sustainability

Review
Comprehensive Review of Crystalline Silicon Solar Panel
Recycling: From Historical Context to Advanced Techniques
Pin-Han Chen 1 , Wei-Sheng Chen 1,2, * , Cheng-Han Lee 1,2 and Jun-Yi Wu 3, *

1 Department of Resources Engineering, National Cheng Kung University, Tainan City 701401, Taiwan;
n48111017@gs.ncku.edu.tw (P.-H.C.); n48091013@gs.ncku.edu.tw (C.-H.L.)
2 Hierarchical Green-Energy Materials (Hi-GEM) Research Center, National Cheng Kung University,
Tainan City 701401, Taiwan
3 Department of Intelligent Automation Engineering, National Chin-Yi University,
Taichung City 411030, Taiwan
* Correspondence: kenchen@mail.ncku.edu.tw (W.-S.C.); wu8053@ncut.edu.tw (J.-Y.W.)

Abstract: This review addresses the growing need for the efficient recycling of crystalline silicon
photovoltaic modules (PVMs), in the context of global solar energy adoption and the impending
surge in end-of-life (EoL) panel waste. It examines current recycling methodologies and associated
challenges, given PVMs’ finite lifespan and the anticipated rise in solar panel waste. The study
explores various recycling methods—mechanical, thermal, and chemical—each with unique ad-
vantages and limitations. Mechanical recycling, while efficient, faces economic and environmental
constraints. Thermal methods, particularly pyrolysis, effectively break down organic materials but are
energy-intensive. Chemical processes are adept at recovering high-purity materials but struggle with
ecological and cost considerations. The review also highlights multifaceted challenges in recycling,
including hazardous by-product generation, environmental impact, and the economic feasibility of
recycling infrastructures. The conclusion emphasizes the need for innovative, sustainable, and eco-
nomically viable recycling technologies. Such advancements, alongside global standards and policy
development, are crucial for the long-term sustainability of solar energy and effective management
of PVM waste.

Citation: Chen, P.-H.; Chen, W.-S.;

Keywords: photovoltaic module recycling; crystalline silicon solar panel; sustainable waste
Lee, C.-H.; Wu, J.-Y. Comprehensive
management
Review of Crystalline Silicon Solar
Panel Recycling: From Historical
Context to Advanced Techniques.
Sustainability 2024, 16, 60. https://
doi.org/10.3390/su16010060 1. Introduction

Academic Editors: Zhitong Yao and

The global surge in solar energy adoption is a response to the imperatives of sus-
Nuria Ortuño García
tainability and the urgent need to combat climate change. Solar photovoltaic (PV) energy,
harnessing solar radiation to produce electricity, has become a prevalent method for terres-
Received: 23 November 2023 trial power generation [1]. At the forefront of this shift are crystalline silicon photovoltaics
Revised: 16 December 2023 modules (PVMs), the primary tools in PV systems for solar energy capture [2]. This growth
Accepted: 19 December 2023
is evidenced by a significant increase in installations, with an over 90% surge in the past
Published: 20 December 2023
decade, from 104 to 1053 gigawatts (GWs) [3].
These PVMs, predominantly silicon-based and representing 95% of global PV pro-
duction in 2020 [4], have a lifespan of 20–30 years [5,6]. Projections indicate that by
Copyright: © 2023 by the authors. 2030, worldwide solar capacity might approach 2840 GW, and by 2050, it could climb
Licensee MDPI, Basel, Switzerland. to 8500 GW [7]. However, given their finite lifespan, it is estimated that approximately
This article is an open access article 78 million tons of solar panel waste will require recycling by 2050 [8]. This rise in end-of-life
distributed under the terms and (EoL) PV modules, subject to variability due to type and mode of failure [9,10], presents
conditions of the Creative Commons significant waste management challenges. The International Renewable Energy Agency
Attribution (CC BY) license (https:// (IRENA) estimates that PV waste could range from 1.7 to 8 million tons in 2030, escalating
creativecommons.org/licenses/by/ to 60–78 million tons by 2050 [5]. Additionally, rapid advancements in PVMs could lead
4.0/).

Sustainability 2024, 16, 60. https://doi.org/10.3390/su16010060 https://www.mdpi.com/journal/sustainability

Sustainability 2024, 16, 60 2 of 16

to premature replacements, increasing EoL waste beyond the projected 78 million tons by
2050 [4].
Currently, PV systems predominantly operate on a linear “take–make–use–dispose”
model, leading to increased landfill waste and environmental concerns [11–14]. To mitigate
these issues, transitioning towards circular strategies and establishing an efficient PV
recycling infrastructure is essential [11]. Adopting a circular lifecycle methodology is vital
for waste reduction and enhancing the sustainability of the expanding PV industry. Regions
such as Europe, the UK, and Washington State have implemented stringent regulations,
mandating up to 80% recycling rates for end-of-life solar panels [15]. Properly managing
EoL PVMs can minimize resource usage, reduce waste, and offer substantial economic
benefits, potentially enabling the production of 2 billion new PVMs by 2050 [2,16].
Therefore, a comprehensive understanding and optimization of PVM recycling are
indispensable for addressing these waste management issues and supporting resource
conservation and the industry’s sustainable direction. As we delve into the intricacies of
PV recycling, understanding the specific methodologies becomes crucial. The subsequent
sections will explore the current state in PV recycling, the composition of crystalline silicon
solar panels, and the mechanical, thermal, and chemical recycling approaches of crystalline
silicon solar panels, discussing their significant findings, recovery efficiencies, advantages,
challenges and limitations, and prospects for future development.

