Resources, Conservation & Recycling 136 (2018) 418–435

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Resources, Conservation & Recycling

journal homepage: www.elsevier.com/locate/resconrec

Recovery of lithium and cobalt from spent lithium ion batteries (LIBs) using T
organic acids as leaching reagents: A review
⁎
Rabeeh Golmohammadzadeha,b, Fariborz Farajia, Fereshteh Rashchia,
a
School of Metallurgy and Materials Engineering, College of Engineering, University of Tehran, Tehran, Iran
b
Department of Chemical Engineering, Monash University, Clayton, Victoria 3800, Australia

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

Keywords: Environmental restrictions and economic benefits have obliged countries to promote recycling processes from
Organic acids secondary resources like spent lithium ion batteries (LIBs) instead of using primary ones. In spite of the de-
Lithium ion batteries velopments have been made on industrial scale for the technologies involved in recycling processes, most of
Recycling process these technologies suffer from lack of efficiency and echo-friendliness. To reduce the footprints of the recycling
Resource recovery
processes, several efforts are made. A major development area is the use of organic acids which are considered as
Environmentally friendly
promising agents for leaching of valuable metals from spent LIBs. In this review paper, we provided an overview
of the recent status of the recycling technologies of spent LIBs using organic acids. For this purpose, necessity of
green processes and advantage of organic acids in recycling of spent LIBs is discussed. To fully understand the
effect of these agents, production, origin, application, and structure of organic acids that have been used in
recovery of metals from spent LIBs are also addressed. Afterwards, recycling processes using organic acids, and
benefits and drawbacks of using them are summarized and possible complexes formed by these agents are
proposed. Eventually, development of different reducing agents, ultrasonic agitation, and evolution and future
prospect of green processes in recycling of spent LIBs is reviewed.

1. Introduction
Changes in the life style of human beings, global developments,
competition between different manufactures and short life span of
electrical and electronic equipment (EEE) have put a greater demand on
EEE (Akcil et al., 2015; Faraji et al., 2018; Gomes et al., 2017; Priya and
Hait, 2017). It is anticipated that 24–46 % of all vehicles in the USA will
be replaced by electrical vehicles by 2030 (Dunn et al., 2012; Wang
et al., 2014a). It is reported that, annual production of waste electrical
and electronic equipment (WEEE) was 43.8 million tons in 2015 and it
is expected to reach 49.8 million tons in 2018 which highly emphasizes
proper management of such wastes (Nekouei et al., 2018).
Batteries, printed circuit boards (PCBs), liquid crystal displays
(LCDs), cathode ray tubes (CRTs), hard disk drives (HDDs), re-
frigerators and cell phones are the integral parts of a typical WEEE
(Zhang and Xu, 2016). These wastes contain precious metals such as
indium, gold, silver, lithium, cobalt, nickel, copper and rare earth ele-
ments (REEs) (Akcil et al., 2015; Zhang et al., 2017). Lithium ion bat-
teries contain Fe, C, Al, Cu, Li, Co and Ni as valuable materials and
LiPF6 as hazardous material. Currently, lithium ion batteries (LIBs) hold
0.3–0.4 wt. % of WEEE (Innocenzi et al., 2017). Due to the higher
voltage per cell, wide range of operating temperature and desirable
discharge resistance, LIBs are widely used in electric vehicles (EVs),
hybrid electric vehicles (HEVs), plug-in hybrid electrical vehicles
(PHEVs), personal computers (PCs), cameras, mobile phones and solar
and wind energy storage devices (Li et al., 2012; Liang et al., 2017;
Ordoñez et al., 2016).
Due to the presence of strategic metals such as cobalt (5–20 wt. %)
and lithium (5–7 wt. %) in spent LIBs (Xu et al., 2008) they are found as
an important secondary resource for the extraction of such valuable
metals (Bigum et al., 2017; Chagnes and Pospiech, 2013; Jandová et al.,
2012; Puca et al., 2017). From another point of view, presence of these
metallic contaminations would affect the environment and threaten life
on the planet (Jagannath et al., 2017; Wei et al., 2018). Thus, the
management of spent LIBs in different countries is highly crucial (Wang
et al., 2014b; Zeng et al., 2015a). It is outlined that 500 thousand tons
of spent LIBs will be produced in 2020, which is equal to 25 billion units
of spent LIBs (Zhang et al., 2016). Based on the US Department of
Transportation (USDT), due to the drastic increase in the production of
electrical vehicles using LIBs, it is anticipated that the required lithium
for production of LIBs in 2025 would become more than the worldwide
lithium reserve and resources (Gaines and Nelson, 2010; Meshram

⁎
Corresponding author.
E-mail address: rashchi@ut.ac.ir (F. Rashchi).

