Journal of Hazardous Materials 404 (2021) 123989

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Journal of Hazardous Materials

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Comparative analysis of I2-KI and HNO3 leaching in a life cycle perspective:

Towards sustainable recycling of end-of-life c-Si PV panel
Jaeshik Chung a, *, 1, Bora Seo b, 1, Jooyoung Lee a, Jae Young Kim b
a
Water Cycle Research Center, Korea Institute of Science and Technology, Seoul 136-791, Republic of Korea
b
Department of Civil and Environmental Engineering, Seoul National University, Seoul 151-744, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Keywords: An iodine-iodide system was investigated as an alternative lixiviant for HNO3 for leaching precious metals from
Energy waste the end-of-life c-Si photovoltaic (PV) cell. A series of batch experiments were conducted for the optimization of
End-of-life PV panel leaching kinetics and thermodynamic equilibrium followed by a life cycle assessment (LCA) using data from the
LCA
experiments. The results showed that more than 95% of Ag and Al leached out within the first 5 min. The op­
Iodine-iodide leaching
Resource recovery
timum conditions for equilibrium leaching were as follows: solid to liquid ratio of 1:10 for Ag (1:9 ml for Al), and
I2 concentration of 0.35 M for Ag (0.3 M for Al), with I- concentration of 0.7 M. In addition, selective leaching of
Ag could also be accomplished by adjusting the reaction pH to 9.6%, and 93% of reproducibility was achieved
via the rejuvenation of the exhausted leaching solution, which can benefit the subsequent recovery process. The
leaching efficiency of iodine-iodide system was nearly comparable to that of HNO3, and the environmental
impacts of the two cycle of continuous process with rejuvenation of the iodine leaching solution can be effec­
tively reduced especially in the acidification & eutrophication, respiratory effect, and mineral extraction cate­
gories with subsequent exclusion of the additional neutralization process.

1. Introduction et al., 2016). The economic feasibility of recycling at full-scale is still

Recent developments in renewable energy have enabled a reduction
of fossil fuel usage and subsequent CO2(g) release. However, the so-
called energy waste, such as end-of-life (EoL) batteries and photovol­
taic (PV) panels, has become a simultaneous emerging issue in the field
of solid waste management. EoL solar panels, as a new type of waste
stream, have distinct characteristics: they are often installed by public
sectors (i.e., government) with large capacity (Xu et al., 2018), have
15–20 years of lifespan that may be reduced because of natural disasters
(e.g. earthquake, landslide, or hurricane etc.) (Mackay et al., 2014), and
contain valuable materials (silver, aluminum, copper, silicon, and glass),
some of which could be harmful to the environment unless treated
appropriately (Xu et al., 2018; Jung et al., 2016b; Corcelli et al., 2017).
A proper PV waste management protocol has not yet been established;
although a few previous studies have focused on the recycling of EoL PV
panels to recover raw materials (Masoumian and Kopacek, 2015; Müller
et al., 2011; Klugmann-Radziemska and Ostrowski, 2010). Recently, a
pilot scale PV panel recycling process, “Full Recovery of End of Life
Photovoltaic project (FRELP)” has been proposed in Europe (Latunussa
questionable and currently under intense investigation (Choi and Fthe­
nakis, 2010; Deng et al., 2019). Furthermore, the environmental sus­
tainability of recycling is also not ensured due to the involvement of
certain intensive energy and resource consuming processes, such as acid
leaching, for the recovery of precious metals (Latunussa et al., 2016). In
case of FRELP, HNO3 leaching is applied to extract Ag from cell scraps,
followed by neutralization by adding H)2 (Latunussa et al., 2016;
Ardente et al., 2019).
Hydrometallurgical recovery of precious metals from mining ores or
electronic wastes usually involves leaching with strong solvents such as
cyanides or nitric acid (Cui and Zhang, 2008; Coderre and Dixon, 1999);
these can pose a significant threat to environment and public health by
causing acidification and eutrophication (Konyratbekova et al., 2015a,
2015b). Recently, alternative leaching reagents have been proposed as
environmentally friendly and non-toxic substitutes for acids, such as
thiourea (Zhang et al., 2012), thiosulfate (Petter et al., 2014), and ionic
liquids (Whitehead et al., 2004; Visser et al., 2001; Dai et al., 2013); the
process involving the use of such substances is termed as green leaching.
Cui and Zhang (2008) comprehensively reviewed various metallurgical

* Corresponding author.
E-mail address: jschung@kist.re.kr (J. Chung).
1
Both authors equally contributed to the manuscript.

