Clean Energy, 2023, Vol. 7, No.

3, 532–546

https://doi.org/10.1093/ce/zkac076
Advance access publication 6 May 2023
Review Article

Development of metal-recycling technology in waste

crystalline-silicon solar cells

Downloaded from https://academic.oup.com/ce/article/7/3/532/7156567 by Indian Institute of Technology Bombay user on 21 January 2024
Dehai Lin1,2,*,†, Zilin Liu1,†, Xiaoduan Li1, Zixiong Cao1 and Rihua Xiong1
1
National Institute of Clean and Low Carbon Energy, 102211, Beijing, China
2
College of Chemical Engineering, Zhengzhou University, 450001, Henan, China
*Corresponding author. E-mail: dehai.lin@chnenergy.com.cn
†These authors contributed equally to this work and should be considered co-first authors.

Abstract
Solar energy is currently one of the most promising clean energy sources and the use of solar energy has led to a rapid increase
in the number of solar cells. As one of the fastest-growing electronic wastes, the resource treatment of solar cells at the end of
their life should not be neglected. This review discusses the trend for the market development of crystalline-silicon solar cells and
analyzes their physical structure and composition. It also discusses the current domestic and international recycling technologies
for crystalline-silicon solar cells, including manual dismantling, inorganic acid dissolution, the combination of heat-treatment and
chemical methods, and organic solvent dissolution. The shortcomings of the above treatment methods are discussed and some views
on the recycling of waste crystalline-silicon solar cells are presented. Constructive suggestions for the green and sustainable develop-
ment of crystalline-silicon solar cells are put forward by comparing different treatment-recycling processes.

Graphical Abstract

Glass cover

EVA
Bus belt

Cell Cell

EVA
Backplane

Junction box

Aluminum frame

Keywords: waste solar cells; crystalline silicon; metal; recycling; dismantling

Introduction energy shortage in the world [3]. As people begin to focus on en-
ergy issues, the solar photovoltaic (PV) industry has received strong
Since the 1980s, fossil fuels, industrialization and rapid popula-
support from countries around the world [4, 5]. Fig. 1 shows the
tion growth have led to three global problems: energy shortages,
production of solar cells worldwide from 2005 to 2021. As can be
ecological damage and environmental pollution [1]. In the face of
seen from Fig. 1, the solar-cell segment in 2021 continued the key
increasingly serious energy, ecological and environmental prob-
expansion of 2020, with a substantial increase in production cap-
lems, solar energy, which is universal, safe, resource-rich and
acity [6]. The total global production capacity of crystalline-silicon
non-polluting, has received increasing attention as a clean energy
solar cells reached 423.5 GW—a year-on-year increase of 69.8%
source [2]. Making effective use of solar energy has gradually be-
[7, 8]. Total production was 223.9 GW, up 37% year on year (data
come a research hotspot. The invention and manufacture of solar
source: China Photovoltaic Industry Association). Although the
cells have, to some extent, alleviated the current situation of an

Received: 11 August 2022. Accepted: 29 November 2022

© The Author(s) 2023. Published by Oxford University Press on behalf of National Institute of Clean-and-Low-Carbon Energy
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 Development of metal-recycling technology in waste crystalline-silicon solar cells | 533

market share of crystalline-silicon solar cells has declined to some
extent, it still occupies most of the market share, accounting for
>80%, and the growth rate has always been >30% [9]. It is predicted
that until 2030, solar cells will continue to grow at a rate of ~25%.
In 2017, the global installed capacity of solar cells exceeded 90 GW,
of which China contributed 48 GW, the USA contributed 12.5 GW,
India contributed 10 GW and Japan contributed 6.8 GW [10].
There are many types of solar cells, including silicon solar cells,
multi-compound thin-film solar cells, polymer multilayer modified
span of a solar cell is typically ~20–30 years [22, 23]. As early as
2012, the latest revision of the EU Waste Electrical and Electronic
Products Management Regulations took the lead in bringing
solar PV modules into the scope of management. Solar cells are
officially classified as electronic waste and require efficient re-
cycling [24, 25]. According to relevant reports, the number of dis-
carded PV modules will reach 78 million tons by 2050 [26]. As can
be seen in Table 1, starting from 2020, the number of solar cells
scrapped in China will increase substantially [27]. Solar cells

electrode solar cells and nanocrystalline solar cells, among which
silicon solar cells are the most mature and dominant [11, 12]. At
present, silicon is the dominant material for solar cells and solar
cells made of silicon materials include: monocrystalline-silicon
solar cells, polycrystalline-silicon solar cells and polycrystalline-
silicon thin-film solar cells [13, 14]. As of June 2010, crystalline-
silicon solar modules represented 85–90% of the global PV module
market [15]. Second, the production cost of crystalline-silicon solar
cells accounts for 60% of the production cost of PV modules and
the production cost of crystalline-silicon wafers accounts for 65%
of the production cost of PV cells [16]. Therefore, the high-purity
silicon and precious metals in the cells can reduce the waste of
resources. The long production path of PV modules has led to
enormous environmental pressure and energy consumption. The
recycling of modules can effectively reduce energy consumption
in polysilicon production and realize closed-cycle production and
application of PV modules [17–19]. Therefore, research on recyc-
ling technology of cells containing silicon and other metals has
extremely important economic and environmental value [20–22].
Since solar cells are installed outdoors, they are prone to
ageing and performance degradation, and the conversion effi-
ciency of the cells will gradually decrease during use. The life-
Downloaded from https://academic.oup.com/ce/article/7/3/532/7156567 by Indian Institute of Technology Bombay user on 21 January 2024
have been classified as electronic waste in the revised Waste
Electrical and Electronic Equipment (WEEE) Directive published
by the European Union in July 2012 [25]. Therefore, the problem
of the electronic waste generated by scrapped solar cells cannot
be ignored.
Recycling and reuse of complete cells are very difficult and
the recycling of large amounts of aluminium, silver, silicon and
other resources in waste cells will become the focus. However,
at present, there are only a few complete sets of related research
data on resource recycling and treatment [28, 29]. Many scholars
have devoted themselves to the study of the purification tech-
nology of crystalline silicon and the conversion efficiency of solar
cells, which has greatly promoted the development of the PV in-
dustry. However, the purification of crystalline silicon is a process
with high energy consumption and high pollution [30, 31], during
which a large amount of waste liquids and gases, such as silicon
tetrachloride hydrogen chloride and chlorine gas, are generated.
These pollutants are difficult to deal with, cause strong corrosion
to equipment and also affect plant growth, causing great harm to
the environment [32, 33]. Research on the resource utilization of
solar cells is not taken into account. With the increasing number
of PV-cell systems, recycling of PV-cell modules is becoming more

