Journal of Cleaner Production 228 (2019) 801e813

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Journal of Cleaner Production

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

Review

Recycling of spent lithium-ion batteries in view of lithium recovery: A

critical review
Chunwei Liu a, Jiao Lin a, b, Hongbin Cao a, Yi Zhang a, Zhi Sun a, *
a
Beijing Engineering Research Center of Process Pollution Control and National Engineering Laboratory for Hydrometallurgical Cleaner Production
Technology, Division of Environment Technology and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, China
b
School of Materials Science & Engineering, Beijing Institute of Technology, Beijing, 100081, China

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

Article history: Due to the rapid expanding of plug-in hybrid electric vehicles (PHEVs), hybrid electric vehicles (HEVs)
Received 11 February 2019 and electric vehicles (EVs), the projectfed demand for lithium-ion batteries (LIBs) is huge and might
Received in revised form result in supply risks for natural lithium-containing reserves. After the service life, spent LIBs continu-
23 April 2019
ously accumulate in the market, and they are excellent secondary resources for lithium recovery. To
Accepted 23 April 2019
Available online 24 April 2019
alleviate resource shortage and to decrease potential environmental pollution caused by improper solid
waste disposal, recycling of spent LIBs is motivated world widely in recent years. Previous studies have
usually focused on the recovery of cobalt and nickel, which create high economic benefit. Recovery of
Keywords:
Recycling
lithium, however, has not been highlighted. In this article, state-of-the-art on spent LIBs recycling is
Spent lithium-ion batteries discussed with emphasis on lithium recovery. In addition to understanding underlying mechanisms and
Review physiochemistry features of various recycling methods, the possibility for industrial realization of each
Lithium recovery method is also evaluated. The complex processing steps limit the industrial implementation of
hydrometallurgy-dominant methods, which usually reclaim lithium in the last step, resulting in a poor
recovery efficiency of lithium. The pyrometallurgy-dominant approach is readily to scale up but lithium
is lost in the slag phase. Therefore, the mild recycling (cleaner production) methods are recommended
for future study since they take advantages of traditional pyrometallurgy and hydrometallurgy, and could
decrease treatment temperature as well as acid/alkaline usage.
© 2019 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 802
2. Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 802
2.1. Criteria for selection of relevant literature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 802
2.2. Extraction of useful information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 803
2.3. Categorization of recycling methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 803
3. Construction of lithium-ion batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 803
4. State-of-the-art for spent LIBs valorization in view of lithium recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 803
4.1. Hydrometallurgy-dominant process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 805
4.2. Pyrometallurgy-dominant process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 806
4.3. Mild recycling methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807
4.4. Comparison of different methods with respect to recycling lithium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 809
5. Current industrial recycling process in view of lithium recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 809
6. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 810
Declarations of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811

* Corresponding author. National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology Institute of Process Engineering, Chinese Academy of
Sciences, No. 1 Beierjie, Zhongguancun, Beijing, China.
E-mail address: sunzhi@ipe.ac.cn (Z. Sun).

https://doi.org/10.1016/j.jclepro.2019.04.304
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
802 C. Liu et al. / Journal of Cleaner Production 228 (2019) 801e813

Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811

1. Introduction 2017). Thereby, the spent LIBs can be considered as a huge reser-
voir of lithium. In recent years, recycling of spent LIBs has been
Since the 1990s, lithium batteries have widely been used in investigated more frequently with an emphasis on the extraction of
portable electronic instruments and more importantly, the lithium- cobalt, which is a high value-added metal (Bertuol et al., 2016;
ion batteries (LIBs) are used to power the next generation of electric Dorella and Mansur, 2007; Golmohammadzadeh et al., 2017; Kim
vehicles (EVs) with the aim to be environmentally friendly (Dunn et al., 2004; Li et al., 2016; Li et al., 2010; Nayaka et al., 2016b;
et al., 2012). It is estimated that the penetration of plug-in hybrid Paulino et al., 2008; Santos et al., 2012; Wang et al., 2017a; Zheng
electric vehicles (PHEVs), hybrid electric vehicles (HEVs) and EVs et al., 2016). In a typical hydrometallurgical approach, cobalt is
into the vehicle market will be at 20% in 2020, resulting in as much recuperated in priority by leaching and precipitation, but the
as a threefold increase of production for the cathode material (Grey lithium usually left in the leaching solution, associated with various
and Tarascon, 2016; Resea, 2009; Swain, 2016). Therefore, the impurities introduced in the previous steps. Current pyro-
consumption of lithium is predicted to continuously increase (Sun metallurgical methods aim to recycle cobalt and nickel but
et al., 2017). Meanwhile, end-of-life LIBs will accumulate, and lithium is lost in the slag. By reviewing the previous studies on
recycling of spent LIBs is a major technological challenge in the near recycling of spent LIBs, it is found that nearly no articles focus on
future. Improper disposal of LIBs triggers threats to the environ- selective recycling of lithium from spent LIBs. For the sustainable
ment and human health because they contain a high percentage of management of natural lithium resources, achieving cleaner pro-
heavy metals and toxic electrolyte (Dorella and Mansur, 2007). The duction as well as closing the loop for a circular economy, it is of
deposited lithium on the anode generated during each subsequent great significance to emphasize and develop revolutionary recy-
discharge-recharge cycle can react with water intensively, resulting cling process to reclaim lithium. The incentive of work is to un-
in a potential threat. derstand the process fundamentals and physiochemistry features
Lithium, viewed as a rare element (Sun et al., 2016), is an of lithium-containing compounds in various recycling approaches.
essential element for various LIBs due to its low density (0.534 g/ An overview of previous studies on recycling LIBs, including lab-
cm3) and high electrochemical potential (
3.04 V versus standard scale investigations and industrial practice, is provided in light of
hydrogen electrode) (Shriver and Atkins, 2009). As shown in Fig. 1, lithium recovery. This article also offers insight toward the devel-
since 2016, batteries, ceramics/glass, and lubricating greases are the opment of techno-economically feasible, environment-friendly and
major end-use markets for lithium, among which batteries repre- sustainable solutions to recycle spent LIBs, especially for lithium.
sent the largest market value of lithium. It is projected that the
requirement of lithium carbonate will increase from 265,000 tons 2. Method
in 2015 to 498,000 tons in 2025 (Choubey et al., 2017). Hence,
lithium is forecast to witness a supply shortage in the commodity With the aim to identify the current state of academic insight
market after 2023 (Choubey et al., 2016; Sonoc et al., 2015). The with regards to recycling of lithium from spent LIBs, the literature
huge gap between market supplies against demand leads to a reviewed in this article were selected through three steps: (i)
continuous increase in the price of lithium carbonate. To avoid the searching the relevant literature by setting criteria in databases for
supply risk and to decrease the production cost, it is indispensable identifying the pieces of target literature; (ii) extracting the useful
to push metallurgical recovery of lithium from all possible information of the selected literature by listing a set of questions;
resources. (iii) categorizing the literature by the differences of major separa-
The concentration of lithium in spent LIBs (5e7 wt%) is far tion steps used in the recycling methods. These steps are described
higher than in the natural resource (Kitajou et al., 2005; Swain, below.