https://doi.org/10.1016/j.jhazmat.2020.123989
Received 30 April 2020; Received in revised form 12 August 2020; Accepted 12 September 2020
Available online 18 September 2020
0304-3894/© 2020 Published by Elsevier B.V.
J. Chung et al.
resource recovery techniques from e-waste and evaluated their eco­
nomic feasibility and environmental impacts. Among the hydrometal­
lurgical alternatives, halide leaching shows a potential competitiveness
based on advantages such as high leaching rate, non-toxic characteris­
tics, reusability, and moderate reagent cost (Zhang et al., 2012). Iodide
has originally been used as replacement of cyanide for gold extraction
from ore (Angelidis and Kydros, 1995; Baghalha, 2012). It has also been
recently utilized for the recovery of precious metals from e-wastes such
as waste printed circuit boards (PCBs) (Xiu et al., 2015; Jung et al.,
2016a; Sahin et al., 2015); however, environmental impacts of these
alternatives from the life cycle perspective has not been properly
addressed as yet.
A number of Life cycle assessment (LCA) studies on PV systems have
been carried out with respect to different stages their life cycle: (1)
production/construction, (2) electricity production (i.e., operation), and
(3) EoL (Vellini et al., 2017). Most of previous studies in the 1990s and
early 2000s investigated the global warming potential (GWP) and en­
ergy efficiency indicators, such as energy payback time (EPBT), of
various PV systems during their manufacturing and operation stages
(Gerbinet et al., 2014; De, 2013). However, few studies have focused on
the EoL management of PV panels in the past, and extensive environ­
mental impacts (e.g. human health, resources, and ecosystem quality,
etc.) have at last been taken into consideration since the 2010s. Gerbinet
et al. (2014) compared the environmental impacts of different types of
PV panels (i.e., mono- and poly-crystalline silicon (c-Si)), which oc­
cupies the majority (more than 80%) of the installed PV systems
worldwide (Paiano, 2015), in different stages (i.e., cradle-to-grave)
emphasizing the significant contribution during the EoL phase. Cor­
celli et al. (2018) and Ardente et al. (2019) demonstrated a comparative
LCA on different recycling scenarios (i.e., high rate vs. low rate recov­
ery) of PV panels to reflect the benefits of resource (e.g. copper,
aluminum, and silver) recovery as avoided impacts. Still, there is an
inherent uncertainty in database using existing literature and quanti­
tative basic unit information is requested especially for a newly devel­
oped process.
Considering the rapid increase of the PV waste generation, a proper
management of EoL PV panel with recovery of precious materials is an
urgent issue that requires both cost-effective and environmentally sus­
tainable solutions. In this perspective, the objectives of this study are
application of iodine-iodide system as an alternative lixiviant for HNO3,
and subsequent evaluation of the corresponding environmental impacts
on the basis of the experimental data; Ag and Al leaching from an EoL c-
Si PV cell was optimized via a parametric study and then a comparative
LCA is demonstrated to assess the differences in their environmental
impacts. Finally, a successive leaching is proposed with the rejuvenation
of the exhausted iodine leachate.
2. Materials and methods
2.1. Preparation of waste c-Si PV cells
The study obtained c-Si PV panels broken as a result of landslides in
Korea. Recycling of EoL PV panel involves mechanical, thermal, and
electro-chemical processes in order (Latunussa et al., 2016; Ardente
et al., 2019; Corcelli et al., 2018); firstly, the aluminum frame is
dismantled, and then the cable and junction box are removed from the
PV sandwich (i.e., solar cell + back sheet). Subsequently, ethylene vinyl
acetate (EVA) that holds the adjacent layers tightly is removed to
separate the glass, solar cell, and plastic back sheet, which is usually
achieved via thermal treatment (Lunardi et al., 2018). This study uses an
electric furnace to decompose all the volatile compounds including
plastic back sheets. After dismantlement of the aluminum frame, the
panels are then thoroughly washed with tap water to remove residual
soil particles and dirt. After drying, the washed panels are heated with
600 ◦ C for 2 h to remove EVA and separate the cell layer from the
sandwich. Scraps of cells and broken glass particles are then sieved
2
Journal of Hazardous Materials 404 (2021) 123989
(between #20 and #18 are collected) to produce a uniform particle size.
Finally, only PV cells are collected by manual handpicking using twee­
zers to overcome the heterogeneity. The total mass composition is
determined by ICP-OES (Vista PRO, USA) after 70% HNO3 digestion.
The scanning electron microscope (SEM) with energy dispersive X-ray
spectrometer (EDS) images of PV cells, before and after the leaching, are
also obtained using Regulus 8230 (Hitachi, Japan).
2.2. Leaching experiments
2.2.1. Kinetic and equilibrium leaching test
Iodine-iodide solution is prepared with analytical grade KI and I2
purchased from SHOWA (Japan) dissolved with freshly prepared
deionized (DI) water (> 18; MΩ cm; PALL Cascada, USA) before the
experiments. All leaching experiments are carried out under ambient
temperature; 1 g of PV cell is placed into 15 ml HDPE tube containing
desired concentration of lixiviant solutions (Table S1). The tubes are
then shaken at 10 rpm for intended times (for kinetics, 1, 3, 5, 10, 30, 60,
120 min, and 12 h for thermodynamic equilibrium) using rotary shaker
(WiseMix RT-10, DAIHAN Scientific, Korea). For equilibrium leaching,
variations are made with initial conditions: different I2 and KI concen­
trations (0–0.5 M for I2, and 0.5–1.0 M for KI, respectively), solid to
liquid ratio (S:L; 1:2–1:14), and different solution pH (3, 7, and 9). After
designated time, the supernatants are filtered through 0.45 µm syringe
filter (Whatman, USA). The dissolved metal concentrations are then
analyzed by using ICP-OES (Vista PRO, USA). The 1000 mg/L multi-
element standard solution (MES-04-1, AccuStandard, USA) is diluted
to prepare a calibration curve (1, 3, 5, 10, 30, and 50 mg/L) and
