REVIEWS
Metallized plastic current collectors
Z. Zhang, Y. Song, B. Zhang,
L. Wang,* X. He* . . . . . . . . . . . . 2302134
Metallized Plastic Foils: A Promising
Solution for High-Energy Lithium-Ion
Battery Current Collectors
(MPCC) play a key role in improving
the energy density and safety of Li-ion
batteries. Here, the advantages of this
echnology are discussed alongside the
challenges including weak interfacial
adhesion force and large internal resis-
tance. Detailed measures are proposed
to address these challenges. Lastly, the
prospects for polymer engineering and
MPCC application to stimulate future
development are discussed.
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
REVIEW
www.advenergymat.de

Metallized Plastic Foils: A Promising Solution for

High-Energy Lithium-Ion Battery Current Collectors
Zhiguo Zhang, Youzhi Song, Bo Zhang, Li Wang,* and Xiangming He*

and lithium-rich oxide cathodes as well

To meet the growing demand for safe and high-energy batteries, particularly from graphite anode to silicon-based and
for the commercialization of electric vehicles, a need for further advancement lithium metal anodes. Throughout these
has arisen. An innovative and promising solution for current collectors in LIBs advancements, the specific energy den-
is a metallized plastic current collector (MPCC) with metal-polymer-metal sity of LIBs has increased from 300 to
500 Wh kg−1 .[1]
multilayer composite structure. This approach offers several advantages. Although a CC is an inert battery com-
First, it effectively reduces the inert weight and thickness of LIBs, thereby ponent for lithium storage, as an im-
enhancing their energy density. Second, a polymer with electrical insulation portant materials carrier, it facilitates the
and high elongation properties in the MPCC significantly improves the safety conductions of electron flow between the
performance of LIBs by preventing thermal runaway. Despite its potential for active material and external battery ter-
minals. Additionally, it significantly in-
large-scale application in LIBs, the MPCC still faces significant challenges,
fluences the capacity, rate, and cycling
such as weak interfacial adhesion force and low electrical conductivity. performance of LIBs.[2] Commercial CCs
Therefore, researchers in the field of energy storage are currently focusing on are expected to meet basic requirements,
the design, modification, and development of practical MPCCs. Hence, in this such as cost-effectiveness, good chemical
review various polymers, preparation approaches, and MPCCs are and electrochemical stability, high elec-
comprehensively analyzed and summarized. Additionally, detailed discussions trical conductivity, weldability, and high
mechanical strength,[3] while occupying
are provided on the advances, key issues, improvements and corresponding as little mass and volume as possible,
mechanisms associated with MPCCs. Finally, valuable guidance and future to optimize the overall performance and
directions are provided for the design and improvement of advanced MPCCs energy density of a battery. Advance-
in high-energy LIBs, thus facilitating the commercialization process. ments in fabrication techniques and im-
proved production conformity over sev-
eral decades have enabled a progressive
reduction in the thickness of Al CC from
1. Introduction 12 to 8 μm. Consequently, the mass ratio of Al CCs in LIBs can
be reduced from 7 to 4.8 wt%. Similarly, the thickness of Cu CC
In the near future, the energy density requirements for commer-
has also undergone reduction from 6 to 4.5 μm, leading to a re-
cial Li-ion batteries (LIBs) used in electric vehicles and portable
duction in its mass ratio from 9 to 6.9 wt%.[4] Therefore, reduc-
electronics will continue to rise. To satisfy the high-energy de-
ing the thickness and proportion of inactive metal materials in
mand, technological innovations of LIBs have been primarily
LIBs has emerged as the main trend and key focus in the develop-
directed toward three areas: (1) optimizing battery systems by
ment of CC technology. Choudhury et al. demonstrated that two
developing higher performance electrode materials and elec-
future possibilities (Cu/Al = 4/8 μm, 3/6 μm) can increase the
trolytes; (2) upgrading the electrode and cell structures of LIBs
specific energy from 370 Wh kg−1 in state-of-the-art CCs (Cu/Al
to improve the mass and volume ratio of active materials; and
= 6/10 μm) to 384–394 Wh kg−1 , corresponding to an increase
(3) functionalizing inactive components, such as the current col-
of 3.8% and 6.5% in specific energy density,[5] underlining the
lector (CC) and separator. Most studies have primarily focused
potential benefits of reducing thickness and optimizing the CC
on battery chemistry systems, and significant developments have
design. In addition, as to the focus on LIBs and clean energy con-
taken place from the earliest LiCoO2 cathode to the most promis-
tinues to grow, the prices of Al and Cu have reached record lev-
ing Ni-rich layered Li(Nix Mny Coz )O2 (NCM, x + y + z = 1)
els. In the case of NCM523/graphite batteries, the costs of Al and
Cu in LIBs account for 1.8% and 7.6% of the total battery manu-
Z. Zhang, Y. Song, B. Zhang, L. Wang, X. He facturing expenses, respectively. In the case of LFP/graphite bat-
Institute of Nuclear and New Energy Technology teries, their costs account for 1.7% and 10% cost, respectively.
Tsinghua University
Beijing 100084, P. R. China These high material costs pose significant challenges in the de-
E-mail: wang-l@tsinghua.edu.cn; hexm@tsinghua.edu.cn velopment of LIBs.[6] Although the thickness of CCs can be fur-
ther reduced, the ultrathin CCs with weak mechanical properties
The ORCID identification number(s) for the author(s) of this article are susceptible to wrinkles and breakage during the coating pro-
can be found under https://doi.org/10.1002/aenm.202302134
cess, additionally, the manufacturing cost increases owing to the
DOI: 10.1002/aenm.202302134