https://doi.org/10.1016/j.resconrec.2018.04.024
Received 2 February 2018; Received in revised form 24 April 2018; Accepted 29 April 2018
Available online 31 May 2018
0921-3449/ © 2018 Elsevier B.V. All rights reserved.
R. Golmohammadzadeh et al.
et al., 2014; Wanger, 2011). It should be noted that 35% of lithium
(Martin et al., 2017) and 25% of cobalt (Bernardes et al., 2004;
Winslow et al., 2018) produced across the world is used in the LIB in-
dustry.
Despite of large investments on the recycling industry made by the
governments on a global scale, only around 32 wt. % of the spent LIBs
in 2017 were recycled (Jiang et al., 2015). Lack of effective regulations,
weak collection systems and old technologies for recycling of spent LIBs
are the important reasons for inefficient management of these waste
batteries in China (Zeng et al., 2015a). Traditional methods of waste
disposal, including landfilling, stabilization and incineration, have
disadvantages such as penetration of metallic contaminations to the soil
and groundwater, emission of toxic gases to the atmosphere, and high
maintenance and operation costs; especially in incineration plants (Guo
et al., 2016; Liu et al., 2017; Pietrelli et al., 2005). Besides, loss of
valuable metals in aforementioned methods is another factor that
should be considered (Zand and Abduli, 2008).
To solve this intractable problem, some countries have established
strict regulations. For example, the USA inhibits landfilling of spent
LIBs by considering them as hazardous materials (Bahaloo-Horeh and
Mousavi, 2017; Wang et al., 2014b). Similarly, recycling of at least 50%
of waste batteries has been obliged by the European union (EU)
(Dewulf, 2010; Hao et al., 2017). Life cycle assessment of spent LIBs
showed that each 100 ton of spent LIBs, requires 8.7 × 105 kg material
and 9 × 103 kJ energy to be recycled (Rocchetti et al., 2013). On the
other hand, spent LIBs recycling reduces energy consumption and
greenhouse gas emissions, and also leads to the conservation of 51.3%
of the natural resource as compared to landfilling (Boyden et al., 2016).
There are different approaches for recycling of spent LIBs.
Nonetheless, in order to save the echo-system, to guarantee the human
health and to manage the waste sustainability, it is crucial to find en-
vironmentally friendly methods for recycling of spent LIBs. Recently,
some attempts have been made to introduce efficient and echo-friendly
methods for recycling of spent LIBs. Among them, use of organic agents
in leaching of lithium and cobalt from spent LIBs have attracted much
more attention. However, there is little information about origin,
structure and effect of each organic acid on recovery of lithium and
cobalt from spent LIBs. In this review paper, we are trying to provide
the readers with the comprehensive record of widespread use of organic
agents as both leaching and reducing agents for recycling processes of
LIBs.
2. Structure of LIBs
A conventional LIB comprises of a cathode, an anode, a separator,
electrolyte solution, collectors (aluminum and copper foils), protective
shells, and containers (Gratz et al., 2014). Fig. 1 shows the schematic
drawing of a LIB and Table 1 illustrates the contribution of each section
(Horeh et al., 2016). Cathode is an aluminum foil coated with cathode
Fig. 1. Shape and components of LIBs.
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Resources, Conservation & Recycling 136 (2018) 418–435
Table 1
Contribution of different sections in spent LIBs (Horeh et al., 2016).
Battery components The contribution (%)
Cathode 35
Anode 18
Plastic 6
Electrolyte 11
Case 26
Loss 4
active materials which are mainly lithium containing components
(mostly oxide) and different active metals (Zeng et al., 2014). The
cathode active materials are made of various compounds such as
LiMPO4 (M = Co, Mn, Fe), LiMO2 (M = Co, Ni, Mn) and in some cases
LiV3O8 and Li3V2(PO4)3 (Chagnes and Pospiech, 2013; Etacheri, 2011;
Gratz et al., 2014; Ordoñez et al., 2016). Despite the development of
new cathode materials, LiCoO2 is still the most common cathode active
material because of the high specific energy density it provides and its
stability (Kang et al., 2006; Stephan, 2006; Zeng et al., 2014). Based on
Table 1, cathode not only has the most contribution in the structure of
spent LIBs, but also it contains valuable metals such as lithium and
cobalt which makes it the most valuable part of spent LIBs for recycling.
Anode is a copper foil covering with carbon graphite; however, there
have been some attempts for introducing new anode materials such as
Li4Ti5O12 (Ordoñez et al., 2016), Mn3O4 (Wang et al., 2010), Sn nano-
particles (Yu et al., 2009), Fe2O3 nanoflakes (Reddy et al., 2007), CuO
nano composites (Wangm et al., 2010).
Polyvinylidene fluoride (PVDF) is used to bind cathode and anode
materials onto the aluminum and copper foils, respectively (Gratz et al.,
2014; Li et al., 2013). It is worthwhile mentioning that the environment
of the LIBs is reactive and a thermal and electrical resistance material as
PVDF can act more efficient than any other materials (Zeng et al.,
2014). Direct contacts of the electrodes lead to short circuiting, thus,
either polyethylene (PE) or polypropylene (PP) is used to separate
cathode and anode foils (Zeng et al., 2014). The electrolyte of LIBs is a
mixture of lithium salts (LiPF6, LiAsF6, LiClO4, LiCF3SO3, Li(SO2CF3)2
and LiBF4) and organic solvents (dimethyl carbonate or ethylene car-
bonate and diethyl carbonate) (Gong et al., 2013; Zeng et al., 2014).
The chemical reactions in LIBs in which cathodes and anodes are made
of LiCoO2 and graphite are (Zhang et al., 1998):
6C + xLi+ + xe− ↔ C6 Li x (Cathodic reaction) (1)
LiCoO2 ↔ Li (1 − x ) CoO2 + xLi+ + xe− (Anodic reaction) (2)
3. Necessity of green recycling processes and economic feasibility
Since spent LIBs are considered as valuable waste, sustainable, eco-
friendly and cost effective approach for recycling of them is required.
To recycle spent LIBs, there have been various approaches including
pyrometallurgy, hydrometallurgy and biohydrometallurgy. In pyr-
ometallurgy the organic electrolyte and binders are burnt off and then
the metals are dissolved using two furnaces (Cheret and Santen, 2007;
Sun and Qiu, 2012). Electrolyte and plastic containers are eliminated in
the first furnace, and molten metals and alloys are formed in the second
furnace (Cheret and Santen, 2007). By melting the scrapes, cobalt,
nickel and copper would effectively be recovered while other compo-
nents such as lithium will be lost in the form of slag and gas (Georgi-
Maschlera et al., 2012). Though, this method is feasible, it needs high
temperatures (500–1000 °C), does not recover organic compounds,
consumes lots of energy, emits large amount of toxic gases, results in
production of non-pure alloys and requires additional refinements
(Garcia et al., 2017; Joulié et al., 2017; Xu et al., 2008).
In hydrometallurgy approach, different processes are involved to
dissolve, separate and concentrate valuable metals in an aqueous
R. Golmohammadzadeh et al.
medium; i.e., acid leaching (Meshram et al., 2015a; Paulino et al., 2008;
Zheng et al., 2017), chemical precipitation (Guzolu et al., 2017; Yang
et al., 2017), solvent extraction (Amato et al., 2017; Paulino et al.,
2008; Yang et al., 2017), and electrochemical methods (Chagnes and
Pospiech, 2013; Garcia et al., 2017; Xu et al., 2008; Zhang et al., 2013).
In this method, either one of the aforementioned methods or combi-
nations of them are applicable for recycling of metals from spent LIBs
(Li et al., 2010b). Recently, bio-hydrometallurgy, as an affordable ap-
proach which requires less industrial requirements, is used in recovery
of metals from solid waste (Brandl and Faramarzi, 2006; Cerruti et al.,
1998; Kim et al., 2016). Recovery of valuable metals from spent LIBs is
also investigated by bacteria and fungi (Bahaloo-Horeh and Mousavi,
2017; Horeh et al., 2016; Mishra et al., 2008; Xin et al., 2009). Despite
its advantages, this method is slow and requires long acting time and
also incubation of microorganisms is a tough task (Zhao et al., 2008).
Hydrometallurgical treatments are flexible, environmentally-
friendly, consume less energy, have acceptable rate of reaction, do not
contaminate air and provide more pure valuable metals (Garcia et al.,
2017; Ku et al., 2016; Sun and Qiu, 2011; Sun et al., 2017). In previous
studies, several agents including acids, alkaline solutions or reducing
agents have been utilized for leaching of metals from spent LIBs (Wang
et al., 2016). Fig. 2 shows the flowchart of a typical hydrometallurgical
process for recycling of spent LIBs. Sulfuric acid (Yang et al., 2017),
hydrochloric acid (Guzolu et al., 2017) and nitric acid (Lee and Rhee,
2003) are examples of conventional leaching agents. Despite the fact
that extensive efforts have been devoted using aforementioned agents
in industrial scale recycling of spent LIBs, they have several
Fig. 2. Flowchart of hydrometallurgical process for recycling of spent LIBs.
420
Resources, Conservation & Recycling 136 (2018) 418–435
environmental downsides such as emission of toxic gases (SO3, Cl2 and
NOx) and water and soil contaminations (Golmohammadzadeh et al.,
2017; Gupta et al., 2012; Li et al., 2013).
Inorganic acids are very strong and their application may result in
consumption of a large amount of water, corrosion of the equipment,
spoiling of nonmetallic components and leaving a lot of secondary
pollutions (Tesfaye et al., 2017). The secondary pollutions generated
from conventional inorganic acids require being treated in a proper way
which needs the consumption of a great deal of water, money and en-
ergy (Innocenzi et al., 2017; Tesfaye et al., 2017). Life cycle assessment
of a hydrometallurgical process using sulfuric acid showed that
5.4 × 105 kg CO2, 2 kg Sb, 1.365 × 103 kg SO2, 9.8 × 10 kg ethane and
1.3 × 102 kg phosphate will be emitted for recycling of spent LIBs
present in 100 tons of WEEE residue (Rocchetti et al., 2013). In another
research, the economical aspect of hydrometallurgical treatments of
spent LIBs from mobile phones using sulfuric acid was surveyed and
results showed that, recycling of one ton powder of spent LIBs results in
1.63 × 103 kg tailing and 6.14 × 103 kg sludge which need to be paid
enough to be disposed properly (Innocenzi et al., 2017). Due to the
presence of variety of toxins in secondary resources, treatment of them
is extremely expensive; for instance, for recycling of each cubic meter of
leachate ca. 3.2 euros should be paid (Cassano et al., 2011). Approxi-
mately 250–725 Canadian dollar is required for treatment of one ton of
the sludge which interprets as 15 billion dollars each year worldwide
(Blais et al., 2005). In addition, several legislations and regulations on
recycling of the spent LIBs have been set across the world. For example,
in Europe, the hazardous waste or residue including the leachate
R. Golmohammadzadeh et al.
generated from mineral acids, should not be landfilled before pre-
treatments prior to the disposal (Duggan, 2005). Similarly, in order to
manage the solid waste and resultant pollutions in china, restrict laws
have been set by the federal and local governments. Based on these
rules, the organizations are required to reduce both solid waste and air
pollutant gases including CO2, SO2 and NO2 (Zhou et al., 2017).
Since organic acids are produced by microorganisms, they are not
considered as potential contamination for the environment (Jadhav and
Hocheng, 2012). By using organic acids as green and efficient leaching
agents, no secondary pollution would be left, the corrosion of the
equipment would be delayed, they have less potential danger to the
operators, and they are also capable of selective leaching of the metals
(Chen et al., 2015; Horeh et al., 2016; Li et al., 2013; Zafar and Ashraf,
2007). In addition, organic agents are biodegradable, do not generally
produce gases, and the waste resulted from the leaching step would be
easily managed (He et al., 2016; Li et al., 2018b). In addition, organic
acids using in leaching processes can be recycled; for instance, Chen
et al. (2015) recovered both citric acid and waste materials using oxalic
and phosphoric acid. Likewise, the organic acids are much stable than
H2O2; therefore, they can be employed in a more effective way if a
reducing agent is required (Meng et al., 2017). Although many of or-
ganic acids are more expensive than the inorganic ones, their applica-
tion is still cost-effective because they don’t lead to the most of the
forthcoming environmental or economic problems associated by in-
organic acids (Blais et al., 2005; Golmohammadzadeh et al., 2017;
Rocchetti et al., 2013). It is worth mentioning that only a group of
organic agents is too costly; in contrary, many of organic agents in-
cluding glucose, sucrose, molasses, acetic acid and etc. are cheap, and
some of them are just a little more expensive than the inorganic acids
including citric acid and maleic acid (Li et al., 2018b; Meng et al.,
2017). Different organic acids have been employed to recycle spent
LIBs; however, recycling of spent LIBs using organic acids is yet limited
due to the lack of comprehensive knowledge about organic agents that
can be applied as leaching agents. To solve this issue, this paper deeply
addresses the production processes, origin, application, and structure of
the organic acids and their effect on recovery of metals from spent LIBs.
Besides, effect of reducing agents and ultrasonic agitation on recycling
of spent LIBs is indexed.
4. Organic acids
Organic acids are mostly produced by microorganisms present in
the environment and their acidity depends on their functional group
(e.g., carboxylic or sulfonic) (Ball, 2008; Theron and Lues, 2007).
Considering these acids are not equal in number of carboxylic groups,
hydroxyl groups, and carbon-carbon double bonds in their molecules,
they are classified according to their typical of carbon chain, saturation,
substitution, and their functional groups (Theron, 2011). Table 2 shows
the main groups of organic acids, their formula, dissociation reactions,
corresponding pKa and structure (Apelblat, 2014; Juanico, 2004;
Lorenzo et al., 1999; Nielsen et al., 2014; Theron, 2011).
Based on Table 2, most of the acids are dissociated in 2 steps except
acetic, lactic and citric acids which dissociate in one and three steps,
respectively. Being the most familiar chemicals to the humanity, acetic
acid (ethanoic acid) is produced from corruption of different fruits and
foods (Fleet, 2003). This acid is naturally produced (vinegar) by various
bacteria and fungi through aerobic and anaerobic processes (Agreda
and Zoeller, 1993). As shown in Table 2, acetic acid with only one
carboxylic group and low ionization constant (pKa1 = 4.76), is con-
sidered as a weak acid (Solomons, 1992; Theron, 2011). Another or-
ganic acid dissociating in one step is lactic acid (2-hydroxy propionic
acid) with only one asymmetric carbon, which is the simplest hydroxyl
acid (Sin, 2012). Lactic acid can be made by either chemical synthesis
or fermentation of different bacteria; i.e., Lactobacilli amylophilus, L.
bavaricus and L. casei (Mozzi and Graciela, 2010; Ren, 2010). It has two
isomers of D and L; in which both of them are produced by bacteria;
421
Resources, Conservation & Recycling 136 (2018) 418–435
however, the L form can be produced in bodies of mammals as well
(Garlotta, 2002). Based on its mild acidic taste, preservative capability,
buffering behavior and not being volatile, food industry is known as the
main application of this acid (Datta and Henry, 2006). Regarding to the
fact that this acid has both carboxylic and hydroxyl groups (Table 2), it
is also applicable in polymerization reactions (De Vries, 1989; Kang
et al., 2001). One of the notable characteristics of aforementioned
agents is their extreme solubility in water which make them appro-
priate agents for leaching processes; however, acetic acid is merely
soluble in ethanol and acetone mixtures and lactic acid is insoluble in
oils (Greenacre et al., 2003).
Ascorbic acid (2,3-enediol-L-gulonic acid) is known as vitamin C
and is an antioxidant in human metabolisms (Kim et al., 2006; Teucher
et al., 2004). This acid is synthesized through conventional seven-step
Reichstein process and has a great solubility in water (ca. 330 g L−1)
(Seib and Tolbert, 1982). In Reichstein process glucose as an input of
the process is exposed to Ni (II) at high temperature and pressure, then,
sorbose will be produced as a result of bacterial fermentation (e.g.,
Gluconobacter oxydans). Afterwards, addition of acetone and sulfuric
acid to the medium leads to formation of diacetone – sorbose. There-
with, diacetone – sorbose is subjected to Pd (II) to generate 2-Keto-
gulonic acid. Henceforth, by adding hydrochloric acid and methanol, 2-
Keto-L-gulonic acid methyl ester is produced. Eventually, addition of
ethanol and exposure to high temperature leads to formation of as-
corbic acid (Bremus et al., 2006; Hancock and Viola, 2002). This or-
ganic acid has a great ability to absorb molecular oxygen and based on
this property, it is considered as a strong reducing agent (Theron,
2011). In contrary, aspartic acid (2-aminobutanedioic acid) with an
amino and a carboxylic group (as shown in Table 2) is naturally pro-
duced as a result of biological processes in which enzymes and bacterial
cells are playing role (Kiss et al., 1989; Smith et al., 1987; Zhang and
Lippard, 2003). For instance, Corynebacterium species and Escherichia
coli are appropriate choices for production of aspartic acid (Fusee et al.,
1981; Yukawa et al., 2009). It should be noted that, it is less soluble in
water (ca. 4.5 g L-1) as compared to ascorbic acid; with wide variety of
applications in industry; i.e., water treatment, paper processing, paint
additive, metabolism of mankind and treatment of some deceases
(Roweton et al., 1997; Specker, 2011).
Iminodiacetic acid (2,2-Azanediyldiacetic acid) is produced through
several chemical methods including hydrocyanic acid method, dietha-
nolamine method, and chloroacetic acid method and biological routes
such as Arthrobacter aurescens and Alcaligenes faecalis bacteria (Su et al.,
2016). Albeit iminodiacetic acid is relatively small, this agent can make
strong chelates with transient metals (Loberg et al., 1976). Regarding
aforementioned property and its great solubility in water (ca. 42 g L−1),
iminodiacetic acid is applicable in wastewater treatment and metal
recycling, in which the metallic contaminations are selectively chelated
and separated by controlling pH of the medium (el Rassi and Horvath,
1986; Wang et al., 2002). Besides, it is applicable in fine chemical in-
dustry including chelating agents, herbicide and surfactants (Dold et al.,
2016; International and McCaleb, 1993).
Maleic acid (Cis-butenedioic acid) with solubility of ca. 478.8 g L−1
in water is one of the most important chemical intermediates which is
not only appropriate for lubricant additives, unsaturated polyester re-
sins, surface coatings, plasticizers, copolymers and agricultural chemi-
cals, but is also an excellent compound for polymerization (Amjad and
Koutsoukos, 2014; Kitano et al., 1987; Wojcieszak et al., 2015). Maleic
acid is the same hydrolyzed form of maleic anhydride and can be
formed through different routes such as aerobic oxidation of furfural
assisting phosphomolybdic acid catalysts (Guo and Yin, 2011; Trivedi,
2013). The mechanism for its production depends on the starting mo-
lecules (furan, furfural or etc.); in which one or two carbon atoms are
removed in presence of a catalyst (commonly vanadium or phosphorus
oxide) (Wojcieszak et al., 2015). In this case, the equation bellow de-
picts maleic anhydride formation from butane (Engel and Straathof,
2008; Felthouse et al., 2001; Wojcieszak et al., 2015):
R. Golmohammadzadeh et al. Resources, Conservation & Recycling 136 (2018) 418–435

