation by ammonium oxalate, of 97% Ni and Li. (2011a, 2011b)
pH 1.5
Spent LIBs 3 M + 0.25 M 90 3 67 – N99% leaching Wang et al.
Na2S2O3 (2012)

on the leaching and separation of metals from the leach solutions are
summarized in Tables 9–11.
3.3.2.1. Metal extraction/recovery from hydrochloric acid leach liquors. In
most processes reported, optimum extraction of metals from the cath-
ode material of spent LIBs was achieved with a 4 M solution of HCl
(Table 8). In the presence of a reducing agent such as hydrogen perox-
ide, metal leaching was possible even in 3 M HCl (Contestabile et al.,
2001; Joulié et al., 2014; Shuva and Kurny, 2013; Zhang et al, 1998).
While H2O2 facilitated the dissolution of Co(II) which was reduced
from Co(III), the dissolution of lithium was also promoted because of
the presence of the two metals in the same oxide. The separation and
recovery of metals from the leach liquors, was carried out either by sol-
vent extraction involving PC-88A, Cyanex 272 etc. to produce the pure
metal salts or the metals that were selectively precipitated as Co(OH)2
and LiCO3 from the leach solutions. Thus, Zhang et al. (1998) used the
steps such as leaching of cathode materials of spent LIBs in HCl, separa-
tion of Co/Li by solvent extraction (PC-88A) and recovery of cobalt as
sulfate and lithium as carbonate. Out of sulfurous acid, hydroxyl amine
hydrochloride and hydrochloric acid, HCl was found to be the most suit-
able lixiviant for economic reasons. The leaching efficiency of N 99% of
Co and Li in a 4 M HCl solution was achieved. The complete extraction
of cobalt from the leach liquor by 0.90 M PC-88A in 1 stage at pH 6.7
and O/A of 0.85:1, scrubbing of lithium by 30 g/L Co at O/A 10:1 and

Table 11
Extraction and recovery of metals from spent LIBs in other organic/inorganic acid systems.

Material Leaching Leaching conditions Highlights References

reagent (with merits/demerits)
Time (h) Temp. (°C) Pulp density (g/L)

LIBs 1 M HNO3 + 1.7 vol.% H2O2 1 75 20 Leaching (%): 95 Co and Li. Lee and Rhee (2002, 2003)
Harmful gas—NOx generated.
LIBs 1 M HNO3 + 1.0 vol.% H2O2 1 80 20 Leaching (%): 100 Co and Li. Li et al. (2011)
Harmful gas—NOx generated.
Spent LIBs 1.5 M DL-malic acid + 2% H2O2 0.67 90 20 Leaching (%): 90 Co and 100 Li. Li et al. (2010a)
Acid can be recycled and reused.
Spent LIBs 1.25 M citric + 1% H2O2 0.25 90 20 Leaching (%): N90 Co and 100 Li. Li et al. (2010b)
Simple and environmental friendly process.
Cylindrical spent LIBs 1.25 mol/L ascorbic acid 0.33 70 25 Leaching (%): 94.8 Co and 98.5 Li. Li et al. (2012)
of mobile phone Reducibility of ascorbic acid displaced H2O2.
204 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208
stripping of cobalt from the loaded organic with 2 M H2SO4 at O/A 5:1,
produced high purity cobalt sulfate. About 80% lithium was recovered
as Li2CO3 by precipitation with saturated soda solution at 100 °C.
The leaching reaction of the waste LiCoO2 with HCl solution can be
represented as:
4LiCoO2ðsÞ þ 12HClðaqÞ →4LiClðaqÞ þ 4CoCl2ðaqÞ þ 6H2 O þ O2ðgÞ : ð15Þ
A laboratory scale process involving leaching of LiCoO2 in HCl and pre-
cipitation of cobalt hydroxide was developed by Contestabile et al. (2001).
The active material of spent LIBs was dissolved in N-methylpyrrolidone at
100 °C to separate aluminium and copper foil. From the leach liquor, car-
bon powder was removed by filtration and Co(OH)2 was precipitated out
from the solution at pH 6–8. In another study over 95% dissolution of Ni,
Co and Mn was reported when the battery material of 120 μm size was
leached at a higher acid concentration (6 M HCl) and lower temperature
(60 °C) in the presence of H2O2 (Li et al., 2009b). Cobalt from the solution
was cemented out by iron powder and iron was removed as goethite.
Finally chlorides of Ni, Mn and Co were added in the purified solution
to prepare the precursor of the cathode material (NixCoyMnz) directly
through co-precipitation with ammonium bicarbonate. The leaching of
metals from the cathode material in 4 M HCl at 80 °C with a metal re-
covery of 99% was also reported by Wang et al. (2009). Manganese in
the leach liquor was precipitated at a molar ratio of Mn2 + to KMnO4
of 2 and pH 2 followed by selective precipitation of nickel with
dimethylglyoxime (DMG) at pH 9. Cobalt was recovered as hydrox-
ide at pH 11 and Li2CO3 was then precipitated; purity of the metals
being 96.97% Li, 98.23% Mn, 96.94% Co and 97.43% Ni. A recent study
by Shuva and Kurny (2013) demonstrated the reductive dissolution of
cathode powder in 3 M HCl in the presence of 3.5% H2O2. Over 95%
cobalt was precipitated as hydroxide at pH 11–12, leaving lithium
(93%) in the leach solution.
Processing of battery ash obtained from the pyrolysis of spent LIBs by
HCl leaching was also attempted. Lin et al. (2003) patented a pyrometal-
lurgical process of waste LIBs combined with hydrometallurgical pro-
cessing. The ash with metal and metal oxides was dissolved in 3–6 M
HCl containing NaCl. Copper and cobalt were separated out using mem-
brane electrolysis. Then Fe(OH)3 and Al(OH)3 were recovered at pH 5–7
followed by the precipitation of lithium carbonate. Recently Joulié et al.
(2014) reported the high leaching efficiency (~100%) of Li, Ni, Co and
Al from the Li–Ni–Co–Al oxide ash of spent LIBs by 4 M HCl at 90 °C
with chloride ions promoting the dissolution. Co(II) in the leach liquor
was oxidized to Co(III) with NaClO and recovered as Co2O3·3H2O by
selective precipitation at pH 3 (Eqs. (16) and (17)). Nickel hydroxide
was then precipitated at pH 11.
2þ − þ 3þ −
2Co þ ClO þ 2H3 O ⇔2Co þ Cl þ 3H2 O ð16Þ
3þ −
2Co þ 6OH →Co2 O3 ⋅3H2 O: ð17Þ
3.3.2.2. Metal extraction/recovery from sulfuric acid leach liquors. In most
leaching processes with sulfuric acid, hydrogen peroxide was used as
a reductant (Castillo et al., 2002; Dorella and Mansur, 2007; Jha et al.,
2013a,b; Kang et al., 2010a, 2010b; Shin et al, 2005). In some cases alkali
leaching followed by acid leaching was considered to remove alumini-
um. Metals from the leach solutions were separated and recovered by
solvent extraction using PC-88A/P507, Cyanex 272 and Acorga M5640
and precipitation processes very similar to that of the HCl system. The
fine sized electrodes were initially contacted with N-methyl pyrrol-
idone (NMP) to dissolve the binder and separate active material
(LiCoO2) from Al and Cu foils (Castillo et al., 2002). The LiCoO2 powder
was leached in 4 M H2SO4 at 80 °C to dissolve Co and Li, and Co(OH)2
was recovered from the leachate by the addition of sodium hydroxide.