2.1. Criteria for selection of relevant literature

We searched for literature in the Google Scholar, Scopus, and

Science Direct databases in November and December of 2018, using
the following criteria and boundaries: (“spent lithium ion batte-
ries” OR “spent LIBs” OR “used lithium ion batteries” OR “used LIBs”
OR “end-of-life lithium ion batteries” OR “end-of-life LIBs”) AND
(recycling OR reuse OR recovery OR regeneration) since the year of
1980. Filters for document type have been set to “articles”, “review”
and “patents”. As a next step, articles have been considered for
review that have the record of at least 80 times citations published
between 1980 and 1990 or have the record of at least 50 times ci-
tations published between 1990 and 2000. Subsequently, the arti-
cles obtained from the original search were screened manually by
reading the abstract. We excluded studies that (i) did not focus on
reasons and mechanisms for the extraction of valuable metals; (ii)
lithium recovery were not considered, and (iii) solely reuse and
Fig. 1. Estimated global market shares for lithium in its major applications. Data from regeneration were investigated (recovery and recycling were not
the U.S. Geological Survey. studied). To include as more relevant literature as possible, the
 C. Liu et al. / Journal of Cleaner Production 228 (2019) 801e813
literature was further expanded by reading the references of the
articles encountered when reviewing other studies. In addition, to
deliver an overview of the industrial recycling processes, the
company websites were scanned.
2.2. Extraction of useful information
The useful information of the selected literature were extraction
by listing a set of questions.
What problem dose the article aim to solve?
What methods are used?
What apparatus are used (developed)?
Are strong acidic and alkaline solution used?
Is high temperature used?
What are the major secondary pollution?
Are the secondary pollution reduced, prevented or treated?
Are the environmental impact studied?
Are the proposed methods sustainable?
Which metals are recovered?
Are the recovered metals mixed or separated?
Which step does the elemental separation take place?
How the lithium is recovered?
What is the reason/mechanism for the separation of these
metals?
What is the energy consumption in the recycling method?
Does the study identify challenges for future research?
2.3. Categorization of recycling methods
To categorize the research that have been performed to recy-
cling spent LIBs, the recycling methods were summarized as three
sub-categories. The categorization is based on the difference of key
processing steps which control elemental separation, as well as the
development trends.
Hydrometallurgy-dominant methods. The separation of
valuable metals are facilitated by leaching, precipitation and sol-
vent extraction in the solution system, which is typically composed
by acid/alkali/organics.
Pyrometallurgy-dominant methods. High temperature is used
to enhance the physicochemical transformation to separate valu-
able metals. This type of research usually carried out at temperature
higher than 1400  C.
Mild recycling methods. The advantages of hydrometallurgy-
dominant and pyrometallurgy-dominant methods are integrated:
the use of acid/alkali/organics are reduced or even avoided; the
high temperature are lowered. This type of research may include
Fig. 2. (a) Schematic drawing showing the shape and components of cylindrical LIBs; (b) Schematic representation and operating principles of Li-ion batteries during discharging;
Adapted from the reference of J. M. Tarascon (Grey and Tarascon, 2016; Tarascon and Armand, 2001).
803
pioneered and conceptual studies to guide the future efforts to
drive the development.
3. Construction of lithium-ion batteries
A LIB is composed of a cathode, an anode, an organic electrolyte
and a separator (Lain, 2001). Taking a cylindrical LIB as an example,
Fig. 2 (a) shows the schematic drawing representing its shape and
components (Tarascon and Armand, 2001). A typical housing of the
battery is iron or aluminum can body (Wakihara, 2001). An anode is
usually a copper foil coated with a mixture of graphite, a conductor,
binder, and electrolyte. The binder is usually made of poly-
vinylidene fluoride (PVDF) and the electrolyte is a solution of
lithium-containing salt (such as LiPF6, LiClO4) dissolved in an
organic solvent (such as ethylene carbonate, dimethyl carbonate).
Similarly, the cathode is an aluminum foil coated with cathode
materials, a conductor, a PVDF binder and fluoride salt (Zhang et al.,
2014a). In order to prevent a short circuit between two electrodes, a
separator is placed between the anode and cathode as a barrier.
Goodenough et al. (Amos et al., 2016; Goodenough and Kim,
2010; Goodenough and Park, 2013; Mizushima et al., 1980;
Thackeray et al., 1983; Yuan et al., 2011) have developed cathode
materials such as LixMO2 (where M is Co, Ni or Mn) and LiFePO4,
whose families of compounds are still used almost exclusively in
today's LIBs. Generally, the LIBs are named after the cathode ma-
terial, i.e. LCO (lithium cobalt oxide), NCM (lithium nickel manga-
nese cobalt oxide), NCA (lithium nickel cobalt aluminum oxide), LFP
(lithium iron phosphate), to name but a few. Fig. 2 (b) shows the
schematic representation of a lithium-ion battery during dis-
charging. Liþ migrates from negative to positive electrodes, while
the current in the outside circuit is in an adverse direction.
The success of lithium-ion technology depends largely on its
excellent properties such as the cost, safety, cycle life, energy, and
power. The major lithium-containing components of most
frequently used LIBs are listed in Table 1. Each system has its own
characteristics, determining its application areas. Cathode mate-
rials play a vital role in controlling batteries properties.
4. State-of-the-art for spent LIBs valorization in view of
lithium recycling
Valorization of spent LIBs mainly includes recovery, repair, and
regeneration. Fig. 3 presents a summary of conventional paths for
the recovery of spent LIBs. Prior to processing, the spent LIBs have
to be discharged to prevent short-circuiting and self-ignition,
consequently to avoid an explosion (Nie et al., 2015). To discharge
804 C. Liu et al. / Journal of Cleaner Production 228 (2019) 801e813

Table 1
Major components of common LIBs and their features.

Component Material Weight percent of Properties Ref.