Table 2
Main groups of organic acids, their formula, dissociation reactions and corresponding pKa and structure.
Type Organic acid Formula No. Dissociation reaction Structure

Monocarboxylic Acetic C2H4O2 (3) HC2 H3 O2 → C2 H3 O2− + H+ (pKa1 = 4.76)

Lactic C3H6O3 (4) HC3 H5 O3 → C3 H5 O3− + H + (pKa1 = 3.86)

Gluconic C6H12O7 (5) HC6 H11 O7− → C6 H11 O7− + H + (pKa1 = 3.86)

Formic CH2O2 (6) HC2 HO2 → C2 HO2− + H + (pKa1 = 3.75)

Diarboxylic Ascorbic C6H8O6 (7) H2 C6 H6 O6 → HC6 H6 O6− + H + (pKa1 = 4.17)
(8) HC6 H6 O6− → C6 H6 O62 − + H + (pKa2 = 11.57)
Aspartic C4H7NO4 (9) H2 C4 H5 NO4 → HC4 H5 NO4− + H + (pKa1 = 2.10)
(10) +
HC4 H5 NO4− → C4 H5 NO42 − + H (pKa2 = 3.86)
Iminodiacetic C4H7NO4 (11) H2 C4 H5 NO4 → HC4 H5 NO4− + H + (pKa1 = 2.54)
(12) HC4 H6 NO4− → C4 H5 NO42 − + H + (pKa2 = 9.12)
Maleic C4H4O4 (13) H2 C4 H2 O4 → HC4 H2 O4− + H + (pKa1 = 1.83)
(14) HC4 H2 O4− → C4 H2 O42 − + H + (pKa2 = 6.07)
Malic C4H6O5 (15) H2 C4 H2 O5 → HC4 H2 O5− + H + (pKa1 = 3.40)
(16) HC4 H4 O5− → C4 H4 O52 − + H + (pKa2 = 5.11)
Oxalic C2H2O4 (17) H2 C2 O4 → HC2 O4− + H + (pKa1 = 1.23)
(18) HC2 O4− → C2 O42 − + H + (pKa2 = 4.19)
Oxaloacetic C4H4O5 (19) H2 C4 H2 O5 → HC4 H2 O5− + H + (pKa1 = 2.22)
(20) HC4 H2 O5− → C4 H2 O52 − + H + (pKa2 = 3.89)
Succinic C4H6O4 (21) H2 C4 H4 O4 → HC4 H4 O4− + H + (pKa1 = 4.22)
(22) +
HC4 H4 O4− → C4 H4 O42 − + H (pKa1 = 5.70)
Tartaric C4H6O6 (23) H2 C4 H4 O6 → HC4 H4 O6− + H + (pKa1 = 3.03)
(24) HC4 H4 O6− → C4 H4 O62 − + H + (pKa2 = 4.37)
Tricarboxylic Citric C6H8O7 (25) H3 C6 H5 O7 → H2 C6 H5 O7− + H + (pKa1 = 2.79)
(26) H2 C6 H5 O7− → HC6 H5 O72 − + H + (pKa2 = 4.30)
(27)
HC6 H5 O72 − → C6 H5 O73 − + H + (pKa3 = 5.65)
Isocitric C6H8O7 (28) H3 C6 H5 O7 → H2 C6 H5 O7− + H + (pKa1 = 3.28)
(29) H2 C6 H5 O7− → HC6 H5 O72 − + H + (pKa2 = 4.71)
(30)
HC6 H5 O72 − → C6 H5 O73 − + H + (pKa3 = 6.39)

C4 H10 + 3.5O2 → C4 H2 O3 + 4H2 O
C4 H2 O3 + H2 O → C4 H4 O4
Malic acid (C4-dicarboxylic) is mainly found in fruits (especially
apple), animals, and vegetables and is considered as a deterrent to
growth of some bacteria (Barbosa-Canovas et al., 2003; Theron and
Lues, 2007). Same as lactic acid, it possesses two forms of isomers; L
and D, in which both forms are synthesized; however, L form can be
naturally produced; i.e., mostly as a result of biological activities by
fungi or in fruits (Kurz and Constabel, 1979; Scheper, 2016). In com-
mercial approach, both D and L isomers of malic acid would be
achieved by hydration of either maleic or fumaric acid at high tem-
peratures and pressures (Wang and Dh, 2007). Malic acid has 558 g L−1
solubility in water, and a great solubility in methanol, ethanol, acetone,
ether, and other polar solvents.
Oxalic acid (Ethanedioic acid) can be produced either biologically
or commercially; however, it is mainly produced by fungi; i.e., brown-
rots, white-rots, mycorrhizae, plant pathogens, and Aspergillus niger
(A.niger) (Tkacz and Lange, 2004). Following equations represent the
formation of oxalic acid by biological and commercial methods, re-
spectively:
C6 H12 O6 + O2 + 2CO2 → C2 H2 O4 + 2C2 H4 O2
C4 H4 O5 + H2 O → C2 H2 O4 + 2C2 H4 O2
In biological approach (Eq. (33)), glucose is transferred to oxalic and
acetic acids at pH values of 4.5–5 by fungal metabolism. In commercial
approach (Eq. (34)), oxaloacetate hydrolysis to produce oxalic and
acetic acids (Sindhu et al., 2014; Villadsen, 2015). It should be noted
that its solubility in water and ethanol are about 143 g L−1 and
237 g L−1, respectively.
(31) Succinic acid (1,4-butanedioic acid) is either produced during a
tricarboxylic acid cycle as a result of anaerobic metabolisms such as
(32) Anaerobiospirillum succiniciproducens or can be manufactured through
hydrogenation of maleic and fumaric acid using a suitable catalyst
(Delhomme et al., 2009). This agent plays a key role in natural meta-
bolisms of both plants and animals and also has a remarkable role in
manufacturing of biodegradable polymers (Hong and Hong, 2005;
Theron, 2011). Its taste is so salty and has high solubility in water and is
merely soluble in ethanol, ether, acetone and glycerine (Kaneuchi et al.,
1988; Schaechter, 2009). In contrast, it is not soluble in benzene,
carbon sulfide, carbon tetrachloride and oil ether (Theron, 2011).
Furthermore, succinic acid is able to transform to the other organic
components such as 1,4-butanediol, g-butyrolactone, tetrahydrofuran,
N-methyl-2-pyrrolidone, 2-pyrrolidone, succinimide, succinic esters,
maleic acid and etc. (Delhomme et al., 2009).
Tartaric acid (2,3-Dihydroxysuccinic acid) with solubility of
1330 g L−1 in water, is a multi-functional molecule with at least three
distinct anion forms; i.e., neutral bi-acid, monotartrate and bitartrate
forms (Pradier and Chabal, 2011). It is abundant in wine and vinegars
and is naturally found in fruits (pineapples and grapes) (Carque, 1974;
Kellogg, 1921). Its taste is similar to citric acid but is smoother and lasts
more, proving that tartaric acid has a wider buffering range of pH
(33) compared to citric acid; i.e., it is a good buffer between pH ranges of 2.1
and 7.4 (Shellis et al., 2015; Theron, 2011). Tartaric acid and its deri-
(34)
vatives are predominantly applicable in synthesis of different organic
compounds because of its chiral reagents (Faigl and Kozma, 2004).
Citric acid (2-hydroxy-1,2,3-tricarboxylic) is mostly produced by
fungi (e.g. A. niger and Candida) through a temperature and aeration
influential process; i.e., tricarboxylic acid cycle (TCA) that different
hydrocarbon sources are transformed into citric acid (Engel and
Straathof, 2008; Tkacz and Lange, 2004; Villadsen, 2015). Citric acid is