Adv. Energy Mater. 2023, 2302134 2302134 (1 of 20) © 2023 Wiley-VCH GmbH

www.advancedsciencenews.com
extra pressing and thinning processes. The thickness of CCs has
been reduced to almost their limit; thus, future efforts must fo-
cus on exploring alternative CC materials and structures.[7] In
2005, Yazici et al. used flexible graphite sheets as both CC and
electrode materials to reduce the weight of LIBs while maintain-
ing good electrical conductivity; however, this approach resulted
in large irreversible capacities because of the presence of un-
functionalized graphite or impurities, as well as the high surface
area of the powder used in the fabrication process.[8] In addi-
tion to graphite flakes, carbon nanofibers, conducting polymers,
and other materials have been investigated as CCs; however, the
corresponding preparation processes are difficult to scale up for
mass-production purpose.[9]
In 2013, our group introduced the concept of utilizing
graphene-coated plastic films (polyethylene terephthalate, sim-
ple named PET) as CCs in low-cost lithium–sulfur batteries, re-
sulting in high energy densities of up to 452 Wh kg−1 . This in-
novative work has opened up new avenue for the use of plastic
film in LIBs.[10] The rapid development of plastic metallization
technique has made the commercialization of MPCC feasible
in LIBs, establishing them as the preferred choice in the field
of energy storage. An MPCC is composed of an electronically
insulating polymer plastic layer and a thin metal layer + poly-
mer layer + metal layer), which can also effectively reduce the
thickness and improve the energy density of commercial LIBs
(Figure 1a–c). This technology exhibits the dual advantages
of polymer substrate and metal foil, such as flexibility (Figure 1d),
low density, high mechanical strength, and conductivity. Fur-
thermore, MPCC has been proven to be effective in enhanc-
ing the mass and volumetric energy densities of commercial
LIBs (Figure 1e), and Rishav Choudhury et al. indicated the
thicker metal-on-plastic film can decrease volumetric energy den-
sity slightly (e.g., 1%−4%) in 2021.[5] It also improves battery
safety (Figure 1f). However, despite these advancements, large-
scale industrial applications of LIBs utilizing MPCCs have not
yet been realized currently. Owing to the ultrathin metal layer
with thickness of no more than 2 μm and the swelling effect of
PET in the electrolyte, several challenges arise during the man-
ufacturing process and long-term usage of MPCCs. These chal-
lenges include weak interfacial adhesion force and welding diffi-
culty (Figure 1g), large internal resistance (Figure 1h), as well as
surface corrosion and metal layer defects including foam, wrin-
kles, and broken region (Figure 1i). Among them, due to the elec-
trically insulating polymer substrate, the MPCC is transversely
insulating, leading to a high resistance of MPCC, which needs to
be addressed to meet the demands of LIBs.
The development of MPCC in LIBs can be broadly divided
into the following stages: 1) development of Al and Cu deposi-
tion technology and assembly of flexible MPCC-based LIBs, and
2) polymer modification and research on mechanisms for safety
improvement. In the initial stage, a significant breakthrough was
achieved by Yun et al. in 2011. They successfully fabricated flex-
ible MPCCs by depositing a thin Cu layer on flexible polymer
films (Figure 2a), including poly(ethylene naphthalate) (PEN),
PET, polyimide (PI), and poly(ether sulfone) (PES), using mag-
netron sputtering for the first time as well as tested the sur-
face resistance of flexible MPCCs with different Cu-sputtered
thicknesses.[11] In 2013, Xu et al. manufactured novel stretchable
interconnect cells by combining thin, low-modulus silicone elas-
Adv. Energy Mater. 2023, 2302134 2302134 (2 of 20)
16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advenergymat.de
tomers as supporting substrates, a 600-nm metal foil deposited
on the PI polymer surface, with a segmented design for ac-
tive materials, and unique “self-similar” interconnect structures
(Figure 2b).[12] In 2015, Jung et al. employed the thermal evapo-
ration method to deposit a 200-nm Cu layer on an etched PI sub-
strate, creating an MPCC. They further deposited a highly reliable
nanohairy Si layer (300 nm) on the MPCC surface and assembled
it to obtain bendable and foldable battery devices (Figure 2c).[13]
In addition, with the increase in the energy density of power bat-
teries, the occurrence of self-ignition and explosions due to ther-
mal runaway in high-energy LIBs have emerged as a critical is-
sue, leading to a heightened focus on enhancing battery safety.[14]
Owing to the high mechanical strength and good electrical con-
ductivity of traditional CCs, internal short circuits caused by the
direct connection of Al and Cu CCs or the contact between the
active materials and opposite electrodes play a crucial role in
safety concerns.[15] In contrast, MPCC have shown remarkable
improvements in enhancing the safety of LIBs (Figure 2d–f),[16]
which are discussed in further detail below. At present, signifi-
cant progress has been made in the manufacturing technology
and consistency of MPCC, accelerating its widespread applica-
tion in LIBs.
Numerous studies regarding MPCCs serve as excellent start-
ing points for scientists and engineers focusing on state-of-the-
art LIBs with high energy density. However, there is a notable lack
of comprehensive reviews discussing the utilization of MPCCs
in LIBs, which is crucial from an industrial perspective. Thus,
to provide insights into the research progress, challenges, and
future directions of MPCCs for LIB applications, to accelerate
the industrialization rate in high-performance LIBs, this review
presents the following sections. 1) Physicochemical characteris-
tics and preparation methods of MPCC and polymer substrates
for LIBs. 2) Advantages of MPCCs, including flexibility, high
energy density, and safety performance, derivative modification
methods, and the corresponding mechanisms. 3) Challenges of
MPCCs that need to be addressed, including weak interfacial
force, welding difficulties, low electrical conductivity, and metal
corrosion. 4) Conclusions and perspectives of MPCC.
2. Characteristic of MPCCs and Polymer
Substrates for LIBs
2.1. Characteristic of MPCCs
To facilitate the large-scale production and widespread utiliza-
tion of MPCCs with PET substrates in LIBs, the design and op-
timization of MPCC are based on the requirements of commer-
cial CCs for LIBs. The intrinsic characteristics of state-of-the-art
CCs and MPCCs from leading manufacturers, including Guang-
dong Enpack Packaging Co., Ltd., Victory Precision Co., Ltd., and
Yangzhou Nali New Material Tech. Co., Ltd., etc., are summa-
rized in Table 1. The reduction in the thickness of Al MPCC to
6 μm and the lower areal densities of both Al and Cu MPCCs
compared to traditional CCs contribute to higher energy densi-
ties of LIBs. Compared with CCs, MPCCs offer higher elonga-
tion at break, leading to excellent electrode ductility during the
coating process, and thus improve the battery safety. In contrast,
the MPCCs sacrifice the electrical conductivity, resulting in an
increased square resistance. Thus, there is a trade-off between
© 2023 Wiley-VCH GmbH
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advenergymat.de

Figure 1. Structure, advantages, and challenges of a metallized plastic current collector (MPCC). a) Schematic diagram of an MPCC-based Li-ion battery.
The sandwich structure of b) Cu-based and c) Al-based MPCCs. Advantages of MPCCs include d) flexibility, e) high energy density, and f) high safety,
and challenges include g) weak interfacial adhesion force and welding difficulty, h) large resistance, and i) surface corrosion and metal layer defects such
as foam, wrinkles, and broken region. MPCC with a “metal layer + polymer layer + metal layer” sandwich structure has been proven to be an available
CC material with a composite structure, which can reduce the inert weight and thickness of LIBs while improving the energy density of commercial LIBs.
However, addressing the issues of weak interfacial adhesion force and low resistance is of urgent importance.

power and energy when using MPCC in LIBs. In addition, it is
of importance to consider surface toughness (>0.2 μm), specific
surface area (>20 m2 g−1 ), nail strength (>200 gf) as well as pore
size and width of MPCs while determining the performance of
MPCCs in LIB applications.
2.2. Polymer Substrate
A substrate plays an indispensable role in MPCC, and its char-
acteristics should be carefully considered, including low cost,
well-established production technology, recycling, low mass den-
sity, wide operating temperature, high mechanical strength, and
high thermostability, in combination with strong acid and al-
kali resistance. High tensile strength can reduce the electrode
breakage rate during roll pressing while high elongation at
break can ensure electrode ductility during coating. The high
thermostability of a substrate plays a crucial role in prevent-
ing spatial holes caused by burning on the substrate during
high-temperature vapor deposition as well as slowing down
the temperature rise during thermal runaway, ensuring a sta-
ble and controlled coating process. Strong adhesive strength is

Adv. Energy Mater. 2023, 2302134 2302134 (3 of 20) © 2023 Wiley-VCH GmbH
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advenergymat.de

Figure 2. A brief historic timeline summarizing the important discoveries of metallized plastic current collectors (MPCCs) in the emergence and develop-
ment of Li-ion batteries (LIBs). a) Flexible LIBs utilizing CC with sputtered Cu layer on various polymeric films. Reproduced with permission.[11] Copyright
2011, IOP publishing. b) Utilization of electric beam evaporation as an MPCC to deposit metal on polyimide (PI) film in stretchable batteries. Repro-
duced with permission.[12] Copyright 2013, Springer Nature. c) Direct integration of MPCCs on PI via chemical vapor deposition for the development
of bendable LIBs. Reproduced with permission.[13] Copyright 2015, Wiley-VCH. d) Fire-extinguishing PI-based MPCCs. Reproduced with permission.[4]
Copyright 2020, Springer Nature. e) Implementation of aluminum-polyethylene terephthalate (Al-PET) MPCCs to mitigate mechanical abuse-induced
short-circuiting. Reproduced with permission.[16b] Copyright 2022, Royal Society of Chemestry. f) Safety mechanism about MPCCs preventing thermal
runaway by retreating from short circuits. Reproduced with permission.[37] Copyright 2021, Elsevier. An increasing number of functions and applica-
tions of MPCCs have been derived from their inherent properties, and the corresponding mechanisms are gradually being revealed to promote further
development.

essential to prevent the peeling and wrinkling of the metal layer
on both sides of the substrate during the coating and stretch-
ing processes. Currently, PET, polypropylene (PP), and PI are
the commonly used polymer substrates in MPCCs, because their
high quality can meet the aforementioned demands. The mass
density of a polymer substrate is the most important param-
eter. In comparison, the mass densities of Cu (8.96 g cm−3 )
are 7, 7, and 10 times the mass densities of PET, PI, and PP,
respectively. The physicochemical characteristics of the com-
mon and other polymers used in MPCCs are summarized in
Tables 2 and 3.
Table 1 provides a comprehensive overview of the physico-
chemical properties of various substrate materials for MPCCs.
Among these materials, PET films exhibit remarkable character-
istics, such as high tensile strength, superior thermal stability,
excellent durability, self-extinguishing property, and remarkable
resistance to flammability Moreover, PET can function effectively
even at temperatures as low as −70 °C.[17] Owing to its excellent
physicochemical properties and low cost resulted from advanced
technology and mass production, PET has emerged as a widely
adopted substrate material for MPCC applications. For example,
Liu et al. successfully deposited 750-nm-thick Al nanocrystals

Adv. Energy Mater. 2023, 2302134 2302134 (4 of 20) © 2023 Wiley-VCH GmbH
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advenergymat.de

Table 1. Physicochemical characteristics of traditional current collectors (CCs) and metallized plastic current collectors (MPCCs) with polyethylene
terephthalate (PET) substrate.