2. Current State in PV Recycling

The PV industry has heavily invested its research and development (R&D) resources
in enhancing the efficiency of crystalline silicon panels [1]. However, there has been a
relatively small emphasis on developing cost-effective strategies for the dismantling and
recycling of PV panel waste [1]. This disparity in focus is partly because most of the PV
systems in use today were installed after 2010, leading to most PV waste originating from
pre-consumer sources such as manufacturing scrap and decommissioned defective panels,
rather than EoL PVMs [17–19].
Recycling PV panels, composed of a mixture of materials such as glass, metals, and
polymers, poses significant challenges [20]. Regions such as Japan, Europe, and the US are
at the forefront of R&D efforts aimed at solar module recycling [21], primarily focusing
on silicon-based panels to recover and recycle key components [21]. The evolution in the
composition of PV panels and fluctuations in raw material prices have led to variations in
recycling processes [10,22].
Despite the limited availability of panels for recycling, academic research has been
concentrated on addressing potential challenges [1]. These include the reduced electricity
generation capacity of PV panels using recycled materials, inefficiencies arising from
manual labor [1], risks of cross-contamination with other types of waste [19], and the
high costs associated with dismantling, transporting, and recycling, especially given the
hazardous elements in PV panel waste [12].
In the realm of PVM recycling, a variety of methodologies have been developed,
each with its unique approach and focus. Bulk recycling, predominantly applied to crys-
talline silicon (c-Si) modules, concentrates on extracting basic materials such as glass and
metals [23]. However, this method tends to overlook the recovery of semiconductor com-
ponents and precious metals, often leading to the production of lower-grade recycled
materials, especially glass [24].
Semi-high-value recycling, on the other hand, adopts a more selective recovery ap-
proach. This method often prioritizes specific components, such as the silicon wafer, but
may neglect other valuable metals [25,26]. In contrast, high-value recycling encompasses a
comprehensive approach, aiming to recover both basic and semiconductor materials [27,28].
This method strives to maximize the value of the recycled output by salvaging a broader
range of components from the PV modules.
Beyond these methods, closed-loop recycling represents a progressive shift towards
enhanced sustainability. Exemplified by practices at Deutsche Solar AG, this method inte-
Sustainability 2024, 16, x FOR PEER REVIEW 3 of 16

Sustainability 2024, 16, x FOR PEER REVIEW 3 of 16

Sustainability 2024, 16, 60 3 of 16
integrates reclaimed cells back into standard PV module production. This approach not
only focuses on resource efficiency but also significantly reduces waste, aligning closely
integrates reclaimed cells back into standard PV module production. This approach not
with sustainable development goals [19,29].
grates reclaimed
only focuses cells backefficiency
on resource into standard PV module
but also production.
significantly reducesThiswaste,approach
aligningnot only
closely
focuses on resource
with sustainable efficiency but
development also
goals significantly reduces waste, aligning closely with
[19,29].
3. Crystalline Silicon Solar Panel Composition
sustainable development goals [19,29].
3. Understanding the Solar
Crystalline Silicon composition and structure of crystalline silicon photovoltaic
Panel Composition
modules (PVMs)Silicon
3. Crystalline is critical in addressing
Solar the challenges and methods of recycling. These
Panel Composition
Understanding the composition and structure of crystalline silicon photovoltaic
widely Understanding
adopted panelsthe feature a multi-layered design, of each layer fulfilling specific func-
modules (PVMs) is critical in addressingstructure
composition and the challengescrystalline silicon of
and methods photovoltaic mod-
recycling. These
tional
ules and protective
(PVMs) roles,
is critical as illustrated
in feature
addressing in Figure
the challenges 1. This section
and methods delves into
of recycling. the detailed
widely adopted panels a multi-layered design, each layer fulfilling These widely
specific func-
composition
adopted of crystalline
panels feature asilicon solar panels,
multi-layered exploring
design, each thefulfilling
layer functionspecific
and significance
functional of
and
tional and protective roles, as illustrated in Figure 1. This section delves into the detailed
each component.
protective roles, as illustrated in Figure 1. This section delves into the detailed compo-
composition of crystalline silicon solar panels, exploring the function and significance of
sition of crystalline silicon solar panels, exploring the function and significance of each
each component.
component.

Figure 1. The Structure of a PVM.