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R. Golmohammadzadeh et al.
appealing in food industry; i.e., production of natural fruit flavors,
stabilizing the commodities and inhibiting their oxidation and etc.
(Apelblat, 2014). Furthermore, it is useful in pharmaceutical and che-
mical industries and is a strong chelating agent (Theron, 2011). Con-
sidering its numerous applications in different fields and its high solu-
bility in water (1477 g L−1), it is considered as an appropriate leaching
agent (Theron, 2011).
5. Environmentally friendly recycling processes
5.1. Pretreatments
Spent LIBs consist of a metal casing, a plastic cover, and an elec-
tronic control unit (Zeng et al., 2014). In addition, cathode, anode and
separator are spiral-wound together to build a cylindrical cell of LIBs
(Romare and Olofsson, 2013). Therefore, pretreatment is necessary to
reduce the volume of scraps prior to leaching (Gao et al., 2017; Sun and
Qiu, 2011). Pretreatment step usually includes mechanical processes
and thermal treatment which is associated with benefits such as de-
creasing the acid consumption, increasing the leaching efficiency, de-
creasing the impurities in further steps and eventually decreasing the
number of purification steps which results in less operation costs (Lee
and Rhee, 2002; Li et al., 2009; Li et al., 2010b; Liu et al., 2006;
Meshram et al., 2015a; Shin et al., 2005).
Due to the potential dangers and self-ignition of spent LIBs which
leads to flame and explosion during dismantling, deactivation should be
prioritized (Diekmann et al., 2017). Deactivation can be carried out in
processes such as short-circuiting or discharging of the whole battery
and thermal pretreatment (Georgi-Maschlera et al., 2012; Li et al.,
2010b). In pretreatment approach, the batteries are exposed to 300 °C
heat in which the solvents and electrolyte solvents are evaporated and
combusted, respectively, leading to opening of the battery cell
(Diekmann et al., 2017; Georgi-Maschlera et al., 2012). It is worth to
mention that preheating of the batteries may lead to decreasing the
energy inside the battery; yet, is not as sufficient like other deactivating
procedures. Soaking in a conductor solution; i.e., sodium chloride so-
lution or 10% w.v−1 sodium sulfate for 24 h is reported as an efficient
method for discharging of the batteries by most of the researchers
(Chen et al., 2017; Contestabile et al., 1999; Nan et al., 2005; Paulino
et al., 2008; Pinna et al., 2017; Zhang et al., 2014).
Mechanical processes are applied to separate and enrich the com-
ponents of spent LIBs including crushing, sieving, magnetic separation,
fine crushing and classification (Chagnes and Pospiech, 2013; Shin
et al., 2005). Mechanical separation processes which are being used to
remove the crust and steel cases of the spent LIBs are based on the
changes in the physical properties of the materials such as density,
magnetic behavior and conductivity (Kim et al., 2004; Xu et al., 2008;
Zhang et al., 1998). However, weakness in separation of all components
of spent LIBs limits widespread usage of mechanical processes (Xu et al.,
2008).
After separation of all components of the spent LIBs (e.g., metal
casing, plastic cover, cathode, and anode), either N-Methyl-2-pyrroli-
done (NMP) or an alkaline agent such as NaOH can be used to separate
aluminum contents of cathode active materials (Pinna et al., 2017). In
the former one, the cathode active materials react with NMP; conse-
quently, active materials are effectively separated from the aluminum
substrate (Chen et al., 2017; Li et al., 2010a, 2010b). In the latter one,
NaOH dissolves aluminum and leads to separation of cathode active
materials and aluminum foil (Fan et al., 2016; Zhang et al., 2016). It
should be noted that, NMP is an expensive agent and NaOH produces
waste aqueous alkaline solution which cannot be treated (Xu et al.,
2008). In a novel approach, thermal treatments was utilized to separate
active materials of current collector, to decompose PVDF and to recover
transition metals (Yang et al., 2016).
To remove binders and carbon contents of the spent LIBs, cathode
materials are usually thermally treated (Georgi-Maschlera et al., 2012;
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Resources, Conservation & Recycling 136 (2018) 418–435
Lee and Rhee, 2002; Sun and Qiu, 2011). To meet the higher leaching
efficiencies, additional milling can be employed due to the appropriate
selective crushing characteristics that spent LIBs (Zhang et al., 2014). It
is worthwhile mentioning that using all these routes alone is merely
efficient and it is recommended to use a combination of mechanical and
thermal treatment approaches (Fan et al., 2016).
5.2. Effect of organic acids in leaching of cathode materials
Strength of organic acids is generally based on several factors in-
cluding relative stability of the conjugate base of the acid and other
groups including, −OH, −OS, enol, alcohol, thiol and phenol groups
which is determined by corresponding pKa (the pH in which acid and
anion concentrations are equal, the lower the pKa, the more strength
acid) (Theron, 2011). Despite the fact that organic acids are weaker
than inorganic ones, most of them are thermally stable, leave smaller
environmental footprint, and are able to form strong chelates (Carrasco
et al., 2010; Deng et al., 2015; Heydarpour et al., 2011; Loberg et al.,
1976). In other words, they are playing a noteworthy role in metal
dissolution through acidolysis and complexolysis mechanisms (Kustin
and Pizer, 1968; Lorenzo et al., 1999; Sindhu et al., 2014; Zahan et al.,
2015). In acidolysis, the hydrogen ions attack the metals and mobilize
them into the solution and in complexolysis, the organic compounds
stabilize the metallic ions by either complex or chelating formation
(Horeh et al., 2016; Saidan et al., 2012). The complexation rate can be
influenced by strength of the bond between hydroxyl hydrogen and
oxygen in carboxylic acids (Knipe, 2007). Along with this, acids with
more numbers of hydroxyl groups usually react faster (Knipe, 2011;
Smith, 2011). Table 3 shows the complexation reactions of aforemen-
tioned organic acids with lithium, cobalt, manganese and nickel present
in spent LIBs, respectively.
Acetic and lactic acids are weak and dissociate in one step (as shown
in Table 2), therefore, there are a few studies on recycling of spent LIBs
using these acids. Recently, it has been reported that in the presence of
acetic acid, maximum ca.75% lithium and ca.30% cobalt can be re-
covered in solid to liquid ratio (S/L) of 30 g L−1 (Golmohammadzadeh
et al., 2017). In case of lactic acid, results showed a high recovery of
lithium 97.7%, cobalt 98.9%, nickel 98.2%, and magnesium 98.4% at
optimum condition of 1.5 M lactic acid, S/L of 20 g L−1, temperature of
70 °C, H2O2 concentration of 0.5 Vol.%, and reaction time of 20 min. (Li
et al., 2017). Despite the fact that lactic acid is a weak acid, the results
might be due to the presence of the carboxylic group adjacent to the
hydroxyl group in its structure, which increases the acidity of this acid
(Li et al., 2017). Fig. 3(a) and (b) illustrate the possible metallic com-
plexes formed by acetic and lactic acids based on Eqs. (35) and (36)
represented in Table 3.
Ascorbic acid (see section 4) can act as both leaching and reducing
compound at the same time. Since it is a 2,3-enediol-L-gulonic acid, it
can release both H+ of the enediol group into the solution which results
in its strong acidity (Kanako, 1989). Moreover, the enediols are con-
sidered as outstanding reducing agents (Kanako, 1989). Li et al. (2012)
recovered 98.5% lithium and 94.8% cobalt from spent LIBs using as-
corbic acid including three main steps; dismantling of spent LIBs and
electrodes separation, immersion of cathode parts in NMP and even-
tually reductive leaching of cathode materials by ascorbic acid. Results
showed that ascorbic acid acts as a reducing agent facilitates cobalt
extraction by conversion of insoluble Co(III) compound to soluble Co
(II) (Li et al., 2012). It was also investigated that C6H6O6Li2 and
C6H6O6Co are the most thermodynamically stable species in the
leaching solution demonstrating in Table 3 and Fig. 4(a) (Li et al.,
2012). However, Li et al. (2013) reported that due to the weak acidity
and low solubility of aspartic acid in water, as mentioned in section 4, it
is an inefficient agent for recovery of lithium and cobalt from spent
LIBs, unless using reducing agents.
Iminodiacetic and maleic acids were employed to completely re-
cover lithium and cobalt at 80 °C from cathode scraps using ascorbic
R. Golmohammadzadeh et al. Resources, Conservation & Recycling 136 (2018) 418–435

