Waste Management xxx (2017) xxx–xxx

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Hydrometallurgical recycling of lithium-ion batteries by reductive

leaching with sodium metabisulphite
Nathália Vieceli a,⇑, Carlos A. Nogueira b, Carlos Guimarães c, Manuel F.C. Pereira c, Fernando O. Durão c,
Fernanda Margarido a
a
Center for Innovation, Technology and Policy Research – IN+, Instituto Superior Técnico, University of Lisbon, 1049-001 Lisboa, Portugal
b
LNEG – Laboratório Nacional de Energia e Geologia, I.P., Campus do Lumiar, 1649-038 Lisboa, Portugal
c
CERENA – Centro de Recursos Naturais e Ambiente, Instituto Superior Técnico, University of Lisbon, 1049-001 Lisboa, Portugal

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

Article history: The hydrometallurgical extraction of metals from spent lithium-ion batteries (LIBs) was investigated. LIBs
Received 19 July 2017 were first dismantled and a fraction rich in the active material was obtained by physical separation, con-
Revised 15 September 2017 taining 95% of the initial electrode, 2% of the initial steel and 22% of plastic materials. Several reducers
Accepted 27 September 2017
were tested to improve metals dissolution in the leaching step using sulphuric acid. Sodium metabisul-
Available online xxxx
phite led to the best results and was studied in more detail. The best concentration of Na2S2O5 was 0.1 M.
The metals dissolution increased with acid concentration, however, concentrations higher than 1.25 M
Keywords:
are unnecessary. Best results were reached using a stirring speed of 400 min
1. The metals leaching effi-
Spent lithium-ion batteries
Recycling
ciency from the active material (Li, Mn, Ni, Co) increased with the temperature and was above 80% for
Sodium metabisulphite temperatures higher than 60 °C. The dissolution of metals also rose with the increase in the liquid/solid
Reductive leaching ratio (L/S), however, extractions above 85% can be reached at L/S as lower as 4.5 L/kg, which is favourable
for further purification and recovery operations. About 90% of metals extraction can be achieved after
only 0.5 h of leaching. Sodium metabisulphite can be an alternative reducer to increase the leaching of
Li, Mn, Co, and Ni from spent LIBs.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction sustainability targets. The EV stock reached 1.26 million in 2015,

Lithium-ion batteries (LIBs) have advantages over other
rechargeable batteries, which have made them widely used in
portable electronic devices, such as personal computers, video
cameras and mobile phones since they were first commercialized
in 1991. For that, contribute excellent properties such as high
energy and power densities, high battery voltage, long charging-
discharging cycles, long lifespan and large operating temperature
range (Zhang et al., 1998).
Given concerns about the carbon dioxide footprint, the interest
in alternative energy sources has increased and represents a great
market for lithium-based batteries, highlighting the electric mobil-
ity (electric (EV), plug-in (PHEV) and hybrid (HEV) vehicles) and
electrochemical energy storage for renewable energy conversion
(solar and wind-powered electric generation) (Goonan, 2012).
Electric vehicles are crucial for the sustainable transport systems
future and their wide global deployment is necessary to meet
⇑ Corresponding author.
E-mail address: nathalia.vieceli@tecnico.ulisboa.pt (N. Vieceli).
100 times more than in 2010 and new registrations of EVs
increased by 70% between 2014 and 2015, with over 550,000 vehi-
cles being sold worldwide in 2015 (OECD/IEA, 2016).
Lithium is classified by the American Physical Society (APS) and
Materials Research Society (MRS) as an ‘‘energy-critical element”,
given its role in emerging sustainable energy sources and the fact
that it might encounter supply risks and a shortage could signifi-
cantly affect the adoption of some energy technologies (Hurd
et al., 2012). Several countries worldwide are establishing national
alternative energy policies that have the potential to considerably
increase lithium demand. Moreover, energy storage systems could
be beneficiaries of the widespread research and development of
LIBs for the transportation sector, which can help make it more
affordable (Jaskula, 2014; Diouf and Pode, 2015). Consumer and
industrial electronics accounted for about 78% of the global
lithium-ion battery market revenues, while transportation applica-
tions such as EVs, HEVs and PHEVs accounted for approximately
20%, and grid applications represented about 2%. Moreover, global
lithium-ion battery consumption increased by an average of 27%
per year from 2011 to 2014 (Jaskula, 2014; Moss et al., 2011).

