Extraction of lithium from primary and secondary sources by pre-treatment,
leaching and separation: A comprehensive review

Pratima Meshram, B.D. Pandey, T.R. Mankhand

PII: S0304-386X(14)00227-8
DOI: doi: 10.1016/j.hydromet.2014.10.012
Reference: HYDROM 3979

To appear in: Hydrometallurgy

Received date: 27 October 2013

Revised date: 4 October 2014
Accepted date: 12 October 2014

Please cite this article as: Meshram, Pratima, Pandey, B.D., Mankhand, T.R., Extraction
of lithium from primary and secondary sources by pre-treatment, leaching and separation:
A comprehensive review, Hydrometallurgy (2014), doi: 10.1016/j.hydromet.2014.10.012

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 ACCEPTED MANUSCRIPT

Extraction of lithium from primary and secondary sources by pre-

treatment, leaching and separation: A comprehensive review

Pratima Meshrama,b, B.D. Pandeya*, T.R. Mankhandb

a
CSIR-National Metallurgical Laboratory, Jamshedpur - 831 007, India

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b
Dept. of Metallurgical Engineering, IIT, BHU, Varanasi - 221 005, India

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Abstract: In this comprehensive review resources of lithium and status of different processes

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/ technologies in vogue or being developed for extraction of lithium and associated metals
from both primary and secondary resources are summarized. Lithium extraction from primary

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resources such as ores/minerals (spodumene, petalite and lepidolite) by acid, alkaline and
chlorination processes and from brines by adsorption, precipitation and ion exchange

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processes, is critically examined. Problems associated with the exploitation of other resources
such as bitterns and seawater are highlighted. As regards the secondary resources, the
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industrial processes followed and the newer developments aiming at the recovery of lithium
from the lithium ion batteries (LIBs) are described in detail. In particular pre-treatment of the
spent LIBs, leaching of metals from the cathode material in different acids and separation of
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lithium and other metals from the leach liquors, are discussed. Although spent LIBs are
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currently processed to recover cobalt and other base metals but not lithium, there is a good
prospect for recovery of lithium in coming years. Varying compositions of batteries for
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different applications require development of a suitable recycling process to recover metals

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from all types of LIBs.

Keywords: lithium, lepidolite, spodumene, brines, LIBs, adsorption, ion exchange, solvent
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extraction, precipitation.

*Corresponding author: Dr. B.D. Pandey (bd_pandey@yahoo.co.uk)

1. Introduction
Lithium is the 25th most abundant element (at 20 mg/kg) in the earth’s crust. Lithium
finds application in rechargeable lithium ion batteries (LIBs) because of its very high energy
density by weight and high electrochemical potential (3.045 V). With a present consumption
level of ~22% of the total lithium produced in LIBs, it is expected to reach to ~40% by 2020
(Wang et al., 2011). Besides batteries, at present it has major applications in glass and
ceramics (30%), greases (11%), metallurgical (4%) industries and also in
chemicals/pharmaceuticals, rubbers, etc. (Holdren, 1971; Garrett, 2004). As per the Madrid
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Report of July 2010, lithium falls in the border-line of low-to-medium in supply and demand,
primarily due to scanty resources (Tedjar, 2013). It is also understood that the demand of
lithium is increasing further due to its application in nuclear and strategic areas. As per recent
estimates of lithium reserves, out of 103 deposits with more than 1,00,000 tons of lithium,

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each deposit has different mineralogical composition and therefore, requires appropriate

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technology to process (Gruber et al., 2011). In view of this, lithium is usually extracted from
its mineral that is found in igneous rocks (chiefly spodumene) and from lithium chloride salts

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found in brine pools, while ignoring other resources including the low-grade ores.

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Rising demand of lithium for various applications thus calls for prospecting and
processing all viable resources. Lithium extraction from ores/minerals utilises roasting

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followed by leaching, while its extraction from brines includes evaporation, precipitation,
adsorption and ion exchange (Garrett, 2004). Lithium can be extracted from LIBs by leaching
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followed by precipitation, ion exchange or solvent extraction and electrolysis (Shuva and
Kurny, 2013). It is estimated that 250 tons of ore (spodumene) or 750 tons of brine or 28 tons
of lithium ion batteries of mobile phone and laptop or 256 batteries of electric vehicles (EVs)
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are required to produce 1 ton of lithium (Tedjar, 2013). Lithium concentrate obtained mainly
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by the flotation of pegmatites (ore), is pulverized and leached in hot acid, and lithium is
precipitated as lithium carbonate (Tahil, 2010). The processing of pegmatites is expensive as
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compared to that of the brines due to heating and dissolution steps involved, but higher metal
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concentration in pegmatites partly compensates for the cost. Because of the cost factor in the
lithium extraction from brine compared to the ores, many deposits of spodumene are not
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currently being mined / processed. Lithium is also present in seawater, but the concentration
is too low to be economical. As regards lithium metal, it can be produced by both
carbothermic reduction and metallothermic reduction of oxide (at times hydroxide) and also
by electrolysis of LiCl (Kipouros and Sadoway, 1998). In view of the scattered literature on
the extraction of lithium from primary resources viz., ores, minerals and the brines, it is
considered worthwhile to review the details and discuss critically the merits and demerits of
various processes in vogue or being developed.
With the increasing use of LIBs in mobile phones, laptops, camcorders, tracking
systems, military and medical devices and in large energy storage systems including that of
transportation applications (>one million EVs expected by 2015), there will be a significant
pressure on lithium resources and its supplies (Kuo, 2011). The disposal of spent batteries
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may involve landfilling, stabilization, incineration or recycling. In landfills, heavy metals

have the potential to leach slowly into soil, groundwater or surface water.

The methods for recycling spent LIBs are based on mainly the pyro-/hydro-
metallurgical processes (Li et al., 2009a). Disadvantage of all pyro-recycling processes is that

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lithium is not recovered. The traditional pyrometallurgical processes can burn off all the

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organic electrolyte and binder, and facilitate the leaching of valuable metals. In the

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hydrometallurgical processes, the dismantled electrodes are dissolved in concentrated acid

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and the metal rich leach solutions are treated to recover the individual metal by different
methods mentioned above. These processes may produce wastewater containing fluoride

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which is difficult to treat, and pollute the environment due to the incomplete recycling of
organic binder and electrolyte. There is inconsistent policy about the fate of discarded lithium
ion batteries in e-waste that is distributed internationally. Lithium batteries also contain
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potentially toxic materials including metals, such as copper, nickel and lead, and organic
chemicals, such as toxic and flammable electrolytes containing LiClO4, LiBF4, and LiPF6.
Defunct Li-ion batteries are classified hazardous due to their lead (Pb) (6.29 mg/kg), cobalt
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(163544 mg/kg), copper (98694 mg/kg) and nickel (9525 mg/kg) content with exceeded
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limits of chromium, lead, arsenic and thallium (Bernardes et al., 2004; Kang et al., 2013).
Human and environmental exposures to these chemicals are typically regulated during the
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manufacture of lithium batteries through occupational health and safety laws, and potential
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fire hazards associated with their transportation. These findings support the need for stronger
government policy at the local, national, and international levels to encourage recovery,
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recycling, and reuse of lithium battery materials. In view of the above, efforts must be made
to develop an environmentally benign and economically viable technology for recycling
spent LIBs.

This review focuses on the primary and secondary resources of lithium available for
exploitation and provides comprehensive details on the conventional / currently practised
lithium extraction methods vis-a-vis the resource type. The resources that are covered include
ores / minerals / clays and brines / seawater and bitterns, and lithium ion batteries for the
hydrometallurgical recovery of lithium.

2. Resources of lithium
2.1 Primary resources - minerals/ clays and brines:
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Lithium is produced from a variety of natural sources, e.g., minerals such as

spodumene, clays such as hectorite, salt lakes, and underground brine reservoirs etc. Lithium
is a minor component of igneous rocks, primarily granite. The most abundant lithium
containing rocks/minerals are pegmatites, spodumene and petalite. Other minerals are

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lepidolite, amblygonite, zinnwaldite and eucryptite (Ferrell, 1985). Zinnwaldite is the impure

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form of lepidolite with higher FeO content (up to 11.5% Fe as FeO) and MnO (3.2%)
(Paukov et al., 2010). Pegmatites contain recoverable amounts of lithium, tin, tantalum,

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niobium, beryllium and other elements. Table 1 lists the principal commercial lithium

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minerals found in pegmatites along with their composition. The theoretical lithium content in
these minerals is 3% to 5.53%, but most mineral deposits have around 0.5%–2% Li and the