Table 3
Complexation reactions of different organic acids and LiCoO2.
Type Reaction No. Complexation Reaction (M=Co2+, Li+, Mn2+, Ni2+)

Acetic metallic complexes (Golmohammadzadeh et al., 2017) (35) n [C2 H3 O2−] + M n + → M [C2 H3 O2 ]n
Lactic metallic complex (Featherstone and Rodgers, 1981; Glebov et al., 2011) (36) n [C3 H5 O3−] + M n + → M [C3 H5 O3 ]n
Ascorbic metallic complexes (Demianenko et al., 2014) (37) n [HC6 H6 O6−] + M n + → M [HC6 H6 O6 ] n
(38) n [C6 H6 O62 −] + 2M n + → M2 [C6 H6 O6 ] n
Asparic metallic complexes (Galhoum et al., 2017; Houchin and Topp, 2008; Sang-aroon and (39) n [HC4 H5 NO4−] + M n + → M [HC4 H5 NO4 ] n
Ruangpornvisuti, 2008) (40) n [C4 H5 NO42 −] + 2M n + → M2 [C4 H5 NO4 ] n
Iminodiacetic metallic complexes (41) [HC4 H5 NO4−] + M n + → M [HC4 H5 NO4]n
(Chaberek and Martell et al., 1952; Thakur et al., 2007) (42) [C4 H5 NO42 −] + 2M n + → M2 [C4 H5 NO4]n
Maleic metallic complexes (43) [HC4 H2 O4−] + M n + → M [HC4 H2 O4]n
(Trivedi, 2013) (44) [C4 H2 O42 −] + 2M n + → M2 [C4 H2 O4]n
Malic metallic complexes (45) n [HC4 H4 O5−] + M n + → M [HC4 H4 O5]n
(Horeh et al., 2016; Saidan et al., 2012) (46) n [C4 H4 O52 −] + 2M n + → M2 [C4 H4 O5]n
Oxalic metallic complexes (47) n [HC2 O4−] + M n + → M [HC2 O4]n
(Horeh et al., 2016) (48) n [C2 O42 −] + 2M n + → M2 [C2 O4]n
Succinic metallic complexes (49) n [HC4 H4 O4−] + M n + → M [HC4 H4 O4 ] n
(Cannan and Kibrick, 1938; Raza et al., 2015; Rived et al., 1998) (50) n [C4 H4 O42 −] + 2M n + → M2 [C4 H4 O4 ] n
Tartaric metallic complexes (51) [HC4 H4 O6−] + M n + → M [HC4 H4 O6]n
(Rived et al., 1998; Shellis et al., 2015) (52) [C4 H4 O62 −] + 2M n + → M2 [C4 H4 O6]n
Citric metallic complexes (53) n [H2 C6 H5 O7−] + M n + → M [H2 C6 H5 O7]n
(Horeh et al., 2016) (54) n [HC6 H5 O72 −] + 2M n + → M2 [HC6 H5 O7]n
(55)
n [C6 H5 O73 −] + 3M n + → M3 [C6 H5 O7]n

Fig. 3. Metallic complexes formed by; a) acetic acid b) lactic acid.
acid as reducing agent (Nayaka et al., 2016b). It should be noted that,
albeit iminodiacetic acid is relatively small, this agent can make strong
chelates with transient metals and is considered as an appropriate agent
for metal mobilization (Fig. 5(a)) (Krishnamurthy et al., 1995; Loberg
et al., 1976). According to UV–vis analysis, it was found that ascorbic
acid plays a key role in formation of CoC4H2O4 (λmax = 280 nm) and
CoC4H5NO4 (λmax = 330 nm) (Nayaka et al., 2016b). Based on Table 2,
the pKa values for maleic acid are 1.83 and 6.07, which induce the fact
that the acidolysis of this agent at the first step is relatively high and
make it an effective agent for metal dissolution (Lightner et al., 1996;
Santos et al., 2005; Shields and Seybold, 2013; Yu et al., 2016).
Malic acid is biodegradable under both aerobic and anaerobic
conditions, therefore, its waste solutions can be treated easily. Presence
of two carboxylic functional groups and its desirable solubility in water,
make this acid capable of dissolving metals from spent LIBs (Li et al.,
2010a). Results obtained from leaching of cathode scraps by malic acid
showed that only 54% and 37% of the lithium and cobalt can be re-
covered; however, by addition of H2O2, these recoveries would reach to
more than 99% and 90%, respectively (Li et al., 2013). Fig. 5 illustrates
the metallic complexes that would be formed in presence of iminodia-
cetic, maleic and malic acids, respectively.
In another research, conductivity of the acidic solution as a function
of temperature and acid concentration was related to the hydrogen ion
transfer rate of DL-malic acid (Li et al., 2010a). it was concluded that
increase in temperature leads to higher conductivity of acid re-
presenting higher ion transfer rate of DL-malic acid (Li et al., 2010a).
Golmohammadzadeh et al. (2017) proved that increasing temperature
from 60 °C to 70 °C, the lithium recovery increases, while by further
increase in temperature, the lithium recovery decreases which is at-
tributed to the decomposition of lithium complex at higher tempera-
tures (Fig. 6 (a)). On the other hand, Fig. 6(b) shows that increase in
temperature from 60 °C to 80 °C, the recovery of cobalt increases which
is attributed to the increase in the rate of reaction due to the breakdown
in strong bonds between cobalt and oxygen in the LiCoO2 structure
(Golmohammadzadeh et al., 2017; Shin et al., 2005).
As shown in Eqs. (17) and (18) (Table 2), oxalic acid is highly in-
clined to release hydrogen ions (pKa1 = 1.25), which makes it the most
acidic organic acid among other organic acids (Mulligan et al., 2004). It
is worthwhile mentioning that this agent has a high tendency to pre-
cipitate majority of metals as oxalate including cobalt and nickel
(Saidan et al., 2012). In compliance with the above-mentioned facts,
oxalic acid can act as an effective agent for selective leaching of cathode
materials (Fan et al., 2016; Nishiki et al., 2001; Sohn et al., 2006; Zeng
et al., 2015b). Sohn et al. (2006) studied the effect of oxalic acid as
leaching agent to recover lithium and cobalt from spent LIBs. Results of
XRD analysis showed that the cobalt precipitates as CoC2O4, while most
of lithium is leached in form of lithium oxalate (Fig. 7 (a)) (Sohn et al.,
2006; Sun and Qiu, 2012). Zeng et al. (2015b) dried and cleaned the
CoC2O4 and exposed it to the excess amount of oxalic acid. It was found
that the pink precipitates of CoC2O4 can be transformed to Co(HC2O4)2
according to the following reaction (Zeng et al., 2015b):
H2 C2 O4 + CoC2 O4 ↔ Co (HC2 O4 )2 (56)
Sun and Qiu (2012) confirmed that lithium and aluminum oxalates
are soluble while cobalt oxalate is insoluble. It was also indicated that
the CoC2O4 residue can be useful in cobalt powder and cobalt oxide
production (Ahmed et al., 2008; Majumdar et al., 2008).
Succinic acid with two carboxylic groups is another organic agent
with variety of applications including leaching agent for hydro-
metallurgical processes. Results illustrated that succinic acid can leach
41.98% and 19.72% of the lithium and cobalt, respectively. However,
addition of 4 Vol. % H2O2 as reducing agent leads to extraction of 96%

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Fig. 4. Metallic complexes formed by; a) ascorbic acid b) aspartic acid.

Fig. 5. Metallic complexes formed by; a) Iminodiacetic acid, b) maleic acid, c) malic acid.

and 100% of lithium and cobalt, respectively (Li et al., 2015). Ther-
modynamic calculations indicated that C4H4O4Co and C4H4O4Li2 are
the most stable species in the medium which is in agreement with Eqs.
(49) and (50) and Fig. 7(b) (Table 3) (Li et al., 2015).
Tartaric acid can produces solutions with a lower pH compared to
DL-malic acid, ascorbic acid, L-aspartic acid, and succinic acid (He
et al., 2016). It was investigated that L-tartaric acid is able to leach
99.31%, 99.07%, 98.64%, and 99.31% of manganese, lithium, cobalt,
and nickel, respectively in the presence of 4 Vol.% H2O2, while in the
absence of H2O2 the aforementioned recoveries were about less than
31% (He et al., 2016). Nayaka et al. (2016b) employed a reductive-
complexing mechanism using tartaric and ascorbic acid to dissolve
more than 95% of the LiCoO2 and then precipitating cobalt as cobalt
oxalate. UV–vis results approved formation of cobalt (II) tartrate (λmax
≈ 300 nm) followed by reduction of cobalt (III) tartrate (λmax ≈
512 nm) (Nayaka et al., 2016a). Fig. 7(c) shows cobalt and lithium

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Fig. 6. Effect of temperature on DL-malic acid leaching of (a) lithium; and (b) cobalt (Golmohammadzadeh et al., 2017; Li et al., 2010a).