https://doi.org/10.1016/j.wasman.2017.09.032
0956-053X/Ó 2017 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Vieceli, N., et al. Hydrometallurgical recycling of lithium-ion batteries by reductive leaching with sodium metabisulphite.
Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.09.032
2 N. Vieceli et al. / Waste Management xxx (2017) xxx–xxx
The increase in the lithium battery market will result in a
growth in the spent battery waste flow, which must be recycled.
Batteries recycling is critical not only from an environmental point
of view, but they are also an important secondary source of metals,
which can be found at very high concentration, sometimes even
higher than those found in the ores of those metals (Dorella and
Borges, 2007; Jha et al., 2013; Bertuol et al., 2016).
Unlike conventional batteries, in LIBs lithium ions move back
and forth between the anode and cathode, forcing electrons to
move with them. When the battery discharges, lithium ions exit
the graphite anode and migrate through the electrolyte and form
chemical compounds with the metal oxide within tiny channels
in the physical structure of the cathode. When an opposing voltage
is applied, it forces the ions back to their starting point, recharging
the battery (Alper, 2002). In general, LIBs consist of a steel and alu-
minium casing, printed circuit boards, plastic covers, copper and
aluminium foils, separators, active electrode materials, carbon,
organic binders, organic solvents, salts, additives, etc (Chagnes
and Swiatowska, 2015). The anode consists of a copper foil coated
with carbon graphite. Similarly, the cathode is comprised of an alu-
minium foil coated with a mixture of active cathode materials. The
active cathodic material is always a lithium containing material,
usually an oxide, but its composition can vary. The most common
was, for many years, lithium cobalt oxide (LiCoO2). The active elec-
trode materials are attached onto the collector foil using a binder,
which is commonly polyvinylidene fluoride (PVDF) because of its
thermoresistance and nonreactive properties. The separator keeps
a space between the anode and the cathode to prevent short circuit
from direct contact of the electrodes. The separator is a microp-
orous film usually made of polymers such as polyethylene (PE)
or polypropylene (PP) (Alper, 2002; Zhang et al., 2014). Although
LiCoO2 was the active cathode material most used for LIBs, due
to the high cost and toxicity of cobalt, Li(Mn,Ni,Co)O2 has gradually
replaced LiCoO2. Thus, it makes the waste flow more complex as
well as the chemical processes for recovery of the spent LIBs
(Chen et al., 2011; Gaines, 2014).
Recycling of spent lithium batteries generally involves mechan-
ical treatment, hydrometallurgical treatment, association of ther-
mal pre-treatment and hydrometallurgical methods or
pyrometallurgical treatment. Mechanical treatments include
crushing and physical separation methods to liberate and separate
specific components and recover the black mass (active electrode
material) that contains valuable metals, such as cobalt, nickel,
manganese and lithium. In the hydrometallurgical treatments,
after a mechanical/physical processing, the metals from the black
mass are dissolved in aqueous solutions containing reagents (usu-
ally acids). The resulting metal rich solution is treated by precipi-
tation, solvent extraction or ion exchange to recover metals.
However, these processes produce wastewater that can be treated.
By the pyometallurgical route, spent LIBs are generally processed
without mechanical treatment. Plastic covers and all the organic
electrolyte and binder are decomposed or combusted, thus, these
processes are often associated with stringent treatment/filtration
standards for gas emissions. Other drawback of pyrometallurgical
processes is that metals such as aluminium, manganese and
lithium are lost in the slag. Therefore, for many authors, the effi-
ciency of pyrometallurgical processes is often considered lower
than hydrometallurgical processes (Chagnes and Swiatowska,
2015; Li et al., 2010; Meshram et al., 2014; Freitas et al., 2010).
Some alternative thermal treatment processes have been devel-
oped. A thermal process for regeneration of LiCoO2 at 900 °C with
solid states synthesis was studied by Nie et al. (2015). A reducing
thermal treatment before acid leaching for recovery of metals from
LIBs was studied by Yang et al. (2016) and a method using oxygen-
free roasting and wet magnetic separation to in situ recycling of
materials from LIBs was proposed by Li et al. (2016). However,
Please cite this article in press as: Vieceli, N., et al. Hydrometallurgical recycling of lithium-ion batteries by reductive leaching with sodium metabisulphite.
Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.09.032
from an environmental and health point of view, hydrometallurgi-
cal treatments are considered more suitable than pyrometallurgi-
cal treatments since offer advantageous such as low energy
consumption, no air emissions and higher recovery of elements
with high purity grade (Li et al., 2015).
Several LIBs leaching studies were performed using inorganic
acids, such as HCl (Li et al., 2015; Joulié et al., 2014; Wang et al.,
2009; Contestabile et al., 2001; Guo et al., 2016), H2SO4 (Joulié
et al., 2014; Meshram et al., 2015a, 2015b; Kang et al., 2010),
HNO3 (Joulié et al., 2014; Lee and Rhee, 2002, 2003). Recently,
many studies involving the use of organic acid have been devel-
oped, for example using citric acid (Chen et al., 2015; Chen and
Zhou, 2014; Nayaka et al., 2015), succinic acid (Li et al., 2015),
DL- malic acid (L- and D- enantiomers) (Li et al., 2010) and the
use of Na2CO3 and Na3PO4 was also proposed as precipitants in
the treatment of the effluent from the LIBs recycling process
(Guo et al., 2017). However, in most of the studies, acids were used
combined with hydrogen peroxide, which is used as a reducer.
Although some studies using different reducers have been per-
formed (Chen et al., 2015, 2016; Meshram et al., 2016), hydrogen
peroxide is still the reducer most widely used in the leaching of
spent LIBs. The aim of using a reducing agent during the leaching
of spent batteries is to promote the reduction of some elements
present in their composition that are more easily dissolved when
they are in a more reduced form. However, hydrogen peroxide
has some drawbacks, since it easily decomposes and thus the effi-
ciency of its use is normally low. Based on this, the main objective
of this study was to test different reducers (Na2SO3, Na2S2O5 and
iron scrap) during the leaching of spent lithium-ion batteries with
sulphuric acid, as well as to compare their effect with that of H2O2,
in order to present alternative approaches for the treatment of LIBs
A more detailed evaluation was carried out using sodium
metabisulphite (Na2S2O5), a commercial reducer widely used in
the industry, such as in leather tanning, water dechlorination, rub-
ber industry, chemical synthesis and in industrial waste water
treatment plants. Moreover, the effect of some variables, such acid
and reducer concentrations, the leaching time and temperature
and the liquid to solid ratio, on the metals dissolution was also
evaluated.
2. Materials and methodology
2.1. Sampling and physical separation
Two hundred and seventy-nine laptop batteries were classified
by their brands and models and their average weight was deter-
mined. In order to obtain a sample, 40 batteries were selected tak-
ing into consideration their representativeness (amount among the
several brands and models) in the initial set. These 40 batteries
were dismantled using pliers, and their plastic case, microcon-
troller board and connectors were removed. Six lithium-ion cells
were contained in each battery and their residual voltage was mea-
sured for safety precautions. Cutting the cell cases can produce
strong heating, given their internal short circuit or self-ignition
(even with a residual charge) when cathode and anode are in con-
tact in the dismantling (Nan et al., 2005). Therefore, some practices
are recommended to prevent flames and explosions hazardous,
such as refrigeration during the cutting, using NaCl solution for dis-
charge, or water and electric iron powder to promote the short cir-
cuit and discharge of the cells (Zhang et al., 2014; Contestabile
et al., 2001; Nan et al., 2005; Fan et al., 2016; Li et al., 2016). Thus,
in this work a cryogenic treatment was performed previously to
crush the cells by their immersion in liquid nitrogen for 4–6 min.
The cells were then shredded in a grab shredder (Erdwich EWZ
2000) using a 6 mm bottom discharge grid.
 N. Vieceli et al. / Waste Management xxx (2017) xxx–xxx 3