Shin et al. (2005) reported almost quantitative leaching of cobalt and lith-
ium with 2 M H2SO4 in the presence of a high amount of H2O2 (15 vol.%)
at 75 °C and 50 g/L pulp density (Table 10). Reductive leaching of the
mechanically treated LIBs in 6 (v/v)% H2SO4 and 1% H2O2 solution resulted
in a relatively lower recovery of metals (~55% Al, 80% Co and 95% Li)
(Dorella and Mansur, 2007). Kang et al. (2010a, 2010b) also reported
the reductive leaching of LIBs with H2SO4. The reactions of LiCoO2 with
H2SO4 and in the presence of H2O2 are shown below:
4LiCoO2ðsÞ þ 6H2 SO4 →4CoSO4 þ 2Li2 SO4 þ 6H2 O þ O2ðgÞ ð18Þ
2LiCoO2ðsÞ þ 3H2 SO4 þ H2 O2ðaqÞ →4CoSO4 þ Li2 SO4 þ 4H2 O
þ O2ðgÞ : ð19Þ
The leaching efficiency of cobalt depends on the reductant concentration.
Among other reducing agents, Na2S2O3 helped in the leaching of N99%
of the metals (Co and Li) in 2 M sulfuric acid at 90 °C in 3 h (Wang
et al., 2012).
Safe dismantling procedures of spent lithium ion batteries have
often been described in the literature (Nan et al., 2005; Tanii et al.,
2003). Zhu et al. (2011) applied a mechanical separation process to
recover copper from these batteries. The anodes from the batteries
were separated by mechanical treatment, pulverization and sieving.
Almost 92% of copper in anode particles was recovered by a gas-
fluidized bed separator.
In the alkali–acid leaching process, the cathode was first treated with
10% (w/w) NaOH at 30 °C to dissolve Al, followed by reductive leaching
of ~97% Co and 100% Li with H2SO4 and H2O2 (Ferreira et al., 2009; Nan
et al., 2005). Acorga M5640 and Cyanex 272 were used to selectively
extract and recover 98% Cu and 97% Co, respectively from the solutions.
About 90% Co was recovered as oxalate with b0.5% impurities. LiCoO2
positive electrode material with a good electrochemical performance
was synthesized by using the recovered compounds.
From the sulfate leach liquor of spent LIBs, 96% copper was recov-
ered as CuSO4·3H2O with ethanol at a volume ratio of 3:1. Cobalt was
recovered in two steps. During the first step, 92% of the cobalt was
recovered as CoSO4 by the use of ethanol at a volume ratio of 3:1. The
remaining Co in the second step was recovered as Co(OH)2 by the addi-
tion of Li(OH)2 at pH 10 (Aktas et al., 2006). Lithium, which remained in
the solution, was then recovered to the extent of 90% as Li2SO4 by the
addition of ethanol (3:1 volume ratio). Aluminium was recovered as
Al(OH)3 with 99% recovery efficiency. It was shown that metals could
be precipitated/separately by the ethanol/sulfate precipitation tech-
nique depending on their concentrations present in the solution.
The waste cathodic active material generated during the manufactur-
ing of LIBs was also leached in H2SO4 in the presence of H2O2 (Swain
et al., 2007). During the separation of Co/Li in a 2-step SX process with
1.5 M Cyanex 272 at O/A 1.6, about 85% Co was recovered. The remaining
cobalt was extracted in 0.5 M Cyanex 272 at O/A 1 and pH 5.35. The
purity of cobalt sulfate in solution was found to be 99.99%. Earlier,
Swain et al. (2006) reported the highest separation factor (Co/Li) of 62
during extraction with saponified Cyanex 272 from a synthetic solution
at pH 6.9.
The mechanism by which a metal ion is extracted from an aqueous
solution using a partially saponified cation exchange extractant is as
follows (Ritcey and Ashbrook, 1984):
2þ − þ
Maq þ Aorg þ 2ðHAÞ2org ↔MA2 ⋅3HAorg þ Haq : ð20Þ
Cobalt is extracted as [CoA2·3HA]org with 65% Na-Cyanex 272. Cobalt can
be completely stripped from the loaded organic with 0.01 M H2SO4 to
produce cobalt sulfate of N 99% purity.
By acid leaching of waste cathodic material and SX with Cyanex 272,
Swain et al. (2008) produced a pure cobalt sulfate solution (99.99%). In
another study quantitative separation of Co(II)/Li was reported using
 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208
the supported liquid membrane (SLM) with a mixed extractant contain-
ing Cyanex 272 and DP-8R as the mobile carrier (Swain et al., 2010).
Very recently, leaching of lithium and cobalt from cathodic material of
waste mobile phone batteries in sulfuric acid in the presence of H2O2
and separation of metals by Cyanex 272 were reported (Jha et al.,
2013a, 2013b). Chen et al. (2011a) recovered cobalt oxalate from the
spent LIBs by using an alkali–acid leach process. After roasting the spent
LIBs at 700–800 °C to burn off carbon and the binder, and leaching with
NaOH to remove Al, and leaching with H2SO4 in the presence of 10 (v)%
H2O2 could recover 95% Co and 96% Li. Iron removal (99.99%) as jarosite
with a loss of b 1% Co was achieved in the pH range 3–3.5 at 95 °C. The
precipitation reaction is shown below:
Fe2 ðSO4 Þ3 þ 12H2 O þ Na2 SO4 →Na2 Fe6 ðSO4 Þ4 ðOHÞ12 þ 6H2 SO4 :
Complete removal of manganese with ammonium persulfate at pH 4 and
70 °C is as follows:
2þ
Mn þ ðNH4 Þ2 S2 O8 þ 2H2 O→MnO2 þ ðNH4 Þ2 SO4 þ H2 SO4
þ
þ 2H :
Copper precipitation (N98.5%) with NaOH was followed by solvent
extraction to recover Co(II) while removing 97% Ni and Li (Zhu et al.,
2012). About 95% Co(II) was extracted selectively from the purified
solution with saponified 25 wt.% P507 (2-ethylhexyl phosphonic acid
mono-2-ethylhexyl ester) at pH 3.5 and stripped with 3 M H2SO4. Cobalt
oxalate was produced from the strip liquor with a purity of 99.9%.
CoC2O4·2H2O and Li2CO3 were also produced by a combination of acid
leaching, SX and precipitation from spent mobile phone batteries (Jian
et al., 2012). From the leach solution of the used batteries, Co(OH)2
was precipitated and was converted to Co3O4 by heating (Yamaji et al.,
2011) as per reactions (23) and (24). Lithium was recovered as carbonate
by adsorption with 2% MnO2 (11.7 mg Li/g).