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pegmatite-bearing ores that are often exploited have <1% Li (Mohr et al., 2010). Spodumene
is the primary lithium mineral being mined.
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Amongst the clay minerals, hectorite, a type of smectite is rich in lithium and
magnesium, and generally contains 0.3 to 0.6% Li. The best known hectorite deposit with
0.7% Li is in Hector, California. Flint clays and other high-alumina clays contain < 0.01 to
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0.5% Li. Jadarite is a newly discovered lithium-boron containing mineral found in Serbia
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(Mohr, 2012). These minerals are often concentrated to around 2%–4% Li for use in the
ceramics and glass industry (Garret, 2004).
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Seawater contains about 0.1-0.2 mg/L Li (Bach and Wasson, 1981). Total amount of
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metallic lithium in seawater (globally) is estimated to be ~230 billion tons. 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
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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 million tons. Chile has
the world’s largest resource of brine (7.5 million tons, 1500-2700 mg/L Li) containing
lithium, followed by Bolivia (resource: 9.0 million tons with 532 mg/L Li) and Argentina
(resource: 2.6 million tons, 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
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published extensively (USGS, 1980, 1986, 2005, 2009, 2010, 2012, 2013; Clarke and
Harben, 2009; Ono, 2009; Gruber et al., 2011).
Lithium rock production began with lithium minerals (1899) in the USA (Garret,
2004). Since the first lithium production from brines at Searles Lake, USA in 1936, brines are

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exploited largely in South America and China. The largest producer of lithium in the world is

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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

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in the United States. Several newer installations (by 2013) are on various stages of

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exploration/ operation from 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

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salt lake brines and sea by sedimentation. Significant quantities of lithium compounds and
ore concentrates are also produced in Australia, Canada, Portugal, Russia and Zimbabwe.
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Currently, Australia produces lithium concentrate from spodumene at the mines in Mt Catlin,
Western Australia. The 160,000 tons/annum concentrate produced in Western Australia is
processed to 16,000 tons/annum lithium carbonate in its Chinese plant. Lithium carbonate is
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mostly produced from ores and brines both and the production figures are often expressed as
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lithium carbonate equivalent (LCE). Other chemicals such as lithium chloride and hydroxide
are also produced in varying amounts.
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In India small pocket deposits mostly comprising of lepidolite in pegmatites of mica

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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
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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 identified in Salal area, Jammu (Roonwal et al., 2005; Krishnaswamy,
1979; Brown and Dey, 1955).
2.2. Secondary resources - lithium ion batteries:
Out of the various secondary resources, spent LIBs are the most prominent 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 the use.
Lithium ion battery is a term generally used for the battery which has lithium metal,
lithium alloy or material adsorbing lithium ions for negative active material. LIB uses carbon
as 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
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batteries are categorised as either primary or secondary. From the legislative view point
batteries are also categorised as portable (household), vehicle or industrial batteries. Primary
cells are constructed with metallic lithium. The metallic lithium in a non-rechargeable
primary lithium battery is a combustible alkali metal that self-ignites at 178 oC, and when

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exposed to water / seawater reacts exothermically and releases hydrogen. Primary batteries

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are single-use as irreversible discharge reactions occur in the cells and after use they are
disposed off. Secondary battery cells have chemistry that allows reversing the discharge

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reaction and are rechargeable. LIBs are of the rechargeable secondary type. The functional

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part of LIBs is: cathode, anode, electrolyte and separator, which is housed in a protective
metal casing.

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The chemical reaction in the cell expressed below shows the forms in which lithium and
cobalt can be present in the spent LIBs.
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- (1)
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The active mass (cathode, anode and electrolyte) of LIBs comprises of almost 40% of
the weight whereas ~ 30% (wt) of these components is carbon (anode). A number of
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chemical species in the cathode material within the lithium-ion family has been reported
including the type, structure of the materials used and their electrochemical properties are
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listed in Table 3. Generally LIBs have short life of 2-3 yrs whether they are used or not. The
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spent batteries are good source of several metals like Li, Co, Ni, Co, Mn etc.
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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 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 processing of
lepidolite, amblygonite and zinnwaldite (Kondás and Jandová, 2006). In 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 decomposition of
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spondumene and lepidolite largely by treatment of potassium carbonate to produce lithium

hydroxide. In alkaline / gypsum process 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 is obtained. Thus most of the alkaline

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processes involve either heating of lithium minerals with alkali salts or in more advanced

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hydrothermal processes by decomposition in solutions containing Na2CO3, NaOH, Na2SO4
and/or other alkali salts at elevated temperature and pressure. Ion-exchange processes are

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applied for processing of the leach liquors obtained from spodumene, petalite and partly from

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zinnwaldite. Tables 4-6 summarise recent work on lithium extraction from its minerals and
clays by using different approaches.

Acid process
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Sulfation roasting of lepidolite followed by water leaching was recently reported by
Yan et al. (2012a). The lithium extraction efficiency 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).
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Roasting at 880 oC with a mass ratio of lepidolite/ Na2SO4/ CaCl2 of 1:0.5:0.3 resulted in
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improved recovery (~95% Li) of lithium (Yan et al., 2012b). Above 99.5% pure lithium
carbonate was obtained by evaporation and precipitation with Na2CO3. Luong et al. (2013)
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examined sulfation roasting of a Korean lepidolite ore with sodium sulfate at 1000 °C, while
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achieving extraction of ~ 90.4% Li. Recently, roasting of lepidolite with iron sulfate at 850
°C and water leaching were investigated by Luong et al. (2014). Leaching of the calcines
obtained from the open and closed systems yielded leach liquors containing ~7.9 g/L Li and
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~8.7 g/L Li, corresponding to the extraction of ~85% and ~93% Li, respectively.
Lithium extraction (>90%) by roasting a low grade zinnwaldite concentrate (0.96%
Li) with sodium sulfate followed by water leaching, was described by Siame and Pascoe
(2011). Study by Sitando and Crouse (2012) showed 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 >11 g/L and Li2CO3 of ~ 99% purity was precipitated by the addition of
Na2CO3 at 95-100 °C. Amer (2008) reported extraction of 90% Li from the Egyptian
montmorillonite type clay containing lithium in 90 min of reaction in sulfuric acid at 250 oC.
In order to process spodumene it is desired to convert α- spodumene to β- phase by
roasting at 1070-1100 oC (Tahil, 2010; Chen et al., 2011b; Clarke, 2013). Tahil (2010)
reported the roasting of spodumene in a kiln at ~ 1100 oC. The calcine was mixed with
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sulfuric acid and roasted at 250 oC and then leached in water to yield a solution of lithium
sulfate. Reaction of β‐spodumene with H2SO4 is shown as (2) (Mcketta, 1988):

(2)

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Lithium carbonate can be recovered by the addition of sodium carbonate to the solution after

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pH adjustment, purification and evaporation (3).

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(3)

The world’s first continuous plant to convert spodumene concentrate to lithium carbonate by

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calcination, roasting of calcine with H2SO4 and water leaching, was commissioned in 2012
by Galaxy Resources in China (Clarke, 2013).
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One of the drawbacks of the sulfuric acid method to treat lepidolite, petalite and
zinnwaldite is the requirement of high concentration of acid and complex purification
processes, whereas spodumene needs to be converted to the more leachable β‐phase at higher
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temperature.
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Alkaline process
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In the alkaline process (Table 5), spodumene or lepidolite ore concentrates are ground
and calcined with limestone at 825-1050 oC. The resulting calcine is crushed, milled and
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treated with water to yield lithium hydroxide which can be converted to chloride by reaction
with hydrochloric acid. The recovery in this method is approximately 85 – 90% (Averill and
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Olson, 1978). The reaction during calcination of spodumene with limestone can be
represented as (4):

Al2 (4)

Lepidolite was pre-roasted at 860 oC under water steam atmosphere for defluorination
followed by pressure leaching of defluorinated mass in a lime–milk autoclave at 150 oC. In
this process 98.9% lithium was extracted (Yan et al., 2012c). During the roasting with steam
formation of phases such as lithium aluminium silicate (beta-eucryptite) and leucite
(KAlSi2O6) was noticed (Karstetter, 1971) as per reaction (5)

(5)
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Extraction of lithium from a zinnwaldite containing waste was investigated by

Jandová et al. (2009). The concentrate (1.40% Li) obtained from dry magnetic separation of
the waste (0.21% Li) was treated by gypsum roast method (with CaSO4 and Ca(OH)2).
About 96% Li was leached out from the sinter made at 950 oC. Earlier the concentrate

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prepared from this waste by gravity and dry magnetic separation, was roasted by gypsum

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method at 975 oC and water leached to recover ~93% Li (Kondas and Jandová, 2006). In
another study Jandová et al. (2010) reported the roasting of the above concentrate with

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CaCO3 Li2CO3 with 99.5% purity was separated from the leach liquors by either converting

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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

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provided higher yield. Siame and Pascoe (2011) obtained recovery of ~84% Li from the
roasted zinnwaldite concentrate at 1050 oC with limestone, gypsum and sodium sulfate. A
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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 >85% Li by roasting
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montmorillonite type clays (0.3–0.6% Li) with KCl–CaSO4 or CaCO3–CaSO4 followed by

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water leaching. Lithium silicate in the clay was converted to Li2SO4 by roasting a pelletized
mixture of clay, limestone and gypsum at 900 oC in a direct gas-fired rotary roaster (Lien,
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1985). Formation of lithium sulphate may be represented as in reactions (6-7)

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(6)
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(7)

The initial product obtained from the alkaline process is lithium hydroxide which can be
converted to carbonate or chloride salt.

