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Peng, Chao; Liu, Fupeng; Aji, Arif T.; Wilson, Benjamin P.; Lundström, Mari
Extraction of Li and Co from industrially produced Li-ion battery waste – Using the reductive
power of waste itself

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Waste Management

DOI:
10.1016/j.wasman.2019.06.048

Published: 15/07/2019

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Peng, C., Liu, F., Aji, A. T., Wilson, B. P., & Lundström, M. (2019). Extraction of Li and Co from industrially
produced Li-ion battery waste – Using the reductive power of waste itself. Waste Management, 95, 604-611.
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 Waste Management 95 (2019) 604–611

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

Extraction of Li and Co from industrially produced Li-ion battery

waste – Using the reductive power of waste itself
Chao Peng a, Fupeng Liu a,b, Arif T. Aji a, Benjamin P. Wilson a, Mari Lundström a,⇑
a
Hydrometallurgy and Corrosion, Department of Chemical and Metallurgical Engineering (CMET), School of Chemical Engineering, Aalto University, Espoo 02150, Finland
b
Institute of Engineering Research, Jiangxi University of Science and Technology, Ganzhou 341000, China

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

Article history: Industrially produced spent lithium-ion batteries (LIBs) waste contain not only strategic metals such as
Received 10 April 2019 cobalt and lithium but also impurity elements like copper, aluminum and iron. The current work inves-
Revised 24 June 2019 tigates the distribution of the metallic impurity elements in LIBs waste, and their influence on the acid
Accepted 29 June 2019
dissolution of target active materials. The results demonstrate that the presence of these, naturally reduc-
tive, impurity elements (e.g. Cu, Al, and Fe) can substantially promote the dissolution of active materials.
Through the addition of Cu and Al-rich larger size fractions, the extraction efficiencies of Co and Li
Keywords:
increased up to over 99%, to leave a leach residue that is rich in graphite. By this method, the use of high
Spent LIBs
Hydrometallurgy
cost reductants like hydrogen peroxide or ascorbic acid could be avoided. More importantly, additional
Recycling Co and Li associated with the Cu and Al electrode materials could be also recovered. This novel approach
Circular economy of metals contributes not only to improved reduction efficiency in LIBs waste leaching, but also to improved total
Sustainability recovery of Co and Li from LIBs waste, even from the larger particle size fractions, which are typically lost
from circulation.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction 1.1. Spent LIBs management and policies

Li-ion batteries (LIBs) are widely used in consumer electronics, Generally, end-of-life LIBs are classified as either portable LIBs
electronic vehicles, energy-storage systems, etc., where high- or LIB modules that are utilized in electric vehicles and energy
energy density and lightweight are of prime importance. It is fore- storage systems. The large-size LIB modules can be easily collected
casted that the worldwide demand for LIBs will reach ca. 900 GWh and treated by recycling companies, whereas spent portable bat-
by 2026 (Drabik and Rizos, 2018). Consequently, this also means teries are more commonly disposed to municipal waste streams,
there will be large quantities of waste LIBs being produced in the landfill or incineration depending on local legislation requirements
near future as the average lifespan of LIBs is only 2–3 years for con- (Terazono et al., 2015; King and Boxall, 2019). Consequently, sig-
sumer electronics and 8–10 years for automotive or energy storage nificant traces of Co and Li can often be found in municipal waste
systems (Richa et al., 2017). Moreover, these end-of-life LIBs con- incinerator bottom ashes (Allegrini et al., 2014; Alam et al., 2019).
tain heavy metals with known toxic effects and flammable elec- According to the Europe Commission, in 2014 (European
trolyte, which can pose a serious environmental risk if they are Commission – DG Environment, 2014), the collection rates of por-
not disposed properly (Zhao and You, 2019). Furthermore, as this table LIBs was only 4.5%, whereas research in California has
waste is a valuable secondary source of raw materials - it contains revealed that the costs associated with the collection of 1 ton of
significant quantities of metals like cobalt (5–20%), nickel (5–10%), waste batteries from the municipal waste streams can be as high
lithium (5–7%) and copper (6–12%) (Zeng et al., 2014) - the recy- as 2700 US dollars (Turner and Nugent, 2016). In order to improve
cling of waste Li-ion batteries (LIBs) has recently garnered signifi- the management of spent batteries (not only LIBs), a policy of
cant interest. ‘extended producer responsibility (EPR)’ has been adopted in the
EU, Canada, USA and elsewhere, with the aim to raise consumer
awareness, expand waste collection infrastructure and shift the
costs of battery collection/recycling from municipalities to stew-
⇑ Corresponding author. ardship organizations (Terazono et al., 2015). In the EU, the 2006
E-mail addresses: [email protected] (C. Peng), [email protected] Battery Directive clearly established EPR requirements for all bat-
(M. Lundström). tery types (not only LIBs) and this also includes strict requirements