CoSO4 þ 2NaOH→CoðOHÞ2 þ Na2 SO4
1 More than 90% of Co could be separated out at pH 5.5–6.0 and A/O
3CoðOHÞ2 þ O2 →Co3 O4 þ 3H2 O:
2 1:2. An ion-exchange resin such as Dowex M4195 was then used to
The advantage of vacuum pyrolysis to prevent the escape of toxic
gases and lower the decomposition temperature of organics while
protecting oxidization of metals in LIBs, was applied by Sun and Qiu
Sulfuric acid Leaching of spent LIBs
Al(III), Cu(II), Co(III), Li(I)
pH 1.5-2.0
Acorga M5640 Solvent Extraction
Cu(II) Al(III), Co(II), Li(I)
pH 2.5-3.0
Solvent Extraction
PC-88A
Al(III) Co(II), Li(I)
pH 5.5-6.0
PC-88A + TOA Solvent Extraction
Co(II)
Fig. 7. SX separation of Al, Cu, Co and Li from sulfate media (Suzuki et al., 2012).
205
(2011). The cathode material was treated in a vacuum furnace at
600 °C for 30 min with the residual gas pressure of 1.0 kPa. Over 99%
Co and Li were recovered from peeled Co–Li oxide by leaching with
2 M H2SO4 at 80 °C. Paulino et al. (2008) examined two approaches for
recycling spent Li/MnO2 and LIBs. In the first process ~90% Li was recov-
ered by calcination at 500 °C followed by leaching with H2SO4 and H2O2
at 90–100 °C, and solvent extraction. The second process involved fusion
with KHSO4 at 500 °C and water leaching with H2O2 at 90 °C. Cobalt and
manganese were precipitated at pH N9 followed by precipitation of LiF
by KF solution.
Extraction of Co and Li from a material of a large scale mechanical
pre-treatment and recycling plant in Northern Italy is described by
Granata et al. (2012). The powder is leached in H2SO4 in the presence
ð21Þ of 50% excess of a reducing agent, glucose — a waste product of the
food factory. Iron, aluminium and copper are partially precipitated
as hydroxides at pH 5.0. Using solvent extraction high purity cobalt
carbonate (47% Co) is obtained by precipitation, whereas without sol-
vent extraction the product containing 36–37% (w/w) Co is obtained.
ð22Þ Lithium is recovered by crystallization (yield 80%) with 98% purity.
The process with solvent extraction shows economical outputs (gross
margin and payback time) than the one without solvent extraction.
Suzuki et al. (2012) developed a process as detailed in Fig. 7. Acorga
M5640 extracted copper within a pH range of 1.5–2.0 leaving Al, Co and
Li in the raffinate. Aluminium is then selectively extracted by PC-88A in
the pH range 2.5–3.0. Cobalt(II) and lithium(I) are separated by PC-88A/
TOA rather than Acorga M5640 due to its higher stripping efficiency
(N98%), although Acorga M5640 provides higher cobalt selectivity.
Synergistic extraction and separation of Co(II) and Mn(II) with
Li(I) from simulated sulfuric acid leaches of waste cathodic materials
using a mixture of Cyanex 272 and PC-88A in N-heptane have been
investigated by Zhao et al. (2011). A mixed extractant system was also
utilized to treat the leach solutions of spent LIBs (Pranolo et al., 2010).
In the first stage Fe(III), Al(III) and Cu(II) were extracted using Ionquest
ð23Þ 801 and Acorga M5640, and the raffinate containing cobalt, nickel and
lithium was treated with 15% (v/v) Cyanex 272 to separate out Co.
ð24Þ
separate Ni(II)/Li(I). The addition of 2% (v/v) Acorga M5640 to 7% (v/v)
Ionquest 801 generated a significant pH isotherm shift for Cu which
resulted in a ΔpH50 of 3.45.
Apart from the hydrometallurgical extraction of valuable metals
from spent LIBs, synthesis of LiCoO2 was also reported (Li and Zeng,
2011). The solvent N-methyl-2-pyrrolidone was used to dissolve the
PVDF agglomerate from Co–Li membrane to separate the aluminium
foil. About 88% Co was recovered during the leaching with sulfuric
acid at pH 0.5 and 80 °C. Then, 1 M citric acid solution was added at
65 °C to prepare a gelatinous precursor. LiCoO2 was obtained with the
gel precursor calcined in a crucible at 450 °C for 4 h.
3.3.2.3. Metal extraction/recovery from nitric acid leach liquors. Mechanical,
thermal, hydrometallurgical and sol–gel steps were applied to recover
Co/Li from spent LIBs and synthesize LiCoO2 as a cathode active material
(Lee and Rhee, 2002, 2003). Reductive leaching in 1 M HNO3 with
1.7 vol.% H2O2 at 75 °C extracted ~ 95% Li and 95% Co (Table 11). The
molar ratio of lithium to cobalt in the leach liquor was adjusted to 1.1
by adding a fresh LiNO3 solution. Then, 1 M citric acid solution was
added to prepare a gelatinous precursor which was calcined at 950 °C
for 24 h to produce purely crystalline LiCoO2. Like in other studies, the
addition of hydrogen peroxide increased the leaching efficiency of
metals (Lee and Rhee, 2003). The reductive leaching of almost 100%
Co and Li from the spent batteries in nitric acid and H2O2 was achieved
at 80 °C by Li et al. (2011). In the nitric acid leaching system pollution
due to harmful NOx gases is a major problem and needs to be addressed.
Li(I) As regards the leaching kinetics, lithium dissolution followed a shrinking
core model. The mechanism of the dissolution of LiCoO2 was controlled
by a surface chemical reaction with an apparent activation energy of
206 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208
52.32 and 47.72 kJ/mol for Co and Li, respectively (Lee and Rhee, 2003).
The leaching reaction with HNO3 solution can be represented as:
2LiCoO2ðsÞ þ 3HNO3ðaqÞ →Li2 NO3ðaqÞ þ 2CoðNO3 Þ2ðaqÞ þ 3H2 O
1 amount of Li2CO3 in the recycled LiCoO2 and calcining it at 850 °C for
þ O2ðgÞ : ð25Þ
2
Recycling of Li-ion and polymer batteries while producing
LiCo x Ni (1− x) O 2 as a cathode material was investigated by Lupi and
Pasquali (2003). The process consists of cathodic paste leaching, Co–Ni
separation by SX and recovery of Ni by electrowinning. The separation
of Ni/Co was performed by solvent extraction using saponified 0.5 M
Cyanex 272. Nickel was electrowon at a current density of 250 A/m2,
50 °C and pH 3–3.2 with an electrolyte of 50 g/L Ni and 20 g/L H3BO3.
Elaborating further, Lupi et al. (2005) reported the current efficiency
and energy consumption of 87% and 2.96 kWh/kg for nickel under the
above conditions as compared to the figures of 96% and 2.8 kWh/kg,
respectively for cobalt at the same current density and temperature,
but at pH 4–4.2 from a solution containing manganese and (NH4)2SO4.
3.3.2.4. Metal extraction using organic acids/reagents. For the sustainable
management of the secondary resource such as LIBs, organic acids
such as DL-malic acid, citric acid etc. which have mild acidity, are sug-
gested for the leaching of metals (Table 11). Li et al. (2010a) reported
that DL-malic acid can dissolve lithium and cobalt of LIBs fairly rapidly
under aerobic and anaerobic conditions as compared to the mineral
acids like HCl, HNO3 and H2SO4, and the waste solutions can be treated
easily. Almost 100% Li and N 90% Co were leached out with 1.5 M malic
acid and 2.0% H2O2 at 90 °C in 40 min. Leaching of lithium and cobalt
in citric acid was also reported after separating the anode and cathode
material by the treatment of NMP (Li et al., 2010b). Nearly 100% Li
and N90% Co were extracted in 1.25 M citric acid and 1.0% H2O2 at 90 °C.