Li in the component

Cathode LiCoO2 7.09 Easy preparation, good capacity, and satisfactory stability; more (Belov and Yang, 2008a,b; Doh et al.,
expansive than others. 2008; Fergus, 2010; Wakihara, 2001)
LiMn2O4 3.84 Easy preparation, safe, ecological, cheap and long life; lower (Fergus, 2010; Molenda et al., 2007;
capacity than LiCoO2. Thackeray, 1999; Thackeray et al.,
1987; Wakihara, 2001)
LiNiO2 7.11 Cheaper, higher energy density (15% higher by volume, 20% (Fergus, 2010; Rougier et al., 1996;
higher by weight); less stable than LiCoO2. Wakihara, 2001; Yamada et al., 2001)
a
LiNiCoMnO2 ~7.20 Cheap, stable, high capacity, stable (higher Ni content allows for (Bak et al., 2014; Nitta et al., 2015; Yoon
LiNiCoAlO2 higher Li extraction without structure deterioration); et al., 2012)
LiFePO4 4.40 Cheap, stable, ecological; low capacity and low Li-ion diffusion. (Amin and Maier, 2008; Biendicho and
West, 2011; Wakihara, 2001)
Electrolyte Lithium salt High ionic conductivity, good electrochemical stability (Nishi, 2001; Scrosati and Garche, 2010;
(LiPF6, Li[PF3(C2F5)3]) Xu, 2004)
a
Varies depending on the specific composition of NCM and NCA.

Fig. 3. Conventional flow sheet of spent LIBs treatment processes.

the spent LIBs, salt-saturated solutions such as NaCl and Na2SO4 are
commonly used (Nie et al., 2015). Once the electrolyte contacts the
salt solution, highly corrosive HF will be generated through reac-
tion 1. In addition to the release of HF, lithium incorporated in the
electrolyte is lost in the solution, which is a waste of lithium.
LiPF6 þ H2 O/LiF þ POF3 þ 2HF[
Recycling of electrolyte is limited by the high recycling costs.
Organic solvents extraction is an effective method to recover
electrolytes from spent LIBs at the expense of introducing solvent
impurities and subsequently hindering the purification operations
(Bankole et al., 2013; Contestabile et al., 2001). Extraction with
supercritical carbon dioxide has been confirmed as a promising
method because it can decrease the solvent impurities and appears
to be more moderate to heat sensitive LiPF6 (DeSimone, 2002;
Grützke et al., 2014; Liu et al., 2014). By using supercritical carbon
dioxide, it is possible to reuse the electrolytes since the electrolytes
do not differ significantly in this approach (Bankole et al., 2013;
Contestabile et al., 2001; Liu et al., 2017).
To improve the recycling efficiency of valuable metals in
subsequent steps, it is suggested to apply a preliminary treatment
before further processing. The pretreatment technology mainly
includes mechanical separation (Pagnanelli et al., 2017; Shin et al.,
2005; Vanitha and Balasubramanian, 2013), thermal process
(Granata et al., 2012a; Hanisch et al., 2015; Paulino et al., 2008; Sun
and Qiu, 2011), dissolution process (He et al., 2015; Li et al., 2009,
2010; Song et al., 2014) and mechanochemical methods (Guan
(1)
et al., 2016; Tan and Li, 2015; Wang et al., 2016c, 2017).
Since the cathode materials are covered/encapsulated by plastic
or iron shell, it is required to dismantle the battery using me-
chanical separation. The mechanical separation is usually done
either by crushing or shredding until acceptable size fractions are
obtained (Georgi-Maschler et al., 2012). Valuable components of
the cells are released after dry or wet crushing (Zhang et al., 2013).
Separation of the fragments can be accomplished by using sorting
and sieving steps, where magnetic separation and air separation
methods can be employed. Due to the significant physical differ-
ence of Cu, Al and anode, they can be easily recuperated through
pretreatment. The separation of anode materials can be achieved
easily by struck owing to the low bonding force between copper foil
and graphite caused by their different malleable property
 C. Liu et al. / Journal of Cleaner Production 228 (2019) 801e813
(Shuguang et al., 2011; Zhang et al., 2014a, 2014b). A technical
challenge in the mechanical separation process is to remove par-
ticulate coating from the current collector foils. A more intensive,
second milling and screening step then can be applied to remove
the coating. But the impurities such as the Al foils may contaminate
the active battery materials after the further milling and screening
(Chagnes and Pospiech, 2013). Alternatively, to separate cathode
materials from Al foil and the organic binder, a thermal process is
commonly used due to its simple and convenient operation. By
heating the samples at 150e500  C for 1 h, organic binders can be
eliminated via decomposition (Zeng et al., 2014). However, the
decomposition releases hazardous gases such as HF, which needs a
further cleaning system. Because of the disadvantage of the thermal
process, an alternative method to peel off binders using organic
reagents was investigated. N-Methylpyrrolidine, g-Butyrolactone,
dimethylformamide, and dimethyl sulfoxide like toxic solvents are
commonly used to dissolve the binders (Song et al., 2014). Recently,
citrus fruit juice was explored as a green reagent for binder
removal, although a relatively high temperature (90  C) is required
(Pant and Dolker, 2017).
The mechanochemical process takes advantage of high-energy
ball milling to induce physical and chemical changes of active
materials (Guan et al., 2016; Wang et al., 2016c). As a result,
mechanochemical process changes or disrupts the inherent crystal
structure of spent materials and enhance the leaching efficiency.
More recently, vacuum pyrolysis is considered as an alternative
pretreatment method. In the course of vacuum pyrolysis at elevated
temperature, the organic materials including electrolyte, separator
and binders are thermally destroyed and decompose to low mo-
lecular products (liquids or gases), which can be reused as fuel or
chemical feedstock. Compared to the traditional thermal process,
vacuum pyrolysis prevents toxic gases from releasing to the open
environment at a lower temperature than under atmospheric
pressure. Due to the oxygen-free atmosphere, Cu and Al avoid being
oxidized and can be recycled in the metallic forms. More impor-
tantly, pyrolysis products or volatiles from lithium-containing
organic compounds could be collected (Sun and Qiu, 2011).
Recently, vacuum pyrolysis was combined with the carbothermic
reduction to enhance lithium recycling efficiency, which will be will
be addressed in the section of mild recycling methods.
After pretreatment, the valorization approaches can be catego-
rized as recycling (Routes 1a and 1b), repair (Route 2) and reuse
(Route 3). In Route 2, spent cathode materials are repaired and
regenerated using a solid phase sintering method (Song et al., 2013;
Yang et al., 2017a). This method is usually cost-effective and it
avoids the loss of valuable metals during the extraction process
(Chen et al., 2016a; Song et al., 2017). Route 3 typically reuses Cu/Al
foils and plastics directly after disassembly, and the rest materials
go through Route 1. Since the present work focuses on the recycling
(extraction) of lithium from spent LIBs, the following sections
discuss Routes 1 in detail.
According to the difference of key processing steps which con-
trol elemental separation, recycling of spent LIBs is categorized as
hydrometallurgy-dominant (Route 1a) and pyrometallurgy-
dominant (Route 1b) paths.
4.1. Hydrometallurgy-dominant process
In a conventional hydrometallurgy-dominant process, the keys
are leaching, precipitation and solvent extraction. Leaching of LIBs,
like other metallurgical processes, is the dissolution of target active
materials by leaching regents. The leaching regents mainly include
inorganic acids, organic acids, and alkaline solutions. At an early
stage, inorganic acids like HCl, HNO3, and H2SO4 were studied
intensively.
805
Taking LiCoO2 as an example, the leaching mechanism by HCl
(Wang et al., 2009; Zhang et al., 1998), HNO3 (Li et al., 2011; Myoung
et al., 2002), and H2SO4 (Ferreira et al., 2009; Nan et al., 2005) can
be represented as reactions (2), (3) and (4), respectively. Through
these reactions, lithium and cobalt can be dissolved into the
solution.
3HCl þ LiCO2 ¼ LiCl þ CoCl2 þ 1:5H2 O þ 0:25O2 (2)
3HNO3 þ LiCO2 ¼ LiNO3 þ CoðNO3 Þ2 þ 1:5H2 O þ 0:25O2 (3)
3H2 SO4 þ 2LiCO2 þ H2 O2 ¼ Li2 SO4 þ 2CoSO4 þ 5H2 O þ 1:5O2
(4)
According to previous studies (Lv et al., 2018; Zeng et al., 2014),
Co3þ is dominated in the cathode materials, but Co2þ is more
readily dissolved than Co3þ in the aqueous phase at room tem-
perature. In the absence of a reductant, the leaching efficiency of Co
is in HCl is higher than in that of HNO3 and H2SO4, since HCl has a
relative higher reducibility. The typical reductant includes
hydrogen peroxide (H2O2) (Gratz et al., 2014; Guo et al., 2016; Li
et al., 2015; Sa et al., 2015; Zou et al., 2013), sodium thiosulfate
(Na2S2O3) (Zhang et al., 2015), and sodium bisulfite (NaHSO3)
(Meshram et al., 2015; Pagnanelli et al., 2014). As illustrated by
reaction (3), the application of H2O2 can facilitate the reduction of
Co3þ in the case of H2SO4 leaching.
Strong organic acids, such as citric acid (Li et al., 2013), formic
acid (Gao et al., 2017), malic acid (Li et al., 2013), aspartic acid (Li
et al., 2013), ascorbic acid (Nayaka et al., 2016a), oxalic acid (Zeng
et al., 2015), and glycine (Nayaka et al., 2016b) are also effective
to leach the cathode material. The leaching reaction, for instance
using citric acid as leachant, could be described by reaction (5)
(Chen et al., 2016b). Other organic acids present a similar reaction
mechanism.
18H3 Cit þ 18LiNi1=3 Co1=3 Mn1=3 þ C6 H12 O6
¼ 6Li3 Cit þ 2Ni3 ðCitÞ2 þ 2Co3 ðCitÞ2 þ 2Mn3 ðCitÞ2 þ 33H2 O
þ 6CO2
(5)
In addition, the alkaline system has been explored with respect
to selectively leach Ni, Co, Cu and Li from the low-grade ore and
different waste material (Meng and Han, 1996; Sun et al., 2015),
whereas Mn is seldom dissolved out (Ku et al., 2016; Zheng et al.,
2017). The formation of Ni and Co-containing ammine complexes
under proper pH values can be described as reactions (6) and (7).
Ni2þ þ nNH3 ¼ NiðNH3 Þ2þ
n (6)
Co2þ þ nNH3 ¼ CoðNH3 Þ2þ
n (7)
Although the leaching efficiency in the ammoniacal system is
usually questionable, the significance of ammonia leaching lies in
its leaching selectivity, i.e., Ni, Co, Zn and Cu are more readily to be
leached out due to their better complexation ability with ammonia
compared with Fe, Mg, Mn and Ca.
It should be noted that both Ni, Co, Mn and Li ions are leached in
inorganic, organic and/or alkaline medium, indicating the separa-
tion of Li from the mixed solution is necessary for the following
steps. In a hydrometallurgy-dominant process, the leaching ki-
netics mainly depends on leaching conditions, such as leachant and
reductant concentrations, agitation speed, temperature, reaction
time and solid-to-liquid ratio. In general, the leaching performance
would be improved by increasing leachant and reductant
806 C. Liu et al. / Journal of Cleaner Production 228 (2019) 801e813