Global cell production (GW) Year-on-year increase (%)

250 140%

120%
200
100%

150
80%

60%
100

40%
50
20%

0 0%
2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020 2021

Fig. 1: Global solar-cell production from 2005 to 2021. Data source: China Photovoltaic Industry Association.

Table 1: Solar-cell scrap and cumulative scrap in China in 2005–34 [27]

Year 2005 2010 2015 2020 2025 2030 2034

Annual MW Scenario 1 0.08 7.3 193 360 980 4322 15 732

Scenario 2 0.08 7.4 200 543 1392 5384 18 647
Accumulated MW Scenario 1 0.08 11.1 540 2045 5245 18 097 59 712
Scenario 2 0.08 11.2 550 2555 7366 23 836 73 536
534 | Clean Energy, 2023, Vol. 7, No. 3
and more important [34]. However, in addressing the problem of
PV power-generation systems, which can be substantially applied
to a large number of needs, the results have not been discussed.
There are currently two types of wafer: one is the end of life of
the PV stencil and the other is production scrap [35]. Despite the
limited use of silicon in batteries, the technology for this element
represents >90% of the market [36]. Many researchers have stated
that it is necessary to obtain useful materials from damaged or
exhausted PV templates for reuse, but so far no feasible solution
has been found to solve this problem [37, 38]. In addition, in the
global PV industry, the upstream crystalline-silicon purification
technology content is the highest, the profit is the highest and the
price accounts for about half of the cost of solar cells [26]. In order
to meet the demand for silicon raw materials in the PV industry
and solve the problem of a shortage of raw materials, it is neces-
sary to find a way to recycle the solid waste of solar cells.
The weight ratio of each component in the solar cell is ~70%
glass, ~10% aluminium, ~10% adhesive sealant, ~5% silicon and
~5% other. Waste crystalline-silicon solar cells have great resource
value [39]. Recyclable parts of crystalline-silicon solar cells in-
clude silicon, aluminium frame, tempered glass and metals such
as silver, aluminium and copper. Some scholars have studied the
leaching toxicity of solar panels and found that lead in cells has
a high leaching toxicity [40]. Therefore, the recycling of solar cells
is of great significance for saving resources and protecting the en-
vironment [41]. To solve the above problems, this review focuses
on the composition and working principle of crystalline-silicon
solar cells and, by reviewing the technology of dismantling PV
modules, the aluminium paste, silver paste and silicon wafers
in crystalline-silicon cells are recycled [42, 43]. Through the re-
search and development of resource-recovery technology, it advo-
cates the establishment of a complete set of controllable recovery
technologies and at the same time realizes resource recovery and
utilization, and achieves a win–win situation for economy and
environment.
This review focuses on the characteristics of waste crystalline-
silicon solar panels and explores the green and clean recyc-
ling methods of waste crystalline-silicon solar cells. First, the
market trend of crystalline-silicon solar cells is reviewed and
their physical structure and composition are analysed. Second,
the existing recycling technologies for crystalline-silicon solar
Table 2: Comparison of several types of solar cells and their advantages and disadvantages
Types of solar cells Highest conversion efficiency (%)
Monocrystalline silicon [51] 24.7 ± 0.5
Polysilicon [52] 20.3 ± 0.5
Amorphous silicon film [53] 14.5 ± 0.7
Polysilicon film [54] 16.6 ± 0.4
Copper indium gallium selenide 19.5 ± 0.6
(CIGS) thin films [55]
Cadmium sulphide (CdS), 16.5 ± 0.5
cadmium telluride (CdTe) cells [56]
Table 3: Composition of crystalline-silicon solar panel materials (kg/kWp) [31]
Materials Si Ag
Weight 3.101 0.030 12.771
cells are discussed according to the development status of
crystalline-silicon solar cells. The shortcomings of the above
treatment methods are discussed and some views on the recyc-
ling of waste crystalline-silicon solar cells are presented. The
shortcomings of the above methods are discussed and some
views on the recycling of waste crystalline-silicon solar cells are
presented.
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1 Crystalline-silicon solar cells
1.1 Solar cells
A solar cell is a semiconductor device that absorbs solar radi-
ation and converts solar energy into electrical energy. Solar cells
are also called PV cells [14, 44]. There are many materials that
can be used to make solar cells, so there are many types of solar
cells, of which crystalline-silicon solar cells account for the ma-
jority of the market (close to 80%) [45–47]. Table 2 shows a com-
parison of several different PV cells and their characteristics [44,
48–50].
1.2 Structure and composition of crystalline-
silicon solar cells
Crystalline-silicon solar cells mainly include monocrystalline-
silicon solar cells and polycrystalline-silicon solar cells [57]. They
all have a diamond lattice; the crystal is hard and brittle; they
have metallic lustre and can conduct electricity; they have semi-
conductor properties. According to estimates, the material com-
position of crystalline-silicon solar panels is shown in Table 3 and
a large amount of solid waste will be generated from the scrapped
PV modules. They are mainly composed of five parts, namely [58]
a metal frame, cover glass, crystalline-silicon cell, backplane and
encapsulation film. The structure is shown in Fig. 2.
1.2.1 Metal frame
The metal frame in the solar-cell module is used to protect the
module and it is bonded to the module by an ethylene–vinyl
acetate (EVA) film. The most commonly used metal frame is an
aluminium alloy frame and the surface of this frame is usually
oxidized [59]. The aluminium alloy frame material commonly
Advantage Disadvantage
High efficiency and mature High cost
technology
High conversion efficiency and Higher cost
mature technology
Simple process and low cost Poor stability
Low cost, good stability and The production process needs to be
high conversion efficiency optimized
Good stability, high conversion Indium and selenium are relatively rare
efficiency, simple process flow and there is a lack of material sources
Low cost, easy mass Cadmium is highly toxic and can cause
production, high efficiency pollution
Al Glass Cu Plastic
54.721 0.451 17.091
 Development of metal-recycling technology in waste crystalline-silicon solar cells |
used is the internationally accepted 6063T6 aluminium alloy ma-
terial and its specific composition is shown in Table 4 [60].