tartrates based on the complexation reactions of Eqs. (51) and (52) in
Table 3.
Citric acid produced by fermentation process is one of the best
chelating agents and is the only organic acid among the mentioned ones
that dissociates in 3 steps; i.e., one mole of citric acid provides 3 mol of
H+ in the solution (Table 2) (Li et al., 2013). This organic acid can
easily produce metal complexes in acidic media and is a strong che-
lating agent (Kavanagh, 2011; Serjeant and Dempsey, 1979; Tkacz and
Lange, 2004). Based on these properties, several researchers studied the
effect of leaching parameters including acid concentration, S/L, tem-
perature, reaction time, reducing agent and ultrasonic power on re-
covery of lithium and cobalt from spent LIBs (Chen et al., 2015; Fan
et al., 2016; Golmohammadzadeh et al., 2017; Li et al., 2010b; Li et al.,
2014, 2013; McKenzie et al., 1987; Saidan et al., 2012; Tzeferis, 1994;
Zheng et al., 2016). It was also found that the LiCoO2 leaching reaction
mechanism using citric acid includes 3 main steps: (1) diffusion of citric
acid to the surface of LiCoO2; (2) production of lithium and cobalt ci-
trates on the surface of LiCoO2; (3) diffusion of product from solid-
liquid interface to the solution (Zheng et al., 2016). Whereas, several
researchers reported that the reaction of LiCoO2 and citric acid takes
place in 2 steps: (1) reduction of Co(III) to Co(II) in presence of H2O2;
(2) production of lithium and cobalt citrates (Li et al., 2014, 2013).
Most of the researchers reported temperature of 90 °C as the best
temperature for recovery of lithium and cobalt while using citric acid
(Fan et al., 2016; Li et al., 2010b; Li et al., 2013; Zheng et al., 2016). In
order to reduce the negative impacts associated with high temperature
processes, several researchers proposed lower temperatures as the best
temperature for recovery of lithium and cobalt; i.e., 60 °C, 70 °C (Chen
et al., 2015; Golmohammadzadeh et al., 2017; Li et al., 2014). It should
be noted that, the dissociation reaction is an endothermic reaction;

Fig. 7. Metallic complexes formed by; a) oxalic acid, b) succinic acid, c) tartaric acid.

426
R. Golmohammadzadeh et al.
Fig. 8. Metallic complexes formed by citric acid.
hence, increase in temperature to 90 °C leads to better leaching effi-
ciencies of both lithium and cobalt (Li et al., 2010b; Li et al., 2013).
However, Golmohammadzadeh et al. (2017) showed that by increase in
temperature from 60 °C to 80 °C lithium recovery decreases which is
attributed to the decomposition of lithium citrate at higher tempera-
tures due to the weak bonding between lithium and citrate anions. It
was also stated that due to the electron configuration of lithium [2s1], it
forms weaker complexes as compared to cobalt with electron config-
uration of [3d7] [4s2] (Golmohammadzadeh et al., 2017).
The optimum level of acid concentration was found to be 1.25; yet,
some investigators reported citric acid concentration of 0.5 and 2 M as
the optimum level for recovery of LiCoO2 (Chen et al., 2015; Fan et al.,
2016; Golmohammadzadeh et al., 2017; Li et al., 2010b; Li et al., 2014,
2013). It was claimed that leaching of lithium depends on H+ con-
centration in the solution while leaching of cobalt depends on both H+
concentration and type of anion in the selected acid
(Golmohammadzadeh et al., 2017; Li et al., 2014). Besides, various
amounts of S/L are reported; i.e., 15, 20, 25, 30, 50 g L−1 (Chen et al.,
2015; Golmohammadzadeh et al., 2017; Li et al., 2010b; Li et al., 2014,
2013; Zheng et al., 2016). Fig. 8 shows the metallic complexes which
may form in presence of citric acid.
Golmohammadzadeh et al. (2017) compared four organic acids in
terms of their ability to leach lithium and cobalt from cathode materials
including citric, DL-malic, acetic and oxalic acids and reported that the
best sequence of the four acids is citric acid > DL-malic > acetic >
oxalic acid. Based on Table 2 citric and DL-malic acids provide more
H+ compared to acetic acid. Despite the fact that oxalic acid provide
adequate H+ in the solution, it has a high tendency to precipitate
metals as oxalate (Cui and Anderson, 2016; Mulligan et al., 2004;
Santhiya and Ting, 2005; Sohn et al., 2006). Li et al. (2013) compared
citric, malic and aspartic acids and discussed that by using malic and
citric acids, more than 90% of lithium and cobalt can be recovered;
whereas, using aspartic acid, minority of these metals can be recovered,
because of its low acidity. Pant and Dolker (2017) employed citrus fruit
juice which is rich in citric, malic and ascorbic acids to separate alu-
minum and copper plates and to leach lithium, cobalt, manganese and
nickel from spent LIBs. Results showed that the use of citrus fruit leads
to separation of aluminum and copper without using toxic solvents such
as NMP. Besides, presence of Na+, Mg+ and Ca2+ in citrus enhanced
the leaching efficiency of the metals by preventing hydroxide formation
(Pant and Dolker, 2017).
5.3. Effect of reducing agents
Some transition metal oxides need an appropriate reducing agent to
be effectively dissolved (Furlani et al., 2009; Joulié et al., 2017; Nayl
et al., 2011; Trifoni et al., 2000). For example, Mn3+ and Co3+ com-
pounds are insoluble and should be reduced to Mn2+ and Co2+ to be
easily dissolved (Ashtari and Pourghahramani, 2016). Since the che-
mical bond between cobalt and oxygen in LiCoO2 structure is strong,
using reducing agents significantly improves the leaching efficiencies
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Resources, Conservation & Recycling 136 (2018) 418–435
(Meshram et al., 2014; Pinna et al., 2017). Toward that end, several
reducing agents, dividing in two groups of organic and inorganic ones,
have been used in recovery of valuable metals from spent LIBs (Chen
et al., 2015; Lee and Rhee, 2003).
The main mechanism of metal dissolution assisting reducing agents
is reduction of metals to their lower oxidation states (Meshram et al.,
2015b). Based on Eh- pH diagrams, changes in valence state make the
metal species dissolution more feasible (Meshram et al., 2015a;
Pourbaix, 1963). Furthermore, by reducing to a lower valence, the
chemical bond becomes weaker; as a result, the corresponding metal
dissolution becomes easier (Pinna et al., 2017). Table 4 shows the effect
of reducing agents in leaching efficiencies of lithium and cobalt from
spent LIBs.
As shown in Table 4, H2O2 is the most common reducing agent used
in recycling of spent LIBs which can considerably facilitate the leaching
efficiency of lithium and cobalt. The mechanism is engaged with re-
duction of Co (III) in the compounds to Co (II), based on the following
reactions (Golmohammadzadeh et al., 2017):
H2 O2 + 2H+ + 2e− → 2H2 OE° = + 1.78V (57)
Co3 + + e− → Co2 +E° = + 1.8V (58)
However, with excess increase in H2O2 concentration, this agent
may act as an oxidizing agent rather than a reducing agent (based on
the Nernst equation) or may decompose to water and oxygen
(Golmohammadzadeh et al., 2017; Skoog and West, 1982). Since some
of the organic acids can act as ligands and reductants, metals leaching
would be effectively increased by using them (Santhiya and Ting,
2006). Transformation of organic acids to a simpler form (oxidation)
results in reduction of the metals during leaching (Okalebo et al.,
2002). For instance, in the case of using formic acid, metals will be
reduced after the acid is changed into CO2 and other simple compounds
(Cenini and Ragaini, 2013). Ascorbic acid as an organic agent, has been
employed to facilitate the leaching efficiencies of lithium and cobalt
from spent LIBs as discussed in Section 5.2 (Nayaka et al., 2016a,
2016b). Furthermore, there are some environmentally friendly and cost
effective reducing agents such as tea waste (TW) and powders of phy-
tolacca Americana branch (PA), that are able to improve leaching of
spent LIBs (Chen et al., 2015). The mechanisms of metal dissolution in
presence of aforementioned agents are presented as follow (Chen et al.,
2015):
LiCoO2 + H3 C6 H5 O7 + TW → Co3 (C6 H5 O7)2 + Co (HC6 H5 O7)
+ Co (H2 C6 H5 O7)2 + Li3 C6 H5 O7
+ Li2 (HC6 H5 O7) + Li (H2 C6 H5 O7)
+ oxidized derivatives (59)
R. Golmohammadzadeh et al. Resources, Conservation & Recycling 136 (2018) 418–435

Table 4
Recovery of lithium and cobalt in presence and absence of reducing agents.
Leaching agent Reducing agent Amount of reducing Recovery without reducing agent (%) Recovery with reducing agent (%) Reference
agent
Li Co Li Co

Lactic acid H2O2 0.5 Vol.% 59 34 98 99 (Li et al., 2017)

Ascorbic acid Ascorbic acid 1.25 M Nr Nr 98 95 (Li et al., 2012)
Iminodiacetic acid H2O2 0.02 Vol.% Nr Nr 99 91 (Nayaka et al., 2016b)
Maleic acid Nr Nr 100 97
Succinic acid H2O2 4 Vol.% 20 42 100 96 (Li et al., 2015)
L-Aspartic acid H2O2 4 Vol.% 1 1 60 60
DL-Malic acid H2O2 2 Vol.% 54 37 99 93 (Li et al., 2013)
Citric acid H2O2 1 Vol.% 54 25 99 92
DL-malic acid H2O2 2 Vol.% Nr Nr 91 84 (Golmohammadzadeh et al., 2017)
Citric acid H2O2 1.25 Vol.% Nr Nr 92 84
Tartaric acid Ascorbic acid 0.02 M Nr Nr > 95 > 95 (Nayaka et al., 2016a)
L-tartactic acid H2O2 4 Vol.% 31 17 99 99 (He et al., 2016)
Citric acid H2O2 1 Vol.% Nr ∼35 Nr 99 (Zheng et al., 2016)
Citric acid H2O2 0.6 g g−1 61 36 99 98
Citric acid TW 0.4 g g−1 61 36 98 96 (Chen et al., 2015)
Citric acid PA 0.4 g g−1 61 36 96 83
Citric acid H2O2 1 Vol.% 54 25 100 90 (Li et al., 2010b)
Citric acid H2O2 1 Vol.% 50 23 98 90 (Fan et al., 2016)
Citric acid H2O2 0.55 Vol.% Nr Nr 100 96 (Li et al., 2014)
Citric acid H2O2 3 Vol.% Nr Nr 100 100 (Santana et al., 2017)
Citric acid Ascorbic acid 20 mM Nr Nr 100 80 (Nayaka et al., 2015)

Nr: Not reported.