concentrations, agitation speed, temperature, as well as reaction
time. The increase of solid-to-liquid ratio, however, decreases the
leaching efficiency and kinetics significantly. Most of the previous
studies focus on optimization of these factors, despite the battery
types and leaching regents. In practical operation, environmental
influence and processing costs should also be taken into consid-
eration when optimizing these factors. Therefore, a comprehensive
understanding of the leaching mechanism, kinetics, and processing
costs will guide future efforts in optimizing hydrometallurgy-
dominant process towards practical operation.
Solvent extraction is used to obtain pure metal or metal com-
pounds by taking advantage of the different relative solubilities of
compounds in immiscible liquids. The extraction mechanism, tak-
ing di-(2-ethylhexyl) phosphoric acid (D2EHPA) and bis (2,4,4-
trimethylphenyl) phosphinic acid (Cyanex 272) as examples, can
be described by reactions (8) and (9) (Granata et al., 2012b; Swain
et al., 2008).

þ
M2þ
Aq þ AOrg þ 2ðHAÞ2Org ¼ MA2 ,3HAOrg þ HAq
or
MOHþ þ
Aq þ 2ðHAÞ2Org ¼ MðOHÞA,3HAOrg þ HAq
where A
Org þ 2ðHAÞ2Org indicates the extractant saponified by the
following reaction
could change the whole process, while a physical process will not
be so impacted (Danai, 2014). The low solid to liquid ratio for high
leaching efficiency may reduce the process throughput (Al-Thyabat
et al., 2013). In addition, a complex purification process for sepa-
rating metals from the solutions is costly and causes a significant
concern of extra wastewater emission. The extra cost for environ-
mental improvement of secondary pollutions is very high. There-
fore, from an economic point of view, hydrometallurgical processes
are sometimes questionable because of the cost and handling of the
reagents (especially if they are not recovered) (Danai, 2014).
With respect to lithium recycling, by summarizing previous
studies, it can be found that Li-ion is easily concentrated in the
leaching solution after acid and/or alkaline leaching. Separation of
Ni, Co, and Mn from the leaching solution through precipitation
and/or solvent extraction has been explored and successfully
developed, yet the recovery of Li was not paid much attention, i.e.
recovery of Li is usually the last step of the process, as indicated by
Fig. 4. In the course of separating Ni, Co and Mn, loss of Li is inev-
(8) itable and accumulated. After extracting Ni, Co and Mn, the solu-
tions generated from washing procedure in each stage of solvent
extraction are merged into the raffinate, leading to a very low
concentration of lithium (0.5e3 g L
1), associated with ammonium
(9) and sodium of approximately 5 g L
1 (Li et al., 2016). Hence, the
overall recovery efficiency of Li is dependent on all the previous
separation phases (Valio, 2017) and not satisfactory, particularly
considered the market potential and value of lithium salts.