https://doi.org/10.1016/j.wasman.2019.06.048
0956-053X/Ó 2019 Elsevier Ltd. All rights reserved.
 C. Peng et al. / Waste Management 95 (2019) 604–611 605

that each member state set target collection rates (e.g. 45% in Consequently, this research investigates the distribution of
2016) and the minimum recycling efficiencies of >50% (Council impurity metals and active materials in industrially processed LIBs
Directive, 2006). Similarly, the Corporation for Battery Recycling waste fractions with different particle size, as well as the influence
(CBR) in the USA proposed an act that requires battery producers of the existing impurity metals on the acid dissolution of active
to participate in a battery stewardship plan, which details the col- materials. Based upon this, we propose for the first time a method
lection points, educational efforts and recycling process of each to utilize the existing Cu/Al rich overflow fractions of battery waste
operator. In contrast, the latest battery recycling edict within China as reducing additives in order to promote the recovery of the
dictates that all the power batteries need to be encoded and a desired valuable metals. The advantages of the current approach
related tracking system is required that traces battery movement is that (i) very efficient reduction i.e. Co dissolution can be achieved
between designer, producers, downstream enterprises and recy- during LIBs waste leaching, (ii) a high cost reducing agent (e.g.
clers (Xu et al., 2017). In terms of other batteries like portable LIBs H2O2, ascorbic acid) is not needed, which contributes to the feasi-
however, the Chinese government has chosen to give a direct bility of the process and that (iii) the total Co and Li recovery can be
financial subsidy to recyclers based on their production capacities. increased as Co and Li present in the overflow fraction (i.e. Cu, Fe,
Although numerous incentives and compulsory policies have been Al rich fraction) that is normally lost, can also be recovered.
adopted in many countries, these strategies often lack any details
about how waste batteries should be managed in an economic
2. Experimental
and environmentally sustainable way.