Testing item Cu Cu MCC Al Al MCC Methods

Thickness [μm] 6 6 13 6 Micrometer

Areal density [g m−2 ] 52 24 35 8.5 Electronic Balance
Tensile strength (MD/TD) [Mpa] 400/380 260/250 205/200 210–230/150–210 Tensile Machine
Elongation at break (MD/TD) [%] 6.0/4.0 80/50 5.0/4.5 30–80/15–45 Tensile Machine
Surface dyne coefficient >38 38 ± 2 >38 38 ± 2 Dyne pen
Square resistance [mΩ] 3 20 ± 2 2.1 30 ± 2 Four-point probe
Shrinkage (MD/TD) [%] / 0.2/0.01 / 0.15/0.01 Oven
(130 °C/0.5 h)

onto 6-μm PET substrate as a replacement for the conventional
14-μm Al foil in LIBs (Figure 3a). This innovative approach led
to an improvement in the cell-level energy density by reducing
the thickness and weight of the metal foil.[16b] Nevertheless, it is
important to note that PET is not stable when exposed to strongly
acidic and alkaline electrolytes. Owing to the presence of a lot of
oxygen-containing ester groups, PET is susceptible to solubiliza-
tion and swelling in these types of electrolytes.[18] Over time, the
chemical bonds between the metal layer and the PET can gradu-
ally deteriorate during long-term usage. This weakening of inter-
facial adhesion force and peeling strength of the metal layer from
the substrate can lead to a decline in cycling capacity. In addition,

Table 2. Physicochemical characteristics of common polymers for metallized plastic current collectors (MPCC).

Abbreviation PET PP PI

Full name Polyethylene terephthalate Polypropylene Polyimide

Operating temperature [°C] −60–120 30–140 −269–280
Tensile strength [Mpa] High, 250 Low, 30 High, 200
Elongation at break [%] 90–150 200–400 >50
Toughness √√ × √
Thermostability √ √ √
Adhesion with metal √ ×× √
Acid and alkali resistance × √ √√
Cost [dollar per ton] 1063 1120 Higher
Mass density [g cm−3 ] 1.29–1.41 0.85–0.99 1.39–1.45
Production technology Well-established Well- Difficult
established
Production stage Mass production Pilot Laboratory
production stage
Recycle √ √ √

Table 3. Physicochemical characteristics of common polymers for metallized plastic current collectors (MPCCs).

Abbreviation PE PVC PS PC PVDF

Full name Polyethylen Polyvinyl Polystyrene Polycarbonate Polyvinylidene

chloride fluoride
Operating temperature −40–90 −40–90 −30–70 −45–135 −40–150
[°C]
Tensile strength [Mpa] Low, 6 Low, 50–80 Low, 36–60 Low, 69 Low, 50–70
Elongation at break [%] 90–950 20–40 1.2–2.5 60–120 10–50
Thermostability √ √ × √ √
Acid and alkali √ √ × × √
resistance
Mass density [g cm−3 ] 0.94–0.96 1.38–1.58 1.05 1.18–1.22 1.77–1.80
Recycle √ × × √ √

Adv. Energy Mater. 2023, 2302134 2302134 (5 of 20) © 2023 Wiley-VCH GmbH
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advenergymat.de

Figure 3. Structural design and types of metallized plastic current collectors (MPCCs). a) Deposition of Al metal layer on polyethylene terephthalate
(PET) substrate. Reproduced with permission.[16b] Copyright 2022, Royal Society of Chemestry. b) Deposition of Cu metal layer on polypropylene (PP)
substrate by electroless plating.[19] c) Deposition of Cu metal layer on graphitized polyimide (PI) substrate by vacuum evaporation. Reproduced with
permission.[22] Copyright 2021, American Chemical Society. To ensure optimal conductivity of the CC, an alternative approach, besides using the polymer
directly as a substrate, involves carbonization or substitution of the metal coating with other conductive materials.

the dissolution of polymer materials into the electrolyte can in-
crease electrolyte viscosity, slow down the ion transportation, and
increase the internal resistance of LIBs. To address this issue, ad-
ditional efforts should focus on electrolyte and electrode mate-
rial engineering or on modifying the polymer polarity by incor-
porating polyester derivatives (amine group, ether oxygen group,
carboxyl group, phenol hydroxyl group, etc.) to facilitate the for-
mation of a greater number of chemical bonds on the substrate
surface.
In contrast, PP is highly stable under strongly acidic and al-
kaline conditions, is a cost-effective substrate option with well-
established technology, making it a favorable substrate for MPCC
applications. Barbic et al., for example, deposited a metal layer
on the surface of a 25-μm porous PP substrate to create an
MPCC. Subsequently, electroactive materials were electrolytically
deposited within the pores of the MPCC to prepare a flexible
ZnO─Mn electrode (Figure 3b).[19] However, it shows weak inter-
facial adhesion force with Cu metal layers and a low production
yield, because it tends to break at high roll pressing speeds. Thus,
improving the adhesive strength of PP is crucial to accelerate its
market penetration.[20]
PI exhibits excellent mechanical properties, chemical stability,
and a wide temperature range, making it another highly desir-
able material for various applications. Despite these merits, the
immature production technology and high cost of PI makes it
difficult to import production line.[21] An alternative method in-
volving carbonized PI as a CC has been explored. For instance,
Hu et al. dissolved appropriate amounts of pyromellitic acid di-
anhydride (PMDA) and 4,4′-diaminodiphenyl ether (ODA) in a
solvent and spin-coated the solution under nitrogen gas atmo-
sphere to obtain polyamino acid (PAA) films. Subsequently, the
PAA films were subjected to a series of steps, including gradient
imidization at different temperatures, carbonization, transfor-
mation into graphene-like thermal film (GTF), rolling to achieve
specific thickness and strength, and finally plasma cleaning to
enhance hydrophilicity. Finally, the Cu atoms were slowly evapo-
rated under vacuum and deposited onto the GTF surface to gen-
erate Cu@GTF CC (Figure 3c).[22]
Table 3 includes several other polymer substrates that have
been investigated for MPCC applications, such as polyethylen
(PE), polyvinyl chloride (PVC), polystyrene (PS), polycarbon-
ate (PC), and polyvinylidene fluoride (PVDF). Cohen et al. de-
veloped a prototype high-energy and high-power thin-film 3D
micro-battery by preparing porous polymer substrates of PVDF,
poly(methyl methacrylate) (PMMA), lithium polyacrylate (Li-
PAA), with different shapes and sizes through low-cost and ef-
ficient micro and nano 3D-printing technology and further fabri-
cated the active materials by electrophoretic deposition.[23] De-
spite its relatively lower mass density compared to traditional
CCs, PE has a high electrode breakage rate during roll pressing.
Additionally, the manufacturing cost of PE remains high because
of immature technology, limiting its practicality in MPCC appli-
cations. PS poses concerns as it releases poisonous substance
when exposed to temperatures over 70 °C, and it cannot be eas-
ily recovered, because of its low thermostability. PVDF shows
a large swelling rate (nearly 50% after 50 h immersion in the
electrolyte).[17] These drawbacks greatly hamper the practicabil-
ity of using the polymers. Though there is no definite interna-
tional or national standard for the polymer quality in MPCC, the
cost, technical difficulty of depositing or coating metal atoms on
substrate, and resistance to acid and alkali of polymer should be
taken into consideration before putting MPCC into production
line.
2.3. Approaches for Depositing Metal Layer on Polymer
To enhance the adhesion force between the MPCC and the con-
ductive layer, facilitate the collection of current generated by the
electrode material, output to the external device, and ensure good