2Naþ þ
Aq þ ðHAÞ2Org ¼ 2NaAOrg þ 2HAq (10) 4.2. Pyrometallurgy-dominant process
Extractants normally have the selectivity of different metal ions,
The pyrometallurgy is usually used to extract target metals from
but the selectivity is highly dependent on the equilibrium pH. For
ore and concentrates through physical and chemical trans-
instance, D2EHPA can selectively extract Cu and Mn ions, whereas
formations enhanced by high temperature. In a pyrometallurgy-
its selectivity on extracting Co ion is poor at pH 2.2e3.0 (Wang
dominant process, the recovery of valuables metals from spent
et al., 2016b). In addition, phase modifier, such as tributyl phos-
batteries is achieved with the application of high temperatures and
phate (TBP) or trioctylamine (TOA) (Darvishi et al., 2005; Virolainen
is usually associated with high amounts of atmospheric emissions
et al., 2017), has been demonstrated as an effective addition to
(unless the emissions are controlled and treated using specific
modify the pH towards a mild operation condition. From the
system), i.e. dioxins, fluoride compounds. Meanwhile, volatile
practical operation point of view, a mild condition is preferred.
metals can be recuperated during the process.
Thereof, studies on the extractants and phase modifiers should be
Smelting and reduction are the key processes in a typical
further carried out in the future.
Precipitation has been widely used to extract metal or metal
compounds from liquid systems. Due to the complexity of the
leaching solution of LIBs, it is a challenge to precipitate a single
metal ion. It has been reported that dimethylglyoxime reagent
(DMG, C4H8N2O2) and ammonium oxalate are capable to effectively
precipitate Ni2þ and Co2þ from the mixed solutions (Chen et al.,
2015). The precipitation mechanisms are shown by following
reactions.

Ni2þ þ 2C4 H8 N2 O2 ¼ NiðC4 H7 N2 O2 Þ2 þ 2Hþ (11)

Co2þ þ ðNH4 Þ2 C2 O4 þ 2OH
¼ CoC2 O4 ,2H2 O þ 2NH3 (12)

2þ 2þ 1þ
After removing Ni and Co , Li can be separated by adding
Na2CO3 or H3PO4, as given by reactions (16) and (17) (Chen et al.,
2015; Pant and Dolker, 2017). Although the impurities associated
with the Li1þ in the remaining solution may be disturbing, this
method provide a feasible approach to recycle lithium from spent
LIBs.

2Liþ þ CO2

3 ¼ Li2 CO3 (13)

3Liþ þ PO3

4 ¼ Li3 PO4 (14)
Fig. 4. Recovery of active cathode materials from spent LIBs in a hydrometallurgy-
In hydrometallurgical techniques, a change in composition dominant process.
 C. Liu et al. / Journal of Cleaner Production 228 (2019) 801e813
pyrometallurgical-dominant path (Bernardes et al., 2004). Batteries
are smelted with the addition of slag formers at a temperature
higher than 1400  C (Georgi-Maschler et al., 2012). The typical
reductant is graphite, which is a crystalline form of carbon and is
the most stable form of carbon under standard conditions. The
graphite may come from the anode material or external addition.
After the reduction, Co is reduced to metallic form by graphite and
carbon monoxide, while Li can be recovered as Li2CO3.
With the application of temperature higher than the melting
point of target metals, the corresponding metals form alloys while
other impurities move to slag phase or form gases. Metals with low
boiling points, for instance, Zn, Cd and Hg will evaporate at a high
temperature. After leaving the molten phase, through control of the
atmosphere, these vapors can either be recovered as metal after
condensation or react with oxygen and generate dust (Müller et al.,
2000). It has been demonstrated that it is possible to reclaim Zn, Ni,
Cd, Pd, and other metals from spent Ni-Cd and/or Zn-Mn batteries
(David, 1995; Espinosa et al., 2004). Slag formers are added before
or during smelting to process a slag carrying the waste (lithium
included) and off-gases. In the pyrometallurgy industry, CaO, SiO2,
Al2O3, and MgO are the most frequently used oxides in slag sys-
tems. To minimize the capacity of slag for target metals (usually Co,
Mn), a simple binary or ternary slag system is preferred. T. Georgi-
Maschler et al. (2012) used FactSage to calculate the theoretical
distribution coefficient for cobalt and manganese between metal
and slag, in order to evaluate the thermodynamic property of
various slag systems. The thermodynamic calculation indicates that
54.5 wt% CaO-45.5 wt% SiO2 and 50.0 wt% Al2O3-45.0 wt% CaO-
5.0 wt% MgO are appropriate to recycle cobalt and manganese from
spent LIBs (Georgi-Maschler et al., 2012). Ren et al. (2017) applied a
fayalite slag (FeO-SiO2-Al2O3) in a smelting reduction process to
recycle spent Libs with Al shells. The optimized slag composition is
FeO/SiO2 ¼ 0.58e1.03 (w/w), and 17.19e21.52 wt% Al2O3. After
smelting at 1450  C for 30 min, an alloy of Fe-Co-Cu-Ni was ob-
tained while the slag was composed of fayalite and hercynite. Yet
the recovery of lithium was not clarified.
In general, a conventional pyrometallurgical-dominant path to
recycle spent LIBs is short and easy to scale up. It can also accept
many variations of LIBs (Hendrickson et al., 2015). There is usually
no safety risk from the leakage of electrolyte. However, a major
drawback of the pyrometallurgical recycling process is that lithium
cannot be effectively recovered (Georgi-Maschler et al., 2012).
Lithium usually ends up in slag, associated with other ignoble
metals (Sun et al., 2016). Although some researchers have investi-
gated the recycling of lithium through the hydrometallurgy method
using the slag, the energy consumption is too high (Yazami and
Touzain, 1983). Usually, high temperature triggers the generation
and emission of off-gas, e.g. carbon dioxide, carbon monoxide,
sulfur dioxide, volatile organic compounds, and dust. Hence, the
pyrometallurgical-dominant path requires a large amount of en-
ergy and a gas cleaning system, which are capital-intensive.
4.3. Mild recycling methods
In addition to the traditional pyrometallurgical-dominant ap-
proaches, there are also other recently developed methods to
recycle the cathode materials (so-called mild recycling method).
The mild recycling methods aim to recycle all valuable metals
(lithium included), decrease the energy/acid/alkaline consumption,
while increase efficiencies in the uses of energy. They are usually
pyrometallurgical-dominant and combines with acid/alkaline free
hydrometallurgy.
Vacuum carbothermal reduction and sulfation roasting are the
main mild recycling methods. Fig. 5 presents the standard free
energy change during carbothermal reduction of battery material
807
Fig. 5. Carbothermal reduction of battery material metal oxide metal oxides at at-
mospheric pressure, calculated by HSC 6.0.
metal oxides. The CO line cuts across the lines of NiO, CoO and MnO
in the calculated temperature range (0e2000  C), indicating that C
is a useful reducing agent to reduce the corresponding metal oxide
to metal. Theoretically, NiO and CoO can be reduced at 400e500  C,
while MnO is stable until 1300  C. However, Li2O cannot be reduced
by C under 2000  C. Considering that reactions kinetics can be
enhanced by high temperature, most of the mild recycling methods
aim to decrease the temperature of traditional pyrometallurgical-
dominant approaches to 500e1000  C.
Roasting under reduced pressure (vacuum) was initially
explored to prevent generating toxic volatile metals and gases
(Konda
s et al., 2006). In reduced pressure, the gas-involved re-
actions are enhanced. Taking CoO as an example, the reduction of
CoO by graphite is described by reaction (15).
CoO þ C ¼ Co þ CO (15)
The Gibbs free energy of reaction (16) is