Figure 1. The
Figure 1. The Structure
Structure of
of aa PVM.
PVM.
3.1. Front Glass (or Cover)
3.1. Front Glasstempered
Comprising (or Cover)
3.1. Front Glass (or Cover)glass, the front cover serves as a protective layer for the solar
cells, safeguarding
Comprisingthem from glass,
tempered environmental factorsserves
the front cover and ensuring optimal
as a protective sunlight
layer pen-
for the solar
Comprising tempered glass, the front cover serves as a protective layer for the solar
etration. This component
cells, safeguarding them is from
crucial for maintaining
environmental the cells’
factors functionality
and ensuring andsunlight
optimal preventingpene-
cells, safeguarding them from environmental factors and ensuring optimal sunlight pen-
efficiency
tration. loss
Thisdue to external
component damagefor
is crucial [30].
maintaining the cells’ functionality and preventing
etration. This component is crucial for maintaining the cells’ functionality and preventing
efficiency loss due to external damage [30].
efficiency loss due to external damage [30].
3.2. Silicon Solar Cells
3.2. Silicon Solar Cells
AtSilicon
3.2. the core of the
Solar Cellspanel, these cells are responsible for converting sunlight into elec-
At the coreas
tricity. Available of monocrystalline
the panel, these cells are responsible silicon,
or polycrystalline for converting
they are sunlight
enhancedinto electric-
with
At the
ity. Available core of the panel,
as monocrystalline these cells
orjunctionare responsible
polycrystalline for converting
silicon, they layer,
are enhanced sunlight
with into elec-
multiple
multiple coatings, including the n-p and anti-reflective for optimized per-
tricity.
coatings, Available
including as monocrystalline
the n-p junction or polycrystalline
and anti-reflective silicon,
layer, for they are enhanced with
formance and minimize efficiency reductions [31,32], as depicted in optimized
Figure 2. The performance
energy-
multiple
and coatings,
minimize including
efficiency the n-p[31,32],
reductions junctionas and anti-reflective
depicted in Figure layer,
2. The for optimized per-
energy-intensive
intensive production of these cells, often reliant on fossil fuels, has significant environ-
formance and
production minimizecells,efficiency reductions [31,32],
fuels,ashas
depicted in Figure 2. The energy-
mental impactsof[33,34].
these often reliant on fossil significant environmental im-
intensive
pacts production of these cells, often reliant on fossil fuels, has significant environ-
[33,34].
mental impacts [33,34].

Figure 2. Layered structure of a silicon solar cell.

Figure 2. Layered structure of a silicon solar cell.

Figure 2. Layered structure of a silicon solar cell.

Sustainability 2024, 16, 60 4 of 16

3.3. Anti-Reflective Coating

This coating enhances sunlight absorption, minimizing reflection loss and thereby
ensuring the maximum amount of sunlight reaches the silicon solar cells for conversion
into electricity [25].

3.4. Backing Film

Positioned behind the silicon cells, this film provides insulation and external pro-
tection. Available in various types, each backing film category has unique constructions
and properties, which will be detailed in Table 1. The choice of film affects both cost and
performance, with recent advancements improving UV durability.

Table 1. Comparative table of the three backing film categories.

Characteristic Double Fluoropolymer Single Fluoropolymer Non-Fluoropolymer

A Polyethylene Terephthalate (PET) core
layer is encased by two external layers of Tedlar or Kynar on the outer side;
Two PET layers and one primer or
Composition fluoropolymer material, potentially Tedlar PET and primer or EVA layers on
EVA layer
(Polyvinyl Fluoride, PVF) or Kynar the inner side
(Polyvinylidene Fluoride, PVDF)
Basic, but improving with
Protection Level Superior Satisfactory
advancements
Price Most expensive Moderate Cheapest
High
UV Durability High Satisfactory
(with recent advancements)
Developed to balance cost and Initially avoided due to
Historical Context Preferred for high protection
performance degradation risks
Significant, leading to highly
Advancements N/A N/A
UV-durable films

3.5. Junction Box and Electrical Connections

Located at the panel’s rear, the junction box houses electrical components crucial for
electricity collection and transfer. Features such as bypass diodes enhance panel perfor-
mance by preventing power loss due to shading [35].

3.6. Frame
Constructed primarily from aluminum, the frame offers essential structural support,
enabling the panel to endure environmental pressures such as wind and snow loads. The
frame’s material contributes significantly to the panel’s total weight [4,21,36].

3.7. Encapsulants
Predominantly composed of ethyl vinyl acetate (EVA), encapsulants are a key compo-
nent in PVMs, offering protection, electrical insulation, and moisture barrier functionalities.
These encapsulants are placed as thin layers around the solar cells and undergo heating at
150 ◦ C to initiate EVA polymerization, solidifying the module’s structure [37]. They must
exhibit high-temperature and UV stability, maintain optical transparency, and possess low
thermal resistance for the module’s efficient function [38,39].

3.8. Composition and Recyclability

A typical crystalline silicon solar panel comprises glass (70%), aluminum (18%), ad-
hesive sealant (5%), silicon (3.5%), plastic (1.5%), and other materials (2%), as outlined
in Table 2. While lacking rare metals found in thin-film solar panels, the materials in
crystalline silicon panels are nonetheless valuable for recycling. The challenge lies in the
separation and recycling of these materials, due to the compact and interconnected nature
of PVMs [13].
Sustainability 2024, 16, 60 5 of 16

Table 2. The composition of a crystalline silicon solar panel.

Main
Unit [4] [40] [41] [12]
Component
Front Glass Glass 70% 70% 63% 54.721%
Silicon 3.56% 3.65% 4% 3.101%
Silver 0.05% 0.05% <0.01% 0.03%
Copper 1.14% 0.11% Not Available 0.451%
Silicon solar cells
Tin <0.1%
0.053% 0.05%
Lead <0.1% Not Available
Aluminum 0.53% 0.53%
19%
Frame Aluminum 18% 18% 12%
Box body (including
Junction Box and copper or plastic Copper: 0.33% Copper: 0.6%
1% Not Available
Electrical Connections terminal), lid, diode, Plastic: 0.67% Others: Not available
cables, connectors
Encapsulants EVA 5.1% 5.1% 10%
Organic:11%
Backing film PVF, PVDF, PET, etc. 1.5% 1.5% 17.091%
The composition of the data will vary depending on the different methods of collection.