Chlorination process
A less common method is chlorination process in which the ore is roasted in the
temperature range 880- 1100 oC 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 temperature (935 oC) while giving 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 quantitatively at higher temperature (1100 oC) in
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2.5 h with Cl2 gas (Barbosa et al., 2014); the recovery is found to be quite low (58%) at the
lower temperature (1000 oC) (Peterson and Gloss, 1959). In the chlorination process, when
the ore is sintered with NH4Cl and CaCl2 in a furnace at 750 oC, ~ 98% of the lithium
contained in spodumene is converted to its chloride which can be water leached (Zelikman et

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al, 1966). Vyas et al. (1975) reported a similar process using CaCO3 and CaCl2 to roast

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Indian lepidolite at 950 oC 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

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represented as:

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(8)

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(9)
(10)
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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 agent, which increases the fluidity of
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chloride melt. This allows diffusion of chlorinating agent to the surface of lepidolite
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facilitating the lithium extraction selectively and yielding pure product. Crocker and Lien
(1987) also reported a process for selective chlorination of hectorite (0.3~0.65% Li) in clays
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with limestone at 750 oC using 20 wt.% HCl.

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Other processes
Chlorination roasting of ores requires corrosion-resistant equipment. To overcome
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this drawback 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
autoclave at liquid / solid ratio of 4 and Na/Li of 1.25 at 225 oC. During pressure leaching
lithium carbonate and analcime slurry are formed according to the following reaction (11).

- (11)

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, 13).

(12)
(13)
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Medina and El-Naggar (1984) developed an alternate method of chlorination to treat

spodumene with a recovery of ~ 87% Li by roasting at 1150 oC with a mixture of 8:1 (wt.)
tachyhydrite: spodumene followed by water leaching. Because the production of lithium
carbonate from spodumene is energy intensive and expensive, lithium carbonate is mostly

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produced from the brines.

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3.2 Lithium extraction from brines /sea water/bitterns
In order to meet the growing demand of lithium, brines and bitterns have received

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increasing attention. Tables 7 and 8 elaborate the summary of work carried out recently for
the extraction of lithium from sea water/brines/bitterns. Production process for brine-water

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lithium costs 30% to 50% less than that of the mined ores (Abe, 2010). As mentioned earlier,
lithium carbonate is produced from brines by evaporative concentration and refining method.
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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 Mg(OH)2. A general flowsheet of
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Li2CO3 production from brine water is shown in Fig. 1.

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The basic approaches for separation of mineral products (K, Mg, Na, Ca, Li) from the
seawater comprises of flotation (using anionic collectors), sorption, ion exchange, solvent
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extraction etc. as described by Koyanaka and Yasuda (1977). The existing evaporation
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process for lithium recovery from brine lakes is time consuming and suffers from low
recovery efficiency. Besides, tremendous burden is posed on the environment due to waste
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generation and substantial water consumption.

Adsorption Process
Various types of adsorbents have been used for selective lithium recovery from
seawater and brines. In the adsorption method certain inorganic ion-exchanger such as
spinel-type manganese oxide shows extremely high selectivity for lithium from seawater (Ooi
et al., 1989; 1991, Yoshizuka et al., 2002; Umeno et al., 2002; Kitajou et al., 2003;
Yoshizuka et al., 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 separation 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
seawater. Extraction /separation of lithium from brines and such resources is summarised in
Table 7.
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The manganese oxide (H1.6Mn1.6O4) prepared from the precursor, Li1.6Mn1.6O4 by

hydrothermal and reflux methods, showed maximum 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

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responsible for its high adsorption capacity towards lithium as compared to other adsorbents.

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Adsorption of lithium from seawater by a spinel type λ-MnO2 produced low purity (~33%)
Li+ ions contaminated with Na+ (Yoshizuka et al., 2006). Chung et al. (2004) synthesized

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nano-manganese oxide (Li1.33Mn1.67O4) through gel process. The ion sieve-type adsorbent

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containing magnesium after acid treatment was then generated which selectively adsorbed
lithium (~30.3 mg/g adsorbent) from seawater. When a polymeric membrane reservoir

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containing inorganic ion-exchange adsorbent inside it with zinc was used, lithium recovery
from seawater was very effective and kinetically favoured with adsorption of 33.1 mg Li / g
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sorbent (Chung et al., 2008). Thus adsorbent 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
solution in a day. By using Mg-doped manganese oxide, Chitrakar et al. (2013) also observed
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very fast adsorption equilibrium (within 24 h) for effective recovery of lithium from salar
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brine (Table 7).

Recently Wajima et al. (2012) prepared HMn2O4 by elution of spinel-type lithium di-
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manganese-tetra-oxide (LiMn2O4) and examined the kinetics of lithium adsorption. The

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intermediate, LiMn2O4, was also synthesized from LiOH H2O and Mn3O4 by acid treatment.
Lithium recovery from seawater reached ~100% at 60 oC using both products.
Aluminium foil immersed in sea water forms a corrosion product on its surface which
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extracts lithium selectively from sea water at the same time, at the optimum temperature of ~
30 oC (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 recovery of lithium
from salt lake bittern by this adsorbent. The adsorbent showed high adsorption and uptake of
0.6-0.9 mg Li /g rather than other alkali or alkaline metal of bitterns. Use of hydrated alumina
for adsorption of lithium was also reported from Egyptian bitterns (Hawash et al., 2010) and
salar brines of Argentina (Clarke, 2013).
The Institute of cean 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 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
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from sea water based on adsorption process [USGS 2009], outcome of which remains
uncertain presently.

Precipitation process

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Some of the precipitation and other procceses used for lithium recovery from

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seawaters /brines are summarised in Table 8. Among various co-precipitating agents used,
aluminium salts show the best performance for lithium recovery from geothermal water. The

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appropriate pH for lithium recovery is 10-13 and use of NaAlO2 seems better than AlCl3.

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With 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).

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Despite being the richest lithium resource (10.2 million ton) Uyuni salar brine
containing a high magnesium concentration (Mg/Li mass ratio ~21.2:1) causes difficulties in
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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
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produced was suitable for use as a precursor for the production of MgO by roasting (Tran et
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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,
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chloride and sulfate. In a 2- stage precipitation process, magnesium and sulfate were removed
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as Mg(OH)2 and gypsum (CaSO4 2H2O) at pH 11.3 by lime in the first stage. Residual
magnesium after lime precipitation and almost all soluble calcium were then removed by
addition of sodium oxalate. In the second stage 99.6% lithium carbonate was precipitated at
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80-90 oC 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) mentioned the use of precipitation method to remove the two metals (magnesium and
calcium) from the salar brine of Argentina to produce LiCl which was further processed to
recover lithium.

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 extraction of lithium
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was proposed by Steinberg and Dang (1975, 1976). The Dowex resin was used for selective
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,

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beryllium and many other elements by eluting lithium with 1 M HNO3 in 80% methanol from

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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 mixed

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acid - methanol solution (1 M HNO3 and 80% methanol) which ensured an extremely good

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separation of lithium from sodium in a single column pass.
Earlier studies showed that organic ion-exchange resins exhibited low selectivity for

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lithium ions (Alberti and Massucci 1970; Ho et al., 1978; Abe and Hayashi, 1984). However,
Bukowsky et al. (1991) demonstrated that precipitation followed by ion exchange can be
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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 concentrated solution to remove divalent metal ions (Mg2+,Ca2+, Sr2+ and Mn2+)
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due to their higher sorption capacity compared to that of mono-valent ions. The separation of
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Li+ from resultant solution with Na+ and K+ was achieved in a packed column of impregnated
resin containing 1-phenyl-1,3-tetradecanedione (C11phβDK) / tri-n-octylphophine oxide
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(TOPO). Li2CO3 was precipitated from the concentrated Li+ solution by (NH4)2CO3 solution
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with an overall yield of 56% and purity of > 99.9%. Earlier this group reported selective
adsorption of Li+ in aqueous chloride media using a novel synergistic solvent impregnated
resin (SIR) containing both 1-phenyl-1,3-tetradecanedione (C11phβDK) and TOPO (Onishi et
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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 with 1.0 mol/L HCl solution with 99.8% purity at a bed
volume (BV) 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 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 ketone in 7- counter current stages. Any co-extracted magnesium was recycled
back to 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 mixture of solvent (20% D2EHPA and 30% TBP in benzene) in 6 - stages to
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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 stripped of its FeCl3 with about 0.3 parts of water
in 6-stages.
Separation of lithium and magnesium is difficult because they exhibit many chemical

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similarities. However, by utilising high charge density of Mg2+ which is twice of Li+ with

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almost same ionic radius and its easy hydrated properties, Zhao et al. (2013) reported a
separation method using LiFePO4/FePO4 as electrodes (Table 8). Lithium exhibits good

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reversibility in LiFePO4/FePO4 structures, and the redox peak separation is 0.592 V

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compared to 1.403 V for Mg2+ indicating its higher polarization. At a voltage of 1.0 V in pure
lithium solution, the inserted capacity of lithium can reach 41.26 mg/g LiFePO4, which is

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93.78% of its theoretical value (44 mg). The subsequent extracted capacity of lithium can be
attained to 38.93 mg/g LiFePO4, which is 94.3% of its inserted capacity, while the extraction
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capacity of Mg2+ from a solution containing magnesium 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.
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3.3 Extraction of lithium from secondary resources- lithium ion batteries

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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,
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whereas low value elements such as iron and phosphorous will be a greater challenge to
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create a profitable recycling program. World over several companies viz., Toxco, OnTo,
Sony, ACCUREC etc. are currently performing and improving battery recycling processes.
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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 lithium
containing wastes. The main product is targeted as appropriate (cobalt / other base metals)
and other component being the lithium hydroxide. Sony uses incineration which is followed
by the hydrometallurgical techniques. The industrial processes in vogue/developed for
recycling LIBs are described in brief.