1.2.2 Cover glass
The solar panel uses low-iron tempered glass as the cover glass,
which has the characteristics of high light transmittance, high
strength, strong mechanical properties, long service life and stable
chemical properties, and its thickness is generally ~3.2 mm. Due
to the high iron content in ordinary glass and the high reflectivity
of the glass surface, the conversion efficiency of solar cells is low.
To reduce the surface reflectance of the cover glass, the manu-
facturers of the cover glass apply a thin-film layer on the surface
of the glass through physico-chemical treatment, which can ef-
fectively reduce the reflectance of the glass. This thin-film layer
is also known as an anti-reflection coating [62]. Coating the glass
with the anti-reflection coating can be realized using the vacuum
deposition method, the etching method and the high-temperature
sintering method. According to the literature, glass manufacturers
choose the etching method more. This process refers to the com-
bination of dip-coating sodium silicate and chemical treatment
to prepare anti-reflection glass, which is economical and simple.
The process flow is roughly as follows: washing, drying, immersion
in sodium silicate solution, extraction of glass, low-temperature
drying (or natural air drying), secondary chemical treatment, ex-
traction and drying detection (transmittance, reflectivity and film
thickness), packaging and delivery. This process method can sig-
nificantly increase the transmittance of glass [63–65].
1.2.3 Crystalline-silicon wafer
Crystalline-silicon wafers are composed of monocrystalline-
silicon wafers or polycrystalline-silicon wafers. Monocrystalline-
silicon wafers are formed using the Czochralski process for
high-purity polycrystalline-silicon wafers. The conversion ef-
ficiency of most monocrystalline-silicon solar cells can reach
~22% [66, 67]. Polycrystalline-silicon wafers are made of rect-
angular crystals that are sliced to form the required squares, so
their price is much lower than that of monocrystalline-silicon
wafers. Polycrystalline-silicon solar cells are similar in size to
Glass cover
EVA
Bus belt
Cell Cell
EVA
Backplane
Junction box
Aluminum frame
Fig. 2: Structure diagram of a crystalline-silicon solar panel
Table 4: Composition of aluminium alloy frame materials [61]
Element Si Fe Cu Mn
Content% 0.4 0.35 0.1 0.1
535
monocrystalline-silicon solar cells, but have slightly lower con-
version efficiencies and relatively lower production costs than
those made of monocrystalline silicon [68].
The structure of the crystalline-silicon wafer is first coated with
an anti-reflection film (Si3N4) on the front of the silicon wafer con-
taining the p–n junction; then, the silver paste is printed on the front
of the silicon wafer by screen printing to form a positive electrode
and the back is coated with aluminium paste and silver. The slurry
forms the back electrode. Therefore, crystalline-silicon solar cells
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are mainly composed of five parts: a silver grid, anti-reflection film,
p–n junction, silicon wafer and back electrode as shown in Fig. 3 [69].
1.2.4 Backplane
As shown in Fig. 4, the back sheet of the solar cell is on the back side
of the solar module, which mainly protects and supports the solar
cell. Since solar cells installed outdoors are exposed to the wind
and sun for a long time, the backplane needs to have reliable insu-
lation, water resistance and ageing resistance, and it is difficult for
single-layer film materials to fully meet the requirements [70]. At
present, the backplane material for solar cells is typically a Tedlar
Polyester Tedlar (TPT) composite film, which is the only backplane
that has been used in outdoor applications for 25 years at this stage.
The TPT composite film has a three-layer structure, which is com-
posed of two layers of Tedlar film and one layer of polyethylene ter-
ephthalate (PET) film. This composite film has good moisture-proof,
moisture-proof and weather-resistant properties. White TPT has a
reflective effect on light, which can improve the working efficiency
of the module, and has the function of improving infrared reflect-
ivity and reducing the working temperature of the module [71, 72].
1.2.5 Encapsulation film
Almost 80% of solar panels use EVA as the packaging material,
and EVA rubber and plastic products are new environmentally
friendly plastic foam materials [73]. EVA has good flexibility, elas-
ticity, transparency, weather resistance, corrosion resistance and
good cushioning, shock resistance, heat insulation, high light
transmittance, low processing temperature, good melt fluidity and
strong fusion bonding, and moisture resistance, and is non-toxic
and non-absorbent, etc. It can be compatible with fillers and col-
orants, it is cheap and it is very suitable for use as a solar-cell
packaging material [74–76]. The encapsulation film of crystalline-
silicon solar cells is generally a hot-melt adhesive with EVA as the
base resin. However, at the same time, EVA has the disadvantage
of easily ageing and yellowing as an encapsulation film, which af-
fects the conversion efficiency and service life of solar cells.
Thermoplastic polyvinyl butyral (PVB) can also be used as
a packaging material for crystalline-silicon solar cells. PVB is
non-toxic, non-corrosive and non-flammable, and has good light
transmission, insulation, wear resistance, water resistance and
aging resistance. The high price limits its application, so it has a
small market share [72, 77].
1.3 Reasons for the failure of crystalline-silicon
solar cells
The theoretical service life of crystalline-silicon solar cells is
25–30 years. But after a long time of use, the crystalline-silicon
Mg Cr Zn Ti V Al Ca
0.6 0.1 0.1 0.1 0.15 97.95 0.05
536 | Clean Energy, 2023, Vol. 7, No. 3
AI foil
Glass + ments [47, 87].
– For polycrystalline-silicon solar cells, polysilicon is obtained
Solar n-si
p-type cell
module p-si
EVA
Backsheet
Fig. 3: Schematic diagram of the structure of a crystalline-silicon solar
cell. Reproduced from [69] with permission from John Wiley & Sons.
solar cell will break down because of the cell. The phenomenon
of EVA foaming, delamination and backplane material cracking
caused by local overheating can easily cause the components
to be corroded by external moisture, air intrusion and some
polluting gases, making EVA more prone to ageing, and with
thermo-oxidative ageing under the action of ultraviolet rays,
EVA denatures and yellowing occurs [78–80]. The long-term ero-