. 
DG ¼ DGQ þ RTln pCO pQ (16)
where DGQ the change of standard Gibbs free energy (J$mol
1), T
temperature (K), pQ the standard pressure (101325 Pa), pCO partithe
al pressure of CO (Pa). Under reduced pressure (pCO < pQ ), DG is
always smaller than DGQ , indicating that the reduction reaction
tends to be easier to take place. By assuming pCO ¼ pQ  10
m is the
total pressure of the system, Eq. (17) can be calculated as
DG
DGQ ¼
19:146mT (17)
Fig. 6 presents the influence of reduced pressure and tempera-
ture on reaction (15), as calculated according to Eqs. (16) and (17).
By reducing pressure or increasing temperature, Gibbs free energy
of the reduction reaction keeps decreasing, indicating the reaction
is easier to take place.
When the reactions reach equilibrium (DG ¼ 0), DGQ ¼
19:146mT. Then the following equation is derived.
DGQ
T¼ (18)
19:146m
It is clear that with reducing gas pressure (increasing m), the
equilibrium temperature is decreased, making vacuum carbo-
thermal reduction a possible approach to recycle cathode materials
as a mild recycling method.
To recycle spent LiMnO2 batteries, the carbothermal reduction
was carried out under reduced pressure at 650  C, which splits the
808 C. Liu et al. / Journal of Cleaner Production 228 (2019) 801e813
Fig. 6. Thermodynamic calculation on the influence of reduced pressure and tem-
perature on the reduction of CoO by graphite.
casings and deactivated the batteries by reduction of LiMnO2 and
MnO2 with residual lithium metal and graphite to form MnO and
Li2CO3. The resultant lithium carbonate was selectively solubilized
in water with the manganese remaining in the residue. High purity
Li2CO3 was subsequently recovered by controlled evaporation
(Jandova et al., 2012; Konda
s et al., 2006).
Li et al. (Li et al., 2016; Xiao et al., 2017a,b) investigated recycling
of spent LiCoO2, LiMn2O4 and LiCoxMnyNizO2 by using vacuum
carbothermal reduction. Graphite, stripped from the anode, was
used as a reductant. The process was “in situ” recycle which means
to transfer the spent LIBs into resources (cobalt or lithium salt) by
its own electrode materials. The furnace was pumped to achieve a
vacuum environment, then the carbothermal reduction was per-
formed at a temperature below 1000  C for 30 min, followed by wet
magnetic separation. The gas production is quite low in this pro-
cess. After the reaction, these gaseous products can be collected to
use as clean energy to avoid disposal cost (Georgi-Maschler et al.,
2012; Ordon ~ ez et al., 2016). Nickle and cobalt are recovered in the
Fig. 7. Plausible pathways for the conversion of mixed powders from spent LiMn2O4 batteries at enclosed vacuum conditions.
metallic form while manganese is recovered as MnO. Li2CO3 is
leached from roasted powders by water and finally, high value-
added Li2CO3 crystals are further gained by evaporating the
filtered liquid.
The reaction mechanism was explored by taking LiMn2O4 as an
example, and the plausible pathway of the conversion reaction is
illustrated in Fig. 7 (Xiao et al., 2017c). Cubic spinel LiMn2O4 starts
collapsing and releasing Li elements, resulting in a distorted
tetragonal spinel Mn3O4 over 400  C because the skeleton O tends
to escape away as O2 at oxygen-free conditions (Hwang et al., 2001;
Treuil et al., 1999). In this stage, some Li elements released from the
O-tetrahedron of collapsed LiMn2O4 transferred into empty O-tet-
rahedrons of other cubic spinel LiMn2O4 to form distorted
Li2Mn2O4. Furthermore, when the temperature rises from 600 to
700  C, the skeleton O was captured by C/CO and the distorted
tetragonal spinel Mn3O4 and LiMnO2 were further collapsed.
Finally, distorted Mn3O4 and LiMnO2 were totally collapsed and
converted into the NaCl-structured MnO. The Li element was fully
released and reacted with CO2 to form Li2CO3.
After vacuum carbothermal reduction, Li is recycled as Li2CO3.
But the solubility of Li2CO3 in water is relatively low (Ullmann,
2003), leading to a low concentration of lithium salt (<0.5 g L
1)
and poor leaching efficiency. To overcome such a significant
drawback, Hu et al. applied carbonated water leaching to treat the
roasted products, then lithium in the roasted products could be
leached as LiHCO3 (Hu et al., 2017) via reaction (19).
Li2 CO3 þ CO2 þ H2 O ¼ 2LiHCO3 (19)
By injecting CO2 gas into water, Li2CO3 in the roasted products
transforms to more soluble LiHCO3. Consequently, the leaching
efficiency can be improved. Wang et al. reported that lithium
concentration was increased to 4.4 g L
1 by carbonated water
leaching under a CO2 flow rate of 20 mL min
1, the liquid-solid ratio
of 10:1, leaching time of 2 h at ambient temperature. It should be
noted that prior to reduction roasting experiments, Hu et al. (2017)
mixed the cathode powder with a certain amount of lignite by a
 C. Liu et al. / Journal of Cleaner Production 228 (2019) 801e813 809