3.3.1 Major industrial processes:

AEA technology: A patented process developed in UK aims at recovery of all battery

materials (Lain, 2002). Casing of the battery is first removed in N2 and cells are cut
mechanically to remove other components wound into a spiral. Anode, cathode and
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separators are shredded (~1 cm2 size) to leach electrolyte and the solvent in acetonitrile at 50
o
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).

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The NMP is evaporated from the filtrate and recycled back. Residue is back-washed and the

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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

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(Fig. 2) which is recovered by decantation. The reaction can be represented as:

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- - (14)

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TOXCO Process (Canada): A variety of batteries is processed in a cryogenic conditions (in
liquid nitrogen) to reduce the reactivity and utilising the mechanical and hydrometallurgical
approach to recover metal values (McLaughlin and Adams, 1998). The process flow-diagram
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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
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dewatered in filter press, are used to produce lithium carbonate. Besides organics, H2 formed
by reaction with lithium, burns off at the surface of the process bath. Sludge from LIBs is
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sent to recover cobalt. The large pieces are mechanically treated while the batteries are
submerged in a process solution of lithium brine, after which ferrous and nonferrous metals
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are recovered. Li-ion fluff (mixture of steel and plastics) can then be separated from the rest
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of the materials (Cu-Co and slurry). Copper is extracted in next step and lithium brine is
treated with Na2CO3 to obtain Li2CO3. Plastics and paper floating at the top are recovered for
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disposal or recycling. The filtered carbon cake from the sludge is un-economical to reuse or
even to burn off. Cobalt in the spent LIBs presents higher economic worth.

ACCUREC GmbH (Germany) process: The process involves mechanical treatment to

separate the electrode material which is treated by pyro-metallurgy to recover 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 electrolyte and solvent including
conductive salts (Fig. 4). The batteries are then crushed and by employing sieving, magnetic
as well as air separator, aluminium, copper and steel are removed. Remaining electrode
material is agglomerated with addition of binder and pressed to briquettes, which are smelted
(reduction) in a furnace to obtain two fractions, the metallic Co-Mn alloy and lithium
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containing slag. By acid leaching of the slag lithium can be extracted as lithium
chloride/carbonate.

Sony/Sumitomo (Japan) process: In this process untreated LIBs are calcined at 1000 °C by
which the cells open and inflammable components such as plastic casing and organic solvent

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burn off. The residue consisting of metallic and metal pieces of iron, copper and aluminium

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can be magnetically separated. The remaining fraction is mainly carbon powder and active

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cathode material (LiCoO2 and/or LiCoxNi(1-x)O2). The powder is treated at the Sumitomo

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plant by hydrometallurgical methods to recover cobalt; lithium is not targeted. Cobalt oxide
of high quality is recovered to use directly in the fabrication of new LIBs and the metallic

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scraps such as copper and stainless steel can be used as the by-products. Large batteries can
also be handled but needs to be punctured prior to introduction to the furnace (Lupi et al.,
2005; Gaines and Cuenca, 2000).
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RECUPYL process (France): This is also called as Valibat process for recycling LIBs.
Mechanical preparation of the spent batteries is performed under an inert atmosphere to
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reduce the reactivity of lithium. Plastics, steel and copper are then separated by physical
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treatment. The fine powder obtained by screening is suspended in stirred water for
subsequent leaching and hydrolysis step. Filtering the hydrolysed solution produces an
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alkaline solution of lithium salt and a suspension of metal oxides and carbon. Lithium is
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precipitated as Li2CO3 using the CO2 obtained from the mechanical treatment. The
suspension of metal oxides is dissolved in H2SO4. Copper is cemented out by the steel shots
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(Tedjar and Foudraz, 2007).The purified solution is oxidized by NaClO to precipitate

cobalt(III) hydroxide (Fig. 5) and cobalt is separated by electrolysis. The remaining lithium in
the solution is precipitated with CO2 gas.

BATREC INDUSTRIE AG process (Switzerland): The company-Batrec mainly runs a

mechanical processing plant for LIBs. In this process batteries are crushed in CO2 gas
atmosphere and the released lithium is neutralised. With completion of the neutralization
step, the protective environment is released and subsequently treated in a gas scrubber to
reduce the emission during process. Scrap material is leached and washed in acidified
aqueous liquid and leach liquor is further processed for recovery of different chemical
substances. Metal containing solid fraction can be separated from liquid and treated to
remove impurities. The flowsheet of the process is presented in Fig.6.
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OnTo Technology (USA): Spent batteries are discharged before dismantling. Batteries are
cleaned and then placed in a high pressure extraction container filled with liquid CO2 and
some additives like alkyl ethers, ammonia etc. The CO2 is transformed in to a supercritical
fluid by increasing the pressure and temperature in the container. With increase in pressure,

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battery casing are breached by fluid. When the desired pressure and temperature are reached

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the electrolyte extraction can either be carried out by circulating CO2 through the system or
by soaking the batteries in the supercritical fluid. Batteries without functional potential are

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subsequently recycled through pulverization and the various materials separated and

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recovered based on the physical properties.

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UMICORE process (Belgium and Sweden): Also called as ValÉas process, this is a combined
pyro-and-hydro- metallurgical process to separate nickel and cobalt without recovering
lithium. The spent batteries are smelted in a furnace. Plastic, solvent and graphite are burnt
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off while the metals are reduced and collected in a melt. The process is operated in Sweden
while the molten metal consisting of Ni, Co, Cu and Fe is cooled and processed in Belgium
by sulfuric acid leaching and solvent extraction. NiSO4 and CoCl2 are separated from the
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solution from which cobalt oxide and Ni(OH)2 are obtained.

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Disadvantage of pyrometallurgical recycling processes including that of Umicore is

that lithium recovery is not targeted and for which a combination of pyrometallurgical and
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hydrometallurgical processing steps are necessary. Umicore process has another drawback of
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losing base metals which are slagged off, besides loss of organic materials as well as carbon.
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3.3.2 Recent development in recycling of lithium ion batteries

Spent LIBs containing lithium and other metals are mostly treated by the
hydrometallurgical process which is used at times in combination with pyrometallurgical
treatment. This may have integrated pre-treatment steps like pyrolysis or mechanical
processing, i.e. crushing and material separation. In order to investigate extraction of cobalt,
nickel, manganese etc. from LIBs by such processes thermodynamic aspects particularly the
stability regions of different phases in aqueous solution under redox conditions may be
examined. For this standard Eh-pH diagrams of Li-H2O, Co-H2O, Mn-H2O and Ni-H2O
systems can be referred from literature (Pourbaix, 1966; Schweitzer and Pesterfield, 2010).

Leaching of LIBs are carried out with different acids like HCl (Zhang et al., 1998;
Contestabile et al., 2001), H2SO4 (Shin et al., 2005; Nan et al., 2005; Dorella and Mansur,
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2007; Swain et al., 2007; Aktas et al., 2006; Kang et al., 2010 a, b), HNO3 (Lee and Rhee,
2002; 2003), and a few organic acids like DL-malic acid (Li et al., 2010 a), citric acid (Li et
al., 2010b) etc. The binder (PVDF) which links the cathode material, LiCoO2 with aluminium
foils does not dissolve easily in the organic reagents such as fatty hydrocarbon or alcohol at

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room temperature making the leaching reactions more difficult to proceed. Important

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development on the leaching and separation of metals from the leach solutions is summarised
in Table 9-11.

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Metal extraction /recovery from hydrochloric acid leach liquors:

In most processes reported, optimum extraction of metals from the cathode material of spent

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LIBs was achieved with 4 M solution of HCl (Table 8). In the presence of a reducing agent
such as hydrogen peroxide, metal leaching was possible even in 3 M HCl (Zhang et al, 1998;
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Contestabile et al., 2001; Shuva and Kurny, 2013; Joulié et al., 2014). While H2O2 facilitated
the dissolution of Co(II) which was reduced from Co(III), the dissolution of lithium was also
promoted because of presence of the two metals in the same oxide. The separation and
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recovery of metals from the leach liquors, was carried out either by solvent extraction
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involving PC-88A, Cyanex 272 etc to produce the pure metal salts or the metals were
selectively precipitated as Co(OH)2 and LiCO3 from the leach solutions. Thus, Zhang et al.
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(1998) used the steps such as leaching of cathode materials of spent LIBs in HCl, separation
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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 suitable lixiviant for economic reasons. The leaching efficiency of >
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99% of Co and Li in 4 M HCl solution was achieved. 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 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 oC. The leaching reaction of the waste
LiCoO2 with HCl solution can be represented as:

(15)

A laboratory scale process involving leaching of LiCoO2 in HCl and precipitation of

cobalt hydroxide was developed by Contestabile et al. (2001). The active material of spent
LIBs was dissolved in N-methylpyrrolidone at 100 oC to separate aluminium and copper foil.
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From the leach liquor, carbon 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 higher acid
concentration (6 M HCl) and lower temperature (60 oC) in the presence of H2O2 (Li et al.,

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2009b). Cobalt from the solution was cemented out by iron powder and iron was removed as

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goethite. Finally chlorides of Ni, Mn and Co were added in the purified solution to prepare
precursor of the cathode material (NixCoyMnz) directly through co-precipitation with

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ammonium bicarbonate. The leaching of metals from the cathode material in 4 M HCl at 80

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o
C with the metal recovery 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

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by selective precipitation of nickel with dimethylglyoxime (DMG) at pH 9. Cobalt was
recovered as hydroxide at pH 11 and Li2CO3 was then precipitated; purity of the metals being
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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
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(93%) in the leach solution.