different wavelengths not overlapped with each other are selected for Ag
(328.068 nm) and Al (237.312 nm and 396.152 nm) based on ISO
22036. Surface of residual solid samples before and after leaching are
analyzed using SEM equipped with EDS. Every experiments were con­
ducted in triplicate and leaching efficiency was calculated based on the
following equation:
q(m) =
c(m) ×vl
(1)
mcell
where q(m) (M/M; mg/g in this study) is the amount of metals leaching
from unit mass of PV cell, c(m) (M/L3) is the concentration of metals in
leaching solutions, vl (L3) is the volume of solvent used in leaching, and
mcell (M) is the mass of PV cell that is used in the leaching experiment.
2.2.2. Rejuvenation of iodine-iodide solution
The rejuvenation of exhausted I2-KI solution is investigated in terms
of saving natural resources and minimizing subsequent waste produc­
tion. After the first cycle leaching is finished, dissolved silver complex
ions in the leachate are precipitated out of the solution by introducing
0.1 g of metallic zinc (Zn0) powder (Sigma-Aldrich, USA) and reduced
Ag0(s) are then filtered out (i.e., metallic replacement or cementation).
After confirming via ICP-OES that there are no Ag complexes remaining
in the solution, an additional amount of I2 (without KI) is added to the
solution to meet the desired I2 concentration (0.35 M) and prepare for
the second cycle of leaching.
2.3. Life cycle assessment on the alternative leaching process
A comparative LCA based on ISO 14044 (The International Standards
Organisation, 2006) is established to compare the environmental im­
pacts of using two different solvents (i.e., HNO3 and iodine-iodide sys­
tem) for resource recovery from EoL c-Si PV cells. An open source
software, OpenLCA (ver. 1.10.2) (Winter et al., 2014) with Ecoinvent
database (ver. 3) (Fthenakis et al., 2010) is used to benchmark the
leaching process (and following neutralization) in FRELP (Latunussa
et al., 2016; Ardente et al., 2019). The environmental impact of pro­
cessing 2 kg (1 kg per cycle) PV cell scrap using HNO3 and iodine-iodide
J. Chung et al.
solution is compared within the system boundary. For calculation of the
environmental impact, Eco-indicator 99 is used as life cycle impact
analysis (LCIA) method by replacing the first end point assessment
method, Eco-indicator 95. A stoichiometry relationship from the opti­
mized iodine-iodide leaching experimental condition is applied to
compare its life cycle impact with that of the conventional HNO3
leaching process followed by neutralization.
3. Results and discussion
3.1. Characterization of the EoL c-Si PV cell
Fig. S1 shows the preparation process of waste PV panels after
washing. Note that the blue cell layer is strongly bounded to the sand­
wich layer by EVA, which makes it difficult to separate. Various physical
and chemical methods have been proposed to effectively separate these
layers (Pagnanelli et al., 2017), which reflects that the current
manufacturing process is unfavorable to recycling and encourages a pre-
consideration of the recycling from the production (i.e., design) stage
(Latunussa et al., 2016). Surface of the untreated cell shows rough
texture with clear silver line on it (Fig. S1b). In Fig. 1, a schematic
structure of the PV cell is presented with the presence of silver rod before
and after the leaching. Compared to the silver rod in the center, the focus
on the adjacent blue SiNx layer is a slightly fuzzy due to the topological
difference (Fig. 1a), which becomes flat after the leaching (Fig. 1b;
Fig. S2). Table S1 shows the total metal content in 1 g of PV cell digested
by 70% HNO3. Silver and aluminum are known to be the most valuable
resources in c-Si PV panel (Peeters et al., 2017) and it is found that the
Ag content (5.5 mg/g cell for silver) is slightly lower than that reported
in previous studies (0.53 wt% of PV waste) (Latunussa et al., 2016;
Kuczyńska-Łażewska et al., 2018).
(a)
Fig. 1. Schematic structure of PV cell (modified from Deng et al., 2019) with optical microscope images (×400) of silver rod (a) before, and (b) after the iodine-
iodide leaching.
3
Journal of Hazardous Materials 404 (2021) 123989
3.2. Optimization of iodine-iodide leaching
Before choosing iodine as the targeted extractant, several feasible
alternatives are selected from previous studies (Cui and Zhang, 2008;
Zhang et al., 2012; Dai et al., 2013), and are evaluated for Ag leaching
from the obtained cell scrap. A total of four alternatives (thiourea, so­
dium thiosulfate, ammonium thiosulfate, and iodine with potassium
iodide) are selected from the previous studies that applied leaching to
solid wastes (mostly e-wastes) (Zhang et al., 2012) and tested for Ag
leaching from PV cell scraps to compare with 70% HNO3. Specific
leaching conditions for each lixiviant is adopted from the original study
(Fig. S3). The results showed that thiourea and iodine-iodide are effec­
tive for the PV cell where thiourea resulted in a negative solution pH
(− 1.73) presumably due to the additive oxidants (i.e., H2O2 and H2SO4).
The leaching mechanism in iodine-iodide system is known to be an
oxidative complex formation mainly driven by tri-iodide (I−3 ) as a pre­
dominant oxidant species and I− as a complexing agent as follows
(Birloaga and Vegliò, 2018; Liu et al., 2016; Brent Hiskey and Atluri,
1988):
I2 + I − = I −3 (2)
2Ag(S) + I −3 + I − = 2[AgI2 ]− (3)
Although elemental iodine itself has very low solubility (ca. 0.29 g/L
at 20 ℃), it dissolves easily to produce I−3 in the presence of I− (KI in this
study) as shown in Eq. (2). Fig. 2a shows a Pourbaix diagram of Ag
(0.01 mM) in iodine-iodide system (1 M each), fractionation of Ag spe­
cies within the experimental Eh ranges at pH 7 (Fig. 2b), and Ag
speciation within entire pH range at experimental Eh condition (ca.
280 mv) (Fig. 2c) drawn by Hydra-Medusa, a program used for chemical
equilibrium calculation. Note that the speciation is not very sensitive to
pH over a wide range (up to ca. 9), and the predominant fraction of Ag in
iodine-iodide system under the experimental condition (pH 3.5–7.0 and
(b)
J. Chung et al. Journal of Hazardous Materials 404 (2021) 123989