Recently ultrasonic assisted leaching of cobalt and lithium from
spent LIBs in the presence of ascorbic acid was investigated (Li et al.,
2012). Leaching efficiencies of as high as 94.8% for Co and 98.5% for Li
were achieved with 1.25 M ascorbic acid solution at 70 °C (Table 11).
Sun and Qiu (2012) used oxalic acid as both leachant and precipitant
to separate and recover cobalt and lithium from the spent LIBs. Cathode
material consisting of LiCoO2 and CoO from the dismantled batteries,
was peeled off from the aluminium foils after vacuum pyrolysis at
600 °C. Leaching was performed using 1 M oxalate at 80 °C with the
reaction efficiency of N 98% of LiCoO2 while separating cobalt and lithium.
The reaction with oxalate for leaching and precipitation proceeds as:
3H2 C2 O4 þ LiCoO2ðsÞ →LiHC2 O4 þ CoðHC2 O4 Þ2 þ 2H2 O þ 2CO2ðgÞ ð26Þ
4H2 C2 O4 þ 2LiCoO2ðsÞ →Li2 C2 O4 þ 2CoC2 O4ðsÞ þ 4H2 O þ 2CO2ðgÞ : ð27Þ
During the oxalate leaching Co3+ was reduced to Co2 + which was
dissolved and precipitated as cobalt(II) oxalate (Sun and Qiu, 2012).
The reduction of Co3+ to Co2+ is also believed to proceed by the reaction
of CO2 radicals generated from oxalic acid (Hoffman and Simic, 1973).
The electrochemical performance of nano-Co3O4 anode material
prepared from the spent LIBs was evaluated by Hu et al. (2013). From
the leach liquor obtained from the alkali and acid process, Al(OH)3,
MnOOH, Cu(OH)2 and Ni(OH)2 were removed at a pH N 5 which was
followed by the precipitation of CoC2O4 at pH 2 by adding a saturated
solution of (NH4)2C2O4. The product CoC2O4 was used to synthesize
nano-Co3O4 by the sol–gel method.
The roasting of batteries under reduced pressure at 650 °C was
reported by Kondás et al. (2006), which was followed by the leaching
of Li2CO3 at ambient temperature and crystallization of pure Li2CO3. A
process for the recycling and synthesis of LiCoO2 from the incisors
bound of Li-ion batteries was developed by Liu et al. (2006). Firstly,
LiCoO2 was separated from aluminium foil with dimethyl acetamide
(DMAC). Polyvinylidene fluoride and carbon powders in the active
material were then eliminated by roasting at 450 °C for 2 h and 600 °C
for 5 h, respectively. Finally LiCoO2 was obtained by adding a certain
12 h.
4. Conclusions
Lithium is one of the rare metals with a variety of applications and
demand for lithium is expected to increase with the ever increasing
use of electrical and electronic devices/hybrid electric vehicles. A few
established technologies are in vogue to produce lithium in the desired
form from its primary resources like its minerals and brine, whereas
limited exploitation of lithium resources from seawater and bitterns
calls for their intensified tapping. Extraction of lithium from its minerals
and clays is fraught with high mining costs and involves high energy,
while extraction from brine and bitterns/seawater needs a long time
for evaporation. Hence these processes need to be adequately modified
to yield efficiency and better economic returns.
Extraction processes from secondary resources like batteries depend
on the chemistry of the battery material. Most processes involve dis-
mantling of LIBs, separation of cathode and anode materials, leaching
of valuable metals like Co, Li, Ni, Mn etc. from the cathode material in
different mineral acids, and separation and recovery of metals from
the solutions by solvent extraction/IX/precipitation. At present no lithi-
um extraction is industrially practiced from LIBs. Therefore, a sufficient
scope exists not only to reduce the process steps followed currently but
also to improve the efficiency of metal extraction and separation, in-
cluding lithium recovery. Points that may be considered include process
intensification to save energy and improve the kinetics of leaching,
while addressing the problem of selectivity and examining the use of
unexplored/synergistic solvents with an ultra high metal loading capac-
ity to cut down the process steps. There is a need to develop appropriate
technology which can address the limitation of current processes for
extraction of all valuable metals from its primary as well as secondary
resources.
Acknowledgements
The authors are thankful to the Director, CSIR-National Metallurgical
Laboratory (NML), Jamshedpur, India for giving permission to publish
the paper.
References
Abe, Y., 2010. Rare metal series — current status of lithium resources. JOGMEC Mineral
Resources Report.
Abe, M., Hayashi, K., 1984. Synthetic inorganic ion-exchange materials. XXXIV.
Selective separation of lithium from seawater by tin(IV) antimonate cation
exchanger. Hydrometallurgy 12, 83–93.
Aktas, S., Fray, D.J., Burheim, O., Fenstad, J., Acma, E., 2006. Recovery of metallic values
from spent Li ion secondary batteries. Miner. Process. Ext. Metall. (Trans. Inst. Min.
Metall. C) 115 (2), 95–100.
Alberti, G.M., Massucci, M.A., 1970. Crystalline insoluble salts of tetravalent metals. IX.
Thorium arsenate, a new inorganic ion-exchanger, specific for lithium. J. Inorg.
Nucl. Chem. 32, 1719–1727.
Amer, A.M., 2008. The hydrometallurgical extraction of lithium from Egyptian
montmorillonite-type clay. J. Met. 60 (10), 55–57.
An, J.W., Kang, D.J., Tran, K.T., Kim, M.J., Lim, T., Tran, T., 2012. Recovery of lithium from
Uyuni salar brine. Hydrometallurgy 117–118, 64–70.
Australia's Mineral Resource Assessment (AMRA), 2013. http://www.ga.gov.au/corporate_
data/77481/77481_AMRA_v2.pdf.
Averill, W.A., Olson, D.L., 1978. A review of extractive processes for lithium from ores and
brines. Energy 3, 305–313.
Bach, R.O., Wasson, J.R., 1981. Lithium and lithium compounds, 3rd edition Ch. in Kirk-
Othmer: Encyclopedia of Chemical Technology vol. 14. Wiley, pp. 448–476.
Banerjee, D.C., Krishna, K.V.G., Murthy, G.V.G.K., Srivastava, S.K., Sinha, R.P., 1994.
Occurrence of spodumene in the rare metal bearing pegmatites of Marlagalla–
Allapatna area, Mandya District, Karnataka, India. J. Geol. Soc. India 44,
127–139.
 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208
Barbosa, L.I., Valente, G., Orosco, R.P., González, J.A., 2014. Lithium extraction from β-
spodumene through chlorination with chlorine gas. Miner. Eng. 56, 29–34.
Bernardes, A.M., Espinosa, D.C.R., Tenório, J.A.S., 2004. Recycling of batteries: a review of
current processes and technologies. J. Power Sources 130 (2004), 291–298.