LiCoO2 + H3 C6 H5 O7 + PA → Co3 (C6 H5 O7)2 + Co (HC6 H5 O7) purpose, recognizing the rate controlling steps in metal dissolution is
crucial. There are certain models that can be applied in determining the
+ Co (H2 C6 H5 O7)2 + Li3 C6 H5 O7
leaching rate, among which, the shrinking core model (SCM) is the most
+ Li2 (HC6 H5 O7) + Li (H2 C6 H5 O7) applied one (Xin et al., 2013). Three simultaneous steps are involved in
+ oxidized derivatives (60) this model, including: 1) diffusion of the leaching agent through the
liquid film surrounding the particles, 2) reaction of the leaching agent
and the cathode materials (formation of solid products), and 3) diffu-
5.4. Effect of ultrasonic agitation on leaching of spent LIBs
sion of mobilized metal ions through solid product (Levenspiel, 1999).
Considering the aforementioned steps, three steps of diffusion through
Ultrasonic agitation is currently used in sludge treatment, removing
liquid film, chemical reaction and diffusion through solid products can
of heavy metals from soil, and metal extraction from ore and wastes and
be considered as the rate affecting mechanisms and the slowest step is
WEEE (Chemat et al., 2017; Li et al., 2010c; Mason et al., 2004). Due to
the rate controlling step (Levenspiel, 1999).
the faster and more effectual metal recovery, and feasibility in use,
The rate controlling mechanism is determined by examining the
ultrasound is commonly used in hydrometallurgical processes instead of
equation of recovery versus time for each mechanism. The equation
conventional stirring approaches (Brothers et al., 2005; Öncel et al.,
with a better correlation coefficient would be considered as the con-
2005; Priego-Capote and Luque De Castro, 2004; Xiao et al., 2018). The
trolling mechanism (Golmohammadzadeh et al., 2017; Levenspiel,
main mechanism of ultrasonic is formation of cavitation bubbles at low
1999). In some cases, leaching may not follow the same trend or not
pressures (Marafi and Stanislaus, 2011; Tyagi et al., 2013; Zhu et al.,
governed by a single mechanism. Therefore, other models, such as
2012). When pressure increases, the vapor cavities implode and gen-
Avrami, would be applicable (Aarabi-Karasgani et al., 2010; Li et al.,
erate a large amount of energy leading to creation of micro cracks at the
2018a, 2017). It is worth mentioning that the conventional method for
surface of the particles, which accelerates diffusion of the leaching
kinetic studies used by most researchers requires lots of calculations
agent into the solid phase (Öncel et al., 2005; Zhang et al., 2008).
and is also incapable of identifying the mixed controlling mechanisms
Furthermore, the ultrasonic waves lead generation of active radicals
(Jha et al., 2013; Takacova et al., 2016). For this purpose, the method
which promote the reactivity of the reagents and decrease the acid
proposed by (Nazemi et al., 2011) for determining the rate controlling
consumption (Yu et al., 2014; Zhu et al., 2012).
step (multi-linear regression analysis, using the least square technique)
Li et al. (2012) separated aluminum foils and cathode active ma-
has been employed (Golmohammadzadeh et al., 2017). In this method,
terials efficiently by means of ultrasonic waves (frequency of 40 Hz,
it was found that the rate of leaching of lithium and cobalt using citric
power of 100 W) and NMP in 20 min. Recently, effect of ultrasonic
acid is controlled by diffusion of the leaching agent through the product
agitation is compared to mechanical stirring method
layer; while, in case of cobalt, at lower temperatures (< 45 °C) chemical
(Golmohammadzadeh et al., 2017). As shown in Fig. 9, ultrasonic
reaction is the rate controlling step (Golmohammadzadeh et al., 2017).
agitation is more efficient than mechanical stirring which might be due
Since dissociation reaction of organic acids is endothermic and heat
to the better diffusion of leaching agent into the surface of LiCoO2 ac-
accelerates the reaction, temperature has a great influence on the
celerating the chelate formation process. In another research, effect of
leaching rate of metals from spent LIBs using organic acid (He et al.,
ultrasonic power (60 W, 90 W, 120 W) on recovery of lithium and co-
2016; Sun et al., 2018). Effect of temperature on the leaching rate can
balt from spent LIBs using citric acid was studied (Fig. 9) (Li et al.,
be investigated by fitting the experimental data to the Arrhenius
2014).
equation which results in determining the apparent activation energy of
metals dissolution and a proper indication of rate controlling step (Li
5.5. Kinetics study
et al., 2018a; Meng et al., 2018). If the apparent activation energy is
greater than a certain value (ca. 42 kJ.mol−1), the leaching is governed
In order to enhance the efficiency of the leaching operation, it is
by the chemical reaction (Li et al., 2017).
vital to facilitate the metal dissolution (Rosenqvist, 1972). For this

428
R. Golmohammadzadeh et al. Resources, Conservation & Recycling 136 (2018) 418–435

Fig. 9. Effect of ultrasonic power and mechanical stirring on recovery of (a) lithium; and (b) cobalt (Golmohammadzadeh et al., 2017; Li et al., 2014).

So far, many studies have been conducted to determine the rate glucose is an affordable reducing agent that can be employed to leach
controlling step in leaching of spent LIBs by organic acids. Li et al. ca. 100% of metals from spent LIBs using sulfuric acid, regarding to the
(2015) suggested that leaching of lithium and cobalt using succinic acid following equation (Granata et al., 2012):
in the first 10 min. of the process is controlled by chemical reaction,
while diffusion through the ash layer is rate controlling at longer times. 24LiCoO2 + 36H2 SO4 + C6 H12 O6 → 24CoSO4 + 12Li2 SO4 + 6CO2
Table 5 summarizes the rate controlling mechanisms and calculation of + 42H2 O (61)
the activation energy related to leaching by acetic, lactic, maleic, malic,
Same reaction can occur in the case of carboxylic acids which act as
oxalic, tartaric and citric acids as leaching agents.
reducing agents in presence of inorganic acids; i.e., glucose is replaced
Particles may not follow identical processes during the leaching
by the organic acid and the stoichiometry is balanced (Sayilgan et al.,
process when organic acids and reducing agents are employed si-
2010).
multaneously. In some researches, (SEM) analysis showed that when
Other reducing agents that are recommended to be employed are
using tartaric acid as the leaching agent (30 min., 2 mol L−1, 17 g L−1,
glucose (Pagnanelli et al., 2014), sucrose (Beolchini et al., 2001), lac-
70 °C, 4% H2O2), the average particle size of the LIBs decreases from 7
tose (Veglio et al., 2000), alcohol (Trifoni et al., 2001), phenol type
to 45 μm to 2-22 μm. Results obtained from analysis of the residue
aromatics (Zhang et al., 2001), citric acid and oxalic acid that are
showed that the remaining residue is mainly PVDF (Li et al., 2015). Li
classified as organic reducing agents (Sahoo et al., 2001; Sayilgan et al.,
et al. (2018b) employed SEM, UV and FTIR analyses to prove that
2010).
particles break after shrinkage in the first 3 min. of the leaching process
In case of inorganic reducing agents, sodium borohydride is a strong
(by either maleic or acetic in presence of H2O2); which suggests the
inorganic reductant that can be utilized in metal dissolution from spent
SCM model would be applicable after 5 min. Moreover,
LIBs (Behnamfard et al., 2013). Pyrite, sodium sulfite (Kanungo and
(Golmohammadzadeh et al., 2017) reported that the particle size re-
Jena, 1988), sodium bisulfite (Meshram et al., 2015b), carbon, am-
mains unchanged if agitation is applied by means of ultrasound.
monium thiosulfate and ammonium sulfite (Niinae et al., 1996) are
some of the other reductants in this category. There are also un-
conventional but effective and low cost reducing agents that can be
6. Future prospective of green processes for recycling of spent
utilized in recycling of spent LIBs; i.e., cornstalk (Cheng et al., 2009),
LIBs
sawdust (Hariprasad et al., 2007), molasses (Su et al., 2008), and
corncob (Tian et al., 2010). Knowing the fact that all the mentioned
As LIBs market demands increases, the number of factories pro-
agents have effectively dissolved metals (Mn, Li, Co and Ni) from dif-
duced also rises to satisfy this demand, thus, the amount of spent LIBs
ferent resources, evaluation of their application in case of metals re-
generated is likewise expected to increase. As a result, spent LIBs are
cycling from spent LIBs is recommended.
becoming increasingly a key source for recycling of lithium and cobalt.
To promote sustainable recycling system, bio-hydrometallurgy
Therefore, echo friendly and efficient processes should be inevitably
which employs microorganisms to dissolve metals, as an inexpensive,
developed in near future due to the environmental regulations and lack
echo friendly and promising method is becoming much more important
of virgin raw materials. As reviewed in this paper, organic acids are
(Cui and Anderson, 2016; Jadhav and Hocheng, 2012; Jagannath et al.,
playing a key role in recovery of lithium and cobalt from spent LIBs as
2017; Kumari et al., 2016; Mirazimi et al., 2015; Noei et al., 2017).
environmentally friendly and effective leaching agents. So far, the or-
Acidithiobacillus ferrooxidans (A. ferrooxidans) and Thiobacillus fer-
ganic acids that have been already used in previous researches are re-
rooxidans (T. ferrooxidans) are the bacteria capable of dissolving metals
viewed in this paper. However, there are some other organic acids as
by simultaneous transforming of Fe (II) to Fe (III) (indirect leaching)
potential candidates for recycling of spent LIBs; i.e., organic acids such
and sulfuric acid generating (direct leaching) which is provided from
as formic acid, propionic acid, butyric acid, glycolic acid, gallic acid,
sulfur in medium (Zeng et al., 2014). The role of bacteria in direct and
gluconic acid, etc. Besides, improvement in kinetics of leaching is de-
indirect metal dissolutions are as follows (Parmar and Singh, 2013):
sirable in industrial scale recycling of spent LIBs. Nevertheless, leaching
kinetics using organic agents has been merely explored. Hence, com- Bacteria
2Fe 2 + (aq) + 0.5O2 + 2H+ (aq) ⎯⎯⎯⎯⎯⎯⎯⎯→ Fe3 + (aq) + H2 O (62)
prehensive study on recycling of spent LIBs using aforementioned or-
ganic acids and much more kinetics investigations is still required. Bacteria
S o (s ) + 1.5O2 (g ) + H2 O ⎯⎯⎯⎯⎯⎯⎯⎯→ H2 SO4 (63)
In order to enhance cobalt recovery by conversion of Co (III) to Co
(II), the use of reducing agents is undeniable. Despite that, effect of Effect of parameters such as Fe (II), elemental sulfur, pyrite (FeS2),
several efficient reducing agents except those mentioned in this paper, initial pH, and S/L has been studied and results showed that using
on recycling of spent LIBs has been purely considered. For instance, Acidithiobacillus ferrooxidans, 65% cobalt and 10% lithium can be