2.1. Input LIBs scraps and the characterizations

1.2. Acid leaching of spent LIBs
The collected waste LIBs scraps were produced by a patented
Acid leaching of spent LIBs is a critical step in the hydrometal- industrial-scale mechanical methodology that included two-step
lurgical recycling of battery waste and this typically involves a crushing, magnetic separation and sieving (Pudas et al., 2015).
reductive process as the target transition metals (e.g. Co, Ni, Mn) From this process, two distinct material streams were obtained,
in active materials exist at higher valences, when compared to i.e. an underflow fraction (UF, <2 mm) rich in active materials
their aqueous solution equivalents. In the case of LiCoO2, for exam- (21 wt% Co and 4 wt% Li) and an overflow fraction (OF, >2 mm)
ple, the dissolution process occurs as follows (HSC Chemistry 9, comprised primarily of aluminum/copper foils (17 wt% Al and
T = 353 K): 12 wt% Cu) as well as active materials attached on the foils
(8 wt% Co and 1 wt% Li), Fig. 1. The former is typically used as
LiCoO2 (s) + e
+ 4Hþ ! Liþ + Co2þ + 2H2 O E = 2.12 V (vs. SHE) the input material for the recovery of Li and Co, whereas OF is sub-
ð1Þ jected to Cu smelting, resulting in the loss of Li and Co to the pro-
cess slags (Tirronen et al., 2017). Fig. 1c and d show two examples
Based on reaction (1), the dissolution process of LiCoO2 can be
of handpicked fractions of overflow, composed of Cu and Al flakes,
enhanced by the addition of acids and reducing agents. As a result,
which were washed with distilled water and then subjected to
recent research has been devoted to the investigation of different
chemical analysis. It was found that in the copper colored fraction
type of acids (Zhuang et al., 2019) and relatively costly reducing
(Fig. 1c), Co content is <1 wt%, while in the aluminum colored
agents like H2O2, NaHSO3, Na2S2O3, as well as ascorbic acid and
flakes (Fig. 1d), the Co content can be as high as 11 wt%. This indi-
ᴅ-glucose (Chen et al., 2015; Gao et al., 2018). Despite this, the
cates that Co and Li in the overflow fraction (Fig. 1b) are not the
majority of the reported scientific research is primarily carried
result of entrainment, but that they are rather carried along with
out with pure active materials from manually dismantled batteries
the binder material on the current collectors (Porvali et al., 2019).
(Chen et al., 2018; Fu et al., 2019) and therefore, does not represent
The distribution of metallic components and active materials in
the industrially crushed battery waste as a whole (Vezzini, 2014).
the underflows was studied further by vibro-sieving the underflow
In industry, the LIB scraps are usually processed through the fol-
(Retsch AS 300) into five fractions via a four-sieve combination
lowing unit processes: discharging, mechanical crushing (or shred-
(0.125 mm, 0.25 mm, 0.5 mm and 1 mm). Results, outlined in
ding), magnetic separation and sieving, resulting in waste
Table 1, show that the target elements (Li, Co, Ni, Mn) are
composed of both active materials as well as some impurity metals
distributed evenly amongst the different fractions, whereas the
(e.g. Cu, Fe, Al) (Tedjar and Foudraz, 2010; Pagnanelli et al., 2017).
presence of Cu, Al, and Fe clearly increase with larger particle sizes.
Furthermore, a small but appreciable amount of the active materi-
In the <0.125 mm fraction Cu, Al, Fe are all >0.6 wt%, whilst
als can also be found within the separated impurity metal fractions
in the larger fractions (1.0–2.0 mm), their content increases sub-
as a result of retention on the Cu/Al electrodes that segregate at
stantially to approximately 20 wt% Cu, 13 wt% Al and 7 wt% Fe.
larger particle sizes (Wang et al., 2016). In consequence, state-of-
XRD and SEM characterization of the fractions – shown in
the-art pre-processing techniques do not provide a complete sepa-
Figs. S1 and S2 - revealed that the active materials in the investi-
ration of active materials (Co, Ni, Mn, Li) from the impurity metals
gated battery waste mainly consist of LiCoO2 and LiCo0.25Ni0.65-
(Fe, Al, Cu) - in contrast to the hand dismantled battery materials
Mn0.1O2, whereas copper is present in the elementary form and
often found in the literature - and therefore the effective treatment
aluminum in both elementary and oxide forms.
of both active materials and larger particle sizes is required.
According to our previous research, the acid dissolution of Li and
Co from industrially processed LIBs materials in the absence of 2.2. Experimental procedures
external additives results in extraction of 90% (Li) and 80%
(Co) (Peng et al., 2018). In contrast, findings from the leaching of 2.2.1. Leaching of underflow fractions with different particle sizes
manually dismantled ‘pure’ active materials under similar condi- Acid leaching experiments for each particle size fractions were
tions show lower levels of ca. 60% for Co and 80% for Li (Vieceli carried out at T = 80 °C, [H2SO4] = 2.0 mol/L, S/L (solid-to-liquid) =
et al., 2018; Li et al., 2017). These results suggest that the acid dis- 100 g/L, t = 1.5 h, based on the operating parameters found in our
solution of industrial LIBs scraps is different from pure active mate- previous research (Peng et al., 2018). Initially, a 40 g of sample
rials and that the presence of metallic impurities within the mixed and 400 mL of pre-heated H2SO4 (2.0 mol/L, 80 °C) were added into
LIBs scrap might influence the acid dissolution behavior of active a cylindrical reactor (V = 1.2 L) fitted with a condenser and agitator
materials. (200 rpm), that was heated with a water bath (Thermo HaakeÒ,
606 C. Peng et al. / Waste Management 95 (2019) 604–611