After shredding, the solids passing the discharge grid were
mixed with the residual material above the grid (about 20% of
the initial sample). Particle size analysis was carried out by the
sieving method (Fritsch analyser). The material was physically pro-
cessed to remove some of the scrap (especially plastics and steel)
from the black mass containing the active electrode materials. A
diagram of this experimental procedure can be seen in Fig. 1,
showing the operations that were addressed in this study (physical
processing and leaching). Other operations that will be required in
the whole process of treatment of these wastes, such as the sepa-
ration of the several metals and purification of the solutions, were
also included in this diagram, although they were not studied in
this work. The objective of this physical processing was to obtain
an electrode-rich fraction for the hydrometallurgical tests, there-
fore, these physical operations were not studied in detail or opti-
mized. Firstly, steel scraps were removed by magnetic separation,
followed by removal of the coarse material by sieving (above 6.7
mm,), mainly composed of plastics, but also containing some Al
and Cu large foils. The fine material still contained some strips of
the electrodes separator, thus, a final density separation in water
was applied to float them. Recovery efficiencies attained in these
separation steps were evaluated and are discussed in Section 3.2.
Only the non-floated fraction was used in the leaching tests,
which was concentrated in active materials (black mass) and had
a lower iron content, since it was magnetic separated. This fraction
was additionally crushed in a cutting mill (Retsch SM2000, dis-
charge grid of 2 mm) for a more efficient sampling. Sampling was
performed in a rotary sample splitter.
2.2. Leaching procedure and analysis
Samples (5 g) were leached in closed glass flasks in a thermo-
static orbital shaker (at 100 rpm). Different leaching conditions
were used in the experiments and will be detailed in the results
section. After leaching, the reaction mixtures were filtered
(Whatman 50 filter paper) and the solid fraction was washed with
demineralized water, then dried in an oven (50 °C for 24 h) and
stored for the eventual need for further analysis. When necessary,
samples from the leach liquor were taken from the leaching vessels
during the reaction time, were subsequently centrifuged and the
clean solutions were analysed for determining the evolution of
the leaching yields over time. The metal content in the leaching
solutions was analysed by atomic absorption spectrometry (AAS,
Thermo Elemental SOLAR 969 AA spectrometer). Solid samples
(battery materials, fractions obtained in physical processing and
final leach residues) were also analysed by the same technique,
after appropriate digestion with concentrated acid mixtures
(HNO3/HCl) in a microwave digester. Metals leaching yields were
usually determined from the leachant concentrations, referring to
the initial solids content. When leaching yields seemed to
approach 90–100%, leach residues were analysed and the yields
determined according to the balance between leachate and residue
contents. Experimental errors affecting the leaching yields ranged
from 3 to 5%. All chemicals used were of analytical grade and dem-
ineralized water was used in the leaching tests and analysis.
X-ray powder diffraction (XRPD) was used to characterize the
initial sample (after the physical separation) and was performed
using a PANanalytical X0 PERT-PRO diffractometer with Cu Ka radi-
ation (scan step size of 0.050 °2h, step time 150 s, generator set-
tings of 35 mA and 40 kV). The interpretation of the results was
made using the X’PERT HIGHSCORE PLUS software and the PDF4
data base.
3. Results and discussion
3.1. Dismantling and physical processing
Initially some batteries were dismantled to evaluate the main
fractions that compose them. The external plastic case comprises
about 11.7% of the batteries weight, the printed circuit boards
and connectors share about 1.3% of the batteries weight, other
components, such as other internal plastics, glue, foam and papers,
represent 1.8% of the batteries weight and the internal cells com-
prise the largest fraction (85.2%). The internal cylindrical cells were
also dismantled and their composition was also evaluated, which

Magnecs
(iron scrap) Coarse

Spent Shredded
baeries baeries Non- Fine Water Floated
Magnetic Sieving
Shredding density
Separation magnecs (6.7 mm) (Plascs)
separation

Non-floated (Black mass)

Secondary L/S
grinding (< 2mm) Leaching Residue (Insolubles)
separation

Leach liquor)

Separation / Purification Lithium

(Solvent Extraction) Li Precipitation carbonate

Manganese Cobalt Nickel

product product product
Fig. 1. Diagram of the process, including the operations studied in this work (physical processing and leaching) and other operations to be studied afterward.