4. Mechanical Processes in PV Recycling

Mechanical recycling of PV panels has garnered significant research attention due to
its implications for sustainable energy solutions. This process typically begins with the
dismantling of panels, which involves removing components such as the aluminum (Al)
frame, encapsulating layers, Ag-printed Si solar cells, back sheets, junction boxes, and
embedded cables [42,43]. Following dismantling, the segregation of primary components,
including Al frames, solar cells, wiring, and laminated glass, is carried out [27].
To facilitate separation, various techniques are employed, ranging from manual meth-
ods to thermal treatments and automated systems [44–53]. Mechanical crushing and
shredding are prevalent approaches, aiming to extract valuable components from the pan-
els [45,54]. The frame, which provides mechanical strength to the panel, can be reclaimed
through secondary metallurgy after separation [50,55,56]. Additionally, methods such as
flotation yield crushed glass fragments sized between 45 and 850 µm [4,57], and mechanical
screening techniques have proven successful in recovering over 85% of glass [4,45]. It is
emphasized that prioritizing glass recycling is crucial for maximizing mass recovery and
ensuring the economic feasibility of the process [54].
Fernández et al. [58] explored recycling’s potential by integrating recycled silicon
solar cells into cement-based systems. Extensive research has refined the mass recovery
process across various PVM types, incorporating rotor crushing, hammer crushing, thermal
treatment for larger fragments, and sieving. This process enables the recovery of nearly
85% of the total panel weight as glass for certain size fractions [45], aligning with Directive
2012/19/EU of the European Parliament and of the Council of 4 July 2012 on waste electrical
and electronic equipment (WEEE) [59] and facilitating the recovery of materials such as
silicon from finer fragments [15,45].
Despite these advancements, mechanical recycling faces challenges related to cost,
environmental impact, and energy efficiency [60]. Innovative solutions such as high-
voltage pulsing, originally developed in the 1930s and recognized for its crushing effects
by the 1950s, are being explored. This technology, effective in diverse sectors such as
ore enrichment [56,60–64], requires operational voltages exceeding 100 kV for efficient
material separation of Cu, Al, Pb, Ag, and Sn in PVMs [65,66]. Furthermore, addressing
the issue of low purity and subsequent low utilization rates after mechanical crushing
remains a challenge. This is due to difficulties in isolating various materials. Lovato
Sustainability 2024, 16, 60 6 of 16

et al. [60] has introduced a method using supercritical CO2 fluid for the rapid delamination
of composite materials in solar panels. Under conditions of pressure greater than 7.39 MPa
and temperatures above 31.06 ◦ C, CO2 achieves a supercritical state. Supercritical CO2
(ScCO2 ) fluid exhibits a rapid penetration rate, allowing it to swiftly permeate the interface
between the solar cell and the EVA layer. This permeation into the EVA induces swelling,
causing the EVA to expand in volume. This expansion generates internal stresses that
counteract the bonding forces between the solar cell and EVA, thus achieving automatic
delamination. Notably, using ScCO2 reduces the delamination time of photovoltaic panels
to about one-third of that at atmospheric pressure [60].
For a comprehensive understanding of these methods and their efficacies, Table 3
compares several mechanical recycling methods and highlights their respective advantages
and limitations.

Table 3. Comparative analysis of mechanical recycling methods on silicon PV panels.

High Voltage
Incorporation Electro-Hydraulic
Fragmentation, Sieving, Crushing and
Method in Cement Fragmentation
and Dense Thermal treatment
Matrices (EHF)
Medium Separation
Selective separation and
Recycling in Recovery of valuable
Primary Use recovery of PV panel Glass recovery
construction materials metals from PV modules
materials
Approx. 85% 99% Cu, 60% Ag, 80%
Recovery Rate Not specified Not specified
(by weight) Pb/Sn/Al
Materials Glass, potential for Si (0.5–2 mm),
Glass, Cu, Sn, Pb, Ag Not specified
Recovered various metals Ag, Cu, Sn, Pb, Al
Decreased mechanical
Emissions management,
Improving Ag strength, increased
Challenges ensuring clean Not specified
recovery ratio porosity, durability
recovered glass
confirmation needed
0.21 JPY/W processing
Environmental and Reduces energy and Economically
costs, potential Not detailed
Economic Impact chemical consumption attractive
commercial viability
Effective separation and Utilization of PV waste,
Applicable to various PV Selective concentration of
recovery of potential for creating
Advantages types, high glass metals, straightforward
various materials, insulation and
recovery rate metal recovery
economically viable soundproofing materials
Additional methods Does not recover materials Emission management,
Disadvantages needed for higher for direct reuse in further processing for Not specified
Ag recovery PV manufacturing metal recovery
Ref. [57] [58] [45] [66]
Triple Crushing along
with Thermal or High Voltage
Method Electrostatic Separation Supercritical CO2
Chemical Treatment for Fragmentation
Selected Fractions
Separation of solar cell
Separation of Cu and Al from Recovery of valuable metals
Primary Use Recycling of PV panels from encapsulation and
waste wires from PV modules
glass layer
Over 96% (glass, Pb
Recovery Rate 91% 68.6% Cu (99% purity) 95% Cu, 96% Ag
filaments, back sheet)
Materials Glass, Pb filaments,
Glass, Al, Cu, (Ag) Cu, Al Cu, Al, Pb, Ag (<1 mm), Sn
Recovered back sheet
Challenges Not specified Not specified Not specified Not specified
Economically feasible
Environmental and
(PBT < 6 years Not specified Not specified Use of toluene
Economic Impact
for 75,000 ton/y)
Sustainability 2024, 16, 60 7 of 16