Fig. 1. Images and the metals predominating in crushed LIB waste fractions (a) underflow (<2 mm), (b) overflow (>2 mm) as well as (c) handpicked copper scraps and (d)
aluminum scraps from overflow fraction (>2 mm).

Table 1
Weight percentages and chemical analysis of main metals in each particle size fraction of LIBs waste (raw material: underflow fraction <2.0 mm). *Rest denotes the residual
material that is primarily a mixture of graphite and plastics.

Fractions (mm) Weight percentages (%) Chemical composition of elements (%)

Li Co Mn Ni Cu Al Fe Rest*
<0.125 41.25 3.34 18.79 1.87 2.99 0.40 0.54 0.37 71.70
0.125–0.25 19.72 4.66 25.02 2.86 4.45 1.44 1.61 0.34 59.62
0.25–0.5 18.39 4.02 25.32 3.05 4.44 5.27 5.37 0.52 52.01
0.5–1.0 18.13 3.29 19.30 2.31 3.65 14.00 10.20 2.41 44.84
1.0–2.0 2.51 2.55 17.20 1.83 3.01 19.50 12.80 7.22 35.89

DC10). The fractions investigated were <0.125 mm, 0.125– ducted with 2.0 mol/L H2SO4, S/L = 100 g/L at 75 °C and the results
0.25 mm, 0.25–0.5 mm, 0.5–1.0 mm and 1.0–2.0 mm. In order to are outlined in the supplementary materials (Fig. S3).
study the behavior of elements as a function of time, intermittent
solution samples were taken at pre-determined time intervals and 2.2.3. Leaching with pure substances
the yields of the elements were calculated following Eq. (2). In In order to define the effect of metallic components on the dis-
order to ensure the accuracy of the results, the leaching residue solution of active materials, initial acid leaching experiments with
were also analyzed to verify the results. pure LiCoO2 powders in the presence and absence of Cu, Al and Fe
were conducted (Table 2). Similar amounts of metal (LiCoO2:
ci ¼ ðC i  V i Þ=ðmi  wi Þ  100% ð2Þ 19.6 g, Cu: 3.2 g, Al: 1.35 g, Fe: 0.33 g) to that of the investigated
underflow battery waste material chemical composition (21.3 wt
where mi ðg Þand wi (%) are the mass of the input materials and the % Co, 4.6 wt% Cu, 3.7 wt% Al, 0.6 wt% Fe) were used. Experiments
compositions of element (i), respectively; C i (g/L) and V i (L) are were conducted with T = 80 °C, [H2SO4] = 2 mol/L, S/L  40 g/L)
the concentration of elements (i) and the volume of leach solution. and the solution samples were taken at pre-defined times and ana-
lyzed by ICP-OES. Yields were calculated based on the analysis of
2.2.2. Leaching of underflow battery wastes in the presence of the solution samples via Eq. (2) in order to allow ease of
additives comparison.
The possibility to use the Cu and Al rich overflow fraction
(>2.0 mm, Fig. 1b) as an additive for the recovery of Li and Co from 3. Results and discussion
underflow fractions was investigated with the following parame-
ters: T = 80 °C, [H2SO4] = 1.5, 2.0, 2.5 mol/L, S/L = 100 g/L, over- 3.1. Investigation of acid leaching of underflow fractions (<2 mm) in
flow/underflow (OF/UF) = 1/10, 1/20 (mass/mass). Overflow was the absence of external reducing agents
added at t = 1 h and the leaching was allowed to proceed for a fur-
ther 1 h. Leaching efficiencies of Co and Li were calculated via In order to study the influence of metallic impurities on the acid
Eq. (2). As a comparison, acid leaching of the underflow wastes dissolution of active materials, experiments with LIBs fractions
in the presence of H2O2 (5%, v/v) reducing agent was also con- that contained different amount of impurities were conducted