sion of moisture and other corrosive gases (such as SO2, etc.)
leads to the cracking of the backplane material and the tin strip
near the outer crack is oxidized and corroded. In addition to the
above phenomena, cell chipping, grid-line disconnection and
grid-line falling-off in polysilicon modules can affect the elec-
trical performance of the module. These are mainly caused by
the long-term cyclic thermal stress inside the module [81, 82].
Therefore, solar-cell failure is a comprehensive reflection of
many aspects, which can be summarized as (i) cell cracking, (ii)
module hotspot phenomenon, (iii) EVA yellowing or delamin-
ation, (iv) diode burnout and (v) failure due to the disconnection
or detachment of the grid wire.
2 Significance of recycling in waste
crystalline-silicon solar cells
Recycling and reuse are the most attractive strategies to offset
the environmental impact and convert waste PV modules into
sustainable resources for the PV industry. Therefore, many efforts
have focused on recovering resources from waste PV modules,
especially crystalline-silicon (c-Si) from c-Si-based PV modules,
which have a major market share [83].
The valuable aluminium frame is removed using chemical
dissolution and thermal decomposition, and the remaining EVA-
encapsulated material can be further recycled after separation
for tempered glass, Si PV cells and Cu ribbon. Solar-grade silicon
can be recycled, then subjected to a chemical etching purification
process and reinjected as a raw material for solar-cell fabrication
[84, 85].
The power-conversion efficiency of silicon solar cells depends
mainly on their electrical and optical properties, including the
quality of silicon wafers (e.g. intrinsic purity and thickness),
metal electrodes, surface passivation and light-harvesting cap-
abilities of surface structures. For non-destructively recycled
silicon wafers, it is difficult to enhance the electrical properties
by increasing their inherent purity, unless they are melted to re-
produce the silicon ingot [86].
However, if silicon from discarded components is recovered
in the form of chips or powders to reuse in ingot production,
the economic and environmental costs are high, resulting in in-
sufficient profitability to maintain the sustainability of the pro-
cess. Furthermore, the regeneration of solar cells from recycled
silicon wafers often shows a trend of declining conversion ef-
ficiency, which is unacceptable for the current competitive PV
market. Therefore, silicon materials obtained using this method
are generally used in applications with lower purity require-
by converting metallurgical silicon into SiHCl3 and then reducing
it using H2 in a single process to obtain solar-grade polysilicon
[88]. Monocrystalline silicon is obtained by dissolving and
straightening the refined polysilicon in a monocrystalline furnace
[89]. Compared with monocrystalline silicon, polysilicon avoids
the production process of preparing monocrystalline silicon from
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polysilicon, so the cost is relatively low [90]. Such polysilicon has
a lower purity requirement, but the conversion efficiency is lower,
while monocrystalline silicon has a higher conversion efficiency
and higher cost. Furthermore, the production of polysilicon pro-
duces SiHCl3 and SiCl4, HCl and other harmful components, which
may cause greater environmental pollution and safety problems.
The industrial silicon powder used in the production of poly-
crystalline silicon for solar cells has strict requirements on the
purity. The impurity content in the purified silicon material should
meet the industrial silicon powder index. Therefore, inductively
coupled plasma–optical emission spectrometry (ICP–OES) is used
to detect the content of various elements in crystalline-silicon
PV cells and compared with the industrial silicon powder indica-
tors to determine the impurities that need to be removed in the
purification of silicon materials. The comparison between the im-
purity content of crystalline-silicon PV cells and industrial silicon
powder indicators is shown in Table 5.
According to the comparison results in Table 4, it is found that
the content of iron, calcium, titanium, boron, phosphorus, carbon
and acid-insoluble fraction in the crystalline-silicon PV cell is
better than the impurity content requirements of industrial
silicon powder. However, the content of aluminium and silver is
relatively high and they must to be removed as a key point. The
blue silicon nitride anti-reflection coating on the cell surface also
needs to be removed as an impurity.
The recovery of silver and silicon materials from waste PV cells
is still in the experimental stage. Yang et al. [91] used a needle-roller
electrostatic sorter to electrostatically sort the cells. The sorting
efficiency for silver was 94.37%, while the sorting efficiency for
silicon was only 78.58%. The separation of the aluminium back
electric field in the PV cells could not be completed, resulting in a
lower purity of the silicon material. According to research, the use
of a mixture of nitric acid and hydrogen peroxide could dissolve
the aluminium back electric field and the silver electrode on the
PV cells at a certain temperature. However, the use of this method
will cause the two metals of aluminium and silver to dissolve in
the same solution, which is not conducive to subsequent separ-
ation and recovery of silver. Dong et al. [92] adopted a step-by-step
recycling method using hydrochloric acid, nitric acid and a nitric
acid–hydrofluoric acid mixture to dissolve and leach aluminium,
silver and the silicon nitride anti-reflection film in PV cells in turn.
This method used the nitric acid–hydrofluoric acid mixture to re-
move the anti-reflection film, which could cause a large amount
of silicon loss, and the silicon-recovery rate was only 85.51%. Li et
al. [93] used sodium hydroxide solution to remove the aluminium
back electric field, ultrasonic cleaning to strip the silver electrode
and hydrofluoric acid solution to remove the silicon nitride film.
The above chemical method is still in the experimental stage and
the raw material used was only ~10 g, and when the industrial
purification of silicon material is carried out, the purified raw ma-
terial must reach at least the kilogram level. The small-scale test
data have a limited guiding effect on industrial purification and
cannot guarantee the purification effect and silicon-recovery rate.
 Development of metal-recycling technology in waste crystalline-silicon solar cells | 537