Please cite this article in press as: Vieceli, N., et al. Hydrometallurgical recycling of lithium-ion batteries by reductive leaching with sodium metabisulphite.
Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.09.032
4 N. Vieceli et al. / Waste Management xxx (2017) xxx–xxx
consisted of 19.2% of steel can, 35.8% of cathode materials, 29.8% of
anode materials, 3.9% of separator and about 8.7% of other compo-
nents. These values are compatible with those found by Yang et al.
(2015), who verified that the spent LIBs consisted of 38.97% cath-
ode, 27.83% anode, 18.88% cell can, 3.32% separator, and 11% other
components.
3.1.1. Particle size analysis
After shredding, particle size analysis was carried out and the
results are shown in Fig. 2a, where it can be seen that the sample
is divided into two main particle size groups: coarser than 2 mm
(about 50% of the sample) and inferior to 2 mm. About 37% of
the sample is constituted by particles with size finer than 500
mm. The cumulative distribution of the initial shredded sample
by elements is presented in Fig. 2b and three distinct behaviours
stand out. The iron curve differs from the others and most of the
iron is contained in coarser particles (about 65% is in particles coar-
ser than 6.7 mm), since it comes mainly from the steel casing of the
cells, which are more resistant to shredding. Copper and alu-
minium had a similar shredding behaviour regarding the particle
size, which was expectable since both are found in the form of sup-
port foils in the electrodes. More than 91 and 95% of the aluminium
and the copper, respectively, were in particles finer than 6.7 mm.
The elements present in the electrodes (Li, Co, Mn and Ni) showed
a similar distribution with the particle size. Between 92 and 98% of
them were in particles inferior to 6.7 mm. Therefore, based on
these results, it seems advantageous to perform a physical separa-
tion of the initial shredded sample by sieving (
6.7 mm) to remove
part of the iron and to concentrate the electrode elements. The
coarse fraction (+6.7 mm) also contained gross fragments from
the plastic components. About 80% of the aluminium and copper
could be removed with particles coarser than 2 mm, however, from
33 to 45% of the electrode materials were contained in this fraction
and, therefore, this approach was not adopted.
3.1.2. Physical separation
Samples from several streams of the physical separation (see
Fig.1) were collected and analysed for the determination of metal
contents (Table 1). The initial composition of the batteries (shred-
ded batteries input) and the final composition of the black mass to
be used in the following leaching experiments is included in
Table 1. The metals composing the electrodes (Li, Co, Ni, Mn) are
progressively concentrated in the main stream as the successive
operations are carried out, while the other fractions are removed
from the circuit. The copper content also slightly increased and
the aluminium content did not change significantly. By the con-
trary, the iron concentration was significantly reduced, indicating
that the magnetic separation was efficient. The magnetic fraction
contains 81% iron and some nickel, the latter probably from the
Fig. 2. Results of the particle analysis of the initial shredded sample (a) and distribution of the elements by particle size (b).
Please cite this article in press as: Vieceli, N., et al. Hydrometallurgical recycling of lithium-ion batteries by reductive leaching with sodium metabisulphite.
Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.09.032
steel composition. The metal content in the floated fraction is very
low since this material is essentially composed of polymeric strips
from the electrodes separator.
Mass balances were performed to quantify the separation effi-
ciencies and recoveries of the different battery components in
the separation circuit. The main five components considered in
the calculations were the electrodes, the Al foil, the Cu foil, the
steel parts and the plastic materials. Essentially, balances were
accomplished by combining the weights of each stream with the
respective chemical compositions. The steel materials, the Al foil
and the Cu foil present in each stream were determined from the
contents of Fe, Al and Cu, respectively. Plastics were determined
by weighting the pieces/strips, collected by visual inspection and
hand picking. This fraction includes the polymeric electrode sepa-
rator as well as other plastic pieces (e.g. insulators, external labels).
The electrode material in each stream was estimated by assessing
two contributions: the active material (LiMO2, M being Co, Ni and
Mn) and graphite. The first one was calculated from the metals
analytical content. The second one was assessed by the balance
after the complete dissolution of the metals in the acid digestion
procedures for chemical analysis (graphite corresponds to the
insoluble material). An average of 17% of graphite, referring to
the overall battery scrap, was estimated. Alternatively, graphite
content can be expressed as 34% of the electrode black mass. Pro-
viding that the active material is known (from the elemental chem-
ical analysis), the graphite was estimated by those ratios and,
therefore, the total electrode material was calculated. The distribu-
tion of the main components in the main streams (magnetic, non-
magnetic, fine, coarse, floated and non-floated) and the resulting
mass balances are presented on the left side of the Sankey Dia-
gram represented in Fig. 3. At the right side of Fig. 3 can be verified
in which final fraction are present the main battery components
(electrodes, Cu and Al foils, plastics, steel, graphite and others).
The item ‘‘others” corresponds to the difference for the balance
adjustment.
About 98% of the steel scrap was removed by magnetic separa-
tion. This is an important result taking into account that iron is a
very deleterious contaminant in the subsequent hydrometallurgi-
cal processing. About 9% of the aluminium foils and 7% of the plas-
tics are also removed in this operation, attached to the steel
fragments. About 3% of the electrodes are lost in the magnetic frac-
tion. In the following sieving operation, the coarse light fraction is
removed, essentially composed of polymeric materials. About 27%
of the total plastics from the feed material is in this fraction. Losses
of electrodes are about 1.7%. A mass proportion of about 44% of the
plastic materials was removed by water density separation. Losses
of metals in this step, namely the electrodes, are negligible. The
final black mass contained about 95% of the initial electrodes, with
only 2% of the initial steel and 22% of the initial plastic materials.
 N. Vieceli et al. / Waste Management xxx (2017) xxx–xxx 5

Table 1
Elemental composition of the battery fractions obtained in the physical separation steps.

Stream Elemental composition (%)

In circuit Out of circuit Li Co Ni Mn Al Cu Fe
Shredded batteries input 2.30 6.33 8.67 5.13 4.14 9.34 18.28
Magnetic 0.08 0.27 2.91 0.38 1.60 0.18 81.40
Non-magnetic 2.92 8.04 10.29 6.47 4.85 11.92 0.48
Coarse 2.00 2.26 6.35 3.75 16.63 31.76 0.07
Fine 2.95 8.23 10.42 6.56 4.47 11.28 0.50
Floated 0.45 0.98 1.11 0.62 0.34 0.09 0.36
Non-floated (Black mass) 3.05 8.53 10.80 6.80 4.64 11.74 0.50

Fig. 3. Distribution of the main components/materials in the physical separation steps.