Table 2
Acid leaching experiments with pure substances (LiCoO2: 19.6 g, Cu: 3.2 g, Al: 1.35 g, Fe: 0.33 g).

No. Input materials Temperature (°C) S/L (g/L) H2SO4 (mol/L)

LiCoO2 Cu Al Fe
p
E1 80 40 2.0
p p
E2 80 40 2.0
p p p
E3 80 40 2.0
p p
E4 80 40 2.0
p p p
E5 80 40 2.0
 C. Peng et al. / Waste Management 95 (2019) 604–611 607

Table 3 active materials and metallic components were studied in more

Yields of Co and Li when different LIBs particle size fractions are leached (T = 80 °C, detail with pure substances (see in Section 3.3).
t = 2.5 h, S/L = 100 g/L, [H2SO4] = 2 mol/L).

Fractions (mm) Yields (%)

Co Li 3.2. Investigation of acid leaching of underflow battery wastes
<0.125 55.0 88.2
(<2 mm) in the presence of overflow fractions as reducing agents
0.125–0.25 56.4 87.7
0.25–0.5 88.6 96.1 As a consequence of the positive effects determined with metal-
0.5–1.0 96.7 98.5 lic components on the acid dissolution of active materials, the Cu
1.0–2.0 95.1 98.7
and Al rich overflow fractions (OF, 2–6 mm) were investigated as
additives to aid the extraction of Li and Co from the underflow frac-
tion (UF, <2 mm). Results related to the Co and Li extraction in the
(T = 80 °C, t = 2.5 h, S/L = 100 g/L, [H2SO4] = 2 mol/L). Results in absence and presence of the overflow fraction are displayed in
Table 3 show that the leaching efficiencies of both Co and Li Fig. 3a and b. As observed, Co and Li concentration increase mark-
increase with laregr fraction particle sizes. For fractions edly with the addition of the overflow fraction and findings
<0.125 mm composed of ca. 0.5 wt% Al, 0.4 wt% Cu and 0.4 wt% demonstrate that higher ratios of overflow to underflow (OF/UF)
Fe, the leaching efficiencies of Co and Li were around 55% and give rise to the almost complete extraction of both Li and Co
88%, which is consistent with previous research based on cathode (>99%). Fig. 3c and d display the XRD patterns of the leach residues
active materials only (Meshram et al., 2016). In contrast, for frac- in the absence (Residue 1#) and presence (Residue 2#) of overflow
tions >0.5 mm - in which the respective contents of Cu, Al, Fe were additions (OF/UF = 1/10). Phase analysis of the XRD results was
above 19.5 wt%, 12.8 wt% and 7.2 wt% - the associated leaching performed by HighScore software using Rietveld fitting (Mahieux
efficiencies of the target metals Co and Li increase to a level of at et al., 2010) confirmed that the level of LiCoO2 left in Residue 1#
least 95%. (8.4 wt%) was substantially greater cf. Residue 2# with an overflow
Additionally, the leaching kinetics with fractions: <0.125 mm addition (0.7 wt%). This is consistent with the chemical analyses of
and 0.5–1.0 mm, in which the Co and Li contents are nearly the Residue 1# (Co: 5.40 wt%, Li: 0.27 wt%) and Residue 2# (Co:
same (Table 1), are outlined in Fig. 2. It is evident from Fig. 2a that 0.07 wt%, Li: 0.03 wt%), shown in Fig. S3.
the dissolution of the larger fractions (0.5–1.0 mm) have a faster Fig. 4 displays the influence of acid concentration on the extrac-
dissolution kinetics for both Li and Co, when compared with the tion of Co and Li with the addition of overflow fractions (OF:
smaller fraction (<0.125 mm). Taking Co dissolution as an example, UF = 1/10) at 80 °C. From the results, it is evident that the leaching