Fig. 2. (a) Pourbaix diagram of Ag (10 mM) in 1 M iodine-iodide system, and (b) fractionation of Ag species within the experimental Eh ranges at pH 6, and (c)
fractionation of Ag complexes with respect to pH at 280 mV.

Eh 0.1–0.5 v) is found to be in the form of AgI(x−

x
1)-
complexes.
5
3.2.1. Effect of I2 and KI concentration on iodine-iodide leaching system 60
Based on Eq. (2), we found that I2 and I- concentrations are both Ag Leaching (mg/g)

Al Leaching (mg/g)
4
crucial to metal leaching efficiency by controlling I−3 formation. An
excessive or insufficient iodine to iodide ratio can lead to a decrease in 3 40
leaching efficiency by forming insoluble metal iodide precipitates (e.g.,
AgI(s) or CuI(s)) (Xiu et al., 2015). Xiu et al. (2015) optimized the 2
leaching conditions for different metals leaching from PCBs including 20
iodine: iodide molar ratio (1:5 for Au and Pd, 1:6 for Ag at the optimum 1 Ag leaching
Al leaching
condition) after supercritical water pretreatment. Fig. 3 shows the
changes in Ag and Al leaching under different I2 concentrations (KI 0 0
concentration is fixed at 0.8 M). Both the metals exhibit sigmoidal 0.5 0.6 0.7 0.8 0.9 1.0
curves with sharp increase in the case of Ag, whereas a gradual increase KI Concentration (M)
is observed in the case of Al. Maximum leaching is observed at I2 con­
centration of 0.35 M for Ag and 0.3 M for Al, with the asymptotic Fig. 4. Effect of KI concentration on the equilibrium leaching amount of Ag and
leached amounts of ca. 4.14 mg/g and 46.06 mg/g, respectively, as Al from 1 g of PV cell in iodine-iodide system (initial concentration of I2 0.35 M,
calculated from Eq. (1). In addition, the optimum KI concentration is S:L of 1 g:10 ml).
found to be 0.7 M (Fig. 4), which is used in the comparative LCA in the
following section. (Zhang et al., 2012). Fig. 5 shows the leaching kinetics of Ag and Al
leaching within 60 min of the reaction time. Note that more than 95% of
3.2.2. Effect of reaction time on Ag and Al leaching in iodine-iodide system total reaction is accomplished within the first 10 min, followed by a
The high reaction rate is one of the advantages of halide leaching gradual increase; this bi-phase leaching represents that there is a

5 60 5 60
Ag leaching
50
Ag Leaching (mg/g)

50
Al Leaching (mg/g)

Ag Leaching (mg/g)

4 Al leaching
Al Leaching (mg/g)

4
40 40
3 3
30 30
2 2
20 20
1 Ag leaching
10 1 Al leaching 10
0 0 0 0
0.0 0.1 0.2 0.3 0.4 0.5 0 10 20 30 40 50 60
I2 Concentration (M) Time (min)

Fig. 3. Effect of I2 concentration on the equilibrium leaching amount of Ag and Fig. 5. Effect of reaction time on the leaching kinetics of Ag and Al from 1 g of
Al from 1 g of PV cell in iodine-iodide system (initial concentration of KI 0.8 M, PV cell in iodine-iodide system (initial concentration of I2 0.32 M and KI 1 M, S:
S:L of 1 g:10 ml). L of 1 g:10 ml).