Adv. Energy Mater. 2023, 2302134 2302134 (6 of 20) © 2023 Wiley-VCH GmbH
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advenergymat.de

Figure 4. Methods of preparing metal layers in metallized plastic current collectors (MPCCs). a) Magnetron sputtering,[24] b,c) vapor deposition, d,e)
electroless metal plating, and f) chemical deposition. These preparation methods can be used individually or in combination to deposit metal layers,
and magnetron sputtering is usually used to initially deposit metal onto the surface of insulating polymers. Subsequently, electroless metal plating or
thermal evaporation is further used to thicken the metal layer.

electrochemical performance of LIBs, numerous approaches,
equipment and processes have been optimized and updated for
depositing metal layers on the polymer surface. Commonly used
methods include magnetron sputtering, vacuum thermal vapor
deposition, electroless metal plating, chemical deposition.
2.3.1. Magnetron Sputtering
As shown in Figure 4a, magnetron sputtering is a physical vapor
deposition (PVD) technology that is ideal for large-scale indus-
trial production of MPCCs.[24] The main equipment involved in
this process includes a power supply, vacuum equipment, sub-
strate station, target position, and working gas mixing chamber.
During the deposition process, the electrons within an electric
field collide with argon gas, leading to the ionization of high-
energy argon atoms. These atoms subsequently bombard the tar-
get surface, causing the target material to sputter, and the sput-
tered particles are then deposited onto the substrate to form a
thin film. This method offers several advantages, including min-
imal temperature rise, rapid deposition rate, stable metal layers,
strong interfacial force, excellent repeatability, and suitability for
continuous large-area coating.[25] An effective method to increase
the film formation rate, purity, and uniformity of the metal layer
deposited on the substrate surface involves utilizing multiple-
target co-sputtering and performing high-speed sputtering at low
pressure. This technique increases the effective ionization rate
of the gas, resulting in improved deposition characteristics. Mag-
netron sputtering has certain disadvantages, including relatively
low efficiency, slow speed, and low target utilization (usually <
30%). In addition, the process requires numerous equipment,
and there is a risk of particle damage to the substrate film if the
magnetic/electric field is not adequately controlled. Therefore,
achieving high uniformity and yield of the metal layers through
sputtering requires two fundamental conditions: a flat polymer
substrate with high tensile strength and equipment with high ac-
curacy.
2.3.2. Vacuum Thermal Vapor Deposition
Vacuum vapor deposition, also known as PVD technology entails
heating the metal source to evaporate it under vacuum or specific
atmospheric conditions. The resulting metal is then deposited
onto the substrate surface, forming a metal layer or metal com-
pound layer (Figure 4b,c).[26] Vacuum vapor deposition allows for
a greater number of metal atoms to be evaporated compared to
magnetron sputtering. Thus, thermal vapor deposition can be

Adv. Energy Mater. 2023, 2302134 2302134 (7 of 20) © 2023 Wiley-VCH GmbH

www.advancedsciencenews.com
employed to increase the thickness of the metal layer on the sub-
strate after using a magnetron sputtering and to effectively im-
prove uniformity. Zaporojtchenko et al. conducted experiments
in which metals (Au, Ag, and Cu) were evaporated onto various
polymers, such as bisphenol-trimethylcyclohexane polycarbon-
ate (TMC-PC), pyromellitic dihydroxydiamine (PMDA-ODA), PI,
polystyrene (PS), and low-dielectric-constant Teflon AF amor-
phous fluoropolymer resin. These experiments led to the forma-
tion of metal-polymer interfaces with different morphologies.[27]
A disadvantage of this technique is that the deposited metal layer
may be loose, resulting in weak interfacial adhesion force be-
tween the metal layer and the substrate. In addition, the high
temperature generated during the process can lead to the defor-
mation of the polymer substrate.
2.3.3. Electroless Metal Plating
The electroless metal plating process involves an ion replacement
reaction and continuous redox reactions. It is based on the re-
duction of metal ions on the substrate surface, leading to the for-
mation of a thin layer of coated metal, while the reducing-agent
undergoes oxidation (Figure 4d).[28] To eliminate the interference
of other cations and ensure the uniformity of the metal plating
layer, it is important to maintain a constant concentration of the
plating metal cations in the solution. With respect to factory ap-
plications, as shown in Figure 4e, the electroplating process in-
volves the deposition of metal onto the substrate surface to form a
metal coating under current. Specifically, the polymer substrate
is connected to the cathode in an electrolyte solution (e.g., cop-
per sulfate), while the metal serve as the anode (e.g., a Cu ball
enclosed in a titanium blue anode bag). Under an external di-
rect current, Cu atoms undergo oxidation into Cu2+ that enter
the electrolyte solution, replenishing the metal ions. Simultane-
ously, the substrate film passes through a roller and is immersed
into the reagent, triggering a reaction that completes ion displace-
ment. The Cu2+ ions in the solution migrate to the substrate sur-
face, acquire electrons and are reduced into Cu atoms, resulting
in the formation of a Cu layer. The electroless plating technology
is relatively easy to control, well-established, and stable, thus it is
widely used in various industries.
2.3.4. Chemical Deposition
Chemical deposition, also known as chemical plating or auto-
catalytic plating, involves the deposition of metal layers onto a
polymer substrate surface. Taking the example of Cu layer de-
position on a polymer substrate (Figure 4f), the process begins
with degreasing and cleaning the surface of the polymer sub-
strate. Subsequently, corrosive K2 Cr2 O7 and concentrated H2 SO4
can be used to create the surface roughness, but the resulting
pollution is difficult to treat. Alternatively, 10% KMnO4 or 10%
NaOH can be used, which generates easier-to-treat pollution. A
sensitizer is then uniformly adsorbed onto the substrate surface,
increasing its catalytic activity and enhancing the interfacial ad-
hesion force between the metal layer and the polymer. From
a thermodynamics perspective, the direct reduction of Cu2+ by
HCHO is not feasible. Instead, Ag and Pb are commonly used as
Adv. Energy Mater. 2023, 2302134 2302134 (8 of 20)
16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advenergymat.de
uniform catalytic crystallization centers on the polymer surface.
This process involves the following steps: (1) Ag+ ions are ad-
sorbed onto the substrate surface, which is then immersed in the
AgNO3 /C2 H5 OH solution. The Ag+ ions are reduced by HCHO,
forming Ag nanoparticles that serve as the catalytic centers for
Cu2+ deposition. (2) The Pd particles are obtained through the fol-
lowing chemical reaction during activation: Sn2+ + Pd2+ → Sn4+
+ Pd.[29] This reaction occurs in acidic solution, where Sn2+ and
Pd2+ act as sensitizers and activators, respectively. Subsequently,
the substrate is then immersed in a chemical plating solution,
and the metal layers are deposited on the substrate with the as-
sistance of the strong reducing action of HCHO in an alkaline
solution and the catalytic activity of Pd or Ag. The corresponding
reactions are as follows:
2HCHO + [CuLx ]2+xp + 4OH− → Cu0 + 2HCOO− + xLp + 2H2
+ 2H2 O (1)
where L represents the ligand that regulates the stability of Cu2+
in solution and the reduction reaction rate; the variables x and
p represent the number of ligand and the charge carried by the
ligand, respectively.[30] The chemical plating technique enables
uniform plating, and can be performed on insulators, without the
need for DC power supply equipment. In addition, chemical plat-
ing is considered an environmentally friendly surface treatment
process in many fields owing to its low environmental pollution
and cost-effectiveness.
Several methods were compared, and it was found that ther-
mal evaporation, owing to high operating temperatures or imma-
ture technology, may lead to the burning and perforation of the
polymer substrate, resulting in compromised film length, consis-
tency, and yield. Moreover, magnetron sputtering requires special
equipment and operating conditions (e.g., high vacuum). How-
ever, chemical deposition involves complex procedures and the
use of expensive precursors. In contrast, electroplating often re-
quire complex treatments for polymer substrates, such as chem-
ical plating with micron-sized metal layers or laser-induced sur-
face carbonization.[31] In conclusion, the low yield and poor qual-
ity associated with the technology and process of depositing metal
layers on polymer surfaces is still the key bottleneck in the indus-
trialization of MPCCs.
2.4. Microstructure of Metal Layer in MPCCs
The microstructure of the metal layers in MPCCs obtained
through the aforementioned preparation methods differ from
those in conventional CCs. The electrical conductivity of the
metal films is highly sensitive to the film thickness and is sig-
nificantly affected by the particle density and interface struc-
ture. In general, the thicker the metal layer or the denser the
particle stacking, the lower are the electron transfer barrier
and resistance.[11,28,32] Al-based MPCC prepared by vapor de-
position method contain nano-Al polycrystals with an average
size of 45.56 nm in the Al metal layer, predominantly expos-
ing the [111] and [200] crystalline planes.[26b,33] The metal films
are thickened and stacked into dense layers by repeating the
same method, with each layer composed of uniform metal parti-
cles. However, owing to the formation of defects at the interface
© 2023 Wiley-VCH GmbH