the Co leaching (0.5–1.0 mm) reaches the equilibrium at around efficiency of Co and Li (with the addition of overflow fraction)
50 min, whereas leaching with the <0.125 mm fraction is unable increases with higher acid concentration. When [H2SO4] 
to achieve equilibrium even with 150 min of reaction time. These 2.0 mol/L, leaching efficiencies of Co and Li maintain a high level
results demonstrate clearly that the presence of metallic impurity of above 99%, however, as H2SO4 concentration is decreased to
components (Fe, Al, Cu) in the battery waste is beneficial for the 1.5 M, the extraction of Co and Li drops to ca. 93% and 95%, respec-
extraction of Li and Co, as it increases both the leaching efficiency tively. Additionally, the dissolution of Co and Li with lower acid
and the associated kinetics. Fig. 2b displays the behavior of other concentration (1.5 mol/L H2SO4) exhibits lower leaching kinetics
impurity metals during the leaching process, showing that the when compared to that with 2 and 2.5 mol/L H2SO4. For example,
Fe, Al dissolution takes place rapidly and reaches nearly 100% at Co dissolution with both 2 and 2.5 mol/L H2SO4 reach a rapid equi-
around 30 min for Fe and 60 min for Al. In addition, Cu partially librium after 45 min, whereas when 1.5 mol/L H2SO4 is used, equi-
dissolves and reaches ca. 45% after 60 min and 55% in 150 min. This librium is not achieved after 60 min irrespective of overflow
suggests the presence of oxidants that can accept the electrons fraction additions (Fig. 4a). The addition of overflow fractions can
produced during the dissolution of Cu (Cu
2e
= Cu2+). Based however, introduce more impurities (e.g. Al, Fe) that may increase
upon the observed enhanced dissolution of Li and Co, the assump- the acid consumption, whilst simultaneously reducing Co and Li
tion is that the target active materials and metallic components extraction. Nevertheless, as the addition of overflow fractions - at
(e.g. Cu) can co-promote mutual dissolution. In order to study a ratio of OF/UF = 1/10 - adds only approximately 1.2 wt% Cu,
the mechanisms related to this phenomena, the acid leaching of 1.7 wt% Al and 0.2 wt% Fe to the total levels within the input mate-

(a) (b)
100 100
Leaching efficiency (%)

Leaching efficiency (%)

80 80

60 60

40 40
Li (< 0.125 mm)
Co (< 0.125 mm) Fe
20 20
Li (0.5 - 1 mm) Al
Co (0.5 - 1 mm) Cu
0 0

0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160

Time (min) Time (min)

Fig. 2. (a) Leaching efficiency of Li and Co as a function of time using battery waste fractions <0.125 mm and 0.5–1.0 mm; (b) Leaching efficiency of impurity elements as a
function of time with the 0.5–1.0 mm battery waste fraction (T = 80 °C, t = 2.5 h, S/L = 100 g/L, [H2SO4] = 2 mol/L).
608 C. Peng et al. / Waste Management 95 (2019) 604–611

(a) (b)
26 Co 3.8 Li Yields = 99.9%
Addition of Yields = 99.6% Addition of

Concentration of Lithium (g/L)

Concentration of Cobalt (g/L)

24 overflow fraction 3.6 overflow fraction Yields = 96.1%

Yields = 92.3%
22 Yields = 92.5%
3.4
20 Yields = 83.5%
3.2
18
3.0
16
Overflow:underflow = 0 2.8
Overflow:underflow = 0
14 Overflow:underflow = 1/20 Overflow:underflow = 1/20
Overflow:underflow = 1/10 Overflow:underflow = 1/10
12 2.6