A
Waste photovoltaic
modules

Frame recycling
Dismantling

Downloaded from https://academic.oup.com/ce/article/7/3/532/7156567 by Indian Institute of Technology Bombay user on 21 January 2024
Junction box and
scrap recycling
Chopped

Glass recycling Silicon slag

Metal stripping
recycling

Hydrometallurg
ical separation
of metals

B C
CRUSHING HAMMER CRUSHING
50 50
45 45
40 40
35 35
30 30
25 25
%
%

20 20
15 15
10 10
5 5
0 0
d

5<

3<

1<

0.

0.

d<
d

5<

1<

0.

0.

d<

>

4<

08
>

4<

08

d<

d<

d<

0.
d<

d<

0.

8
8

<d
d<

08
<d
d<

08

3
8

m
m

<0
m

1
<0
m

m
m

m
m

m
.4
m
.4

m
m

m
m

m
m

THERMAL TREATMENT
D 50
45
40
35
30
25
%

20
15
10
5
0
d

5<

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0.

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d<
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8

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m
m

Fig. 4: (a) Process flow diagram of the recovery of crystalline-silicon cells by mechanical treatment; size distribution of CdTe modules after partial
treatment by (b) crushing, (c) hammering and (d) heat treatment, d > 1 mm. Reproduced from [30] with permission from Elsevier.
538 | Clean Energy, 2023, Vol. 7, No. 3
Table 5: Comparison of impurity content between crystalline-silicon photovoltaic cells and industrial silicon powder
Composition PV (%) Industrial silica fume (%)
Al 1.25 ≤0.20
Ag 0.04 – The content is higher, the treatment focus
Fe 0.01 ≤0.40
Ca – ≤0.10
Ti – ≤0.05
P 0.003 ≤0.0050
B – ≤0.0030
C – ≤0.10
Acid-insoluble – ≤1.00
Si 98.70 ≥99.3
Therefore, the recovery and purification technologies of metals
in crystalline-silicon solar cells need to go beyond the laboratory
and further towards the development of industrial application.
3 Status quo of crystalline-silicon solar-cell
waste recycling
3.1 Physical method
3.1.1 Mechanical treatment
The mechanical treatment method uses physical methods, such
as crushing and sorting, to separate the components and then
reuse them. The flow chart is shown in Fig. 4a. Granata et al. [30]
used two different types of crusher for coarse crushing and fine
crushing of waste solar cells, respectively, as shown in Fig. 4b–d.
The results show that the glass-recovery rate for the fraction of
>0.08 mm can reach 80–85%, and the part that is <0.08 mm needs
to be further processed. Zhang et al. [94] studied the electrostatic
separation of Si and PET in waste solar panels and obtained the
optimal parameter settings for the separation of Si particles and
PET particles, respectively. Yingli Solar has developed a process
[95] for the mechanical treatment of waste PV modules: after the
junction box and aluminium frame are removed, it is crushed to
remove glass and bus strips, and the mixed powder of Si, Ag and
Al is obtained through low-temperature grinding and electro-
static separation of EVA pellets and backplane pellets. The mech-
anical treatment method does not use any chemical reagents and
has less pollution to the environment, but the products typically
obtained are not of high purity and further research is needed to
improve the recovery rate and purity of materials.
3.1.2 Heat treatment
Heat treatment is a method of removing the EVA encapsulation
film by incineration so that the PV-cell sheet and the cover glass
can be separated. The flow chart is shown in Fig. 5.
EVA is generally used as a packaging material because of
its low cost, good performance and stable chemical proper-
ties. Therefore, the removal of EVA has become key to the tech-
nology. Some scholars have studied the pyrolysis characteristics
and products of EVA materials. Tian et al. [97] used a combined
thermogravimetric–infrared technology to study the pyrolysis
characteristics of EVA. The results showed that the thermal de-
composition of EVA in a nitrogen atmosphere was divided into
two stages. The gas released in the first stage was mainly acetic
acid and, in the second stage, the main releases were vola-
tile aliphatic hydrocarbons, including 1-hexene, 1-heptene,
1-isopropene, etc. Dong et al. [98] analysed the products of EVA
Comparing results
The content is higher, the treatment focus
Better than silica fume demand
Better than silica fume demand
Better than silica fume demand
Better than silica fume demand
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Better than silica fume demand
Better than silica fume demand
Better than silica fume demand
heat treatment through tube furnace experiments. The results
showed that the gas products of the EVA heat treatment were
carbon dioxide, alkanes and alkenes with five carbons or less,
and the liquid products were mainly long straight-chain alkanes
and alkenes, and a small amount of aromatic compounds and
alcohols. Zhang et al. [99] studied the pyrolysis characteristics
and pyrolysis products of plastic components in waste PV mod-
ules. The results showed that at a temperature of 773 K and a
nitrogen flow rate of 0.5 L/min, all organic components could be
decomposed. When the temperature exceeded 773 K, benzene,
its derivatives and other harmful substances were easily gener-
ated. Frisson et al. [100] used a high-temperature fluidized bed
to process solar panels to decompose the plastic components in
them. Studies have shown that EVA can decompose after 45 min
at 450°C and rupture of silicon wafers can be prevented in ni-