www.advancedsciencenews.com
between adjacent layers, the thin metal layer exhibits relatively
low electrical conductivity.[16b] In addition to electrical conduc-
tivity, the mechanical properties of metal films are also closely
related to the structure of the metal layer. Hamasha et al. stud-
ied the crack structure and corresponding resistance of an Al
metal layer on a polyester surface under tensile stress. The in-
vestigation of crack development and resistance change in the
thin metal layer revealed that as the metal layer thickness in-
creases, the cracks become wider and less frequent. This phe-
nomenon allows for greater strain release, inhibits electron mi-
gration within the metal layer, and consequently leads to an in-
crease in resistance.[34]
3. Advantages
Safety is of utmost importance in high-energy batteries.[35] The
use of MPCCs can not only effectively improve the energy den-
sity but also significantly enhance the safety performance of LIBs.
The inherent properties of the polymer substrate in MPCCs, such
as good ductility and low melting point, enable timely interrup-
tion of the internal short circuits during mechanical collision
and extrusion, thus playing a crucial role in battery safety. In ad-
dition, LIBs using MPCCs offer several advantages, including
light weight, flexibility, and excellent portability, making them
highly practical and promising for next-generation bendable, im-
plantable, and wearable energy storage devices.
3.1. High Energy Density
Currently, the typical thickness of a polymer layer in MPCC is
≈4 μm, while the metal layers are ≈ 1–2 μm thick. Compared with
conventional Cu foils with the same thickness of 6 μm, the Cu-
based MPCCs can reduce the weight of the Cu foil by 60%. Sim-
ilarly, the thickness of the 6 μm Al composite collector can be re-
duced by half compared with the conventional rolled aluminium
collector (10–12 μm). As depicted in Figure 1d, the utilization of
both Al- and Cu-based MPCCs can improve the energy density of
NCM batteries by 6.1%, while using only Cu-based MPCCs leads
to a 3.3% improvement. In a study conducted by Liu et al., the
Al-PET design achieved significant reductions in weight (70.4%),
volume (46.4%), and metal usage (89.3%) compared to the com-
mercial 14-μm Al foil, resulting in a 3.0% increase in the en-
ergy density of the pouch cell compared to conventional cells.[16b]
Similarly, Ye et al. realized a 16%–26% improvement in the spe-
cific energy of a pouch cell assembled with an ultralight PI-based
MPCC, which had a thickness of ≈ 9 μm and a density of 1.54 mg
cm−2 , when compared to a conventional pouch cell equipped with
the thinnest commercially available Cu||Al metal CC (≈ 6 μm).
3.2. High Safety Performance
Safety problem of next-generation high-energy LIBs has gar-
nered widespread concern, especially regarding thermal runaway
caused by overheating or nail penetration, hindering their large-
scale application. The implementation of MPCCs has emerged as
a promising solution to mitigate battery safety failures resulting
from mechanical strength mismatch between flexible and ductile
polymer insulation layers and the thin metal layer deposited on
the surface.
Adv. Energy Mater. 2023, 2302134 2302134 (9 of 20)
16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advenergymat.de
3.2.1. Mechanisms for Safety Improvement
During charge/discharge cycling, the growth of lithium den-
drites in lithium metal batteries using conventional CCs has been
identified as a major cause of capacity decay and cycle life degra-
dation. These dendrites can also penetrate the separator, lead-
ing to internal short circuit, thermal runaway, and other severe
safety problems. In contrast, as shown in Figure 5a, MPCC with
good ductility exhibits wrinkles that effectively alleviates the local
compressive stress caused by lithium dendrite growth, promotes
uniform lithium ion deposition, slows lithium dendrite growth,
and improves lithium battery safety.[36] MPCC has advantages to
improve battery safety, when the battery is subjected to extreme
conditions such as vibration, mechanical shock, collision, and ex-
trusion. Generally, traditional metal foils are both longitudinally
and transversely conductive and susceptible to internal short cir-
cuiting, resulting in thermal runaway. Taking the nail penetration
measurements of LIBs using CCs and MPCCs for example, the
high mechanical strength of traditional CCs leads to low distor-
tion and offsetting of electrodes, which usually have direct elec-
trical contact with the inserted nail to form immediate short cir-
cuits. The sharp serrations produced by metal foils around the
inserted nail can easily penetrate the separator and also trigger in-
ternal short circuits and safety hazard. For comparison, MPCC ef-
fectively suppresses the thermal runaway of fully charged pouch
cells in the nail penetration test. Specifically, during the measure-
ment, the resistance of LIBs equipped with MPCCs gradually in-
creases, as the tensile strain increases, and the deformation of
battery in turn weakens interfacial adhesion force between the
coated electrode materials and the metal layer of the MPCCs.
Moreover, the limited ductility of the thin metallic film (which
is significantly lower than that of the plastic substrate) results in
effective delamination when subjected to straining (Figure 5b).
Pham et al. have reported that at high temperature during me-
chanical abuse, the electrical isolation of electrode materials is at-
tributed to the shrinkage of the polymer substrate (Figure 5c).[37]
During the nail penetration test of LIBs, the elastic and highly
stretchable MPCC provides an additional strain buffer to pre-
vent strain localization and brittle fracture in the Al layer. When
MPCC suffers from large deformation, the easily deformable and
electronically insulating polymer substrate can wrap around the
sharp edges between the broken metal layer and the inserted nail
edges, effectively cutting off the internal electrical circuit, while
the severely cracked Al layer breaks up the long-range electronic
percolation. (Figure 5d). The different ductility of the polymer
layer and metal layer in the MPCC as well as the inherent charac-
teristics of the polymer can promptly prevent continuous current
flow and temperature rise during internal short circuits, greatly
reducing the thermal runaway of LIBs and thus improving bat-
tery safety.[16b,37]
3.2.2. Functionalized Modification of MPCCs to Further Improve
Battery Safety
Polymer engineering offers an additional avenue to enhance bat-
tery safety, with various approaches including incorporation of
inorganic/organic flame retardants into polymers or the develop-
ment of temperature-sensitive and thermally responsive MPCC
© 2023 Wiley-VCH GmbH
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advenergymat.de

Figure 5. Mechanisms and methods for improving the safety of Li-ion batteries (LIBs). a) Metallized plastic current collector (MPCC) mitigates local
stress caused by lithium deposition and reduces the growth of lithium dendrites. Reproduced with permission.[36] Copyright 2018, Springer Nature.b–d)
Different ductility of the metal and polymer layers in MPCCs leads to metal layer fracture, disrupting the electronic connection during stretching or
squeezing deformation of battery. During nail penetration, the highly deformed polymer either shrinks in an overheated environment, or wraps around
the sharp edges of the electronic conductive nail, cutting off the abused internal circuitry. Reproduced with permission.[37] Copyright 2021, Elsevier. e)
Incorporating a fast and reversible thermoresponsive polymer that switches between graphene-coated Ni nanoparticles and polyethylene mixture material
inside batteries that enables rapidly shut down under abnormal conditions, such as overheating and short circuiting, thereby preventing thermal runaway.
Reproduced with permission.[42] Copyright 2016, Springer Nature. f) Shape-memorized polymers can successfully prevent battery thermal runaway when
the internal temperature of LIBs becomes excessively high. Both mixing flame retardants in polymers and preparing temperature-sensitive polymers
in MPCCs have a positive temperature-coefficient effect on LIBs under overheating conditions, effectively enhancing the safety performance of LIBs.
Reproduced with permission.[43} Copyright 2022, American Chemical Society.