Brown, J.C., Dey, A.K., 1955. India's Mineral Wealth, 3rd edition. Geoffrey Cumberlege,
Oxford University Press, Bombay, p. 271.
Bukowsky, H., Uhlemann, E., Steinborn, D., 1991. The recovery of pure lithium chloride from
“brines” containing higher contents of calcium chloride and magnesium chloride.
Hydrometallurgy 27 (3), 317–325.
Castillo, S., Ansart, F., Laberty, R., Portal, J., 2002. Advances of recovering of spent lithium
battery compounds. J. Power Sources 112, 247–254.
Chen, L., Tang, X., Zhang, Y., Li, L., Zeng, Z., Zhang, Y., 2011a. Process for the recovery of
cobalt oxalate from spent lithium-ion batteries. Hydrometallurgy 108, 80–86.
Chen, Y., Tian, Q., Chen, B., Shi, X., Liao, T., 2011b. Preparation of lithium carbonate
from spodumene by a sodium carbonate autoclave process. Hydrometallurgy
109, 43–46.
Chitrakar, R., Kanoh, H., Miyai, Y., Ooi, K., 2001. Recovery of lithium from seawater using
manganese oxide adsorbent (H1.6Mn1.6O4) derived from Li1.6Mn1.6O4. Ind. Eng. Chem.
Res. 40, 2054–2058.
Chitrakar, R., Makita, Y., Ooi, K., Sonoda, A., 2013. Magnesium-doped manganese oxide
with lithium ion-sieve property: lithium adsorption from salt lake brine. Bull. Chem.
Soc. Jpn. 86 (7), 850–855.
Chung, K.S., Lee, J.C., Kim, E.J., Lee, K.C., Kim, Y.S., Ooi, K., 2004. Recovery of lithium from
seawater using nano-manganese oxide adsorbents prepared by gel process. Mater.
Sci. Forum 449–452, 277–280.
Chung, K.S., Lee, J.C., Kim, W.K., Kim, S.B., Cho, K.Y., 2008. Inorganic adsorbent containing
polymeric membrane reservoir for the recovery of lithium from seawater. J. Membr.
Sci. 503–508.
Clarke, G.M., 2013. Lithium-ion batteries: raw material considerations. Am. Inst. Chem.
Eng. 44–52.
Clarke, G.M., Harben, P.W., 2009. Lithium Availability Wall Map (LAWM), (Self published
& distributed).
Contestabile, M., Panero, S., Scrosati, B., 2001. A laboratory-scale lithium ion battery
recycling process. J. Power Sources 92, 65–69.
Crocker, L., Lien, R.H., 1987. Lithium and its recovery from low-grade Nevada clays. Bul-
letin 691. US Bureau of Mines, Department of Interior, (http://digicoll.manoa.
hawaii.edu/techreports/PDF/USBM-691.pdf).
Dong, Q., Li, Y., Piao, X., Zhu, S., 2007. Recovery of lithium from salt lake bittern using
aluminium salt adsorbent. Chin. J. Rare Met. 3, 357–361.
Dorella, G., Mansur, M.B., 2007. A study of the separation of cobalt from spent Li-ion
battery residues. J. Power Sources 170, 210–215.
Espinosa, D.C.R., Bernardes, A.M., Tenório, J.A.S., 2004. An overview on the current processes
for the recycling of batteries. J. Power Sources 135, 311–319.
Evans, R.K., 2008. An Abundance of Lithium. http://www.che.ncsu.edu/ILEET/phevs/
lithium-availability/An_Abundance_of_Lithium.pdf.
Evans, R.K., 2010a. The lithium–brine reserve conundrum. North. Miner. 96 (35), 2–6.
Evans, R.K., 2010b. Lithium's future supply, demand. North. Miner. 96 (35), 11–13.
Fergus, J.W., 2010. Recent development in cathode materials for lithium ion batteries.
J. Power Sources 195, 939–954.
Ferreira, D.A., Prados, L.M., Majuste, D., Mansur, M.B., 2009. Hydrometallurgical separation
of aluminium, cobalt, copper and lithium from spent Li-ion batteries. J. Power Sources
187, 238–246.
Ferrell, J.E., 1985. Lithium. Mineral Facts and Problems (1985). U.S. Dept. of the Interior,
Bureau of Mines, Washington, D.C., pp. 461–470.
Gaines, L., Cuenca, R., 2000. Costs of lithium-ion batteries for vehicles. United States
Department of Energy, Center for Transportation Research: Energy Systems Division,
Argonne National Laboratory, Argonne.
Garrett, D.E., 2004. Handbook of Lithium and Natural Calcium Chloride: Their
Deposits, Processing, Uses and Properties, 1st ed. Elsevier, Amsterdam, The
Netherlands 0-12-276152-9.
Granata, G., Moscardini, E., Pagnanelli, F., Trabucco, F., Toro, L., 2012. Product recovery
from Li-ion battery wastes coming from an industrial pre-treatment plant:
lab scale tests and process simulations. J. Power Sources 206, 393–401.
Gruber, P.M.P., 2010. Global Lithium AvailabilityThesis—Master in Science University of
Michigan, USA.
Gruber, P.W., Medina, P., Keoleian, G.A., Kesler, S.E., Everson, M.P., Wallington, T.J., 2011.
Global lithium availability. J. Ind. Ecol. 15 (5), 760–775.
Hawash, S., Abd, E.K.E., El, D.G., 2010. Methodology for selective adsorption of lithium ions
onto polymeric aluminium (III) hydroxide. J. Am. Sci. 6 (11), 301–309.
Ho, P.C., Nelson, F., Kraus, K.A., 1978. Adsorption on inorganic materials: VII. Hydrous tin
oxide and SnO2-filled carbon. J. Chromatogr. A 147, 263–269.
Hoffman, M.Z., Simic, M., 1973. Rate of reduction of cobalt(III) complexes by car-
bon dioxide (CO − 2 • ) radicals in aqueous solution. Inorg. Chem. 12 (10),
2471–2472.
Holdren, J.P., 1971. Adequacy of lithium supplies as a fusion energy source. Lawrence
Livermore Laboratory, UCID-15953.
Hu, C., Guo, J., Wen, J., Peng, Y., 2013. Preparation and electrochemical performance of Nano-
Co3O4 anode materials from spent Li-ion batteries for lithium ion batteries. J. Mater. Sci.
Technol. 29 (3), 215–220.
Industrial Minerals & Rocks: Commodities, Markets, and Uses 2006. 7th Edition, Ed. Kogel
J.E., Trivedi N.C., Barker J.M., Krukowski S.T. USA. ISBN-13: 978-0-87335-233-8. ISBN-
10: 0-87335-233-5.
Jandová, J., Vu, H.N., Belková, T., Dvořák, T., Kondás, J., 2009. Obtaining Li2CO3 from
zinnwaldite wastes. Ceramics-Silikáty 53 (2), 108–112.
Jandová, J., Dvořák, P., Vu, Hong N., 2010. Processing of zinnwaldite waste to obtain
Li2CO3. Hydrometallurgy 103 (1–4), 12–18.