429
R. Golmohammadzadeh et al. Resources, Conservation & Recycling 136 (2018) 418–435

extracted. However, by using mixed culture (acidophilic sulfur-oxi-

(Golmohammadzadeh et al., 2017)

dizing and iron-oxidizing bacteria), 90% of cobalt and 80% of lithium
can be extracted (Mishra et al., 2008; Xin et al., 2009).
Considering the fact that the bacteria is better fitted with either
sulfur or iron containing mediums, fungi is an appropriate alternative in

(Zheng et al., 2016)

(Zeng et al., 2015b)
(Meng et al., 2018)
(Gao et al., 2018)
this field (Bosecker, 1997). The main superiorities of fungi over bacteria

(Sun et al., 2018)

(Li et al., 2018b)

(Li et al., 2018b)

(Li et al., 2018a)

(He et al., 2016)
(Li et al., 2017)

(Li et al., 2015)

are ability to produce organic acids, activity in a wider range of pH (1.5
to 9.8), faster leaching rates, selectivity in leaching, and economical
benefits (Pant et al., 2012; Santhiya and Ting, 2005; Wu and Ting,
Ref.

2006; Xu et al., 2014). The main mechanism in fungal bioleaching is

transformation of carbon resources to organic acids and mobilization of
11.40 (second step)

58.94 (second step)

metals by acidolysis and complexolysis in which the former one is de-
Apparent activation energy (kJ.mol−1)

25.47 (first step)

58.18 (first step) tachment of metals from the surface by hydrogen ions; the latter one is
stabilization of metal ions by chelate formation (Amiri et al., 2012;
Saidan et al., 2012). Aspergillus niger (A. niger) and Penicillium simpli-
54.22
41.20

62.83

30.40

86.57
45.72
Co

Nr

Nr

Nr
Nr

Nr

Nr
cissimum (P. simplicissimum) are the most common fungi which produce
citric, oxalic, gluconic and malic acids (Calgaro et al., 2015; Horeh
53.86 (second step)

et al., 2016; Kavanagh, 2011; Tkacz and Lange, 2004).

54.03 (first step)

In case of Aspergillus niger effect of different pulp densities, sucrose

concentration, initial pH and inoculum size, and bioleaching approach
including one step (adding samples in the first day of incubation), two
52.04
41.33

62.81

21.30

66.86
Nr

Nr

Nr

Nr
Nr

Nr

step (adding samples after sudden drop in pH, usually 3rd day) and
Li

spent medium (adding samples to fungous free medium after 14 days of

Reaction control (both metals, 15-30 min,
Mixed control (both metals, 60-180 min)

Mixed control (both metals, 20-40 min)

fungal activation and acid production) on recycling of spent LIBs is

Ash diffusion (both metals, 15-30 min)

Chemical reaction (both metals, 5 h)

surveyed (Bahaloo-Horeh and Mousavi, 2017; Horeh et al., 2016). It

was found that due to the toxicity of the containing metals, the spent
medium approach (which had greater concentrations of organic acid)
resulted in the best recoveries (Horeh et al., 2016).
While in several researches on the effect of Aspergillus niger on LIBs
recycling, it has been stated that low rate of reaction which leads to
longer time of leaching and hardships associated with sterilization and
Second step

adaptation steps, limits their application (Giaveno and Donati, 2001;

Jadhav and Hocheng, 2012). Despite the fact that, exploring the rate
slow)
Nr
Nr
Nr
Nr
Nr

Nr

Nr

Nr

Nr

controlling mechanism is crucial in enhancing the rate of reaction, no

kinetic study is conducted in this field. Thus, kinetic studies using Pe-
Reaction control (both metals, ∼15 min,

Chemical reaction (both metals, 60 min)

Reaction control (both metals, 120 min)

Reaction control (both metals, 30 min)

Reaction control (both metals, 10 min)

Reaction control (both metals, 60 min)

Reaction control (both metals, 30 min)

Reaction control (both metals, 10 min)

nicillium simplicissimum, is extremely recommended to solve issues re-

Ash diffusion (Li), Chemical reaction
Ash diffusion (both metals, 120 min)

Chemical reaction (both metals, 5 h)

Ash diffusion (both metals, 60 min)

Ash diffusion (both metals, 60 min)

lated to fungal bioleaching.

Controlling mechanisms and calculation of activation energy related to the leaching processes.

Ash diffusion (both metals, 5 h)

7. Conclusions
Controlling mechanism

Due to the inevitable rise in worldwide population and in-

dustrialization, waste management has become aggravated. For this
purpose, recycling processes have become a priority for nations seeking
First step

to secure a sustainable resource management and preserve environ-

ment. Thus, in this study we reviewed the recent improvements and
fast)

(Co)

future prospects for recycling of LIBs using organic agents. According to

the information provided by this study, following conclusions are made:
2 M, 30 g L−1, > 45 °C, 1.25 % H2O2, ultrasound

2 M, 30 g L−1, < 45 °C, 1.25 % H2O2, ultrasound

1 Landfilling, stabilization, and incineration of the spent LIBs can

1.25 M, 0.1 g in.150 mL, 70 °C, 8 v, Pt anode

contaminate soil and underground water due to the solubility of

metals in water, therefore, it is highly worth recovering these ele-
ments from spent LIBs in terms of environmental conservation,
1.5 M, 20 g L−1, 70 °C, 0.5 % H2O2

1.2 M, 40 g L−1, 80 °C, 1.5 % H2O2

0.5 M, 2 g L−1, 90 °C, 1.5 % H2O2

3.5 M, 40 g L−1, 60 °C, 4 % H2O2

1.5 M, 15 g L−1, 70 °C, 4 % H2O2

0.6 M, 15 g L−1, 90 °C, 1 % H2O2

health care, and resource recovery.

1 M, 20 g L−1, 70 °C, 2 % H2O2
2 M, 20 g L−1, 70 °C, 3 % H2O2

2 M, 17 g L−1, 70 °C, 4 % H2O2

2 Hydrometallurgy is an exploitable technology in comparison with

pyro metallurgy and bio-hydrometallurgy which is applicable for
3.5 M, 40 g L , 60 °C

2.5 M, 15 g L−1, 95 °C

recovery of valuable metals from spent LIBs. Use of inorganic

leaching agents have several environmental downsides. Despite the
−1

fact that organic acids are weaker than inorganic ones, they are
considered as strong chelating agents with less risk of environmental
Condition

agitation

agitation

impacts; i.e., invulnerable atmosphere for operators, lack of sec-

ondary pollution, hindering from corrosion of the equipment, se-
Nr: Not reported.

lective leaching of the metals and etc.

Succinic acid
Tartaric acid
Maleic acid

Oxalic acid
Acetic acid

3 Due to the strong bond between cobalt and oxygen in LiCoO2

Lactic acid

Malic acid

Citric acid
Acid type

structure, using reducing agents such as ascorbic acid, H2O2, TW,

Table 5

and PA insures much better leaching efficiencies. The main me-

chanism of metal dissolution assisting reducing agents is known to

430
R. Golmohammadzadeh et al.
be reduction of metals to their lower oxidation states which strongly
improves metal dissolution. In this case, reduction of Co (III) to Co
(II) plays a key role.
4 Even though, the acidity of oxalic acid is high, it has a high tendency
to precipitate cobalt as oxalate. With respect to aforementioned fact,
oxalic acid is an appropriate agent for selective leaching of cathode
materials.
5 Leaching of lithium depends on presence of H+ in the leaching so-
lution; while, leaching of cobalt depends on both H+ concentration
and type of anion in the selected acid. Thus, the organic acid using
for leaching experiments plays a key role in leaching of cobalt.
6 Using conventional method, the rate controlling step in the leaching
of lithium and cobalt from spent LIBs using organic acids was found
to be chemical reaction. Whereas, using multi-linear regression
analysis using the least square technique suggested that rate of li-
thium and cobalt leaching using citric acid is controlled by diffusion
of the leaching agent through the product layer, while at lower
temperatures (< 45 °C) chemical reaction is rate controlling in case
of cobalt.
7 Agreeable transitivity in water, better metal extraction, and feasi-
bility in use, hassled to widespread use of ultrasound agitation in
hydrometallurgical processes. In the matter of aforementioned issue,
ultrasonic agitation can facilitates both pretreatments and leaching
steps.
8 To promote a trustful technology applicable for recovery of valuable
metals from spent LIBs, effect of other organic acids such as formic,
propionic, butyric, glycolic, gallic, and gluconic acids is re-
commended to be investigated.
9 In case of metals recycling from spent LIBs, other reducing agents
are recommended to be employed including glucose, sucrose, lac-
tose, alcohol, phenol type aromatics, citric acid, oxalic acid, sodium
borohydride, pyrite, sodium sulfite, sodium bisulfite, carbon, am-
monium thiosulfate, ammonium sulfite, cornstalk, sawdust, mo-
lasses, and corncob.
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