The separation processes did not allow removing the Al and Cu
foils (respectively 81 and 91%, of the initial foils are present in
the final material).
The results demonstrated that mechanical pre-treatments and
separation methods of spent LIBs are necessary for the separation
and removal of several unwanted scrap components contained in
this heterogeneous waste. The literature also addresses this issue
(Ekberg et al., 2015), referring the importance of applying an effi-
cient physical processing to recover the black mass containing
valuable elements such as nickel, cobalt and lithium. According
to Ordoñez et al. (2016), a preliminary physical separation reduces
the waste volume and also separates and enriches the batteries
components, moreover, it improves the recovery efficiency of met-
als in the leaching step. Additionally, according to Takacova et al.
(2016), the LIBs active mass (containing a powder mixture of the
cathode and anode active material (graphite) and electrolyte
(organic solvent with dissolved lithium salts) can be obtained by
mechanical pre-treatment using crushing, grinding and sieving.
The active mass can also be contaminated by electrode foils and
separators, being a mixture of several components with different
behaviours during leaching.
According to Saloojee and Lloyd (2015), a combination of phys-
ical and chemical treatment is used in the industrial process Recu-
pyl, in which batteries are first treated by crushing, magnetic
separation and density separation, producing a fine powder that
is used in the hydrometallurgical process.
A water density separation similar to the used in this study was
employed by Marinos et al. (2016), who have first shredded the
LIBs to liberate their constituents and then passed the shredded
material through a low-intensity magnetic separator to remove
the ferromagnetic material, mainly from the steel battery shell.
The remaining material was leached at room temperature for 1 h
using distilled water and in this process, Li present in the elec-
trolyte as LiPF6 is dissolved. According to Marinos et al. (2016),
the water density separation can be performed in a flotation cell
and the air flow can help the low-specific gravity particles (plastic
and some fine particles that are stuck on the plastic) to float. The
overflow was then wet sieved into coarse and fines, to wash the
plastics and separate fine particles that are stuck on the plastic
material. Plastics can then be recycled and the fine material col-
lected to treat separately. The remaining pulp is sieved in different
size fractions that will be treated separately.

Please cite this article in press as: Vieceli, N., et al. Hydrometallurgical recycling of lithium-ion batteries by reductive leaching with sodium metabisulphite.
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6 N. Vieceli et al. / Waste Management xxx (2017) xxx–xxx
3.2. Characterization and leaching tests with different reducers
The leaching experiments were conducted using the sample
obtained after the physical concentration, referred as the black
mass, whose the elemental composition is depicted in Table 1.
The XRPD patterns of the sample used in the leaching tests are pre-
sented in Fig. 4, where it can be seen the presence of graphite and
different oxides, such as LiNiO2, LiCoO2 and LiMn2O4. These results
are compatible with the common battery composition comprised
of Li(Mn,Ni,Co)O2.
In a first phase, tests using different reducers were performed
and the results are shown in Fig. 5. Different scales of the ordinates
axis were used to show in more detail the metals behaviour. The
reducers tested were Na2S2O5 (0.1 M), Na2SO3 (0.1 M), H2O2 (6
vol%) and iron scrap (added as solid, equivalent amount to 0.1
M). The L/S ratio was fixed at 10 L/kg, the H2SO4 concentration at
0.5 M and the leaching temperature at 60 °C. A test using only dis-
tilled water (without acid or reducer) and other using just acid and
water (without reducer) were carried out to evaluate the acid
influence and the absence of reducers. It can be seen that when
neither reducer or acid were used the dissolution of all metals is
almost null, with the exception of lithium, which had some disso-
lution even when only water was used (without acid and reducer),
probably due to the dissolution of lithium from the electrolyte.
The dissolution of Li, Mn, Ni and Co increased by 1 h of leaching
and after that remained stable or slightly increased until 4 h of
leaching. Lower lithium dissolution was reached when Na2SO3
and iron scrap were used, which had a similar effect on the lithium
extraction, while an intermediate effect was observed when H2O2
was used. When only acid (without reducers) or H2SO4 with Na2S2-
O5 were used, the highest lithium extraction was achieved (about
60%), indicating that lithium does not need to be reduced, under
the tested conditions. However, when compared with the other
reducers, the addition of Na2S2O5 seems to favour its extraction.
Other metals from the cathode (Co, Mn and Ni) presented a similar
leaching behaviour with the different reducers. High extractions
(about 60–70%) were reached when Na2S2O5 was used. Lower met-
als dissolution yields were reached when only acid (without reduc-
ers), Na2SO3 and H2O2 were used. Worst results were obtained
when iron scrap was used as a reducer, except for Mn, whose the
worst dissolution was verified with H2O2, probably due to difficul-
ties of maintaining its soluble form (with oxidation state II) in
hydrogen peroxide medium.
The dissolution of Cu, Al and Fe increased until 1 h of leaching
and then decreased, which is positive since these metals are con-
sidered contaminants of the solution and can turn difficult the
purification of the leaching solution for obtaining the metals of
interest (from the cathode). It is worthwhile to mention that cop-
per recovery from batteries should be an objective of a global recy-
cling process, but it was not a goal of this specific investigation,
Fig. 4. XRPD patterns of the initial sample (after physical separation). LCO: Lithium cobalt oxide, LMnO: lithium manganese oxide, LNO: lithium nickel oxide, G: graphite.
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mostly based on the electrode materials recovery by leaching. Cop-
per separation could be attained in the physical processing steps
(not optimized here) and the copper remaining in the black mass
used in the leaching is, therefore, a contaminant that should be
minimized in the leachate. The highest dissolution of copper was
reached with H2O2, and after 1 h of leaching was about 23%. When
iron scrap and only acid (without reducer) were used, the copper
dissolution reached 13 and 17% after 1 h of leaching, respectively.
From the point of view of the purification of the solutions, the best
results for the copper dissolution were reached when Na2S2O5 and
Na2SO3 were used, since the dissolution was always low and
decreased with the increase in the leaching time to very low values
(inferior to 1%). The aluminium dissolution was inferior to 26% for
all tested conditions. The effect of using iron scrap, H2O2 and Na2-
SO3 on the aluminium dissolution was similar and lead to the high-
est dissolutions. When only acid was used (without reducer) the
aluminium dissolution increased by 1 h of leaching (about 26%)
and then sharply decreased to about 10% after 4 h of leaching.
The lowest dissolution was observed from 0.15 to 2 h when Na2S2-
O5 was used and it can be considered the best result, since the alu-
minium dissolution is not desired in terms of leachate purification.
Regarding the iron dissolution, when iron scrap was used as the
reducer, the highest values were reached, as expected, and they
increased from 0.15 h to 1 h and then slightly decreased. The iron
dissolution above 100%, in this case, is due to the addition of iron as
reducer which partially dissolves and increases its concentration in
the leachate. When Na2S2O5 was used a dissolution of about 95% Fe
was also reached at 1 h of leaching. The iron dissolution decreased
with the leaching time when Na2SO3, H2O2 and only acid (without
reducer) were tested. The lowest extraction (about 17%) was
reached when only acid was used and after 4 h of leaching. From
the point of view of the solutions purification, low dissolution of
iron would be desirable, however, it is important to highlight that
although high Fe dissolution was reached in some tests, most part
of the iron was removed in the physical separation as magnetic
fraction and, therefore, its concentration in solution was low (the
maximum concentration when Na2S2O5 was used, at 1 h of leach-
ing, was about 0.38 g Fe/L).
The impurities behaviour (Al, Fe and Cu) was somehow similar
but not always due to the same reasons. The copper behaviour can
be explained by changes in the oxidation state. Initially part of the
copper dissolves in acid media but the reductive conditions of the
reaction do not allow attaining high concentrations in the leachate
and part of the Cu(II) is reduced again to the metallic form. Regard-
ing Al and Fe, the decrease in the solution concentration after a cer-
tain reaction time is attributed to the acid consumption and the
subsequent increase in the pH for which precipitation of hydrox-
ides could be expected.
Based on these results obtained by the comparison of the use of
different reducers, it was decided to perform a detailed study using
 N. Vieceli et al. / Waste Management xxx (2017) xxx–xxx 7