planetary ball mill for 1 h, yet it is not clarified whether the
mechanochemical treatment effect the reduction reaction and
leaching. Previous studies have reported that by using mechano-
chemical activation, the crystal face which is more readily
destroyed may transform to disordered states, and subsequently,
the leaching efficiency is significantly enhanced (Guan et al., 2016;
Wang et al., 2016c, 2017; Yang et al., 2017b). Therefore, a compre-
hensive understanding of the fundamentals of mechanochemical
activation and carbothermal reduction on recycling of spent LIBs is
necessary, especially for lithium recovery.
Besides vacuum carbothermal reduction, sulfation roasting is
also a promising method to recycle spent LIBs in mild operating
conditions. Combination of sulfation roasting and water leaching
has been successfully applied to recycle rare-earth elements (REEs)
€
from bauxite residue (Borra et al., 2016) and NbFeB magnets (Onal
et al., 2015), as well as to recycle nickel from laterite and chro-
miferous overburden (Kar and Swamy, 2000). In general, sulfation
roasting is mainly composed of three stages, namely sulfation,
roasting, and leaching. Sulfation employs sulphuric acid or
aggressive salt sulfate to transfer powdered samples into a sulfate
mixture, i.e., most oxides are converted to their corresponding
sulfates during the sulfation process. During subsequent roasting,
some unstable sulfates decompose to oxides. Other sulfates, on the
other hand, are relatively stable during roasting. In the final phase,
the stable sulfate can dissolve during water leaching, leaving the
other oxides in the residue. Most of the researches focus on the
effects of temperature, roasting time, amount of acid/salt and
external additions on leaching of the different elements.
Wang et al. (Wang et al., 2014; Wang et al., 2016a) studied the
elemental transfer during sulfation roasting of spent LiCoO2. The
sulfation was done by mixing a certain amount of K2S2O7 with
LiCoO2 powder, then the mixture was roasted for 0.5 h at the
temperature less than 600  C. It was demonstrated that Co and Li
gradually transfer to KLiSO4, K2Co2(SO4)3, accompanied with SO2,
O2 gas releasing. However, Wang et al. aimed to convert all the
metals elements into water-soluble salts, but the decomposition of
sulfates was neglected.
Obviously, the efficiency of sulfation roasting is determined by
the thermodynamic stability of most of the considered metal sul-
fates, which is calculated (see the supplementary S1) and listed
below in increasing order (in the temperature from 500 to 1000  C)
(Saikkonen, 1984).
Al2(SO4)3 < Fe2(SO4)3 < CuSO4 < NiSO4 < CoSO4 < MnSO4 < Li2SO4
Li2SO4 is the most stable one among these sulfates. Hence, with
an appropriate selective roasting treatment. It is possible to trans-
form the sulfates of almost all impurity metals (except for lithium)
into their respective oxides while lithium remains in its sulfate
form. However, the relative stability of metal sulfates cannot be
predicted simply by thermodynamic data. It should also be noted
that the thermal stability of any metal sulfate is also dependent on
other factors (e.g., heating rate) that could shift its decomposition
range from the reported cases (Poston et al., 2003; Wendlandt,
1958; Wendlandt and George, 1961).
Although selectivity of roasting with aggressive salt sulfate is
poor, it shows the feasibility to recycle lithium and lower the en-
ergy consumption. To provide a better selectivity, it is suggested to
employ sulphuric acid instead of sulfate salt to react with spent
cathode materials, then the mixture is subjected to roasting and
water leaching. Compared to the traditional pyrometallurgy-
dominant process, sulfation roasting consumes lower energy, but
the application of sulfur triggers aggressive corrosion of the furnace
due to the release of SO2 and SO3. Hence, it is still a challenge to
implement sulfation roasting technologies in industrial production.
4.4. Comparison of different methods with respect to recycling
lithium
Table 2 presents the comparison of different treatment methods
with emphasis on the recycling of lithium. Overall, it is possible to
recycling high-purity lithium using hydrometallurgy-dominant
method at the expense of long processing flow. In a traditional
pyrometallurgy-dominant process, recycling of lithium cannot be
effectively achieved since it easily ends up in the slag phase. Mild
recycling method integrates the pyrometallurgy and hydrometal-
lurgy treatments, indicating promising research and application
prospects.
5. Current industrial recycling process in view of lithium
recycling
Recycling of spent LIBs is relatively new in comparison with the
recycling of other sorts of batteries, for instance, NiCd and Pb-acid
batteries. At present, the recycling of spent LIBs is combined with
existing large-scale processes (e.g. extractive cobalt or nickel met-
allurgy), which are normally not dedicated to battery recycling. This
approach is common practice and very often an economical
advantage (Georgi-Maschler et al., 2012). Table 3 summarizes the
current industrial recycling process with emphasis on lithium
recycling.
Umicore technology deploys a typical pyrometallurgy-
dominant path, where potentially hazardous pretreatment is
avoided (Daniel and Sven, 2014; Meshram et al., 2014). The spent
batteries are directly melted down using a unique ultra-high tem-
perature (UHT) technology with the addition of slag formers. After
that, an alloy of valuable materials (Co, Ni, Cu, Fe) is obtained (Sonoc
et al., 2015). Plastics, solvent and graphite are burnt and leave as
gases. The lithium, aluminum and manganese are not recovered
and end up in the slag (Georgi-Maschler et al., 2012). The UHT
technology is designed to safely treat large volumes of different
types of complex metal-based waste streams. Batteries are com-
bined with coke and slag formers (limestone, sand) and fed into the
furnace. The feed should contain 30-50 wt% spent batteries in order
to produce a product with an economically viable content of cobalt
and nickel (Daniel and Sven, 2014). Air, pre-heated to 500  C, is fed

Table 2
Comparison of different methods with respect to recycling lithium.

Different treatments Advantages Disadvantages

Hydrometallurgy-dominant process
Pyrometallurgy-dominant process
Mild recycling method
Possible to recycle lithium; room temperature
operation; purity is high;
Easy to scale up; simple pretreatment;
acid/alkaline-free;
Relatively lower energy; satisfactory
recycling efficiency;
Low concentration of lithium (0.5e3 g L
1) with high impurities in the
solution after extraction of other metals; recycling efficiency is questionable;
consumption of acid/alkaline solution;
High energy consumption; emission of off-gas; lithium ends up in the slag
(further treatment is needed);
Emission of off-gas;
810 C. Liu et al. / Journal of Cleaner Production 228 (2019) 801e813

Table 3
Current major commercial processes for recycling spent LIBs (2018a; 2018b; 2018c; 2018d; 2018e; 2018f; Knights and Saloojee, 2015; Lv et al., 2018; Pistoia et al., 2001).