Table 3. Cont.

Triple Crushing along

with Thermal or High Voltage
Method Electrostatic Separation Supercritical CO2
Chemical Treatment for Fragmentation
Selected Fractions
High recovery rate,
Single scheme for different reduced solvent usage,
High purity in recovered Specific size crushing,
PV types, reduced thermal and delamination time
Advantages metals, adaptable to concentration of select
waste, single shortened to one-third
industrial scale materials in size fractions
equipment uses compared to
atmospheric pressure
Model improvement for Al
particles needed and further
Disadvantages Not specified Not specified Not specified
development for
industrial application
Ref. [54] [56] [65] [60]

5. Thermal Processes in PV Recycling

Thermal processes play a crucial role in the recycling of encapsulated crystalline
silicon photovoltaic modules (c-Si PVMs), particularly in disassembling them into indi-
vidual components. A key step involves the removal or debonding of the ethylene vinyl
acetate (EVA) copolymer layers used as adhesives [67,68]. Although techniques such as
mechanical crushing and chemical soaking have been explored, thermal decomposition is
often favored [47,68]. This preference stems from the fact that thermal methods, compared
to chemical methods which might involve hazardous and expensive chemicals, tend to
better preserve the integrity of the glass and silicon cells [5,69]. However, this approach is
not without drawbacks, as significant energy consumption and consequent emissions are
primary concerns [70].
In this context, pyrolysis stands out as a prominent technique. It involves thermochem-
ical decomposition at high temperatures in an oxygen-deprived environment, breaking
down organic elements into gases and liquids while leaving inorganic components such
as metals and glass largely intact [68]. This method is particularly effective in handling
complex waste compositions, such as those found in waste from electrical and electronic
equipment (WEEE) streams, which often contain diverse plastics mixed with other materi-
als [68]. The anoxic conditions in pyrolysis help prevent oxidation and the formation of
harmful by-products such as dioxins and PCBs [71].
Numerous studies have demonstrated that pyrolysis treatments can effectively remove
over 99% of the polymers from photovoltaic (PV) modules [70]. Kang’s research [72]
emphasized thermal decomposition’s effectiveness in separating the adhesive layer, thereby
aiding semiconductor recovery to a purity of 99.999%. During the thermal decomposition
process, EVA typically undergoes carbonization. However, in this experiment, the PV cells
were heated at 600 ◦ C for 1 h under an inert gas atmosphere, with a flow rate of 200 mL/min.
EVA starts to decompose at around 350 ◦ C, reaching complete decomposition at 520 ◦ C.
Consequently, by maintaining the temperature at 600 ◦ C for 1 h in a furnace, the EVA was
entirely removed, resulting in the retrieval of PV cells that showed no evidence of surface
carbonization. Wang [70] introduced a two-stage thermal technique for delaminating
the c-Si PVM. The process began by setting the temperature to 150 ◦ C for 5 min, which
softened the EVA binder and facilitated the effortless and complete removal of the TPT
backing materials from the solar panels. The next step involved the elimination of the
EVA binder through pyrolysis, conducted at 500 ◦ C. The study further revealed that at
lower temperatures (300–400 ◦ C), acetic acid was the primary product, while at higher
temperatures (above 410 ◦ C), a range of olefins were produced.
Other studies have underscored the environmental advantages of thermal treatments
over methods involving organic solvents [68]. Pyrolysis’s role in efficiently salvaging
undamaged silicon cells, a valuable market commodity, has been particularly highlighted
Sustainability 2024, 16, 60 8 of 16

in recent research [73,74]. To provide a comprehensive overview of these methodologies,

Table 4 details various pyrolysis-based recycling approaches for removing EVA.

Table 4. Synthesis of pyrolysis-based recycling approaches for EVA removal.