0 20 40 60 80 100 120 0 20 40 60 80 100 120

Time (min) Time (min)

(c)
Leaching Residue 1# in the absence of overflow fraction (d) Leaching Residue 2# in the presence of overflow fraction
35000 Lithium Cobalt Oxide (0.5/1/2) 8.4%
Graphite 91.6% 35000 Lithium Cobalt Oxide (0.5/1/2) 0.7%
30000 Graphite 99.3%
30000
Intensity (CPS)

25000
25000
Intensity (PCS)

99.3%
20000 91.6% 20000
15000 8.4% 15000
0.7%
10000 10000
5000 5000
0 0
10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 90
Scattering angle, 2 (Co K radiation) Scattering angle, 2 (Co K radiation)
Fig. 3. Comparison of LIBs leaching in the absence and presence of overflow fractions (T = 80 °C, S/L = 100 g/L, [H2SO4] = 2 mol/L). (a) Co extraction as a function of time; (b) Li
extraction as a function of time; XRD patterns of leach residue in the (c) absence (Residue 1#) and (d) presence (Residue #2) of the overflow fraction (OF:UF = 1/10).

(a) (b)
Yields = 99.6% Yields = 99.9%
24 Co 3.8 Li
Addition of Addition of
Concentration of Lithium (g/L)
Concentration of Cobalt (g/L)

22 overflow fraction overflow fraction

3.6
Yields = 92.9%
20 Yields = 94.8%
3.4
18
3.2
16
3.0
14 1.5 M H2SO4 1.5 M H2SO4
2.0 M H2SO4 2.8 2.0 M H2SO4
12
2.5 M H2SO4 2.5 M H2SO4
10 2.6

0 20 40 60 80 100 120 0 20 40 60 80 100 120

Time (min) Time (min)

Fig. 4. Behaviors of (a) Co and (b) Li as a function of H2SO4 concentration and time (T = 80 °C, S/L = 100 g/L, [H2SO4] = 1.5, 2.0, 2.5 mol/L, mass ratio of OF:UF = 1/10).

rial, this will only consume a limited amount of acid (0.1 mol Li (as shown in Fig. S3). For comparison, the extraction of Co and
H2SO4 per 10 g of overflow fraction added). Li in the presence of one of the most commonly reported reduc-
From the results it is clear that addition of overflow fractions tants - hydrogen peroxide - was also studied, based on our previ-
can enhance the extraction of both Co and Li to >99%, resulting ous research (Aaltonen et al., 2017). With the addition of an
in leaching residue that contains only 0.07 wt% Co and 0.03 wt% optimum 5% (v/v) H2O2, Co recovery was only 95% and the Co
 C. Peng et al. / Waste Management 95 (2019) 604–611 609