207
Jha, M.K., Kumari, A., Jha, A.K., Kumar, V., Hait, J., Pandey, B.D., 2013a. Recovery of lithium
and cobalt from waste lithium ion batteries of mobile phone. Waste Manag. 33 (9),
1890–1897.
Jha, A.K., Jha, M.K., Kumari, A., Sahu, S.K., Kumar, V., Pandey, B.D., 2013b. Selective separa-
tion and recovery of cobalt from leach liquor of discarded Li-ion batteries using
thiophosphinic extractant. Sep. Purif. Technol. 104, 160–166.
Jian, G., Guo, J., Wang, X., Sun, C., Zhou, Z., Yu, L., Kong, F., Qiu, J., 2012. Study on separation
of cobalt and lithium salts from waste mobile-phone batteries. Proced. Environ. Sci.
16, 495–499.
Joulié, M., Laucournet, R., Billy, E., 2014. Hydrometallurgical process for the recovery of
high value metals from spent lithium nickel cobalt aluminium oxide based lithium-
ion batteries. J. Power Sources 247, 551–555.
Kang, J., Senanayake, G., Sohn, J., Shin, S.M., 2010a. Recovery of cobalt sulphate from spent
lithium ion batteries by reductive leaching and solvent extraction with Cyanex 272.
Hydrometallurgy 100, 168–171.
Kang, J.G., Sohn, J.S., Chang, H.K., Senanayake, G., Shin, S.M., 2010b. Preparation of cobalt oxide
from concentrated cathode material of lithium ion batteries by hydrometallurgical
methods. Adv. Powder Technol. 21, 175–179.
Kang, D.H.P., Chen, M., Ogunseitan, O.A., 2013. Potential environmental and human health
impacts of rechargeable lithium batteries in electronic waste. Environ. Sci. Technol.
47, 5495–5503.
Karstetter B.R., 1971. Glass-ceramic article and method. US patent 3,585,054. June 15.
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.
Kipouros, G.J., Sadoway, D.R., 1998. Towards new technologies for the production of
lithium. J. Met. 50 (5), 24–26.
Kitajou, A., Suzuki, T., Nishihama, S., Yoshizuka, K., 2003. Selective recovery of lithium
from seawater using a novel MnO2 type adsorbent II—enhancement of lithium ion
selectivity of the adsorbent. Ars Separatoria Acta 2, 97–106.
Kondás, J., Jandová, J., 2006. Lithium extraction from zinnwaldite wastes after gravity
dressing of Sn-W ores. Acta Metall. Slovaca 12, 197–202.
Kondás, J., Jandová, J., Nemeckova, M., 2006. Processing of spent Li/MnO2 batteries to
obtain Li2CO3. Hydrometallurgy 84, 247–249.
Koyanaka, Y., Yasuda, Y., 1977. Concentration of lithium in seawater by ion exchange
resin. Suiyo Kaishi 18, 523–526.
Krishnaswamy, S., 1979. India's Mineral Resources, 2nd edition. Oxford & Publishing Co.,
New Delhi, p. 349.
Kuo, I., 2011. Is One Million Electric Cars by 2015 Too Ambitious? VB News February 10,
2011. http://venturebeat.com/2011/02/10/one-million-electric-cars-2015/ (and http://
www1.eere.energy.gov/vehiclesandfuels/pdfs/1_million_electric_vehicles_rpt.pdf).
Lain, M., 2002. Recycling of lithium ion cells and batteries. J. Power Sources 97, 736–738.
Lee, C.K., Rhee, K.I., 2002. Preparation of LiCoO2 from spent lithium-ion batteries. J. Power
Sources 109, 17–21.
Lee, C.K., Rhee, K.I., 2003. Reductive leaching of cathodic active materials from lithium ion
battery wastes. Hydrometallurgy 68, 5–10.
Legers, L., 2008. The Trouble with Lithium — 2: Under the Microscope. Meridian Int. Res.,
(May 29, 2008).
Li, Y.J., Zeng, G.S., 2011. Hydrometallurgical process for recovery and synthesis of LiCoO2
from spent lithium-ion batteries. IEEE, (978-1-4577-0290-7/11).
Li, J., Li, X., Zhang, Y., Hu, Q., Wang, Z., Zhou, Y., Fu, F., 2009a. Study of spent battery
material leaching process. Trans. Nonferrous Metals Soc. China 19, 751–755.
Li, J., Zhao, R., He, X., Liu, H., 2009b. Preparation of LiCoO2 cathode materials from spent
lithium-ion batteries. Ionics 15, 111–113.
Li, L., Jing, G., Renjie, C., Feng, W., Shi, C., Xiaoxiao, Z., 2010a. Environmental friendly
leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries.
Waste Manag. 30, 2615–2621.
Li, L., Ge, J., Wu, F., Chen, R., Chen, S., Wu, B., 2010b. Recovery of cobalt and lithium from spent
lithium ion batteries using organic citric acid as leachant. J. Hazard. Mater. 176, 288–293.
Li, L., Chen, R., Sun, F., Wu, F., Liu, J., 2011. Preparation of LiCoO2 films from spent lithium
ion batteries by a combined recycling process. Hydrometallurgy 108, 220–225.
Li, L., Jun, L., Yang, R., Xiao, X.Z., Ren, J.C., Feng, W., Khalil, A., 2012. Ascorbic-acid-assisted re-
covery of cobalt and lithium from spent Li-ion batteries. J. Power Sources 218, 21–27.
Lien, R.H., 1985. Recovery of lithium from a Montmorillonite-type clay. Bureau of Mines,
Report of Investigations RI 8967.
Lin J.R., Fan C., Chang I.L., Shiu J.Y.; 2003. Clean process of recovering metals from waste
lithium ion batteries. 2003. US Patent 6,514,311 B1.
Liu, Y.J., Hu, Q.Y., Li, X.H., Wang, Z.X., Guo, H.J., 2006. Recycle and synthesis of LiCoO2 from
incisors bound of Li-ion batteries. Trans. Nonferrous Metals Soc. China 16, 956–959.
Löf, G.O.G., Lewis, W.K., 1942. Lithium chloride from lepidolite. J. Ind. Eng. Chem. 34 (2),
209–216.
Luong, V.T., Kang, D.J., An, J.W., Kim, M.J., Tran, T., 2013. Factor affecting the extraction 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, 8–16.
Lupi, C., Pasquali, M., 2003. Electrolytic nickel recovery from lithium-ion batteries. Miner.
Eng. 16, 537–542.
Lupi, C., Pasquali, M., Dell'Era, A., 2005. Nickel and cobalt recycling from lithium-ion
batteries by electrochemical processes. Waste Manag. 25, 215–220.
Mcketta, J.J., 1988. Lithium and lithium compounds. Encyclopedia of Chemical Processing
and Design vol. 28. Marcel Dekker.
McLaughlin W., Adams T.S., 1998. Li reclamation process. US Patent 5888463 A.
Medina, L.F., El-Naggar, M.M.A.A., 1984. An alternative method for the recovery of lithium
from spodumene. Metall. Trans. B 15, 725–726.
Miyai, Y., Ooi, K., Katoh, S., 1988. Recovery of lithium from seawater using a new type of
ion sieve adsorbent based on MgMn2O4. Sep. Sci. Technol. 23, 179–191.