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Processing of battery ash obtained from the pyrolysis of spent LIBs by HCl leaching
was also attempted. Lin et al. (2003) patented a pyrometallurgical process of waste LIBs
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combined with hydrometallurgical processing. The ash with metal and metal oxides was
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dissolved in 3-6 M HCl containing NaCl. Copper and cobalt were separated out using
membrane electrolysis. Then Fe(OH)3 and Al(OH)3 were recovered at pH 5-7 followed by
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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 oC 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 (Eq. 16,17). Nickel hydroxide was then precipitated at pH 11.

- - (16)

- (17)

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; Shin et al, 2005; Dorella and Mansur, 2007; Kang et al. 2010; Jha et al.,
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2013a, b). In some cases alkali leaching followed by acid leaching was considered to remove
aluminium. 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

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N-methyl pyrrolidone (NMP) to dissolve the binder and separate active material (LiCoO2)

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from Al and Cu foils (Castillo et al., 2002). The LiCoO2 powder was leached in 4 M H2SO4
at 80 oC to dissolve Co and Li, and Co(OH)2 was recovered from the leachate by the addition

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of sodium hydroxide. Shin et al. (2005) reported almost quantitative leaching of cobalt and

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lithium with 2 M H2SO4 in the presence of high amount of H2O2 (15 vol.%) at 75 oC and 50
g/L pulp density (Table 10). Reductive leaching of the mechanically treated LIBs in 6 (v/v)%

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H2SO4 and 1% H2O2 solution resulted in relatively lower recovery of metals (~ 55% Al, 80%
Co and 95% Li) (Dorella and Mansur, 2007). Kang et al. (2010) also reported the reductive
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leaching of LIBs with H2SO4. The reactions of LiCoO2 with H2SO4 and in the presence of
H2O2 are shown below:

(18)
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(19)

The leaching efficiency of cobalt depends on the reductant concentration. Amongst other
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reducing agents, Na2S2O3 helped in leaching of >99% of the metals (Co and Li) in 2 M
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sulfuric acid at 90 oC in 3 h (Wang et al., 2012).

Safe dismantling procedures of spent lithium ion batteries have often been described
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in the literature (Tanii et al., 2003; Nan et al., 2005). 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 oC to dissolve Al, followed by reductive leaching of ~97% Co and 100% Li with
H2SO4 and H2O2 (Nan et al., 2005; Ferreira et al., 2009). 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 < 0.5% impurities. LiCoO2 positive
electrode material with a good electrochemical performance was synthesized by using the
recovered compounds.
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From the sulfate leach liquor of spent LIBs, 96% copper was recovered 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

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addition of Li(OH)2 at pH 10 (Aktas et al., 2006). Lithium, which remained in the solution,

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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

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that metals could be precipitated /separately by the ethanol/sulphate precipitation technique

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depending on their concentrations present in the solution.
The waste cathodic active material generated during the manufacturing of LIBs was

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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
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recovered. 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
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272 from a synthetic solution at pH 6.9.

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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):
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(20)
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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 >99%
purity.
By acid leaching of waste cathodic material and SX with Cyanex 272, Swain et al.
(2008) produced pure cobalt sulfate solution (99.99%). In another study quantitative
separation of Co(II)/Li was reported using the supported liquid membrane (SLM) with a
mixed extractant containing 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 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 alkali–acid leach process. After roasting the spent LIBs at 700–800
°C to burn off carbon and binder, and leaching with NaOH to remove Al, leaching with
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H2SO4 in presence of 10 (v)% H2O2 could recover 95% Co and 96% Li. Iron removal
(99.99%) as jarosite with a loss of <1% Co was achieved in the pH range 3-3.5 at 95 oC. The
precipitation reaction is shown below:

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(21)

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Complete removal of manganese with ammonium persulfate at pH 4 and 70 oC is as follows:

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SC
(22)

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Copper precipitation (>98.5%) 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
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extracted selectively from the purified solution with saponified 25wt.% 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
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were also produced by a combination of acid leaching, SX and precipitation from spent
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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
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reactions (23-24). Lithium was recovered as carbonate by adsorption with 2% MnO2 (11.7
CE

mg Li/g).

(23)
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(24)

Advantage of vacuum pyrolysis to prevent escape of toxic gases and lower the
decomposition temperature of organics while protecting oxidization of metals in LIBs, was
applied by Sun and Qiu (2011). The cathode material was treated in a vacuum furnace at
600 oC 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 oC. Paulino et al.
(2008) examined two approaches for recycling spent Li/MnO2 and LIBs. In the first process
~90% Li was recovered by calcination at 500 oC followed by leaching with H2SO4 and H2O2
at 90-100 oC, and solvent extraction. The second process involved fusion with KHSO4 at 500
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o
C and water leaching with H2O2 at 90 oC. Cobalt and manganese were precipitated at pH >9
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

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in H2SO4 in presence of 50% excess of a reducing agent, glucose- a waste product of food

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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,

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whereas without solvent extraction the product containing 36–37% (w/w) Co is obtained.

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Lithium is recovered by crystallization (yield 80%) with 98% purity. Process with solvent
extraction shows economical outputs (gross margin and payback time) than the one without

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solvent extraction.
Suzuki et al. (2012) developed a process as detailed in Fig.7. Acorga M5640 extracted
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copper within a pH range of 1.5-2.0 leaving Al, Co and Li in the raffinate. Aluminum 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
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(>98%), although Acorga M5640 provides higher cobalt selectivity.

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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
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in n-heptane have been investigated by Zhao et al. (2011). A mixed extractant system was
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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 801 and Acorga M5640, and the
raffinate containing cobalt, nickel and lithium was treated with 15% (v/v) Cyanex 272 to
AC

separate out Co. More than 90% of Co could be separated out at pH 5.5- 6.0 and A/O 1:2. An
ion-exchange resin such as Dowex M4195 was then used to separate Ni(II)/Li(I). Addition of
2% (v/v) Acorga M5640 to 7% (v/v) in Ionquest 801 generated a significant pH isotherm
shift for Cu which resulted in a ∆pH50 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 (NMP) was used to dissolve the PVDF agglomerate from Co-Li membrane to
separate aluminium foil. About 88% Co was recovered during the leaching with sulfuric acid
at pH 0.5 and 80 oC. Then, 1 M citric acid solution was added at 65 oC to prepare a gelatinous
precursor. LiCoO2 was obtained with the gel precursor calcined in crucible at 450 oC for 4 h.

Metal extraction /recovery from nitric acid leach liquors:

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Mechanical, thermal, hydrometallurgical and sol–gel steps were applied to recover Co/Li
from spent LIBs and synthesize LiCoO2 as cathode active material (Lee and Rhee, 2002,
2003). Reductive leaching in 1 M HNO3 with 1.7 vol.% H2O2 at 75 oC extracted ~ 95% Li
and 95% Co (Table 11). The molar ratio of lithium to cobalt in the leach liquor was adjusted

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to 1.1 by adding a fresh LiNO3 solution. Then, 1 M citric acid solution was added to prepare

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a gelatinous precursor which was calcined at 950 oC for 24 h to produce purely crystalline
LiCoO2. Like in other studies, the addition of hydrogen peroxide increased leaching

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efficiency of metals (Lee and Rhee, 2003). Reductive leaching of almost 100% Co and Li

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from the spent batteries in nitric acid and H2O2 was achieved at 80 oC by Li et al. (2011). In
the nitric acid leaching system pollution due to harmful NOx gases is a major problem and

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needs to be addressed. As regards the leaching kinetics, lithium dissolution followed
shrinking core model. The mechanism of the dissolution of LiCoO2 was controlled by surface
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chemical reaction with apparent activation energy of 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:
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(25)
P TE

Recycling of Li-ion and polymer batteries while producing LiCoxNi(1-x)O2 as a

cathode material was investigated by Lupi and Pasquali (2003). The process consists of
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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.
AC

Nickel was electrowon at a current density of 250 A/m2, 50 oC 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.