materials.[38] These modifications aim to introduce a positive
temperature coefficient effect, whereby the conductivity of the
material reduces with rising temperature, or under overheating
conditions. Such strategies can effectively mitigate the risk of
thermal runaway and enhance the overall safety performance of
batteries.
Flame Retardancy: The polymer substrate in MPCC provides
a carrier and space for flame retardant and effectively separates
the flame retardant from the electron/ion path and chemical re-
action of the battery.[39] Incorporating additional flame retardants
(both organic and inorganic materials) through mixing, com-
posting, or grafting with a polymer substrate can enhance self-
extinguish property or early braking, which is of great signifi-
cance to reduce battery thermal runaway and ensure battery sta-
bility. Triphenyl phosphate (TPP) is a commonly selected flame
retardant because it is halogen-free, cost-effective, and one of
the most effective and environmentally friendly flame retardants.
More importantly, its low melting point can shorten the fire re-
sponse time in the event of a fire. In a study conducted by Ye et al.,
Cu-based MPCC with a metal layer thickness of ≈ 500 nm was
developed using a TPP-embedded PI matrix. This MPCC exhib-
ited rapid self-extinguishing property when subjected to extreme
conditions, such as short circuits and thermal runaway.[4] To im-
prove the dispersion homogeneity of inorganic flame retardants
in polymers and enhance the tensile strength and toughness of
Al-based MPCC, Wang et al. conducted a pretreatment of inor-
ganic flame retardants using polyolefin (POs), which exhibited a
strong adhesion force with the flame retardant and good compat-
ibility with polymer substrates. They also utilized silica sol, oleic
acid, nanosilica, and a silane coupling agent to prepare MPCCs.
The pretreatment approach resulted in an improved stability and
safety performance of LIBs in nail penetration tests.[40]
Thermosensitivity: Liu et al. invented a novel heat-shrinkable
MPCC using polymer substrates consisting of PET, multilayer
coextruded PO, biaxially oriented PP, PVC, PE, and oriented
PS. This distinct substrate composition enables the MPCC to
shrink during thermal runaway, increasing the thermal runaway
temperature and enhancing battery safety performance.[41] Chen
et al. developed a highly promising LIB using a fast and re-
versible thermosensitive MPCC (Figure 5e), which can rapidly
shut down under abnormal conditions, such as overheating and
short circuit, further improving battery safety. The self-regulating
material is fabricated by mixing graphene-coated spiky nickel
nanoparticles and a polymer with a high thermal expansion

Adv. Energy Mater. 2023, 2302134 2302134 (10 of 20) © 2023 Wiley-VCH GmbH

www.advancedsciencenews.com
coefficient and exhibits a high conductivity of up to 50 S cm−1
at ambient temperature. In addition, its resistance rapidly in-
creases by 7–8 orders of magnitude when exposed to high tem-
peratures. Once the temperature returns to room temperature,
the polymer reverts to its initial state without sacrificing the bat-
tery performance.[42] Jia et al. employed a bisphenol A epoxy
monomer (EPON) cross-linking network with shape memory
performance as the primary component to control the shape
transformation of an MPCC, thereby ensuring the safety perfor-
mance of a battery. The EPON network is formed via a one-step
cross-linking reaction between the diglycidyl ether of EPON and
the poly(propylene glycol)bis(2-aminopropyl)ether curing agent.
(Figure 5f). This network exhibits ideal conductivity at room
temperature, and undergoes rapid surface tearing, transitioning
from conductive to insulative, at overheating temperatures, ef-
fectively preventing the occurrence of battery combustion and
explosion.[43]
3.3. Flexibility
The high-energy and lightweight LIBs using flexible MPCCs
have the huge potential in various application fields composed
of implantable medical devices, wearable photovoltaics, epider-
mal health/wellness monitors, and soft surgical tools. Yim et al.
successfully integrated multiple solid layers on a flexible poly-
mer substrate to create a 3D flexible microcell, which exhibited
high reversible specific capacity of 20 μA h μm−1 cm−2 over a
charge/discharge voltage range of 4 V and a high pulse power ca-
pability with a radius of curvature up to 9 mm. Furthermore, the
conductive layer, active material, and solid electrolyte was coated
onto a modified PI surface using on-axis RF magnetron sputter-
ing. Furthermore, laser pulse irradiation was used to anneal the
anode material to obtain better adhesion between the MPCC and
the electrode material layer during the crystallization process.[20]
The strong interface force between conventional silicon anodes
and traditional CC leads to cracking and exfoliation of active ma-
terials. To address this issue, Jiang et al. deposited a Si anode via
magnetron sputtering on a soft nylon substrate with a Cu─Ni
buffer layer (MPCC) using a polymer-assisted metal technique.
Because the isotropic stress–strain behavior of amorphous Si is
favorable for alleviating pulverization, flexible Si-graphite dual-
ion batteries were fabricated, which showed excellent rate capa-
bility up to 150 C with a capacity retention of ≈70% and excellent
cycling stability over 2000 cycles at a rate of 10 C with a capacity
retention of 97%.[44]
4. Challenges and Improvement Measures
Although MPCCs can improve the energy density and safety per-
formance of batteries, they encounter some challenges. (1) The
electrical conductivity of an MPCC, which is inversely propor-
tional to the reduced thickness of the Al/Cu layers of 1.0–2.0 μm
(Figure 1h), may not fully meet the demands of commercial bat-
teries. To overcome this limitation, it is necessary to optimize
the preparation technology to improve the electrical conductiv-
ity of metal layers. Moreover, exploring the rational design and
preparation approaches of polymer substrates with good electri-
cal/thermal conductivity is crucial for the development of high-
performance MPCCs. (2) During manufacturing and cycling, the
Adv. Energy Mater. 2023, 2302134 2302134 (11 of 20)
16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advenergymat.de
metal layers in MPCC easily collapse, break up, and separate
from the substrate layer,[13] resulting in electrode failure. The
volume variations of the electrode materials during cycling gen-
erate stress, which in turn affects the metal layers deposited on
the soft polymer substrate and leads to the formation of wrinkles
or foams when the threshold membrane strain is exceeded. To
address these challenges effectively, adhesive polymer substrates
can be used or the surface roughness of polymer substrates can
be increased using techniques like oxygen plasma sputtering or
chemical etching. (3) The metal oxide, metal layers and polymer
substrates in MPCCs may be corroded by the electrolyte or par-
asitic reactions products (Figure 1i), which seriously affects the
long-term cycling stability of the battery.[2] To improve interfacial
adhesion force, enhance electronic conductivity, and inhibit cor-
rosion of the metal layer, this section summarizes the research
progress and improvement measures.
4.1. Improving Interfacial Adhesion Force
Strengthening the interfacial adhesion force between the metal
layer and polymer substrate is crucial for improving the mechani-
cal and electrochemical properties of MPCCs.[45] Polymer surface
modifications have been carried out using various techniques,
including corona discharge treatment,[16a] ion beam etching,[45b]
plasma etching,[46] and chemical etching.[47] These methods in-
crease the polymer surface roughness and enhance the interfa-
cial adhesion force by altering the surface microstructure, intro-
ducing chemical functional groups and bonds, or dissolving spe-
cific chain segments from the surface polymer.[48] Furthermore,
the incorporation of organic adhesion layers, such as amines,[49]
silanes,[50] or inorganic adhesion layers, such as Ti,[51] between
the metal layer and polymer substrate is another alternative to
enhance the interfacial adhesion force.
4.1.1. In Situ Surface Modification
Corona Discharge Treatment: The mechanism of increasing
surface roughness and interfacial adhesion force through corona
discharge treatment under different gas atmospheres is oxida-
tion, which can introduce polar groups on the polymeric sub-
strate surfaces.[52] In a study conducted by Yao et al., the surface
roughness and surface area of PET film using corona discharge
treatment were increased, resulting in increased interfacial ad-
hesion force. Subsequently, a 10–15-nm Al layer was deposited
on the PET film surface through pulsed magnetron sputtering
under argon gas and the Al layer was further thickened through
vacuum evaporation.[16a] However, it is worth noting that the sur-
face tension of the corona-treated polymer film showed a limited
increase and was unstable after a period of storage, caused by the
migration of additives.[53]
Plasma Etching: Plasma etching (Figure 6a–c) is the most
widely used method to increase the polymer surface roughness
and interfacial adhesion force between the polymer and metal
layer. Choi et al. prepared a flexible MPCC with high electri-
cal conductivity by sputtering a thin Cu layer (<1 μm thick)
onto the surface of a porous PP film treated with O2 plasma
RF magnetron sputtering (Figure 6a). The resulting fibrillate
© 2023 Wiley-VCH GmbH
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advenergymat.de