4
J. Chung et al.
difference in accessibility to the leaching sites on the cell surface. The
first order reaction rate coefficients are evaluated with a simple
shrinking particle model (Bas et al., 2014) as follow:
1 − [1 − R] 1/3
= kt
where R [-] is the leached fraction, k (T− 1) is the leaching rate constant,
and t (T) is the time. During the first 5 min, Ag and Al are calculated to
be 5.05 × 10− 2 min− 1 and 4.08 × 10− 2 min− 1, respectively; these con­
centrations are fairly high compared to those obtained using HNO3
(1.92 × 10− 4 min− 1 for Al). This is also consistent with the previous
study (Bas et al., 2014) that treated the manufacturing scrap TV boards.
The high reaction rate from iodine-iodide leaching is well reported in
previous studies (Konyratbekova et al., 2015a, 2015b; Birloaga and
Vegliò, 2018), which eventually enables the handling of large amount of
PV panels within the designated processing time.
3.2.3. Effect of S:L on Ag and Al leaching in iodine-iodide system
The S:L is one of the important design parameters for batch type
operation that controls the leaching efficiency via enabling active mass
transfer (Chen et al., 2015); it also makes the process economically
feasible. Fig. 6 shows the changes in Ag and Al leaching under different
S:L. For Ag, an abrupt increase in leaching is observed between 1:6 and
1:8, with maximum at 1:10, whereas a gradual increase is observed in
the case of Al with the maximum S:L of 1:9. The poor efficiency at low S:
L is attributed to a limited contact chance towards leaching sites with
reduced mass transfer rate. Alternately, the slight decrease in leaching
amount at excessively high S:L is consistent with that reported in a
previous study that assumes the precipitation of excess iodides, when
combined with base metals (e.g. residuary Cu2+), on the surface of the
target material (Xiu et al., 2015).
3.2.4. Selective leaching and recovery of Ag in iodine-iodide system
Considering that the goal of resource recovery is obtaining pure
substances, separation and purification of the recovered metals in
leaching solution are of great importance. In the iodine-iodide PV cell
leaching system, Ag and (higher concentration of) Al are coexisting,
which makes it difficult to separate in the recovery stage. According to
the speciation dominance in Ag-I system (Fig. 2), pH has a minimal
impact in the range of experimental conditions, whereas Al precipitates
out of the weakly alkaline solution as aluminum hydroxides, which
could be utilized in the separating process. Fig. 7 demonstrates the
selectivity of iodine-iodide system towards Ag and Al leaching by
adjusting the solution pH (4.01, 7.0, and 9.6); to control the pH without
affecting the solution chemistry, acetate and borate are used to prepare
the buffer solution with the designated pH. By adjusting the solution pH
from 7 to 9.6, the entire Al precipitates out of the solution, where only
slight decrease in Ag leaching capacity (from 4.36 to 3.67 mg/g) is
5 70
Ag Leaching (mg/g)
Al Leaching (mg/g)
4 60
3 50
2 40
1 Ag leaching 30
Al leaching
0 20
1:2 1:4 1:6 1:8 1:9 1:10 1:12 1:14
Solid:Liquid ratio
Fig. 6. Effect of KI concentration on the equilibrium leaching amount of Ag and
Al from 1 g of PV cell in iodine-iodide system (initial concentration of I2 0.35 M
and KI 1 M).
Journal of Hazardous Materials 404 (2021) 123989
5 60
Ag
Al 50
Ag Leaching (mg/g)
Al Leaching (mg/g)
4
(4) 40
3
30
2
20
1 10
0 0
pH 4.01 pH 7.0 pH 9.6
Fig. 7. Selectivity of iodine-iodide leaching system with different solution pH
(initial concentration of I2 0.35 M and KI 1 M, S:L of 1 g:10 ml).
observed. Fig. 8 shows the surface properties of recovered silver particle
obtained from the reduction using sodium borohydride (NaBH4) as a
chemical reducing agent. Note that the weight (%) of Al is kept to a
minimum by using the leaching sample with pH being adjusted to 9.6.
3.2.5. Rejuvenation of the iodine-iodide leachate
Despite the above-mentioned superiority of leaching kinetics and
equilibrium properties, the main disadvantage of iodine-iodide system is
the high cost of reagent (Konyratbekova et al., 2015a; Zhang et al.,
2012), which could be overcome by rejuvenation and reuse of the
already used leaching solution (Konyratbekova et al., 2015a; Birloaga
and Vegliò, 2018). According to Lucheva et al. (2017), ca. 85% of
rejuvenation efficiency is accomplished by adding 98.06 mg/L H2SO4
and 34.01 mg/L H2O2 (to meet the desired pH and Eh conditions) after
the first cycle of iodine-iodide leaching process. It is reported that up to
99% of iodine rejuvenation can be achieved based on the posttreatment
methods (Konyratbekova et al., 2015a).
Before the proceeding to the second cycle, silver needs to be removed
from the solution in advance. Recovery of solubilized silver from the first
cycle extractant is achieved by metal replacement (i.e., cementation)
with metallic Zinc (Zn0) (Abdel-Aal and Farghaly, 2007). An excessive
amount (0.1 g) of Zn0 power is applied to the first-cycle extractant to
replace the dissolved Ag-complex ions with Zn2+, which has a lower
standard reduction potential, E0 (− 0.76 V) than that of silver (iodides)
(− 0.15 to 1.9 V) (Harris, 2010).
As aforementioned in the previous Section 3.2, Iodine-iodide system
is mainly composed of three products, I2 , I− and I−3 , which promotes the
oxidation/reduction reaction pair in accordance with solid metal in Eq.
(2). I− in the leaching solution is continuously monitored using iodide
ion selective electrode (9653BNWP, Thermo Scientific) throughout the
following successive processes: 1) adding KI in DI water (0.7 M), 2)
adding I2 (0.35 M) in the KI solution, and finally 3) adding cell scraps in
the I2-KI solution (Fig. S4). The I− is still abundant in the remaining
solution after the first cycle, and the limiting component in the system is
found to be I2 in this case. By adding an additional amount of I2 (to meet
the concentration as in the first cycle; 0.35 M) as an oxidant, Ag leaching
in the second cycle is successfully achieved (Fig. S5), presumably with
the aid of already existing complexing ligand, I− in the solution. Spe­
cifically, the leached amount of Ag in each cycle is 4.14 mg/g and
3.85 mg/g for first and second cycles, respectively (ca. 93% of repro­
ducibility). Moreover, while Lucheva et al. (2017) used an additional
chemical such as H2SO4 and H2O2 for the solution regeneration, no pH/
Eh adjustment was required in this study other than the replenishment
of the deficient iodine after the first cycle.
3.3. Life cycle impact of iodine leaching: HNO3 vs. iodine
The objective of the comparative LCA is to compare the environ­
mental impact of leaching (and following neutralization) processes
5
J. Chung et al. Journal of Hazardous Materials 404 (2021) 123989

Fig. 8. SEM image (×4500) and EDS mapping of recovered Ag from the sample (solution pH adjusted to 9).

using HNO3, and iodine-iodide solution, a promising alternative pro­
posed in this study. For quantitative analysis, a stoichiometry of HNO3
leaching and subsequent electrolysis and neutralization processes are
adopted from FRELP process (Latunussa et al., 2016; Ardente et al.,
2019) where those for iodine-iodide leaching are from the experimental
data from previous (Fig. 9). The processing of the cell scrap collected
from the waste PV panel is defined as a function, where the 2 kg (i.e.,
1 kg per cycle) of PV cell scraps for recovering precious metals (Ag and
Al) is defined as a functional unit. The system boundaries comparing two
systems with input/output parameters are shown in Fig. 9. Note that the
additional neutralization process is required to treat the acidic waste­
water in the HNO3 leaching, and two cycles (closed loop) of rejuvenation
is considered for iodine-iodide leaching. As aforementioned, one of the
advantages in using iodine-iodide is reusability and the particular unit
information is adopted from the experiment in Section 3.2.5.
Reflecting these advantages, we calculated the environmental
impact up to two cycles of sequential process treating 1 kg of PV cell
scrap under closed loop system and compared with the single batch
process (no rejuvenation) for 1 kg of PV cell recycling (system boundary
is shown in Fig. S6). As a result of calculation, the environmental impact
of the single cycle process did not show a significant difference between
HNO3 and iodine-iodide systems (Fig. S7). However, including the
rejuvenation process within the two cycles of iodine-iodide leaching
provides a significant reduction in multiple impact categories; iodine-
iodide is superior to HNO3 in 9 out of 14 categories, and three cate­
gories (acidification & eutrophication, respiratory effect, and mineral
extraction) are excellent in comparison (Fig. 10). Furthermore, relative
contributions (i.e., sensitivity) of sub-processes (leaching – filtration -
electrolysis (-neutralization)) within each system are compared and the
results showed that the neutralization process occupies a considerable
amount (e.g. 27.22% in climate change impact category) in the HNO3
case (Fig. S8), where the I2-KI leaching doesn’t have the neutralization
process. I2-KI system also has an additional rejuvenation process though,
the contribution within the process is found to be minimal (additional I2
is separately considered in the next leaching cycle), and the impact was
cut-off.
Overall, the endpoint analysis showed that the iodine-iodide system
is very good in ecosystem quality and human health, where the re­
sources category is slightly superior in the HNO3 case. This is presum­
ably due to the nitrogen circulating through the atmosphere, soil, and