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 suggested 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
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mineral acids like HCl, HNO3 and H2SO4, and the waste solutions can be treated easily.
Almost 100% Li and >90% Co were leached out with 1.5 M malic acid and 2.0% H2O2 at 90
o
C in 40 min. Leaching of lithium and cobalt in citric acid was also reported after separating
the anode and cathode material by treatment of NMP (Li et al., 2010b). Nearly 100% Li and

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> 90% Co were extracted in 1.25 M citric acid and 1.0% H2O2 at 90 oC.

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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

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as 94.8% for Co and 98.5% for Li were achieved with 1.25 M ascorbic acid solution at 70 oC

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(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

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and CoO from the dismantled batteries, was peeled off from the aluminium foils after
vacuum pyrolysis at 600 oC. Leaching was performed using 1 M oxalate at 80 oC with the
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reaction efficiency of >98% of LiCoO2 while separating cobalt and lithium. The reaction with
oxalate for leaching and precipitation proceeds as:
D

(26)
TE

(27)
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During the oxalate leaching Co3+ was reduced to Co2+ which was dissolved and precipitated
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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,
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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 pH >5 which
was followed by precipitation of CoC2O4 at pH 2 by adding saturated solution of (NH4)2C2O4.
The product CoC2O4 was used to synthesize nano-Co3O4 by sol-gel method.
Roasting of batteries under reduced pressure at 650 oC was reported by Kondás et al.
(2006), which was followed by leaching of Li2CO3 at ambient temperature and crystallization
of pure Li2CO3. A process for 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 oC for 2 h and 600 oC
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for 5 h, respectively. Finally LiCoO2 was obtained by adding a certain amount of Li2CO3 in
the recycled LiCoO2 and calcining it at 850 oC for 12 h.

4. Conclusions

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Lithium is one of the rare metals with a variety of applications and demand of lithium

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is expected to increase with ever increasing use of electrical and electronic devices/ hybrid
electric vehicles. A few established technologies are in vogue to produce lithium in the

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desired form from its primary resources like its minerals and brine, whereas limited

SC
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

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involves high energy, while extraction from brine and bitterns / seawater needs long time for
evaporation. Hence these processes need to be adequately modified to yield efficiency and
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better economic returns.

Extraction processes from secondary resources like batteries depend on the chemistry
D

of the battery material. Most processes involve dismantling of LIBs, separation of cathode
and anode materials, leaching of valuable metals like Co, Li, Ni, Mn etc. from the cathode
TE

material in different mineral acids, and separation and recovery of metals from the solutions
by solvent extraction / IX / precipitation. At present no lithium extraction is industrially
P

practised from LIBs. Therefore, sufficient scope exists not only to reduce the process steps
CE

followed currently but also to improve the efficiency of metal extraction and separation,
including lithium recovery. Points that may be considered include process intensification to
AC

save energy and improve kinetics of leaching, while addressing the problem of selectivity and
examining the use of unexplored / synergistic solvents with ultra high metal loading capacity
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
Authors are thankful to the Director, CSIR-National Metallurgical Laboratory (NML),
Jamshedpur, India for giving permission to publish the paper.
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LIST OF TABLES
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Table 1: Principal commercial lithium minerals with composition

Table 2: Geographical availability for various lithium resources and their lithium contents
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Table 3: Various components of LIBs, materials used and their merits

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

Table 5: Lithium extraction processes from its minerals/clays by alkali process
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Table 6: Lithium extraction processes from its minerals/clays by chlorination process

Table 7: Adsorption processes for lithium extraction with efficiency and product synthesised
from seawater, brines and bitterns
Table 8: Precipitation and other processes for lithium extraction from seawater and brines
Table 9: Extraction and recovery of metals from spent LIBs in hydrochloric acid system
Table 10: Extraction and recovery of metals from spent LIBs in sulfuric acid system

Table 11: Extraction and recovery of metals from spent LIBs in other organic/inorganic acid
systems
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FIGURE CAPTIONS
Fig.1: A flowsheet for Li2CO3 production from brine
Fig.2: Process flowsheet of AEA technology
Fig.3: TOXCO’s hydrometallurgical recycling process for LIBs

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Fig.4: Flow-sheet of ACCUREC recycling process

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Fig.5: RECUPYL process for LIBs recycling

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Fig.6: BATREC Industrie AG process flowsheet

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Fig.7: SX separation of Al, Cu, Co and Li from sulfate media (Suzuki et al., 2012)

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MA
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P TE
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Brine

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Evaporation concentration

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Concentrated brine

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Lime milk
Magnesium removal

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Filtration /Washing
Magnesium
hydroxide
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Calcium-lithium-salt solution
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Lithium Calcium removal

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carbonate
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Filtration Calcium carbonate

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Lithium salt solution

Roasting
Evaporation
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Na2CO3
Precipitation crystallization
Hydration

Filtration/Washing

Lithium carbonate

Fig. 1
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Spent lithium ion batteries

Dry N2 gas Cut up

50 oC Steel

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Acetonitrile Dissolution of electrolyte

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50-60 oC

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Acetonitrile Solvent evaporation

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Electrolyte stored

NMP
50 oC NU
Dissolution of binder
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Filtration Sorting of solids

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90 oC
NMP Solvent evaporation Cu Al Plastics
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Water + LiOH Electrolysis

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LiOH solution Decantation

Washing
CoO

CoO

Fig. 2
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Spent lithium ion batteries

Conveyor

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Disposal/ steel
Hammer mill Li-ion fluff

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recovery

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Water spray Copper -cobalt
Shaker table
product

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Slurry

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Primary metal
Lithium brine Mixing & Holding production or other
tank applications
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Cobalt filter
Filter press
cake
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Lithium brine
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Na2CO3 Mixing tank

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Spent brine Product filter

to disposal
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Washing

Drying

Li2CO3(s)

Fig. 3
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Spent lithium ion batteries

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Mechanical pre-treatment Electronics, plastic casing

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250 oC
Electrolyte, solvent,

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Vacuum thermal treatment
conductive salt

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Mechanical crushing

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Sieving, magnetic,
air separation
Al, steel, Cu, plastics
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< 0.2 mm electrode material
Binder Agglomeration
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Slag former Reducing meltdown Cobalt manganese

alloy
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Acid Leaching Residue

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Precipitant
Precipitation Filtration
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Lithium chloride

Fig. 4
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Spent lithium ion batteries

Mechanical treatment CO2 & inert gas mixture

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Physical treatment Steel, copper, plastics

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pH > 12
LiOH(aq) Leaching of fines Li(aq)

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Precipitation
Soluble lithium

Mixed oxides +

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Precipitation inserted Li + Carbon Li2CO3(s)

Lithium phosphate Leaching H2SO4

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Cu and other
Purification Soda
impurities
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NaClO Oxidation Li2SO4(aq)

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Cobalt(III) hydroxide
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Fig. 5
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Spent lithium batteries

Protective
CO2

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atmosphere

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Feeder &
CO2

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Shredder

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Moist air Neutralization

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Release of protective
Gases
atmosphere
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Acidified Gas Scrubber
Leaching & washing
aqueous liquid
SO2(aq), Cl2(aq)
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Leach liquor
Metal fractions
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& plastics
Hydrometallurgical
processing Residue
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(SX/Precipitation)
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Recovered chemical
substances
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Fig. 6
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Sulfuric acid Leaching of spent LIBs

Al(III), Cu(II), Co(III), Li(I)

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pH 1.5-2.0

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Acorga M5640 Solvent Extraction

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Cu(II) Al(III), Co(II), Li(I)
pH 2.5-3.0

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PC-88A Solvent Extraction
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Al(III) Co(II), Li(I)
pH 5.5-6.0
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PC-88A + TOA Solvent Extraction

P TE

Co(II) Li(I)
CE
AC

Fig.7
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Table 1: Principal commercial lithium minerals with composition*

Mineral Formula % Lithium content
Theoretical Range in commercial
minerals
Spodumene LiAlSi2O6 or Li2O Al2O3 4SiO2 3.73 1.9-3.3
Lepidolite LiKAl2F2Si3O9 or LiF KF Al2O3 3SiO2 3.56 1.4-1.9

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Amblygonite LiAlFPO4 or 2LiF Al2O3 P2O5 4.74 3.5-4.2

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Triphylite LiFePO4 or Li2O 2FeO P2O5 4.40 2.5-3.8

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Petalite LiAlSi4O10 or Li2O Al2O3 8SiO2 2.27 1.6-2.21
Bikitaite LiAlSi2O6 H2O 3.28 1.35-1.7

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Eucryptite LiAlSiO4 5.53 2.34-3.3
Montebrasite Li2O Al2O3 2SiO2 3.93 0.9-1.8

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Jadarite LiNaSiB3O7(OH) 3.39 0.096-0.1
Zinnwaldite LiKFeAl2F2Si3O10 or LiF KF FeO Al2O3 3SiO2 1.7 1.21-1.3
Hectorite Na0.3(Mg,Li)3Si4O10(F,OH)2 0.56 0.36
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Zabuyelite Li2CO3 18.75 -
*(Schaller, 1937; Siame & Pascoe, 2011; Industrial Minerals & Rocks, 2006; Norton & Schlegel, 1955)
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Table 2: Geographical availability for various lithium resources and their lithium contents