208 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208
Mohr, S.H., Mudd, G.M., Giurco, D., 2010. Lithium resources and production: a critical
global assessment. Report Prepared for CSIRO Minerals Down Under Flagship.
Department of Civil Engineering, Monash University Institute for Sustainable Futures,
University of Technology, Sydney, Australia.
Mohr, S.H., Mudd, G.M., Giurco, D., 2012. Lithium resources and production: critical
assessment and global projections. Minerals 2, 65–84.
Nan, J., Han, D., Zuo, X., 2005. Recovery of metal values from spent lithium-ion batteries
with deposition and solvent extraction. J. Power Sources 152, 278–284.
Nazri, G.-A., Pistoia, G., 2004. Lithium Batteries — Science and Technology. Kluwer Academic
Publishers, Boston.
Nelli J.R., Arthur T.E., 1970. Recovery of lithium from bitterns. U.S. Patent 3,537,813.
Nishihama, S., Onishi, K., Yoshizuka, K., 2011. Selective recovery process of lithium from seawa-
ter using integrated ion exchange methods. Solv. Extr. Ion Exch. 29, 421–431.
Norton, J.J., Schlegel, D.M., 1955. Lithium resources of North America: a brief sum-
mary of the geology, distribution, production and reserves. Geological Survey
Bulletin 1027-G.
Onishi, K., Nakamura, T., Nishihama, S., Yoshizuka, K., 2010. Synergistic solvent impregnat-
ed resin for adsorptive separation of lithium ion. Ind. Eng. Chem. Res. 49, 6554–6558.
Ono, K., 2009. Lithium Resources and Demand — Lithium Supply & Markets Conference
2009 (LSM'09) Report — JOGMEC Current Topics vol. 09–21.
Ooi, K., Miyami, Y., Katoh, S., Maeda, H., Abe, M., 1989. Topotactic Li+ insertion to λ-MnO2
in the aqueous phase. Langmuir 5, 150–157.
Ooi, K., Miyai, Y., Sakakihara, J., 1991. Mechanism of Li+ insertion in spinel-type manganese
oxide. Redox and ion-exchange reactions. Langmuir 7, 1167–1171.
Paukov, E.I., Kovalevskaya, Y.A., Kiseleva, I.A., Shuriga, T.N., 2010. A low-temperature heat
capacity study of natural lithium micas — heat capacity of zinnwaldite. J. Therm. Anal.
Calorim. 99, 709–712.
Paulino, J.F., Busnardo, N.G., Afonso, J.C., 2008. Recovery of valuable elements from spent
Li-batteries. J. Hazard. Mater. 150, 843–849.
Peterson J.A., Gloss G.H., 1959. Lithium values recovery process. US Patent 2,893, 828.
Pourbaix, M., 1966. Atlas of Electrochemical EquilibriaEnglish edition by James A. Franklin
Pergamon Press, Oxford, London.
Pranolo, Y., Zhang, W., Cheng, C.Y., 2010. Recovery of metals from spent lithium-ion
battery leach solutions with a mixed solvent extractant system. Hydrometallurgy
102, 37–42.
Ritcey, G.M., Ashbrook, A.W., 1984. Solvent Extraction Principles and Applications to
Process Metallurgy, Part-1. Elsevier Science Publishers B.V., Amsterdam, The
Netherlands, pp. 99–100.
Roonwal, G.S., Shahriar, K., Ranjbar, H., 2005. Mineral Resources and Development. Daya
Publishing House, Delhi, p. 150.
Schaller, W.T., 1937. Lithium minerals: industrial minerals and rocks. Am. Inst. Min. Met.
Eng. 427.
Schweitzer, G.K., Pesterfield, L.L., 2010. The Aqueous Chemistry of the Elements, 1st edition.
Oxford Univ. Press, London.
Shin, S.M., Kim, N.H., Sohn, J.S., Yang, D.H., Kim, Y.H., 2005. Development of a metal recovery
process from Li-ion battery wastes. Hydrometallurgy 79, 172–181.
Shuva, M.A.H., Kurny, A.S.W., 2013. Hydrometallurgical recovery of value metals from
spent lithium ion batteries. Am. J. Mater. Eng. Technol. 1 (1), 8–12.
Siame, E., Pascoe, R.D., 2011. Extraction of lithium from micaceous waste from China clay
production. Miner. Eng. 24, 1595–1602.
Sitando, O., Crouse, P.L., 2012. Processing of a Zimbabwean petalite to obtained lithium
carbonate. Int. J. Miner. Process. 102–103, 45–50.
Sojka, R., 1998. Innovative recycling technologies for rechargeable batteries. Proc. of the
Fourth International Battery Recycling Congress, Hamburg, Germany.
Steinberg, M., Dang, V.D., 1975. Sustainable energy—without hot air. Chem. Abstr., BWL
report 20535-R 86.
Steinberg, M., Dang, V.D., 1976. Geological survey professional paper 1005. , p. 79.
Strelow, F.W.E., Weinert, C.H.S.W., Van Der Walt, T.N., 1974. Separation of lithium from
sodium, beryllium and other elements by cation-exchange chromatography in nitric
acid–methanol. Anal. Chim. Acta. 71, 123–132.
Sun, L., Qiu, K., 2011. Vacuum pyrolysis and hydrometallurgical process for the recovery of
valuable metals from spent lithium-ion batteries. J. Hazard. Mater. 194, 378–384.
Sun, L., Qiu, K., 2012. Organic oxalate as leachant and precipitant for the recovery
of valuable metals from spent lithium-ion batteries. Waste Manag. 32 (8),
1575–1582.
Suzuki, T., Nakamura, T., Inoue, Y., Niinae, M., Shibata, J., 2012. A hydrometallurgical
process for the separation of aluminium, cobalt, copper and lithium in acidic sulfate
media. Sep. Purif. Technol. 98, 396–401.
Swain, B., Jeong, J., Lee, J.C., Lee, G.H., 2006. Separation of cobalt and lithium from mixed
sulphate solution using Na-Cyanex 272. Hydrometallurgy 84, 130–138.
Swain, B., Jeong, J., Lee, J.C., Lee, G.H., Sohn, J.S., 2007. Hydrometallurgical process for
recovery of cobalt from waste cathodic active material generated during manufactur-
ing of lithium ion batteries. J. Power Sources 167, 536–544.
Swain, B., Jeong, J., Lee, J.C., Lee, G.H., 2008. Development of process flow sheet for recov-
ery of high pure cobalt from sulfate leach liquor of LIB industry waste: a mathemat-
ical model correlation to predict optimum operational conditions. Sep. Purif. Technol.
63, 360–369.
Swain, B., Jeong, J., Yoo, K., Lee, J.C., 2010. Synergistic separation of Co(II)/Li(I) for the
recycling of LIB industry wastes by supported liquid membrane using Cyanex 272
and DR-8R. Hydrometallurgy 101, 20–27.
Tahil, W., 2010. How much lithium does a Li ion EV battery really need? Meridian Int. Res.,
(March 5, 2010).
Takeuchi, T., 1980. Extraction of lithium from sea water with metallic aluminium. J. Nucl.
Sci. Technol. 17 (12), 922–928.
Tanii T., Tsuzuki S., Honmura S., Kamimura T., Sasaki K., Yabuki M., Nishida K., 2003.