trogen. Cell-recycling rates can reach 80% and the recycling rates
are close to 100%. The waste gas can be used for secondary use
and can provide a heat source for the reactor. Furthermore, Doni
et al. [101] proposed a method to separate the glass and the cell
sheet based on an electric heating process generated by a chan-
ging magnetic field, as shown in Fig. 6b and c. Its characteristic is
that the separation temperature is lower than that of traditional
pyrolysis. Although the EVA can be completely removed using the
heat-treatment method, exhaust gas will be generated during the
treatment process, and the PV-cell cells are easily broken during
the heat-treatment process, so a complete silicon wafer cannot
be obtained.
3.2 Chemical method
3.2.1 Organic solvent dissolution
The organic solvent dissolution method refers to a method
of selecting several organic solvents to soak and remove the
crystalline-silicon cell of the backplane and dissolving the
packaging material EVA with an organic solvent to achieve sep-
aration of the glass and the cell [102]. The flow chart is shown in
Fig. 6a. Doi et al. [103] found that trichloroethylene could dissolve
EVA at a temperature of 80°C but the reaction time of this method
was ≥7 days and the recovery rate was low. In response to the slow
dissolution rate of organic solvents, Kim et al. [104] applied ultra-
sonic technology to improve the dissolution rate. Different kinds
of organic solvent were used to dissolve the EVA in PV modules
and ultrasonic waves were added to accelerate the dissolution of
the EVA. The effects of solvent concentration, temperature, time
and ultrasonic power were studied. The results showed that when
the ultrasonic power was 900 W, the temperature was 70°C and
the concentration of o-dichlorobenzene was 3 mol/L, the EVA
could be completely dissolved after 30 min (as shown in Fig. 6b).
 Development of metal-recycling technology in waste crystalline-silicon solar cells |
Complete PV modules Muffle furnace burning
B FLIR
RF Signal generator
& power amplifier
Transmission
cables
Teflon base
Top view
Fig. 5: (a) Process flow diagram for the recycling of crystalline-silicon cells by heat treatment; (b) radio frequency (RF) heater for photovoltaic panels.
Reproduced from [96] with permission from the Royal Society of Chemistry.
This method greatly shortened the reaction time. Because EVA
will expand in organic solvents, it will lead to fragmentation of
silicon wafers and at the same time a large amount of waste
organic solvents will be generated to be disposed of, which will
cause great environmental pollution.
3.2.2 Inorganic solvent dissolution method
The inorganic solvent dissolution method refers to a method
of selecting several inorganic solvents to soak and remove the
crystalline-silicon cell of the backplane and dissolving the encap-
sulation material EVA with an inorganic solvent to achieve sep-
aration of the glass and the cell. The flow chart is shown in Fig.
7a. Dias et al. [85] crushed the solar panel directly to <0.5 mm,
leached Ag with nitric acid and precipitated Ag in the form of
AgCl. Radziemska et al. [31] used chemical methods to recover
silicon from crystalline-silicon solar cells using 30% KOH at
80°C to remove aluminium, 40% HNO3 at 40°C to remove silver
and 83.33 mL HNO3 (65%) + 50 mL HF (40%) + 50 mL CH3COOH
539
Separate components Glass recycling
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Cell recycling
Camera
Copper tape
SWCNT film
on alumina
43 °C
21 °C
Thermal image
(99.5%) + 1 mL Br2 to remove the anti-reflection film and semi-
conductor materials to obtain a pure silicon wafer. Lee et al. [105]
tried leaching aluminium using nitric acid, hydrochloric acid,
sulphuric acid and sodium hydroxide, and leaching silver using
nitric acid and recovered aluminium sulphate and silver. The
results showed that the silver and aluminium recoveries could
reach 100%. Park et al. [106] used H3PO4 + HF + HNO3 to remove
the electrode and anti-reflection film, as shown in Fig. 7b; the
research results show that this method could obtain a flat and
smooth silicon wafer with almost the same performance as the
silicon wafer raw material, which could be directly used to make
new solar cells (see Fig. 8c). Shin et al. [89] used HNO3 and KOH
to remove Ag and Al, used a phosphoric acid-containing etching
paste to remove the anti-reflection layer, used 0.05% KOH solu-
tion to remove other impurities to obtain a complete silicon wafer
and finally used the recycled silicon wafer to recreate lead-free
solar energy panels with the same conversion efficiency as panels
made from new silicon wafers [107]. Liu et al. [108] used waste
lye produced in the solar-cell production process to remove
540 | Clean Energy, 2023, Vol. 7, No. 3

Complete PV modules Remove the backplane Soak in organic solvent Separate components

Wafer recycling Chemical etching

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B
C
25 °C, 60 min 55 °C, 60 min 70 °C, 30 min 25 °C, 60 min 55 °C, 60 min 70 °C, 30 min

100 100
Dissolution ratio of EVA / area %

Dissolution ratio of EVA / area %

80 80

60 60
3 M TCE, 25 °C
3 M TCE, 55 °C
3 M TCE, 70 °C
40 3 M O-DCB, 25 °C 40
3 M O-DCB, 55 °C
3 M O-DCB, 70 °C

20 20

0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time/min Time/min

D E
25 °C, 60 min 55 °C, 60 min 70 °C, 60 min 25 °C, 60 min 55 °C, 60 min 70 °C, 60 min