Resources Li content %(w/w) Location of largest amount References

Pegmatites
Spodumene 1.9 -3.3 Australia
Lepidolite 1.53 -3.6 Zimbabwe Industrial Minerals & Rocks, 2006;

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Zabuyelite 17-18.75 China Legers, 2008; Clarke, 2013; AMRA,
Petalite 1.6 -2.1 Zimbabwe 2013

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Amblygonite 3.5 -4.2% Canada, Brazil, Surinam

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Eucryptite 2.34 Zimbabwe
Sedimentary Rocks

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Smectite 0.27-0.7 Hector, California. and Industrial Minerals & Rocks, 2006
(Hectorite) Nevada, US
Lacustrine evaporites 1.8% Lithium oxide Jadar Valley, Serbia
Brine

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Continental < 2700 mg/L (with K, Chile Evans, 2008;
B) Legers, 2008;
~532 mg/L Bolivia Clarke, 2013;
Mohr et al., 2012
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Geothermal < 400 mg/L (With Mn United States
and Zn)

Oil field < 700 mg/L (with Br) United States

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Sea water 0.18 mg/L Chile, Argentina, China and

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Tibet
Secondary Resource
Spent LIBs 2–7% -- Shuva and Kurny, 2013
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CE
AC
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Table 3: Various components of LIBs, materials used and their merits*

Wt% of total Material Structure Properties/merits

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Component weight of

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battery
LiCoO2 Layered High structural stability and can be cycled for > 500 times with 80-

CR
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,

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20% higher by weight), but less stable & less ordered as compared
to LiCoO2
LiFePO4 Olivine Suitable for biomedical applications because of higher safety levels

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Cathode Li2FePO4F Olivine and lower cost.

MA
LiCo1/3 Ni1/3Mn1/3O Layered/spinel Possesses high capacity with structural and thermal stability, and
Li(LiaNixMnyCoz)O2 Layered/spinel safe to use.
Anode 39.1 ± 1.1 Carbon graphite Low cost and availability. It has the ability to reversibly absorb and

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release large quantity of Li (Li:C = 1:6)

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Hard carbon microspheres

Electrolyte Lithium salt like LiPF6, Li[PF3(C2F5)3] or Withstands high temperature and possesses high mobility of Li

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LiBC4O8 in organic solvents ions

Plastic case 22.9 ± 0.7

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Polyethylene terephthalate layers, a polymer Hermetically sealed battery body which converts chemical energy
layer and a polypropylene layer, layers of to electrical energy in order to generate current.
carbonized plastic
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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 & diethyl Non-aqueous
carbonate
Electrical contact 2.0 ± 0.5 Aluminium and copper Conductive
*Wakihara and Yamamoto, 1998; Gaines and Cuenca, 2000; Nazri and Pistoia, 2004; Paulino et al., 2008; Fergus, 2010
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Table 4: Lithium extraction from its minerals/clays by acid process

Raw Material % Li Experimental conditions % Li Li2CO3 References

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Pre-treatment Roasting Time Water leaching Extraction purity

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temp. (h) (%)
( oC) L/S ratio Temp., Time

CR
( °C) (h)
Lepidolite conc. 2.0 Sulphation roasting 850 0.5 2.5:1 room 0.5 91.6 - Yan et al., 2012a
temp. (RT)

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Lepidolite conc. 2.0 Salt roasting with 880 0.5 0.8:1 RT 0.5 ~90 > 99.5 Yan et al., 2012b
Na2SO4+CaCl2

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Lepidolite conc. 2.55 Sulphation roasting 1000 0.5 15:1 85 3 90.4 - Luong et al.,

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Na2SO4 : Li molar ratio= 2013
2:1
Lepidolite conc. 1.79 Roasting with iron 850 1.5 1:1 RT 1 85 (Open - Luong et al.,
sulphate system) 2014

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93 (Closed

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system)
Zinnwaldite 0.96 Roasting with sodium 850 1 10:1 RT 0.5 >90 > 90 Siame & Pascoe,
conc. sulphate 2011

P
Petalite/ 1.9 Calcination- 1100 2 7.5/1 50 1 97.3 99 Sitando &
Lepidolite
Roasting (H2SO4)-
CE
300 1
Crouse, 2012

Spodumene 4.21 Calcination- 1100 1 Leaching & - - 90 - Mcketta, 1988;

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precipitation Tahil, 2010

Roasting (H2SO4)- 250 0.167
Spodumene 2.81 Roasting 1050-1090 0.5 1:4 225 1 96 ~99.6 Chen et al., 2011;
& H2SO4 leaching Clarke, 2013
Montmorillonite 1.2% Without roasting - - 5:1 (H2SO4 250 1.5 90 Li2SO4 Amer, 2008
clay Li2O leach)
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Table 5 : Lithium extraction from its minerals/clays by alkali process

Raw Material % Li Experimental conditions % Li Li2CO3 References
Pre-treatment Roasting Water leaching extraction purity (%)

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temp. ( oC), Time Temp. (L/S ratio)

IP
time (h) (h) (oC)
Lepidolite 1.4 Defluorination 860, 0.5 h 1 150 4:1; lime: 98.9 99.9 Yan et al., 2012c

CR
concentrate defluor.
lepidolite: 1
Zinnwaldite 1.4 Gypsum roast 950, 1 h 0.167 90 10:1 96 99 Jandová et al., 2009

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concentrate
Zinnwaldite (tailing 2.07% Gypsum roast 1050 0.5 85 10:1 84 -

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sample) Li2O
Zinnwaldite 0.19 Roasting with gypsum & 975 1 90 5:1 93 - Kondas and Jandová,

MA
concentrate 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

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Zinnwaldite 1.29 Roasting with CaCO3 825 4 95 10:1 84 - Vu et al., 2013
concentrate

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Montmorillonite 0.3 –0.6 Roasting with Lien, 1985; Crocker
clay-hectorite CaCO3 750 - RT - 80 99 and Lien, 1987
CaCO3–CaSO4

P
900
CE
AC
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Table 6: Lithium extraction from its minerals/clays by chlorination process

T
Raw Material Experimental conditions % Li Product References

IP
Roasting temp. Time (h) Leaching extraction
( °C) L/S ratio Temp. Time

CR
( °C) (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

US
Lepidolite concentarte (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

N
Lepidolite ore (3.70% Li2O) With CaCO3 + CaCl2, 950 5 10:1 90 1 80.0 LiCl Vyas et al, 1975

MA
D
P TE
CE
AC
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Table 7: Adsorption process for lithium extraction with product synthesised from seawater,
brines and bitterns

Source/Raw Adsorbent used Conditions Adsorption / Remarks Product References

material
Seawater H1.6Mn1.6O4 Adsorbent: 200 mg, Max. uptake : 40 mg -- Chitrakar et
sea water: 50 L, 4 Li /g adsorbent al., 2001

T
weeks; Desorption

IP
by 0.5 M HCl, 1 day
Seawater (Li Spinel type Mn- 30 oC, 15 days < 90% Li, LiCl Umeno et al.,
0.17 mg/L) oxide Li uptake: 10.6 mg /g 2002

R
adsorbent
Seawater (Li λ-MnO2 150 days Recovery- 264 g LiCl LiCl Yoshizuka et

SC
0.15 mg/L) (granulated) in 791 g dried al., 2006
precipitated salt (816
m3 seawater)
Artificial Ion-sieve type Mn- Adsorption at 0.4 M Adsorption: 88% Li by LiCl Chung et al.

NU
seawater (Li 0.2 oxide spinels : HCl, 5 days adsorbent I and 89% 2004; 2008
mg/L, 8.01 pH) HMg0.5Mn1.5O4(I) Li by adsorbent II.
HZn0.5Mn1.5O4 (II) Equil. sorption: 30.3
mg /g (I) and 33.1 mg/g
MA
(II).
Seawater (1 HMn2O4 60 oC, 24 h Loading capacity: 1.53 Li salt Wajima et al.,
mmol/L Li) mmol /g sorbent 2012
Brine (Salars de LimMgxMnIIIyMnIV 24 h, pH 6.5 Adsorption capacity: Li2CO3 Chitrakar et
Uyuni, Bolivia) zO4 (0 < x ≤ 0.5) 23–25 mg/g adsorbent al., 2013
D

Seawater (Li Surface deposition 30 oC, 10 days 34% Li -- Takeuchi,

0.192 mg/L) on corrosion 1980
TE

product of Al
Salt lake Hydrated alumina: pH 5.8 Adsoption:0.6-0.9 mg / - Dong et al.,
bitterns LiOH = 2 M ratio g sorbent 2007
Egyptian Al(OH)3 30 ºC , pH 9 Adsorption capacity: LiAlO2 Hawash et al.,
P

bitterns (19.5, 123 mg/g adsorbent 2010

CE

5.5, 8.8 mg/L)

Brine (Salar de Hydrated alumina LiCl solution- Adsorbed Li eluted by Li2CO3 Clarke, 2013
Hombre 1% Li (20 times acid and precipitated
Muerto, conc.) by solar by sodium carbonate
AC