System boundary of Leaching process with System boundary of Leaching process with
1M HNO3 (1kg of PV cell scrap*2 cycle) Iodine mixed solution (1kg of PV cell scrap*2 cycle)

Upstream Upstream

1 kg of cell scrap 1 kg of cell scrap (1, 2C) 1cycle (1C) +

1cycle * 2
KI Rejuvenated
70% HNO3, I2, 0.81 kg (1, 2C) cycle (2C)
Acid I2-KI
1.26 kg KI, 1.33 kg (1C)
Leaching Leaching
Water, 10 L / 0 kg (2C)
(10kg) Water, 10 kg (1C) 13.14 kg of Iodine, Leaching (1C)
11.882 kg of Nitric acid, Leaching
/ 0.2 kg (2C) / 2.01 kg (2C)
0.8385* kg of 0.8385* kg of
Metallurgical Metallurgical
Filtration Filtration
Grade-Silicon Metal Grade-Silicon Metal
(1, 2C)
11.04 kg of Nitric acid, Filtered 12.30 kg of Iodine, Filtered (1C)
/ 1.17 kg (2C)
Water, 2.42* kg Water, 2.42* kg 0.067 kg of Aluminum (A)
0.0020* kg of NOx (1, 2C) (1,2C)
Electricity, Electrolysis 0.072 kg of Aluminum (A) Electrolysis 0.00414 kg of Silver (A)
0.0055 kg of Silver (A) Electricity,
1.29* kwh (1C) / 0.00385 kg (2C)
1.29* kwh (1, 2C)
13.38 kg of Nitric acid, Electrolysised
14.65 kg of Waste water, Electrolysised (1C)
Water, 1.69* kg / 3.52 kg (2C)
Neutralization
Ca(OH)2, KI, 100% rejuvenation
14.40* kg of waste water,
1.69* kg Additional unit process 2.36* kg of sludge (1.33 kg)
Reused
in Leaching with HNO3

* Numerical value from Literature

Downstream (F. Ardente et al., 2019) Downstream (A): Avoided Product

Fig. 9. System boundary of leaching process with 1 M HNO3 and 0.35 M I2-0.7 M KI solution (two cycle comparison).