Figure 6. Methods to modify polymer substrates, increase surface roughness, and enhance metal-polymer interfacial adhesion force. Introduction of
oxygen-containing functional groups on the polymer surface by O2 plasma sputtering: a) fibrous morphology resulting from the interconnection of
nanopores, promoting an increase of the interfacial contact area and interfacial adhesion force between the sputtered Cu layer and polymer. Reproduced
with permission.[54] Copyright 2013, Wiley-VCH. b) Formation of covalent bonds between the Al metal layer and the polymer through the introduction
of oxygen-containing polar functional groups.[55] c) Profile of microstructure for the PET surface after the treatment of O2 plasma sputtering.[56] In-
troduction of oxygen-containing functional groups on the polymer surface by chemical etching: d) NaOH etching pretreatment induces the breakage
and hydrolysis of the imide ring of PI, resulting in the introduction of carboxyl functional groups. This increases the surface hydrophilicity of PI, and
improves the interfacial adhesion force between PI and Cu layer.[57] e) KOH treatment of the PP film introduces carboxyl and amide groups that form
ligand chemical bonds with Cu2+ to strengthen the adsorption of Cu2+ on the PI surface.[58] f) Thiosulfate etching makes epoxy resin substrates enable
adsorption of an Ag+ catalytic activation layer, thereby increasing the adhesion between deposited Cu layer and epoxy resin. Both plasma etching and
chemical etching methods can create bonding pairs at the polymer-metal ion interface to increase surface roughness and improve interfacial adhesion.
Reproduced with permission.[32] Copyright 2017, Royal Society of Chemestry.
surface formed from the interconnections of the nanopores and sive properties of PMMA to Al layers. The plasma treatment
improved the adhesion force and stability of sputtered Cu layers introduced oxygen-containing functional groups (C─O, C─O,
during cycling.[54] Kouicem et al. performed in situ pulsed DC O─C─O, and COOH) onto the PMMA surface, and Al─O─C co-
plasma pretreatment with O2 enrichment within a short time valent bonds were formed at the PMMA interface during the early
on the PMMA surface, which substantially improved the adhe- stage of Al layer deposition, thereby enhancing the interfacial

Adv. Energy Mater. 2023, 2302134 2302134 (12 of 20) © 2023 Wiley-VCH GmbH

www.advancedsciencenews.com
adhesion force between the two layers. Besides, the interaction
between plasma species and the polymer surface results in sur-
face degradation by splitting the carbon chains. This synergistic
effect resulted in a slight increase in PMMA surface roughness,
which further increased the interfacial contact area and adhesion
(Figure 6b).[55] Park et al. utilized O2 plasma sputtering to gen-
erate the small nanostructures on PET surfaces within a short
time (Figure 6c) and investigated the effects of the nanostructure
shape and the size of the etched polymer surface on interfacial ad-
hesion. They found that with an increase in the plasma treatment
time, the nanostructure diameter remained unchanged, but the
height gradually increased, while a finely divided hairy morphol-
ogy with high aspect ratios occurred, and the gap between the
nanostructures gradually widened. When the Cu nanoparticles
were gradually deposited on the nanostructures of the plasma-
etched PET surface, the Cu particle size increased as the etching
time increases extended to 60 min. This could be attributed to the
fact that the gaps between the nanostructures are larger than the
deposited particles. Consequently, the Cu particles were not hin-
dered by the surrounding nanostructures and could grow freely
without interference.[56] Moreover, the oxygen plasma treatment
activated the polymer surface, leading to the generation of vari-
ous functional groups that can bond with the metal ions, which
enhanced the wettability of the polymer surface and improved
the interfacial adhesion force between the polymer and the metal
layer.
Chemical Etching: Chemical etching (Figure 6d–f) offers the
ability to introduce specific functional groups to improve the in-
terfacial force between the polymer and metal layers. Pan et al.
etched PI film in an alkali solution, followed by the deposition
of a Cu layer using magnetron sputtering (Figure 6d). The re-
sulting PI/Cu MPCC exhibited a low area density, highly rough
surface, and a high conductivity of 2.25 × 105 S cm−1 , enabling
the prepared cell to achieve a high energy density and good rate
performance.[57] Wang et al. treated the PI surface using alkaline
permanganate and KOH to promote the formation of imine ring,
followed by simultaneous cleavage and the formation of carboxyl
amide groups on the PI surface to enhance surface roughness
(Figure 6e). These modifications were beneficial for the forma-
tion of coordination chemical bonds with the chemically plated
Cu2+ , enhancing the adsorption and adhesion strength of Cu
on the PI substrate.[58] Similarly, Wang et al. developed a con-
venient and low-cost MPCC by depositing a Cu layer on the sur-
face of an epoxy resin through surface modification of thiosul-
fate (S2 O3 2− ) . This approach not only promoted the formation
of an Ag-based catalytic activation layer to achieve a highly dense
Cu layer for low-temperature electroless plating, but also signifi-
cantly enhanced the adhesion force betweem the Cu metal layer
and the polymer surface (Figure 6f).[32]
4.1.2. Adding Adhesive Layer
Apart from in situ surface modification, the interfacial adhe-
sion force can be improved by adding thin adhesive layer. Yang
et al. introduced two adhesive layers (A and B) between the poly-
mer and metal layers to improve the adhesive strength through
coating and baking the A and B solution on the polymer sub-
strate in turn. The stacking order is polymer substrate, layer
Adv. Energy Mater. 2023, 2302134 2302134 (13 of 20)
16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advenergymat.de
A, layer B, and metal layer, respectively. Consequently, Layer A
next to the polymer substrate reacted with the ester, hydroxyl,
or carboxyl groups on the polymer surface to form hydrogen
bonds at the polymer-metal interface. Layer B was located ad-
jacent to the metal layer and contained oxygen-containing func-
tional groups. Thus, the layer B facilitated the reaction with metal
ions to form ionic bonds at the polymer-metal interface. Layer
A consisted of polyurethane, epoxy resin, isocyanate, and un-
saturated polyester, whereas layer B consisted of ethylene-acrylic
acid copolymers, silicone resins, maleic anhydride-grafted poly-
olefin resins 𝛼-cyanoacrylates, and phenolic resins.[59] More im-
portantly, the interfacial adhesion force between layer A and B
was stronger than those at the interfaces of polymer-A and B-
metal layers. Another approach utilized by Qiu et al. involved
forming adhesive layers on polymer substrates by spraying metal
composites or metals, such as Ni, Ni alloys, SiC, Si3 N4, or Al2 O3
coatings, to prevent metal film peeling.[60] Chen et al. proposed
the use of various adhesive layers composed of Al2 O3 , TiO2 , Al-Ti
alloy, Ni, and Ni-based alloys by electroplating them onto a poly-
mer surface can improve the adhesion between the conductive
metal layer and the polymer substrate. However, the processes
are relatively complex and not conducive to industrialization.[61]
In contrast, Zhu et al. introduced a relatively simple method
to modify a polymer substrate by chemically vapor depositing
(CVD) polyethylene glycol, which can form both covalent bonds
with the polymer and ions bonds with metal ions to enhance the
interfacial adhesion force between polymer and metal layer.[62]
Compared to conventional methods, such as coating, spraying
and corona treatment to add an adhesive layer, the CVD tech-
nique is more efficient, and the treated polymer film with a high
surface tension is very stable even after three months.
4.2. Improving Electrical Conductivity of MPCCs
Current MPCCs face a significant challenge of low conductiv-
ity, thereby inevitably sacrificing battery power performance and
making LIBs using MPCCs challenging to fast charge. The key
issue needs to be solved scientifically and technologically, based
on advancements in structural design and polymer engineering.
4.2.1. Thickening Metal Layer and Reducing Defects
It is straightforward from Figure 1h that the electrical conductiv-
ity of MPCCs increases with an increase of metal layer thickness.
Achieving a targeted sheet resistance of 60 mΩ for a 0.75-μm-
thick Al MPCC and thickening the Al layer can adequately satisfy
the demand of fast charging for most of battery applications.
In general, MPCC undergoes multiple consecutive magnetron
sputtering or vapor deposition steps to thicken the single nano-
scale Cu/Al metal layer into the micron-scale level, and metal de-
fects usually are formed in the metal layer. Liu et al. reported that
the electrical conductivity was also affected by the defects located
in the deposited nanocrystalline Al, especially in the earlier de-
posited Al layers and high-density grain boundaries, which easily
resulted in electrons scattering during long-range transport.[63]
Thus, thickening the metal layer and reducing manufacturing de-
fects are effective approaches to enhance the electronic conduc-
tivity of the deposited metal layer, and further reduce the sheet
© 2023 Wiley-VCH GmbH
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advenergymat.de