Argentina) evaporation.
 ACCEPTED MANUSCRIPT

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

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

IP
(%
purity)

R
Synthetic Precipitation pH 12.5 for [Al]: 70% Li -- Yoshinaga et
solution, 50-1000 mg/L al., 1986

SC
Geothermal
water (Li = 10
mg/L)

NU
Synthetic Precipitation followed Precipitation with Good usable Li salt Bukowsky et
solution (2.5 M by IX using Poly BD® volume cap. of solution al., 1991
LiCl, 0.3 M R45HTLO (MC50), 1.8 M Na2CO3 at resin TP207:
MA
CaCl2 and 0.15 Lewatit® (TP 207), 56.4 g/L
80 oC.
M MgCl2) Dowex®(Y80)
IX- 50 oC, 30 min
D

Seawater (0.12– Integrated Ion- 1st Stage: sorption 56% yield Li2CO3 Nishihama et
0.16 mg/L Li) Exchange method on λ-MnO2, 150 al., 2011;
TE

days (> 99.9) Onishi et al.,

2010
( 264 g LiCl in
816 m3 seawater);
P
CE

2nd stage: Sep. of

Mg(II), Ca(II),
Sr(II) and Mn(II)
with SK110 resin
AC

(pH 9)

Seawater (0.18- Two stage precipitation 1st stage pH : 11.5 Recovery of Li2CO3 Um and
0.20 mg/L Li) -12.5; pure lithium (99.4) Hirato, 2012
carbonate
2nd stage: Na2CO3
at 100 oC

Uyuni Salar Two stage precipitation 1St stage pH: Precipitation as LiCO3 An et al.,
brine, Bolivia, with lime & Na-oxalate 11.3, Li2CO3 (99.55) 2012; Tran et
15–18 g/L Mg, al., 2013
0.7–0.9 g/L Li 2nd stage: sodium
oxalate, 80-90 oC

Brine from Salar Precipitation (2.5 g/L Separation of Mg LiCl salt feed LiCl Clarke, 2013
de Hombre LiCl from solar pond) as hydroxide and for Li extr. in a
Muerto, with lime and Na2SO4 Ca as sulphate chemical plant
Argentina
 ACCEPTED MANUSCRIPT

Brine (high Electrochemical Electrolyte: 0.5 M ~94% Li ; -- Zhao et al.,

Mg/Li ratio) NaCl, 10 h 2013
Li sorption:
28.65 mg /g
LiFePO4

T
R IP
SC
NU
MA
D
P TE
CE
AC
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Table 9: Extraction and recovery of metals from spent LIBs in hydrochloric acid system

Material Leaching Conditions Extraction / Highlights References

separation-
Acid Temp Tim Pulp parameters (with
concentratio . e (h) densit merits/demerits
n (M) y (g/L) )

T
(oC)

IP
Cylindrical 4 80 1 100 SX with SX: > 99.9 Co Zhang et
-shaped 0.29 M and 12.6% Li al., 1998

R
LIBs D2EHPA with 0.9 M PC-
and 0.90 M 88A,

SC
PC-88A
Higher
selectivity with

NU
PC 88A.

Spent LIBs 4 80 1 100 Precipitation Co(OH)2 Contestabil

: pH 6-8 separated easily. e et al.,
MA
with 4 M 2001
NaOH, NixCoyMnz a
precursor to
Synthesis of cathode
precursor material
D

material by
co-
TE

precipitation
.
P

LIBs 4 80 1 20 Precipitation Purity (%): 96.9 Wang et al.,

: pH 2 with Li, 98.23 Mn, 2009
CE

KMnO4 for 96.94 Co and

Mn(II),. pH 97.43 Ni
9 for Co by
AC

DMG and
Li2CO3

LIBs 3 M acid + 80 1 50 Precipitation Recovery (%): Shuva &

3.5% H2O2 : pH 11-12 95 Co and 93 Li Kurny,
with NaOH in precipitate 2013
for Co;
Na2CO3 at
100 oC for
Li

Ash from 4 90 18 50 Precipitation Recovery (%): Joulié et al.,

LIBs by NaClO 100 Co and 2014
at pH 3 and 99.99 Ni.
base
addition at HCl gives higher
pH 11 leaching
efficiency.

57
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Table 10: Extraction and recovery of metals from spent LIBs in sulphuric acid system

Materia Leaching Conditions Extraction / Highlights Reference

l Acid Temp Tim Pulp separation- (with s
parameters merits/demerits

T
concentratio . ( e (h) density(g/L
n o
C) ) )

IP
LIBs 2 M acid + 15 75 0.16 50 - Leaching (%): Shin et al.,
waste vol.% H2O2 7 95 Co and 100 2005
Li. Harmful gas-

R
SOx generated.
Square- 3 M acid 70 4 200 Precipitation & Precipitation: Nan et al.,

SC
shaped SX using 90% Co 2005
LIBs Acorga M5640 SX: ~97% Cu
and Cyanex by Acorga
272 M5640, 97% Co

NU
by Cyanex 272
LIBs 6 % acid + 65 33.3 Precipitation Leaching (%): ~ Dorella
1% H2O2 with NH3 at pH 55 Al, 80 Co and
5. Co/Li and 95 Li. Manusr,
MA
separation by Extraction 2007
diluted (0.72 (%):~85 Co by
M) Cyanex Cyanex 272.
272
LIB 2 M acid + 75 0.5 100 SX by 0.5 M Leaching (%): Swain et
D

wastes 5% H2O2 Cyanex 272, 93 Co and 94 Li. al., 2007

pH 5.35 and CoSO4 solution:
TE

O/A = 1 in 1- 99.99% pure.

stage
Spent 4 M acid + 80 4 Precipitation Co recovery: Aktas et
P

LIBs H 2O 2 using ethanol, 92% as CoSO4 al., 2006

ethanol/solutio and
CE

n = 3:1; 15 8% Co as
min, room Co(OH)2 by
temperature adding Li(OH)2
at pH 10.
AC

Syntheti - - - - SX by Cyanex Separation factor Swain et

c 272 and DP-8R (Co/Li): 497 at al., 2010
solution pH 5
(10
mol/L
Co(II)
and 20
mol/L
Li2SO4
Spent 2 M acid + 60 1 100 Precipitation at Leaching (%): Kang et
LIBs 6% H2O2 pH 6.5 for Cu, >99 Co, al., 2010
Fe and Al SX: 99.9% Co in
SX by 50% 2 stages;
saponified 0.4 Separation factor
M Cyanex 272, 750 (Co/Li) and
pH 6, O/A = 2 Co/Ni at pH 6.
Spent 1 M acid + 80 2 714 Precipitation Max. Co Li and
LIBs 30% H2O2 by 1M citric leaching (%): Zeng,
acid, 2 h, 65 88.3; 2011
o
C; calcined at Crystalline
450 oC, 4 h LiCoO2
synthesised

58
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Spent 4 M acid + 85 2 100 SX by 25% SX: 98% Co and Chen et

LIBs 10% H2O2 P507 removal of 97% al., 2011
Precipitation Ni and Li.
by ammonium
oxalate, pH
1.5
Spent 3 M + 0.25 M 90 3 67 - > 99% leaching Wang et

T
LIBs Na2S2O3 al., 2012

R IP
SC
NU
MA
D
P TE
CE
AC

59
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Table 11: Extraction and recovery of metals from spent LIBs in other organic/inorganic acid
systems

Material Leaching Leaching Conditions Highlights References

T
reagent
Time Temp. Pulp (with merits/demerits)

IP
(h) ( oC) densiity
(g/L)

R
LIBs 1M 1 75 20 Leaching (%): 95 Co and Lee and

SC
HNO3 Li. Rhee, 2002,
+1.7 2003
vol.% Harmful gas-NOx
H2O2 generated.

LIBs 1M
HNO3
+1.0
1 80
NU 20 Leaching (%): 100 Co and
Li.
Li et al., 2011
MA
vol.% Harmful gas-NOx
H2O2 generated.

Spent LIBs 1.5 M 0.67 90 20 Leaching (%): 90 Co and Li et al.,

D

DL- 100 Li. 2010a

Malic
TE

acid + Acid can be recycled and

2% H2O2 reused.
P

Spent LIBs 1.25 M 0.25 90 20 Leaching (%): >90 Co and Li et al.,

citric 100 Li. 2010b
CE

acid +
1% H2O2 Simple and environmental
friendly process.
AC

Cylindrical 1.25 0.33 70 25 Leaching (%): 94.8 Co Li et al., 2012

spent LIBs of mol/L and 98.5 Li. Reducibility
mobile phone ascorbic of ascorbic acid displaced
acid H2O2.

60
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Highlights

 Review highlights reserves, technologies and R&D on Li extraction from different

resources.
 Practice and problems of extraction of Li from primary resources-ores/minerals/clays
are described.

T
 Analyzed advantages / drawbacks of recovering Li from brine/bittern, the major

IP
source of production .
 Industrial processes & R&D efforts to recover Li/ other metals from LIBs are

R
critically examined.

SC
 Need of recycling spent LIBs-the secondary resource of Li and base metals, is
highlighted.

NU
MA
D
P TE
CE
AC

61