present within the leach residue was over 2% (Fig. S3). This is prob- small quantity Fe (0.006 mol) increased Co dissolution (E3-Co,
ably resulted from the fact that H2O2 can readily decompose in the Fig. 5a) up to 77% and an equilibrium was reached within
presence of metal ions like Fe2+, Mn2+, Cu2+ and Cr3+ (Magalhães 120 min. A similar trend can also be observed for the Cu dissolu-
et al., 2007). Furthermore, the Li (1.4 wt%) and Co (8.4 wt%) present tion in Fig. 5b, which also accelerated after the addition of Fe
in the overflow fractions, due to association with the electrode (E3-Cu), which demonstrates that Fe addition promotes both the
materials, can also be recovered when using overflow fractions as oxidation (of Cu) and reduction (of LiCoO2) processes. The results
additives. suggest that the presence of dissolved Fe ions (Fe2+ or Fe3+) play
In addition, neutralization tests with leaching solutions the key role in enhancing the leaching kinetics. Nevertheless, elec-
(Table S1) in the absence and presence of overflow fractions trons produced by the dissolved Fe ions (Fe2+ M Fe3+, 0.006 mol e
)
(OF/UF = 1/10) were investigated and the results, detailed in are not sufficient to provide all the reductive power for the disso-
Fig. S4, reveal that the introduction of impurities from overflow lution of LiCoO2 from 58% to 78% (LiCoO2 ? Co2+, 0.04 mol e
) or
fractions do not cause any discernible increase in the chemical the dissolution of Cu from 25% to 100% after 120 min (Cu ? Cu2+/
burden for the subsequent purification stage. Details about the Cu+, 0.0375–0.075 mol e
). Therefore, it is postulated that the dis-
neutralization process can be found in supporting materials. solved Fe ions have a catalytic action (Hiroyoshi et al., 1997),
(Hidalgo et al., 2018), that facilitates electron transfer between
3.3. Influence of metallic components on the dissolution of LiCoO2 LiCoO2 and Cu via the following reactions (Eqs. (3) and (4)):
þ
In order to determine the effect of the individual elements pre- LiCoO2 ðsÞ þ Fe2þ þ 4Hþ ! Feþ3 þ Co2þ þ Li þ 2H2 Oc
sent in the overflow material on the reduction and yield of Co and Dr Ghm ¼
138:21 kJ=mol ð3Þ
Li, experiments that utilized pure substances were undertaken as
outlined in Table 2. It is clear from Fig. 5a that acid dissolution of
2Fe3þ þ Cu ! Cu2þ þ 2Fe2þ Dr Ghm ¼
66:71 kJ=mol ð4Þ
pure LiCoO2 (0.2 mol) has slow kinetics in the absence of reduction
agents (E1-Co), with Co dissolution only seen to increase from 38% Similar effects between Fe and Al were also found (Fig. 5c and d)
to 55% over 180 min. With the addition of metallic Cu (0.05 mol), as the addition of Al only lead to a minor increase in Co dissolution,
Co dissolution displays a marginal increase from 55% to 60% whereas after the addition of Fe (0.006 mol) Co dissolution
(E2-Co), which suggests that metallic copper has only a minor increased by 20% from 55% to 75% (LiCoO2 ? Co2+, 0.04 mol e
).
reductive effect on the dissolution of LiCoO2. The addition of a Moreover, the Al dissolution kinetics were seen to improve in the

(a) (b)
80 100
90
Leaching efficiency (%)

Leaching efficiency (%)

70 80
70
60 60
50
50 40
30
40 E1-Co
E2-Co 20 E2-Cu
E3-Co 10 E3-Cu
30
0 E3-Fe
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Time (min) Time (min)

(C) (d)
80 100
90
Leaching efficiency (%)

Leaching efficiency (%)

70 80
70
60 60
50
50 40
30
40 E4-Al
E1-Co 20
E4-Co E5-Al
30 E5-Co
10 E5-Fe
0
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (min) Time (min)

Fig. 5. Leaching of (a) Co in experiments E1, E2, E3; (b) Cu and Fe in experiments E2, E3; (c) Co in experiments E1, E4, E5; and (d) Al and Fe in experiments E4, E5. Input
materials are as follows: E1: LiCoO2, E2: Cu + LiCoO2, E3: Cu + Fe + LiCoO2, E4: Al + LiCoO2, E5: Al + Fe + LiCoO2.
610 C. Peng et al. / Waste Management 95 (2019) 604–611

initial stage of leaching after Fe was added. This behavior might Appendix A. Supplementary material
result from the reactions between Al and Fe3+ (Eq. (5)), however,
due to the passivation of Al, the equilibrium dissolution of Al only Supplementary data to this article can be found online at
increases ca. 5%. https://doi.org/10.1016/j.wasman.2019.06.048.

Dr Ghm ¼
679:91 kJ=mol

3þ
3Fe3þ þ AlðsÞ ! Al þ 3Fe2þ ð5Þ References
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