Thermal Treatment at Organic Solvents, Thermal

Method 170 ◦ C and 500 ◦ C Pyrolysis for 30 min to 1 h Treatment (600 ◦ C for 1 h),
Mechanical Force and Chemical Etching
EVA extracted with
similar properties to A > 99% polymer removal; 75% of
Significant An 86% silicon recovery
commercial EVA; polymers degrade between 400 ◦ C
Findings yield; a purity of 99.999%
thermally stable and 500 ◦ C
until 215 ◦ C
Eco-friendly, no material
Advantages degradation or Significant removal of polymers Efficient silicon recovery
gas emission
Challenges and Mass loss rate decreases significantly
Not specified Not specified
Limitations above 500 ◦ C
Solves issues related to
Reuse of extracted EVA
silicon supply,
Potential in solar modules and
Not specified manufacturing costs, and PV
Applications possibly in packaging
module end-of-life
and textile industries
management
Ref. [49] [68] [72]
Method Thermal Treatment up to 600 ◦C Two-Stage Heating (150 ◦C and 500 ◦ C)
Significant Detection of metals (including hazardous Integral recovery of TPT backing materials; EVA
Findings ones) in gas emissions and solid residues binder removed
Highlights the emission of hazardous metals Detailed analysis of EVA pyrolysis; potential for
Advantages
for management environmental friendliness
Challenges & Emissions need to be adequately managed to
Management/treatment of pyrolysis products
Limitations prevent environmental impact
Potential Environmentally friendly and efficient recycling
Not specified
Applications of waste crystalline silicon solar panels
Ref. [48] [70]

6. Chemical Processes in PV Recycling

Chemical processes are integral to the recycling of photovoltaic (PV) panels, especially
given the high purity levels required for silicon in solar applications. These methods excel
in recovering high-purity silicon, silver, and other valuable metals, optimizing the use of
resources [43,75,76].
One significant focus of chemical recycling is the removal of the ethylene vinyl ac-
etate (EVA) layer. Doi’s study [77] explored the effectiveness of organic solvents, such as
trichloroethylene, in debonding EVA from crystalline silicon solar panels. Another research
investigated various organic solvents, including toluene, for EVA dissolution, finding that
ultrasound significantly accelerates this process [47]. However, concerns arise due to the
production of hazardous by-products, such as lead, raising environmental safety issues [72].
The recovery of silver (Ag) from PV modules is a paramount area of research due
to its economic and technological value. Studies have shown the efficacy of nitric acid
leaching, enhanced by electrolysis, as a method for Ag extraction [78–81]. Characterization
experiments, involving steps such as immersion in H2 SO4 , HNO3 leaching, and X-ray
Sustainability 2024, 16, 60 9 of 16

fluorescence analysis, have been conducted to locate and measure the silver content in
modules [82].
Dias’ comprehensive study [67] assessed two methodologies for Ag extraction from
PVMs: one combining mechanical and hydrometallurgical techniques, and the other in-
corporating a pyrolysis stage. Results indicated that a pyrolysis stage did not improve
Ag extraction, suggesting that silver recovery should precede pyrolysis. The mechanical
and hydrometallurgical combined procedure that efficiently concentrated up to 94% of the
silver from PV modules, involving manual frame removal, module milling, sieving, and
nitric acid leaching, was followed by AgCl precipitation using sodium chloride.
For Ag recovery, methods such as extraction with cyanide solution or nitric acid have
been proposed [83]. However, these methods pose environmental risks, including waste
acid solution production and harmful fume emissions [82,83]. In response, researchers
have proposed using a methanesulfonic acid (MSA) mixture with an oxidant for Ag oxida-
tion [84]. This approach offers several advantages, including increased metal salt solubility,
conductivity, and environmentally responsible effluent treatment. Additionally, the ability
to regenerate MSA during the AgCl precipitation process underscores its sustainability [75].
Optimal conditions for Ag dissolution were found with a 90:10 MSA to oxidizing agent
ratio [75], achieving 99.8% (2N8) purity in recovered Ag, which could be further refined to
99.995% (4N5) through electrorefining, reducing contaminants such as Sn and Pb [75].
While chemical processes hold considerable promise in PV recycling, particularly for
precious metal recovery, their application must be carefully balanced with environmental
sustainability and economic feasibility. To provide a systematic overview of these chemical
methods, Table 5 summarizes the chemical approaches discussed throughout this context.

Table 5. Summary of chemical methods for the recycling of a silicon PV panel.

Mechanical and Nitric Nitric Acid

Method Organic Solvent Organic Solvent
Acid Leaching Leaching
Target
Ag Si, Cu, Ag, Pb Si Si
Material
Milling, Sieving, Leaching in
Key Process 5M Nitric Acid, Agitation Trichloroethylene at 80 ◦ C with
HNO3 , Precipitating o-Dichlorobenzene at 120 ◦ C
/Agent at 200 rpm mechanical pressure
with NaCl
Si: 80%, Cu: 79%, Ag: 90%,
Efficiency Successfully recovered without Successfully recovered without
94% silver concentration yield Pb: 93%
/Outcome damage after 7–10 days damage after 1 week
removal
Handling of acids and
Concerns Swelling and cracking of PV Swelling of EVA, potential
Energy consumption heavy metal
/Issues cells if pressure not applied for cracking
disposal
Ref. [68] [28] [77] [77]
Solvent Extraction Sulfurization and
Method Acid Precipitation Chemical Etching
and Electrowinning Neutralization Treatment
Target
Cu Ag Pb Si
Material
HCl Precipitation, NaOH,
Key Process LIX84-I extraction, H2 SO4 NaOH Neutralization, HF, HNO3 , H2 SO4 ,
Hydrazine Hydrate Reduction,
/Agent Stripping, Electrowinning Na2 S Sulfurization CH3 COOH, surfactant
Electrolytic Refining
Efficiency 99.99% purity 86% yield,
Not specified 93% removal
/Outcome after refining 99.999% purity
Concerns Handling of Handling of chemicals,
Handling of toxic Pb compounds Handling of strong acids
/Issues chemicals high-temperature processes
Ref. [28] [28] [28] [72]
Ultrasonic Chemical Chemical Recovery
Method Chemical Refinement
Irradiation Refabrication and Electrorefining
Target
EVA Si Si Ag
Material
Methanesulfonic acid (MSA)
O-DCB, TCE, Thermal or Chemical Separation, Wet chemical process
Key Process mixed with H2 O2.
Benzene, Toluene, followed by using a mixture of HNO3
/Agent Purification by
Ultrasonic Power Chemical Refinement and HF
Electrorefining
Sustainability 2024, 16, 60 10 of 16

Table 5. Cont.