100 100
Dissolution ratio of EVA/area %

Dissolution ratio of EVA/area %

80 80

60 60 3 M Toluene, 25 °C
3 M Toluene, 55 °C
3 M Benzeme, 25 °C 3 M Toluene, 70 °C
3 M Benzeme, 55 °C
40 3 M Benzeme, 70 °C 40

20 20

0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time/min Time/min

Fig. 6: (a) Process flow diagram for recovery of crystalline-silicon cells by organic solvent dissolution method; EVA dissolution as a function of
processing time, temperature and solvent type: (b) O-DCB, (c) TCE, (d) benzene and (e) toluene (solvent concentration: 3 M, ultrasonic power: 900 W).
Reproduced from [104] with permission from Elsevier.
 Development of metal-recycling technology in waste crystalline-silicon solar cells |
Complete PV modules Remove the backplane
B C
Recovered virgin-like c-Si wafer Degaraded c-Si solar cells
A B C D
Recovering processed
Fig. 7: Process flow chart for recovery of crystalline-silicon cells by inorganic solvent dissolution method; (b) wet etching process; (c) carrier lifetime
mapping results of recovered wafers. Reproduced from [106] with permission from the Royal Society of Chemistry.
aluminium from waste crystalline-silicon solar cells, and used
HNO3 and HF to remove silver electrodes and silicon nitride layers
to obtain pure silicon wafers. The acid–base method has the advan-
tages of fast reaction speed and high efficiency, but the generated
acid–base waste liquid has certain pollution for the environment.
3.3 Combination of physical and chemical
methods
The combination of physical and chemical methods can be used
for the comprehensive recovery of all materials and is currently
the most commonly used method. It refers to placing the PV-cell
plate with the backplane removed in a tube furnace or muffle fur-
nace and removing the EVA packaging material to obtain a pure
PV-cell sheet. Then, chemical methods are used to remove the
anti-reflection layer, silver paste and aluminium on the surface of
the cell to obtain a pure silicon wafer. The flow chart is shown in
Fig. 8. Wang et al. [109] used a two-step high-temperature heating
method to separate and recover the glass, first using a tempera-
ture of 330°C to remove the backing material. Then the tempera-
ture was raised to 400°C for 120 min to remove the EVA and the
recovered glass could be reused directly. The test results showed
that the performance of the recovered glass was almost the same
as that of the new glass. The silicon wafer and copper were re-
covered using a chemical method, the back electrode Al was re-
moved using HCl/H2O2/H2O = 1:1:5, the SiNx was removed using
5% HF and finally the p–n junction was removed using 25% NaOH,
processed to recover the copper. The recovery rate of silicon was
62% and the purity was close to 100%; the recovery rate of the
copper could reach 85%. Kang et al. [110] found that toluene dis-
541
Soak in inorganic solvent Separate components
Wafer recycling Chemical etching
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03
)%( ecafruS
02
01
0
6.1 4.2 6.1
)au( emitefiL
solved EVA at 90°C for 2 days, which could better separate glass
and cells; high-temperature decomposition was used to remove
residual EVA on cells; finally, HF (48%), HNO3 (70%), H2SO4 (97%),
CH3COOH (99%) and surfactant CMP-MO-2 removed metals,
anti-reflection coatings and p–n junctions. When the mass frac-
tion of the surfactant CMP-MO-2 was 20% and the reaction time
was 20 min, the recovery rate of the silicon wafers could reach
86% and the purity could reach 99.999%. Paganaelli et al. [111]
crushed and screened waste solar panels and divided them into
three fractions of <0.4, 0.4–1 and >1 mm; for the part of 0.4–1 mm,
glass could be directly recovered, and the part of >1 mm should
be heat treated to remove the EVA. The metal was mainly con-
centrated in the particle size of <0.4 mm, using 3 mol/L sulphuric
acid and 5% hydrogen peroxide, leaching under the conditions
of a solid–liquid ratio of 3:1, a temperature of 60°C and a time of
3h; the comprehensive recovery rate of the final product reached
91%. Dias et al. [59] studied the separation of different compo-
nents of waste crystalline-silicon solar cells by combining phys-
ical methods with inorganic acids. First, the solar cells with the
aluminium frame removed were ground and the cell powder was
sieved into fraction sizes of <0.5, 0.5–1 and >0.5 mm, and then
the PV-cell powder was immersed in sulphuric acid and hydro-
fluoric acid to remove EVA and to separate the PV-cell sheet and
glass[112]. The results show that sulphuric acid can remove EVA
after 5 days and the separation effect of particle size >1 mm is the
best. German SolarWorld has developed a method that combines
heat-treatment and chemical methods to treat waste solar cells
[113]. . First, they undergo pyrolysis to remove the plastic part
and the remaining cells, glass and metal are separated by hand.
542 | Clean Energy, 2023, Vol. 7, No. 3

A B

Complete PV modules
Moving diamond wire Si Kerf Slag

SoG- Si Ingot

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Muffle furnace burning

Diamond wire sawing process

recycling

Slag
Wafer

Si
Step 1 Melting Step 2 Pouring Step 3 Cooling

Slag treatment process

Cells
Remove the anti-
reflection layer

Si Ingot
Purified Si
Filter Crush
Comminution
Dry
electrode metal

Wash/Etch
Removal

Acid leaching process

Fig. 8: (a) Process flow chart for recovering crystalline-silicon cells by combining physical and chemical methods. (b) The silicon notch is recovered
and purified from diamond-wire sawing silicon waste by slag treatment and acid leaching. Reproduced from [22] with permission from Elsevier.