6
J. Chung et al.
Fig. 10. LCIA result of two cycles of leaching (1 M HNO3 vs 0.35 M I2-0.7 M KI solution with rejuvenation); the charts show the relative indicator results of the
respective project variants. For each indicator, the maximum result is set to 100% and the results of the other variants are displayed in relation to the former.
water.
4. Conclusion
This is the first attempt to evaluate the iodine-iodide system as an
alternative lixiviant that can replace the previous HNO3 leaching and
the following neutralization process in PV panel recycling system. Under
the optimized conditions, the leaching efficiency of iodine-iodide system
is almost comparable to that of HNO3 with the additional selectivity and
reusability, which can benefit the subsequent recovery process. Finally,
the environmental impacts of the continuous process (involving two
cycles) with rejuvenation of the iodine leaching solution can be effec­
tively reduced (especially in the acidification & eutrophication, respi­
ratory effect, and mineral extraction categories) with subsequent
exclusion of the additional neutralization process. Life cycle interpre­
tation stage in LCA needs to be extremely cautious because most of LCA
studies has employed the data from the existing literatures, which im­
poses a significant bias arising from spatiotemporal uncertainties. In this
perspective, a comparative LCA based on feasible data from the exper­
imental results is expected to provide creditable model results with
minimized uncertainty. For the practical application of the invented
method, further investigation of economic aspect needs to be pursued.
CRediT authorship contribution statement
Jaeshik Chung: Conceptualization, Writing - original draft. Bora
Seo: Methodology, Writing - review & editing. Jooyoung Lee: Software,
Validation. Jae Young Kim: Conceptualization, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
This study was financially supported by the Korea Institute of Science
and Technology (KIST) institutional programs (2E29474 and 2E30503).
The authors are grateful to the Korea Environment Corporation for
kindly providing EoL PV panel samples, and also internship students at
KIST for setting up the experiment.
7
Journal of Hazardous Materials 404 (2021) 123989
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jhazmat.2020.123989.
References
Abdel-Aal, E.A., Farghaly, F.E., 2007. Preparation of silver powders in micron size from
used photographic films via leaching-cementation technique. Powder Technol. 178,
51–55. https://doi.org/10.1016/j.powtec.2007.03.041.
Angelidis, T.N., Kydros, K.A., 1995. Selective gold dissolution from a roasted auriferous
pyrite-arsenopyrite concentrate. Hydrometallurgy 37, 75–88. https://doi.org/
10.1016/0304-386X(94)00020-4.
Ardente, F., Latunussa, C.E.L., Blengini, G.A., 2019. Resource efficient recovery of critical
and precious metals from waste silicon PV panel recycling. Waste Manag. 91,
156–167. https://doi.org/10.1016/j.wasman.2019.04.059.
Baghalha, M., 2012. The leaching kinetics of an oxide gold ore with iodide/iodine
solutions. Hydrometallurgy 113–114, 42–50. https://doi.org/10.1016/j.
hydromet.2011.11.013.
Bas, A.D., Deveci, H., Yazici, E.Y., 2014. Treatment of manufacturing scrap TV boards by
nitric acid leaching. Sep. Purif. Technol. 130, 151–159. https://doi.org/10.1016/j.
seppur.2014.04.008.
Birloaga, I., Vegliò, F., 2018. Overview on hydrometallurgical procedures for silver
recovery from various wastes. J. Environ. Chem. Eng. 6, 2932–2938. https://doi.
org/10.1016/j.jece.2018.04.040.
Brent Hiskey, J., Atluri, V.P., 1988. Dissolution chemistry of gold and silver in different
lixiviants. Miner. Process. Extr. Metall. Rev. 4, 95–134. https://doi.org/10.1080/
08827508808952634.
Chen, M., Huang, J., Ogunseitan, O.A., Zhu, N., Wang, Y. Min, 2015. Comparative study
on copper leaching from waste printed circuit boards by typical ionic liquid acids.
Waste Manag. 41, 142–147. https://doi.org/10.1016/j.wasman.2015.03.037.
Choi, J.K., Fthenakis, V., 2010. Economic feasibility of recycling photovoltaic modules:
survey and model. J. Ind. Ecol. 14, 947–964. https://doi.org/10.1111/j.1530-
9290.2010.00289.x.
Coderre, F., Dixon, D., 1999. Modeling the cyanide heap leaching of cupriferous gold
ores: part 1: introduction and interpretation of laboratory column leaching data.
Hydrometallurgy 52, 151–175.
Corcelli, F., Ripa, M., Leccisi, E., Cigolotti, V., Fiandra, V., Graditi, G., Sannino, L.,
Tammaro, M., Ulgiati, S., 2018. Sustainable urban electricity supply chain –
Indicators of material recovery and energy savings from crystalline silicon
photovoltaic panels end-of-life. Ecol. Indic. 94, 37–51. https://doi.org/10.1016/j.
ecolind.2016.03.028.
Corcelli, F., Ripa, M., Ulgiati, S., 2017. End-of-life treatment of crystalline silicon
photovoltaic panels. An emergy-based case study. J. Clean. Prod. 161, 1129–1142.
https://doi.org/10.1016/j.jclepro.2017.05.031.
Cui, J., Zhang, L., 2008. Metallurgical recovery of metals from electronic waste: a review.
J. Hazard. Mater. 158, 228–256. https://doi.org/10.1016/j.jhazmat.2008.02.001.
Dai, Y., van Spronsen, J., Witkamp, G.J., Verpoorte, R., Choi, Y.H., 2013. Natural deep
eutectic solvents as new potential media for green technology. Anal. Chim. Acta 766,
61–68. https://doi.org/10.1016/j.aca.2012.12.019.
Deng, R., Chang, N.L., Ouyang, Z., Chong, C.M., 2019. A techno-economic review of
silicon photovoltaic module recycling. Renew. Sustain. Energy Rev. 109, 532–550.
https://doi.org/10.1016/j.rser.2019.04.020.
De Wild-Scholten, M.J., 2013. Energy payback time and carbon footprint of commercial
photovoltaic systems. Sol. Energy Mater. Sol. Cells 119, 296–305. https://doi.org/
10.1016/j.solmat.2013.08.037.
J. Chung et al.
V. Fthenakis, R. Frischknecht, M. Raugei, H.C. Kim, E. Alsema, M. Held, M. de Wild-
Scholten, Methodology Guidelines on Life Cycle Assessment of Photovoltaic
Electricity, Methodol. Guidel. Life Cycle Assess. Photovolt. Electr. IEA PVPS T (2011)