Ultrasonic Chemical Chemical Recovery

Method Chemical Refinement
Irradiation Refabrication and Electrorefining
Optimal Ag extraction was
Silicon recovery with Re-fabrication achieved a high achieved with a 90:10
Efficiency Complete dissolution in 3 M resultant new cells efficiency of 17.6%, an 18.9% rise MSA:H2 O2 ratio. Initial purity of
/Outcome O-DCB at 70 ◦ C, 900 W, 30 min achieving 13–15% compared to the Ag powder was around 99%
efficiency original efficiency (2N), improved to 99.995% (4N5)
after electrorefining.
Managing the balance between
Determining the optimal ratio of
Absence of SiNx MSA and H2 O2 to avoid
Concerns PV cell damage in HNO3 to HF to avoid
antireflective coating on excessive H2 O2 decomposition
/Issues other solvents incomplete etching or deposition
resultant cells and ensuing H2 O generation
of Ag particles
which dilutes the solution.
Ref. [47] [25] [85] [75]

7. Current Challenges in Solar Panel Recycling

The recycling of silicon solar panels, pivotal to the sustainability of solar energy, is
confronted with a multitude of challenges. These challenges span technical, environmental,
and economic aspects, each intertwining to influence the feasibility and effectiveness of the
recycling process. The rapid growth in solar panel installations worldwide has not been
matched by equally swift advancements in recycling technologies, leading to significant
gaps in capability and capacity. This section delves into the primary challenges faced by the
recycling of silicon solar panels, highlighting the complexities and constraints that hinder
the development of efficient recycling methods.

7.1. Volume Concern

The surge in silicon solar panel installations, particularly in regions such as China,
has led to an increase in EoL panels. Current recycling methods in these areas often fall
short of international standards, struggling to keep pace with the growing volume of solar
waste [15]. There is a pressing need for the development of scalable and advanced recycling
solutions to manage EoL silicon solar panels efficiently and sustainably. Additionally, the
high costs associated with transporting large quantities of EoL panels, especially those
installed at high altitudes for maximum sun exposure, pose a significant challenge. To miti-
gate this, simple and quick pretreatment methods at local sites are suggested to reduce the
volume of solar panels, thereby decreasing transportation costs. Given that glass is the main
component of solar panels, prioritizing its recycling and local utilization could offer a more
sustainable waste management approach [54]. The remaining components, which contain
valuable metals, can then be collected, and processed at specialized solar panel recycling
facilities, further enhancing the efficiency and sustainability of the recycling process.

7.2. Material Recovery

Recovering materials from silicon solar panels is fraught with challenges, including the
production of harmful dust which contains glass and noise pollution during the crushing
process [21]. The loss of materials, including rare and conventional ones such as silver,
aluminum, and glass, is a significant issue during disposal [76]. For instance, nitric acid
dissolution can effectively remove the EVA and metal layer from the wafer, potentially
enabling the recovery of the entire cell. However, this process can lead to cell defects due
to the use of inorganic acid, consequently reducing the recovery rate of valuable metals
contained within the cells [21]. A high recovery rate method, such as vacuum blasting, has
the advantage of removing the semiconductor layer without chemical dissolution, and the
recovery of glass. However, this technique also has drawbacks, including the emission
of metallic fractions and a relatively long processing time [21]. The risk of releasing
hazardous substances such as lead from damaged encapsulating glass of silicon PV cells
raises environmental and health concerns [86]. Silicon dust inhalation and the release of
compounds from EVA and other manufacturing chemicals also pose serious risks [42,86].
Innovative, efficient recovery and recycling processes are crucial to mitigate these risks,
Sustainability 2024, 16, 60 11 of 16

optimize resource utilization, minimize environmental impact, and ensure the sustainable
use of silicon PV technology.

7.3. Environmental Impact

Recycling solar panels presents several environmental challenges. These include the
release of harmful gases such as hydrofluoric acid during chemical treatments, exposure
to toxic dust and noise during physical processes such as high voltage crushing, and the
high energy consumption of thermal methods [23,42,85,87]. Additional issues such as
nitrogen oxide emissions during EVA layer separation by nitric acid dissolution [21,56],
waste disposal complications, and the prolonged dissolution time of the EVA layer using
traditional organic solvents [88]. Typically, the utilization of organic solvents in the dis-
solution of EVA from PV panels needs extended time periods, resulting in less efficiency
and the additional challenge of wastewater treatment. For example, isopropanol is used to
dissolve the polymer over a span of two days, and trichloroethylene requires a duration of
ten days at a temperature of 80 ◦ C. Moreover, an alternative method combining organic
solvent and ultrasonication has been explored. In this process, EVA is fully dissolved in
3 M O-dichlorobenzene (O-DCB) at 70 ◦ C, with an irradiation power of 900 W, achieving
dissolution in 30 min. However, this ultrasonic approach increases processing costs and
leads to the generation of organic liquid waste, presenting further environmental and
handling challenges. Given these constraints, there is a growing need to develop more
environmentally sustainable and cost-effective methods for EVA dissolution. Future re-
search could focus on identifying solvents that balance efficiency, environmental impact,
and economic feasibility.