Fig. 5. Dissolution of different metals from spent LIBs with the leaching time using different additives. Leaching conditions: L/S: 10 L/kg; 0.5 M of H2SO4; leaching
temperature: 60 °C.

Na2S2O5 for this function, given its potential to promote the disso-
lution of metals from the cathode without dissolving high amount
of elements such as Al and Cu, which could be deleterious in the
purification step. The influence of some variables on this process
was studied and the results are presented below.
3.3. Leaching with sodium metabisulphite as reducer
3.3.1. Influence of temperature
Some tests varying the leaching temperature were performed.
The leaching time was fixed at 1 h, the L/S at 10 L/kg, the concen-
tration of Na2S2O5 at 0.1 M, while the concentration of H2SO4 in
one test was 0.75 M (Fig. 6a) and in the other 1.0 M (Fig. 6b). The
Li, Co, Mn and Ni extractions had a similar behaviour with the tem-
perature for both acid concentrations tested and it was expected
since they come from the same solid phase (the battery cathode).
The leaching of cathode elements reached about 80% at 60 °C when
the acid concentration was 0.75 M. For 1.0 M H2SO4 the leaching
yields reached about 80% at 40 °C. The aluminium dissolution
increased with the temperature for both acid concentrations
tested. For 0.75 M H2SO4, the slight decrease observed for the high-
est temperature (95 °C) can be explained by the consumption of