International Energy Agency Photovoltaic Power Sys.
Gerbinet, S., Belboom, S., Léonard, A., 2014. Life Cycle Analysis (LCA) of photovoltaic
panels: a review. Renew. Sustain. Energy Rev. 38, 747–753. https://doi.org/
10.1016/j.rser.2014.07.043.
Harris, D.C., 2010. Quantitative Chemical Analysis, 7th ed. Macmillan.
Jung, I., Joe, A., Choi, J., Song, Y., Park, P., Park, K., Lee, S., Park, J., 2016. Leaching
behavior of gold from CPU chip grinding products in iodide/iodine solution.
J. Korean Inst. Resour. Recycl. 25, 3–9. https://doi.org/10.7844/kirr.2016.25.1.3.
Jung, B., Park, J., Seo, D., Park, N., 2016. Sustainable system for raw-metal recovery
from crystalline silicon solar panels: from noble-metal extraction to lead removal.
ACS Sustain. Chem. Eng. 4, 4079–4083. https://doi.org/10.1021/
acssuschemeng.6b00894.
Klugmann-Radziemska, E., Ostrowski, P., 2010. Chemical treatment of crystalline silicon
solar cells as a method of recovering pure silicon from photovoltaic modules. Renew.
Energy 35, 1751–1759. https://doi.org/10.1016/j.renene.2009.11.031.
Konyratbekova, S.S., Baikonurova, A., Akcil, A., 2015. Non-cyanide leaching processes in
gold hydrometallurgy and iodine-iodide applications: a review. Miner. Process. Extr.
Metall. Rev. 36, 198–212. https://doi.org/10.1080/08827508.2014.942813.
Konyratbekova, S.S., Baikonurova, A., Ussoltseva, G.A., Erust, C., Akcil, A., 2015.
Thermodynamic and kinetic of iodine-iodide leaching in gold hydrometallurgy.
Trans. Nonferrous Met. Soc. China 25, 3774–3783. https://doi.org/10.1016/S1003-
6326(15)63980-2 (English Ed.).
Kuczyńska-Łażewska, A., Klugmann-Radziemska, E., Sobczak, Z., Klimczuk, T., 2018.
Recovery of silver metallization from damaged silicon cells. Sol. Energy Mater. Sol.
Cells 176, 190–195. https://doi.org/10.1016/j.solmat.2017.12.004.
Latunussa, C.E.L., Ardente, F., Blengini, G.A., Mancini, L., 2016. Life Cycle Assessment of
an innovative recycling process for crystalline silicon photovoltaic panels. Sol.
Energy Mater. Sol. Cells 156, 101–111. https://doi.org/10.1016/j.
solmat.2016.03.020.
Liu, K., Zhang, Z., Zhang, F.S., 2016. Direct extraction of palladium and silver from waste
printed circuit boards powder by supercritical fluids oxidation-extraction process.
J. Hazard. Mater. 318, 216–223. https://doi.org/10.1016/j.jhazmat.2016.07.005.
Lucheva, B., Iliev, P., Kolev, D., 2017. Recovery of gold from electronic waste by iodine-
iodide leaching. J. Chem. Technol. Metall. 52, 326–332.
Lunardi, M., Alvarez-Gaitan, J.P., Bilbao, J.I., Corkish, R., 2018. A review of recycling
processes for photovoltaic modules. Sol. Panels Photovolt. Mater. 9–27.
Mackay, A.A., Gan, P., Yu, R., Smets, B.F., 2014. Seasonal arsenic accumulation in stream
sediments at a groundwater discharge zone. Environ. Sci. Technol. 48, 920–929.
https://doi.org/10.1021/es402552u.
Masoumian, M., Kopacek, P., 2015. End-of-life management of photovoltaic modules.
IFAC-PapersOnLine 48, 162–167. https://doi.org/10.1016/j.ifacol.2015.12.076.
Journal of Hazardous Materials 404 (2021) 123989
Müller, A., Wambach, K., Alsema, E., 2011. Life cycle analysis of solar module recycling
process. MRS Proc. 895, 1–6. https://doi.org/10.1557/proc-0895-g03-07.
Pagnanelli, F., Moscardini, E., Granata, G., Abo Atia, T., Altimari, P., Havlik, T., Toro, L.,
2017. Physical and chemical treatment of end of life panels: an integrated automatic
approach viable for different photovoltaic technologies. Waste Manag. 59, 422–431.
https://doi.org/10.1016/j.wasman.2016.11.011.
Paiano, A., 2015. Photovoltaic waste assessment in Italy. Renew. Sustain. Energy Rev.
41, 99–112. https://doi.org/10.1016/j.rser.2014.07.208.
Peeters, J.R., Altamirano, D., Dewulf, W., Duflou, J.R., 2017. Forecasting the
composition of emerging waste streams with sensitivity analysis: a case study for
photovoltaic (PV) panels in Flanders. Resour. Conserv. Recycl. 120, 14–26. https://
doi.org/10.1016/j.resconrec.2017.01.001.
Petter, P.M.H., Veit, H.M., Bernardes, A.M., 2014. Evaluation of gold and silver leaching
from printed circuit board of cellphones. Waste Manag. 34, 475–482. https://doi.
org/10.1016/j.wasman.2013.10.032.
Sahin, M., Akcil, A., Erust, C., Altynbek, S., Gahan, C.S., Tuncuk, A., 2015. A potential
alternative for precious metal recovery from e-waste: iodine leaching. Sep. Sci.
Technol. 50, 2587–2595. https://doi.org/10.1080/01496395.2015.1061005.
The International Standards Organisation, 2006. International standard assessment —
requirements and guidelines. Int. J. Life Cycle Assess. 2006, 652–668. https://doi.
org/10.1007/s11367-011-0297-3.
Vellini, M., Gambini, M., Prattella, V., 2017. Environmental impacts of PV technology
throughout the life cycle: importance of the end-of-life management for Si-panels
and CdTe-panels. Energy 138, 1099–1111. https://doi.org/10.1016/j.
energy.2017.07.031.
Visser, A.E., Swatloski, R.P., Griffin, S.T., Hartman, D.H., Rogers, R.D., 2001. Liquid/
liquid extraction of metal ions in room temperature ionic liquids. Sep. Sci. Technol.
36, 785–804. https://doi.org/10.1081/SS-100103620.
Whitehead, J.A., Lawrance, G.A., McCluskey, A., 2004. “Green” leaching: recyclable and
selective leaching of gold-bearing ore in an ionic liquid. Green Chem. 6, 313–315.
https://doi.org/10.1039/b406148a.
Winter, S., Rodríguez, C., Ciroth, A., Srocka, M., 2014. GreenDelta, openLCA Advanced
Training, GreenDelta.
Xiu, F.R., Qi, Y., Zhang, F.S., 2015. Leaching of Au, Ag, and Pd from waste printed circuit
boards of mobile phone by iodide lixiviant after supercritical water pre-treatment.
Waste Manag. 41, 134–141. https://doi.org/10.1016/j.wasman.2015.02.020.
Xu, Y., Li, J., Tan, Q., Peters, A.L., Yang, C., 2018. Global status of recycling waste solar
panels: a review. Waste Manag. 75, 450–458. https://doi.org/10.1016/j.
wasman.2018.01.036.
Zhang, Y., Liu, S., Xie, H., Zeng, X., Li, J., 2012. Current status on leaching precious
metals from waste printed circuit boards. Proc. Environ. Sci. 16, 560–568. https://
doi.org/10.1016/j.proenv.2012.10.077.