Company/process Capacity (tonnes/year) Main products Technology Li recovery

TOXCO (Retriev) 4500 Li2CO3, mixed metal oxides Hydro-dominant Yes

Accurec GmbH 6000 Co alloy, Li2CO3 Pyro-dominant Yes
Inmetco 6000 Co alloy Pyro-dominant No
Green Eco-Manufacture Hi-Tech Co 20,000 NiCo alloy, Ni, Co, Co3O4 Hydro-dominant No
Akkuser Ltd 4000 Metal powder Pyro-dominant No
Bangpu Ni/Co High-Tech Co. 3600 Cathode materials, Co3O4 Hydro-dominant No
Sumitomo-Sony 150 Co alloy, Co metal Pyro-dominant No
Batrec AG 200 Battery scraps Pyro-dominant No
SNAM 300 NR Pyro-dominant No
ERAMET (Valdi) 20,000 Raw materials for special steel Pyro-dominant No
Nippon Recycle Center Co. 5000 Raw materials for special steel Pyro-dominant No
DK Recycling und Roheisen GmbH NR NR Pyro-dominant NR
Umicore 7000 Ni-Co alloy, NiCO3, NiSO4, CoCO3, CoSO4 Pyro-dominant No
Glencore plc. (Xstrata) 7000 Co alloy Pyro-dominant No

NR: not reported.

through the bottom of the furnace. The furnace is divided into three
temperature zones: the pre-heating zone, the plastic pyrolyzing
zone and the smelting zone, as shown in Fig. 8 (Knights and
Saloojee, 2015).
As shown in Table 3, most of the industrial process focus on
recycling Co and Ni, except for TOXCO and Accurec GmbH process
which also aim to recycle lithium.
TOXCO process is one of the early hydrometallurgy-dominant
processes that are devoted to the recycling of LIBs (McLaughlin
and Adams, 1999). It includes submerging spent batteries in
liquid nitrogen followed by crushing and placing the batteries in
aqueous solution with high pH controlled by lithium hydroxide.
Different lithium salts were precipitated, filtered, and finally,
lithium carbonate was formed by pumping CO2 into the solution.
The Accurec GmbH process uses the pyrometallurgical method to
recover cobalt manganese alloy and lithium chloride. The process
starts with the removal of electronics and plastic casings followed
by vacuum thermal treatment and pyrolysis. The electrode material
is pressed to form briquettes which are put in a smelting furnace for
reduction. As a result, a metallic cobalt manganese alloy and a slag
that contains the lithium are obtained. The slag is leached with acid
and the lithium is precipitated as lithium chloride (Gabriel, 2016).
Recently, to recover all battery components especially Li, and
realize cost-neutral and sustainable, Accurec GmbH cooperates
with other researchers (Tr€ager et al., 2015) launches a project which
shows that a pyrometallurgical recovery of lithium from lithium-
ion traction batteries is possible. The underlying decomposition
and evaporation reactions take place under vacuum and under a
nitrogen atmosphere. They start already at about 1400  C and can
be accelerated at a higher temperature, but the decomposition and
evaporation of lithium compounds from automotive Li-ion batte-
ries are not explored yet.
6. Conclusions and outlook
Recycling of spent LIBs alleviates environmental pollution and
reliefs the shortage of natural resources, contributing to the sus-
tainability of the environment, economy, and humans. Most of the
previous studies have focused on recycling cobalt and nickel, but
few highlights the selective extraction of lithium. The underlying
mechanism and physiochemistry features of various recycling
methods have been summarized. Based on the difference of major
separation steps, these recycling approaches are categories as
pyrometallurgy-dominant, hydrometallurgy-dominant, and mild
recycling methods. Both lab-scale investigations and industrial
practice are reviewed with emphasis on lithium recovery. At pre-
sent, seldom lithium extraction is industrially implemented from
spent LIBs. Therefore, future efforts are suggested to focus on not
only shortening the process steps but also improving the efficiency
of metal extraction and separation, especially for lithium recovery.
Specifically, the following conclusions could be reached:

(1) High recycling costs limits lithium recovery from the elec-
trolyte (LiPF6). Improper disposal of the spent electrolyte is a
waste of lithium. Supercritical carbon dioxide method ap-
pears to be a promising method to recover lithium from the
electrolyte, but more efforts in this field are needed.
(2) Recent lab-scale studies have developed based on
hydrometallurgy-dominant methods, which are normally
complex to recover the valuable metals in a long process
with high cost. Though literature investigation shows that
recycling efficiency using hydrometallurgy-dominant
methods is satisfied, whether the lab-scale technologies
can be implemented at industrial scale is questionable.
Moreover, Li-ion is easily concentrated in the leaching solu-
tion, associated with Ni, Co and Mn ions. Most of the previous
studies highlight recovery of Ni, Co and Mn, but Li is usually
the last step of the process. Consequently, the recovery effi-
ciency of Li is not satisfactory. Therefore, future studies are
suggested to consider process intensification while
Fig. 8. Temperature zones in the UHT technology used in Umicore. addressing selective extraction of Li.
 C. Liu et al. / Journal of Cleaner Production 228 (2019) 801e813
(3) The pyrometallurgy-dominant approach is the most
frequently used method in the industry since it is short and
readily to scale up. But the energy consumption is high and
lithium usually lost in slag. Treatment of off-gas and dust
results in longer processing steps. Hence, points that should
be considered include decrease the energy consumption and
recycle lithium effectively.
(4) As an alternative method to traditional recycling methods,
mild recycling method to recycle the cathode materials has
been explored. The mild recycling methods combine low-
temperature pyrometallurgy (below 1000  C) and mild con-
dition hydrometallurgy (acid and alkaline free). With the aim
to recycle lithium, decrease the energy consumption, and
avoid the application of acid or alkaline, vacuum carbo-
thermal reduction and sulfation roasting have shown
promising potentials, although the mechanisms of physical
and chemical changes in the recycling process need to be
deeply explored. Also, the mechanochemistry-assisted car-
bothermal reduction should be further studied.
Declarations of interest
None.
Acknowledgment
The authors acknowledge the financial support on this research
from the National Key Research and Development Program of China
(2017YFB0403300/2017YFB043305), National Natural Science
Foundation of China under Grant No. 51425405 and 51874269, as
well as 1000 Talents Program of China (Z.S.). Chunwei Liu gratefully
acknowledges the financial support of China Postdoctoral Science
Foundation (2018M631579) and Postdoctoral International Ex-
change Program (199100).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2019.04.304.
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