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8 N. Vieceli et al. / Waste Management xxx (2017) xxx–xxx
Fig. 6. Metals dissolution according to the temperature. Leaching conditions: L/S: 10 L/kg; Na2S2O5 concentration: 0.1 M; leaching time: 1 h; H2SO4 concentration: (a) 0.75 M
and (b) 1.0 M.
acid by the reaction of the electrodes, decreasing the free acid
available for Al dissolution. In order to avoid the Al dissolution,
lower temperatures would be favourable, providing that they are
not too low to hinder the reaction of the electrode elements. The
iron behaviour was more variable than the other metals and it
can be related to the low concentration of this metal in the sample
used in the leaching tests. The copper dissolution increased at low
temperatures and reached a maximum at 60 °C, however, it was
always below 10%. For higher temperatures copper dissolution
decreased, since it may be easily reduced to the metallic form.
The decrease in the copper dissolution with the increase in temper-
ature during the LIBs leaching with sulphuric acid was also verified
by Dorella and Borges (2007).
3.3.2. Influence of the concentration of H2SO4 and Na2S2O5
Some tests were carried out varying the concentration of the
acid and the reducer and the results can be seen in Fig. 7. When
the reducer concentration was varied the acid concentration was
fixed at 0.75 M and the leaching time and temperature at 1 h and
60 °C, respectively (Fig. 7a). The elements present in the electrodes
active fraction (Li, Mn, Ni and Co) demonstrated a similar beha-
viour and their extraction increased with the increase of the redu-
cer concentration until 0.1 M. The reducer favours the leaching
reaction since it reduces the metals (mainly Co, Ni, Mn, to the
valence II) making them more stable in solution. Above the reducer
concentration of 0.1 M, its excess does not affect the dissolution of
metals from the electrodes. Al and Fe had a similar leaching beha-
viour decreasing with the increase in the reducer concentration.
Considering that the acid concentration used in these tests (0.75
M) was not much higher than the stoichiometry amount, with
the progress of the leaching the acid remaining is low, demon-
strated by the final pH values, in the range 3–4. The effect is more
pronounced as more electrode react, consuming more acid, as
found when the reducer concentration was increased until 0.1 M.
Fig. 7. Metals dissolution according to the acid and reducer concentrations. The leaching conditions were L/S: 10 L/kg; leaching time: 1 h; leaching temperature: 60 °C;
(a) Na2S2O5 concentration: 0.1 M, and (b) H2SO4 concentration: 0.75 M.
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For copper, the dissolution increased along with the reducer con-
centration but after 0.05 M it is re-precipitated in the metallic
form, given the leachant reducing conditions. Therefore, the
increase in the reducer concentration promotes the decrease in
the leaching yields of Al, Fe and Cu, which is advantageous regard-
ing the solution purity. Thus, the reducer concentration of 0.1 M
seems to be the best among the tested conditions, since allows
obtaining high extractions of Li, Mn, Ni and Co, while promoted
low extractions of Al, Fe and Co.
The general equation that describes the reductive leaching can
be written as (1).
4LiMO2 þ Na2 S2 O5 þ 6H2 SO4 ! 2Li2 SO4 þ 4MSO4
þ 2NaHSO4 þ 5H2 O ð1Þ
where M represents any of the transition metals present in the elec-
trode phase (Co, Ni, Mn). The reaction mechanisms can be, however,
much more complex, since metabisulphite in aqueous media can be
involved in several equilibrium side reactions, such as,
Na2 S2 O5 þ H2 O ! 2NaHSO3
NaHSO3 þ H2 SO4 ! SO2 þ H2 O þ NaHSO4
This means that the reduction of the transition metals in elec-
trode material can be done by several reducing agents that are in
equilibrium with metabisulphite, such as bisulphite or even sul-
phur dioxide. However, Eq. (1) can always represent a general
approach when using metabisulfite as the reducer.
It is important to highlight that the industrial use of sulphur-
based compounds, such as the reducer used in this paper, is always
subject to potential emissions of sulphurous gases. However, such
compounds are widely used in several industries, including in
hydrometallurgy. Therefore, special cares regarding gas emissions
and their treatment are necessary, mainly at an industrial scale.
 N. Vieceli et al. / Waste Management xxx (2017) xxx–xxx
A gas treatment that could be adopted in the process proposed is
the scrubbing in alkaline solutions, for example.
When the acid concentration was varied (Fig. 7b), the reducer
concentration was fixed at 0.1 M. In general, the leaching of the
metals from the electrode materials increased with the acid con-
centration and results above 90% were reached for a concentration
of 1.25 M or higher. Aluminium and iron showed a similar beha-
viour. However, copper leaching is different, showing an increase
in dissolution until 0.75 M H2SO4, reaching a maximum of about
11%, and then it decreased in more acid conditions. A similar beha-
viour was found by Dorella and Borges (2007) during the leaching
of spent LIBs using sulphuric acid in the absence of reducer.
It is important to highlight that the use of small amounts of
acid, preferably near to the stoichiometric value, is desirable not
only from the economic point of view of the consumption of
reagents but also in order to simplify the treatment of final solu-
tions and waste water.
3.3.3. Influence of Liquid/Solid ratio
Tests varying the L/S ratio were performed. In the first case
(Fig. 8a) the L/S was varied keeping the concentration of acid and
reducer fixed at 1.25 M and 0.15 M (different amounts), respec-
tively. The dissolution of Li, Co, Mn and Ni increased with the
increase in the L/S and yields of about 90% were reached when
the L/S was 10 L/kg. The dissolution of Fe and Al also increased
with the L/S and the same was observed for Cu but at a low effi-
ciency. Additional tests were performed varying the L/S and keep-
ing the amount of acid and reducer fixed at 7.5 mol and 1.0 mol/kg
solid, respectively, by varying their concentrations (Fig. 8b). The Li,
Co, Ni and Mn presented a similar behaviour and when the L/S was
3 L/kg, lower dissolutions were achieved. For LS ratios above
4.5 L/kg, their dissolution remained constant. Since the reagents
amount was always the same, the low yields observed for L/S of
3 L/kg could be related to the increase in the pulp density with
the corresponding increase in the metal concentrations attained
in solution, inhibiting the reaction to proceed, and also due to
the high viscosity of the pulp that hinders stirring and diffusion.
The Fe and Al dissolutions had a peculiar behaviour, initially
decreasing with the increase in the L/S to 4.5 L/kg and then increas-
ing or remaining almost constant. The high values obtained for the
lower L/S are probably related to the high initial acid concentration
in this test, that allowed a higher leaching rate in the beginning of
the process. The Cu dissolution slightly increased with the L/S, but
it never exceeded 10% Cu.
3.3.4. Influence of reaction time
Tests varying the leaching time from 15 min to 2 h were car-
ried out and the results are shown in Fig. 9. The leaching temper-
ature was 80 °C and two different L/S ratios were tested (5 and
Fig. 8. Metals dissolution according to the L/S ratio (L/kg). Leaching conditions: leaching time: 1 h; leaching temperature: 60 °C. (a) constant reagent concentrations: 1.25 M
H2SO4 and 0.15 M Na2S2O5; (b) constant reagent amounts: H2SO4: 7.5 mol/kg and Na2S2O5: 1.0 mol/kg.
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9
10 L/kg) keeping the acid and reducer amounts fixed in both con-
ditions (12.5 H2SO4 mol H2SO4/kg solid and 1.5 mol Na2S2SO5/kg
solid). The reagent amounts were fixed by varying their concen-
tration according to the L/S ratio. For all metals from the elec-
trode materials, when using an L/S ratio of 5 L/kg, the reaction
rate is much more favourable and the leaching yields are substan-
tially higher in the first leaching minutes. This is explained by
higher reagents concentration used for the lower L/S, allowing a
higher initial rate. With the consumption of the reagents, the
leaching yields tend to approach. The dissolution of lithium, for
example, reached 32% at 15 min when the L/S was 10 L/kg and
about 85% when the L/S was 5 L/kg, and a similar behaviour
was observed for Co, Mn and Ni. After 0.5 h of leaching the
lithium dissolution was similar (about 90%) for both L/S ratios.
On the other hand, the extraction of Co, Ni and Mn was always
higher when the L/S was 5 L/kg, but have a trend to be closer
as the reaction time increases. The Al dissolution was also higher
when the L/S was 5 L/kg and reached 80% at 2 h. The Fe and Cu
had a different behaviour from the other metals and although ini-
tially the L/S ratio of 5 L/kg has led to a higher dissolution of
these metals, after 30 min of leaching, higher extraction was
achieved for the L/S of 10 L/kg. The iron dissolution increased
by 0.5 h (81%) using the L/S of 10 L/kg and remained almost
unchanged by 2 h of leaching. For the L/S of 5 L/kg it stabilized
at 30 min of leaching (64%). The copper dissolution increased by
0.5 h of leaching when the L/S was 10 L/kg (about 5%) and then
decreased to low values (about 0.1%) at 2 h. The maximum value
for the L/S of 5 L/kg was reached at 15 min (about 4%) and then it
also decreased with the time. The reduction in the copper disso-
lution may be related to its precipitation with the progress in the
leaching time. Therefore, it is possible to conclude that an L/S
ratio of 5 L/kg is better for the extraction of metals from spent
LIBs, since lead to higher extractions of metals from the active
material using more concentrated solutions that are favourable
from the point of view of the leaching solutions purification.
It is important to highlight that although high extraction of the
metals of great interest (Li, Mn, Co and Ni) are reached at 0.5 h of
leaching, their extraction increase for higher leaching times (2 h),
therefore, the interaction of the several factors affecting this pro-
cess (temperature, time, L/S amount of reagents) should be studied
in more detail to evaluate the possibility of reaching higher extrac-
tions at lower leaching times.
The concentration of the metals after 2 h of leaching is pre-
sented in Table 2 for both L/S tested keeping the reagents amount
fixed and the results are compatible with those presented in Fig.9.
It is important to highlight the high concentrations achieved for
the metals of interest, and the very low concentration of the con-
taminants Cu and Fe, for both conditions. Aluminium is the major
contaminant of these solutions.
10 N. Vieceli et al. / Waste Management xxx (2017) xxx–xxx