7.4. Economic Viability

The economics of recycling silicon solar panels are currently not favorable. The costs
of establishing and operating recycling infrastructure are high compared to the benefits,
especially considering the limited number of panels being decommissioned [14,89]. This
economic challenge diminishes the incentive for manufacturers to engage in recycling ef-
forts, pushing them towards landfilling or low-value recycling without material separation.
Evaluating the potential for the recovery of valuable materials to offset overall recovery
costs is essential to enhance the economic feasibility of silicon solar panel recycling and
boost the competitiveness of PV technologies [90].
Many studies have carried out life cycle assessments (LCA) on the EoL PVM recycling.
These LCAs have established that recycling PV panel waste can reduce both energy de-
mands and the emissions linked to landfill disposal [91]. Additionally, while some studies
analyzing energy and resource use, as well as air emissions during panel recycling, suggest
that under current conditions, recycling PV waste might not be economically feasible [14,89].
Yet, a comprehensive understanding in this area remains limited. The task of comparing
the economic and environmental impacts of different PV recycling technologies is hindered
by several factors. These include variations in system boundaries, functional units, the
degree of material recycling, and the ways in which LCA results are interpreted [91].
Pablo et al. [92] performed an LCA study comparing a simplified recycling method
with a full recovery approach and landfilling. This simplified method involves deframing
the module, shredding the laminate, and concentrating materials through electrostatic
separation. This process results in two fractions: one being a valuable mix (comprising
only 2–3 wt%) of silver, copper, aluminum, and silicon, and the other primarily consisting
of glass, silicon, and polymers. An economic assessment of this method suggests it could
be more profitable than full recovery, particularly for lower waste volumes (less than
4 kt/y), due to reduced capital costs for equipment. This study indicates that, under certain
conditions, streamlined recycling processes can offer a more cost-effective alternative to
comprehensive methods, potentially leading to more sustainable and economically viable
solutions in the field of PV waste management.
Sustainability 2024, 16, 60 12 of 16

8. Conclusions
The transition to sustainable energy sources, epitomized by the global surge in solar
photovoltaic (PV) energy adoption, presents both opportunities and significant challenges.
This review has explored the intricate aspects of crystalline silicon photovoltaic module
(PVM) recycling, delving into the current state, methodologies, and challenges associated
with this crucial process.
The examination of the recycling landscape reveals that while technological advance-
ments in PV module production have been remarkable, recycling practices have not kept pace.
The growing volume of EoL silicon solar panels, particularly in rapidly expanding markets
such as China, underscores the urgency for scalable and advanced recycling solutions.
Our exploration into the composition of crystalline silicon solar panels underscores the
complexity involved in recycling these multi-layered devices. Each component, from the
protective front glass to the crucial silicon cells, poses unique challenges in recycling, neces-
sitating diverse strategies such as mechanical, thermal, and chemical processes. Mechanical
processes, while efficient in certain aspects, face challenges in terms of cost, environmental
impact, and energy efficiency. Thermal processes, particularly pyrolysis, offer promising
results in breaking down organic elements but are not without significant energy demands
and emissions. Chemical processes, effective in recovering high-purity materials, must
contend with balancing environmental sustainability and economic feasibility.
The primary challenges in recycling silicon solar panels are multifaceted, encompass-
ing technical, environmental, and economic aspects. The production of harmful dust, the
potential release of hazardous substances, and the environmental impact of various recy-
cling processes are key concerns that need addressing. Additionally, the current economic
model of solar panel recycling is not incentivizing enough for manufacturers, suggesting a
need for more cost-effective and resource-efficient methods.
As the solar industry continues to grow, it is imperative that recycling strategies
evolve concurrently. Future research and development should focus on creating more
energy-efficient, environmentally friendly, and economically viable recycling methods.
Innovations in mechanical separation, advancements in thermal processing techniques,
and the development of less hazardous chemical processes are critical areas for exploration.
Furthermore, the establishment of global standards and policies that mandate recycling
and encourage the development of sustainable recycling infrastructure is essential.

Author Contributions: Conceptualization, P.-H.C. and W.-S.C.; methodology, J.-Y.W.; validation,

C.-H.L. and J.-Y.W.; formal analysis, P.-H.C.; investigation, P.-H.C.; resources, P.-H.C.; data curation,
C.-H.L.; writing—original draft preparation, P.-H.C.; writing—review and editing, C.-H.L.; visual-
ization, J.-Y.W.; supervision, W.-S.C. and J.-Y.W. All authors have read and agreed to the published
version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The authors wish to extend their sincere gratitude to the members of the
laboratory team for their invaluable administrative assistance throughout this study.
Conflicts of Interest: The authors declare no conflicts of interest.

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