Method for crushing cell. US Patent No. 6,524,737 B1.
Tedjar, F., 2013. Challenges for recycling advanced Li‐ion batteries. Proc. International
Battery Association (IBA2013), Barcelona, March 11‐15, 2013 (http://congresses.
icmab.es/iba2013/images/Oral_26FEB.pdf).
Tedjar F., Foudraz J.C., 2007. Method for the mixed recycling of lithium-based anode
batteries and cells. US Patent 7,820,317 B2.
Tran, K.T., Luong, T.V., An, J.W., Kang, D.J., Kim, M.J., Tran, T., 2013. Recovery of magnesium from
Uyuni salar brine as high purity magnesium oxalate. Hydrometallurgy 138, 93–99.
U.S. Bureau of Mines and U.S. Geological Survey, 1980. Principles of a Resource/Reserve
Classification for Minerals: U.S. Geological Survey Circular 831. http://pubs.usgs.
gov/circ/1980/0831/report.pdf.
U.S. Bureau of Mines and U.S. Geological Survey, 1986. Principles of a Resource/Reserve
Classification for Minerals. BuMInes Miner. Commod. Sum. 1986, pp. 182–185.
U.S. Geological Survey, 2005. Mineral Commodity Summaries, (January).
U.S. Geological Survey, 2009. Mineral Commodity Summaries, (January).
U.S. Geological Survey, 2010. Mineral Commodity Summaries. U.S. Geological
Survey, Reston, VA, USA.
U.S. Geological Survey, 2012. Mineral Commodity Summaries. January 2012. http://
minerals.usgs.gov/minerals/pubs/commodity/lithium/mcs-2012-lithi.pdf.
U.S. Geological Survey, 2013. Mineral Commodity Summaries. January 2013. http://
minerals.usgs.gov/minerals/pubs/commodity/lithium/mcs-2013-lithi.pdf.
Um, N., Hirato, T., 2012. A study on lithium recovery from seawater: separation of lithium
from hydrochloric acid solutions containing CaCl2, MgCl2, MnCl2, NaCl, KCl and LiCl.
Zero-Carbon Energy Kyoto (2012). In: Yao, T. (Ed.), Green Energy and Technology,
pp. 149–152.
Umeno, A., Miyai, Y., Takagi, N., Chitrakar, R., Sakane, K., Ooi, K., 2002. Preparation and
adsorptive properties of membrane-type adsorbents for lithium recovery from
seawater. Ind. Eng. Chem. Res. 41 (17), 4281–4287.
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.
Vyas, M.H., Sanghavi, J.R., Seshadri, K., 1975. Lithium extraction from Indian lepidolite
ores. Res. Ind. 20, 68–70.
Wajima, T., Munakata, K., Uda, T., 2012. Adsorption behavior of lithium from
seawater using manganese oxide adsorbent. Plasma Fusion Res. 7. The Japan
Society of Plasma Science and Nuclear Fusion Research, pp. 2405021-
1–2405021-4.
Wakihara, M., Yamamoto, O., 1998. Lithium Ion Batteries Fundamentals and Performance.
Kodansha Ltd., Tokyo 1998.
Wang, R.C., Lin, Y.C., Wu, S.H., 2009. A novel recovery process of metal values from the
cathode active materials of the lithium-ion secondary batteries. Hydrometallurgy
99, 194–201.
Wang, J., Chen, M., Chen, H., Luo, T., Xu, Z., 2012. Leaching study of spent Li-ion
batteries. Proc. Environ. Sci. (The 7th Int. Conf. waste manage. Technol.) 16,
pp. 443–450.
Yaksic, A., Tilton, J.E., 2009. Using the cumulative availability curve to assess the threat of
mineral depletion: the case of lithium. Resour. Policy 34, 185–194.
Yamaji, Y., Dodbiba, G., Matsuo, S., Okaya, K., Shibayama, A., Fujita, T., 2011. A novel flow
sheet for processing of used lithium-ion batteries for recycling. Resour. Process. 58
(1), 9–13.
Yan, Q., Li, X., Wang, Z., Wu, X., Wang, J., Guo, H., Hu, Q., Peng, W., 2012a. Extraction of
lithium from lepidolite by sulfation roasting and water leaching. Int. J. Miner. Process.
110–111, 1–5.
Yan, Q., Li, X., Wang, Z., Wu, X., Guo, H., Hu, Q., Peng, W., Wang, J., 2012b. Extraction of
valuable metals from lepidolite. Hydrometallurgy 116–118.
Yan, Q., Li, X., Yin, Z., Wang, Z., Guo, H., Peng, W., Hu, Q., 2012c. A novel process for
extracting lithium from lepidolite. Hydrometallurgy 121–124, 54–59.
Yan, Q., Li, X., Wang, Z., Wang, J.X., Guo, H., Hu, Q., Peng, W., Wu, X.F., 2012d. Extraction of
lithium from lepidolite using chlorination roasting–water leaching process. Trans.
Nonferrous Metals Soc. China 22 (7), 1753–1759.
Yoshinaga, T., Kawano, K., Imoto, H., 1986. Basic study on lithium recovery from lithium
containing solution. Bull. Chem. Soc. Jpn. 59, 1207–1213.
Yoshizuka, K., Fukui, K., Inoue, K., 2002. Selective recovery of lithium from seawater using
a novel MnO2 type adsorbent. Ars Separatoria Acta 1, 79–86.
Yoshizuka, K., Kitajou, A., Holba, M., 2006. Selective recovery of lithium from seawater using a
novel MnO2 type adsorbent III—benchmark evaluation. Ars Separatoria Acta 4, 78–85.
Zelikman, A.N., Krein, O.E., Samsonov, G.V., 1996. Metallurgy of Rare MetalsTranslated
from Russian & published by NASA and National Science Foundation, Washington
D.C., p. 458.
Zhang, P., Yokoyama, T., Itabashi, O., Suzuki, T.M., Inoue, K., 1998. Hydrometallurgical
process for recovery of metal values from spent lithium-ion secondary batteries.
Hydrometallurgy 47, 259–271.
Zhao, J.M., Shen, X.Y., Deng, F.L., Wang, F.C., Wu, Y., Liu, H.Z., 2011. Synergistic
extraction and separation of valuable metals from waste cathodic material of
lithium ion batteries using Cyanex272 and PC-88A. Sep. Purif. Technol. 78
(3), 345–351.
Zhao, Z., Si, X., Liu, X., He, L., Liang, X., 2013. Li extraction from high Mg/Li ratio brine with
LiFePO4/FePO4 as electrode materials. Hydrometallurgy 133, 75–83.
Zhu, S., He, W., Li, G., Zhou, X., Huang, J., Zhang, X., 2011. Recovering copper from spent lithium
ion battery by a mechanical separation process. Proc. International Conference on Materials
for Renewable Energy & Environment (ICMREE), Shanghai vol. 2, pp. 1008–1012.
Zhu, S.G., He, W.Z., Li, G.M., Zhou, X., Zhang, X.J., Huang, J.W., 2012. Recovery of Co
and Li from spent lithium-ion batteries by combination method of acid
leaching and chemical precipitation. Trans. Nonferrous Metals Soc. China 22,
2274–2281.