Fig. 9. Effect of the leaching time on the metals dissolution from spent LIBs for two L/S ratios (values in L/kg). Leaching conditions: Temperature: 80 °C, acid amount 12.5
H2SO4 mol H2SO4/kg solid, reducer amount: and 1.5 mol Na2S2O5/kg solid.

Table 2
Metals concentration for two L/S ratios. Leaching conditions: Temperature: 80 °C, acid amount 12.5 mol H2SO4/kg solid, reducer amount: 1.5 mol Na2S2O5/kg solid, leaching time:
2 h.

L/S (L/kg) Concentration (g/L)

Li Co Cu Ni Mn Al Fe
5 5.98 17.9 0.03 22.5 14.2 7.49 0.43
10 2.84 8.47 0.01 10.2 5.57 2.53 0.29

3.3.5. Influence of stirring speed
Two tests using different stirring speeds were carried out, one
at 150 min
1 (Fig. 10a) and another at 400 min
1 (Fig. 10b). The
acid concentration was fixed at 0.75 M, the concentration of
Na2S2O5 at 0.10 M and the temperature at 60 °C. The leaching
yields of the cathode elements (Li, Co, Ni and Mn) showed a similar
behaviour and seem to be slightly higher when the stirring speed
was 400 min
1, mainly in the beginning of the reaction. The Cu dis-
solution decreased when the stirring speed was 150 rpm, the iron
extraction was not substantially different for both stirring condi-
tions, while the aluminium yield seems to decrease with the
increase in the stirring speed. Therefore, stirring speeds of 150
min
1 or lower are not the most suitable for the dissolution of met-
als from spent LIBs, in the tested conditions.
He et al. (2017) studied the leaching of LiNi1/3Co1/3Mn1/3O2
using sulphuric acid and hydrogen peroxide and verified that the
extraction of Li, Mn, Co and Ni increased with the stirring speed,
however, above 400 min
1 the yields remained almost constant,
thus, 400 min
1 was considered the best stirring speed in that
study. An alternative stirring procedure was tested by
Golmohammadzadeh et al. (2017), who compared the mechanical
stirring to ultrasonic agitation and verified that the cavitation can

Fig. 10. Metals dissolution according to the stirring speed. The leaching conditions were L/S: 10 L/kg; leaching temperature: 60 °C; H2SO4 concentration: 0.75 M; Na2S2O5
concentration: 0.1 M; stirring speed of 400 min
1 (a) and 150 min
1 (b).

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 N. Vieceli et al. / Waste Management xxx (2017) xxx–xxx
enhance the recoveries of lithium and cobalt from LIBs in the
leaching using citric acid.
4. Conclusion
The physical separation used allowed obtaining a final product
with about 95% of the initial electrodes and only 2% of the initial
steel and 22% of plastics. However, Al and Cu foils were not
removed in this step and about 81 and 91% of the initial foils,
respectively, were present in the final material.
In the leaching phase, several reducers were tested for the
extraction of metals from spent LIBs by H2SO4 leaching. Best
results were obtained using Na2S2O5 as reducer, even more than
when hydrogen peroxide was used. The most favourable concen-
tration of Na2S2O5 for the dissolution of metals from spent LIBs
was 0.1 M, since allows obtaining high extractions of metals from
the active fraction (Li, Co, Mn and Ni) without promoting high dis-
solution of metals that could be considered contaminants, such as
Cu, Al and Fe, since they would make the purification of the leach-
ing solution more difficult.
The metals dissolution increased with the increase in the acid
concentration, however, concentrations above 1.25 M H2SO4 seem
not to be necessary. The increase in the leaching temperature also
had a positive effect on the increase in the dissolution of metals
from the active material. The stirring speed of 400 min
1 was more
favourable than 150 min
1 and led to a higher and faster dissolu-
tion of the metals from the active fraction. The dissolution of the
metals from the active material also increased with the increase
in the L/S ratio, when the concentration of the reagents was con-
stant, however, keeping the reagents amount constant, it is possi-
ble to reach high dissolution of these elements at lower L/S ratios,
which is favourable to attain a high concentration of metals in the
leachate, facilitating the subsequent purification and recovery
steps. Extractions of the metals from the electrode black mass of
about 90% were reached after only 0.5 h of leaching, for several
combinations of the factors, showing that the use of sodium
metabisulphite as reducer can be a promising route for hydromet-
allurgical treatment of spent LIBs. Therefore, the interaction of sev-
eral factors affecting this process (temperature, time, L/S, amount
of reagents) should be addressed in further investigation, taking
into account techno-economic aspects that are relevant for the
process, in order to determine the conditions that allow to reach
higher extractions with lower operating cost.
Acknowledgements
The author N. Vieceli acknowledges the doctorate grant ref.
9244/13-1 supplied by CAPES Foundation, Ministry of Education
of Brazil.
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