Separated glass and metal are further processed and the cells are
etched to remove residual impurities and reused. Recovery effi-
ciency reaches 84%. The heat generated by the incinerator can be
used for other processes or preheating.
In general, because of a lack of investment in scientific re-
search and the short research history, recycling technology will
focus on the recycling of cells and silicon wafers, but it is not
possible to recover other metals from cells. The reason is that
precious metals are recycled, the technology is not mature yet
and many new energy materials have scattered materials, a small
number of individual products and exist in products in the form
of complex alloys, which brings great challenges to recycling.
and even precious metals. The question of how to resource solar
cells under the dual purpose of saving resources and protecting
the environment is worth focusing on. In order to separate the
higher-purity substances, the recovery of each modular distri-
bution is performed by disassembly. Effective recovery of metals
from used crystalline-silicon solar cells can be achieved by phys-
ical methods, chemical methods and a combination of physical
and chemical methods.
4.2 Outlook
However, each current recycling technology has its advantages
and disadvantages, and in order to promote the development of
recycling technology, the following issues need to be addressed:

4 Summary and outlook

(i) The dismantling of the solar cell ensures the environ-
4.1 Summary
In summary, solar energy has a series of advantages such as abun-
dant resources and no pollution to the environment, and has a
broad development prospect. However, a large number of waste
solar cells will be generated from 2020 onwards. In the revised
WEEE Directive announced by the EU in July 2012, solar cells were
classified as e-waste. Therefore, the problem of e-waste generated
by end-of-life solar cells cannot be ignored. When the elemental
composition of discarded crystalline-silicon solar cells is ana-
lysed, it can be found that they contain large amounts of metals
mental benefits of the dismantling process and realizes
the effective separation and harmless treatment of each
part of the PV-cell module. The technology of dismantling
and processing crystalline-silicon solar cells is still very
immature. The physical method is to roughly separate
the solar cells. If the fine components are not processed,
it will still cause a waste of resources and will not fully
realize the secondary utilization of resources. The heat-
treatment method can achieve the complete separation
of the cover glass, the backplane and the PV-cell sheet
543 | Clean Energy, 2023, Vol. 7, No. 3
to a certain extent, but the EVA and the backplane are
completely reduced to ashes, accompanied by the gener-
ation of gas. If it is not handled properly, it will cause air
pollution; the backplane can be considered for reuse and
burning it directly is a waste of resources in a sense. The
organic solvent dissolution method can achieve complete
separation of the panels, but how to effectively treat the
generated organic waste liquid is a key issue.
(ii) Research on the reuse performance of PV modules of solar
cells realizes the secondary utilization of resources such
as cover glass and crystalline-silicon wafers and unifies
the environment and economic benefits. With the devel-
opment of society, crystalline-silicon solar cells will face
a large amount of waste in the next few decades. Starting
from the principle of ‘harmless, recycling and reducing’ of
waste, the waste of crystalline-silicon solar cells will be
discarded. Recycling is an urgent problem to be solved.
(iii) Currently, the removal methods for EVA mainly include
the heat-treatment method and the organic solvent
method. Both of these methods have certain shortcom-
ings: waste gas is generated during the heat-treatment
process; the organic solvent method generates a large
amount of organic waste liquid; and there is a problem
with environmental pollution. Therefore, further research
is needed for the removal of EVA.
(iv) Both the existing heat-treatment method and the organic
solvent method have the problem of fragmentation of sili-
con wafers and it is necessary to explore a method for the
complete recovery of silicon wafers.
(v) In metal- and Si-recycling research, the nitric acid method
has the problem of producing waste acid in the treatment
process and, while the nitric acid–hydrogen peroxide
method is less polluting, it has the disadvantage of being
expensive, so these issues need further research.
(vi) More research is needed on the resource utilization of sili-
con in solar cells after metal and Si recovery.
Due to the different end-of-life times of PV power plants, EU coun-
tries have carried out research and practice on module recycling
and disposal earlier, while the USA is relatively late and China
has just started. The reasons for this are both the scattering of
valuable elements in the waste, the existence of complex forms,
recycling, technical difficulties and other objective factors, but
also imperfect policies, implementation not being in place, the
low degree of data and information sharing between enterprises
and departments, and other subjective issues. Summarizing the
effectiveness of the work in recent years, at the policy level, the
current PV waste disposal is still facing the following aspects of
the problem. First, the principle is strong, but the operability is
low. Second, the system has poor, unclear responsibilities. Third,
the target is low, and enforcement and punishment are weak.
Fourth, the relevance to PV waste is low.
Recycling and disposing of waste PV modules require the par-
ticipation of many parties in society. It is recommended that the
government should advance the layout, top-level design and
planning as soon as possible to introduce the management of
waste PV modules, including the revision of existing policies, and
the recycling and disposal of waste PV power plant components
and equipment into the policy system. A relevant trading plat-
form established and a fund set up as soon as possible. At the
same time, under the guidance and supervision of the govern-
ment, it is recommended that a non-profit organization be es-
tablished to exercise some of the functions of the government’s
environmental protection department.
In addition, different types of enterprises should have their
own roles, such as module manufacturing, and should explore PV
module products from the design side and manufacturing side
that meet the standards of reduction, resourcefulness and harm-
lessness, and pay the environmental protection fund as required.
PV power plant enterprises should pay the environmental pro-
tection deposit as required and submit the dismantled module
Downloaded from https://academic.oup.com/ce/article/7/3/532/7156567 by Indian Institute of Technology Bombay user on 21 January 2024
equipment to a formal disposal enterprise. Disposal enterprises
are required to dispose of waste according to the standards of
green factories and green production, and explore new processes
and methods to improve the reuse rate of waste.
Funding
This work was supported by the National Key R&D Program of
China (SQ2019YFC190083).
Conflict of interest statement
None declared.
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