Figure 7. Polymer modification approaches to enhance electrical conductivity. a,b) Preparation of a porous metal foil with a 3D interconnected or
through-hole structure as a support, followed by polymer filled in the pores. c–e) Polymerization with conductive polymers, addition of a conductive
adhesive layer, and co-blending with conductive materials. The structure design is based on the integrated porous Cu film with a through-pore structure
reported in the literature.[65] The filled polymer is desired to increase the mechanical strength and prevent the metal impurities into the electrolyte.

resistance of MPCCs to enable fast charging of the LIBs. Never-
theless, it remains a great challenge to obtain MPCCs with thick
metal layer and few metal defects, due to the technical bottleneck.
4.2.2. Polymer Engineering
Through-Hole or 3D Interconnected Structure: The polymer
substrate, being electrically insulating, contributes to the high
resistance of MPCCs. Regardless of techniques employed, the
development of a polymer structure capable of facilitating sta-
ble and fast electron conduction in MPCCs, such as 3D inter-
connected (Figure 7a) or through-hole structure (Figure 7b) is
crucial for the practical LIBs in the future.[64] First, a 3D inter-
connected structure is fabricated by integrating a bidirectional
porous metal layer using powder sintering.[65] Subsequently, the
polymer solution is poured into the pores and then baked, mean-
while the metal layer remains exposed to establish contact with
the electrode materials. This approach is assumed to effectively
avoid the drawback associated with the common method of de-
positing metal layers on a polymer substrate during thermal va-
por deposition, such as burned polymer substrate at high metal
vapor temperature, which yet has never been reported.
Polymer Modification: Several promising polymer modifica-
tion approaches can enhance the conductivity of MPCC and
accelerate its applications in various LIBs. The ways include
engineering conductive polymers, polymerization with conduc-
tive polymers (Figure 7c), incorporating a conductive adhe-
sive layer (Figure 7d), and co-blending with conductive materi-
als (Figure 7e). As depicted in Figure 7c, a polymerized 3, 4-
ethylenedioxythiophene (EDOT) layer was prepared on an Al sur-
face using a simple industrially scalable spraying oxidant and
CVD technique. This technique can be further scaled up using
roll-to-roll process.[66,67] Moreover, the addition of a small amount
of CNTs to carbon black/polyethylene composites remarkably im-
proves their electrical conductivity (Figure 7e),[68] which has been
widely used in transistors, sensors and actuators, but needs to be
validated in LIBs application.
4.3. Improving Welding Quality
In addition to the insulating polymer substrate in a sandwich-
structure MPCC, poor welding quality is another important fac-
tor that reduces electrical conductivity and increases internal re-
sistance of LIBs using MPCCs. The polymer exhibits instability

Adv. Energy Mater. 2023, 2302134 2302134 (14 of 20) © 2023 Wiley-VCH GmbH
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advenergymat.de

Figure 8. Approaches to minimize welding resistance. a) Addition of metal foils of adapters and utilization of a roll welding device to minimize contact
welding resistance and enhance welding rate. b) Variation of stacking modes for MPCCs and CCs. The welding resistance contributes to the internal
resistance of LIBs. The stacking mode of metal layers and MPCCs, along with factors such as gear shape, size, orientation, and welding parameters
significantly influence the welding resistance of MPCCs, which should be optimized until an acceptable resistance level is attained.

and rheological property at high temperatures during welding,
which affects the surface smoothness of metal layer and even
leads to the surface breakage.[69] Additionally, the thin metal layer
is difficult to weld and prone to produce welding defects and dry
joints, which increases the internal resistance and further pro-
duces high polarization and excessive heat generation of the bat-
tery during charging–discharging cycles. To improve the welding
quality, reduce welding defects, and accelerate charge transfer,
researchers have commonly introduced and stacked pure metal
foils or adapters on the two sides of the MPCCs during the weld-
ing (Figure 8a). Moreover, ultrasonic double-sided roll welding
equipment has been explored to optimize the welding depth and
contact surface between the adjacent layers, thereby improving
the welding quality and rate. According to numbers of MPCC,
the welding resistance can be effectively reduced by changing the
stacking mode of MPCCs and CCs, such as stacking mode A, or
B, as shown in Figure 8b. Our research group is currently en-
gaged in this investigation and will provide a detailed report in
the near future.
4.4. Inhibiting Metal Corrosion
or heat-pressing a mixture of polymers (PP, PE, PTFE, nylon, etc.)
or conductive carbon materials on the polymer surface.[71] Bernd
et al. implemented a surface activation technique by applying
phosphate, fluoride, and polymerized homopolymer or copoly-
mer of vinylpyrrolidone to the metal surfaces to prevent corro-
sion. However, the effectiveness of polymerization is limited on
the surface of polymer substrate with low activity or uniformly
active sites.[72] In a non-alkaline battery, Wen et al. prepared a
corrosion-resistance layer with strong adhesion force to electrode
materials on CC by combining conductive carbon materials with
potent polymeric binders such as polyacrylates, phenolic resins,
and epoxy resins, which offered superior adhesion strength.[73]
This approach can be applied to MPCCs as well. Furthermore,
metal oxide protective layers provide a more cost effective and
easily manufacturable alternative to conductive and corrosion-
resistance polymers for improving the adhesion force between
the metal layer and electrode material. An effective method in-
volves conducting direct current etching of the Al surface in a
mixed solution of sulfuric acid and phosphoric acid, which leads
to the formation of a dense Al2 O3 layer and significantly reduce
the corrosion resistance of the metal surface.[74]

During cycling of MPCC-based LIBs, the metal layer and PET
within the MPCC might be corroded by electrolyte, HF or ROLi
generated by side reactions in the electrolyte,[70] which reduces
battery stability and cycle life. Several effective methods can be
used to improve the corrosion resistance of the metal layer while
preserving efficient electron transfer. These methods include
copolymerizing or homopolymerizing organics, vacuum coating,
spraying, and hot pressing the corrosion resistance layer onto
the surface of the metal layer. However, the implementation of
these methods poses challenges, for instance, coating defects in
the metal layer caused by non-uniformity may be corroded.
Stable and conductive layers offer an alternative approach for
reducing the corrosion of metal surface while maintaining elec-
trical conductivity. The components typically consist of carbon
materials, such as activated carbon, carbon nanotubes, graphite,
acetylene black, fullerene C60, as well as conductive polymers,
such as polyacetylene, polypyrrole, polythiophene, polypheny-
lene sulfide and its derivatives, PI, and polyacrylonitrile. To mit-
igate corrosion, Wang et al. proposed methods, such as uni-
formly dispersing conductive agents through blowing, moulding,
5. Conclusion and Perspectives
An ultralight MPCC with a sandwich structure has attracted
much attention, owing to its ability to minimize the inactive
“dead weight” within LIBs and significantly increase energy den-
sity. In addition, the inherent characteristics and functionalized
modifications of MPCCs contribute to preventing thermal run-
away of LIBs during mechanical and thermal abuse and enhanc-
ing safety features. To optimize the performance and accelerate
market application of MPCCs, a comprehensive understanding
of their physicochemical characteristics, as well as the advan-
tages, challenges, improvements, and underlying mechanism, is
crucial, as discussed in this review. In facing these challenges
including weak interfacial adhesion force and large resistance,
some measures and approaches have been proposed, such as
polymer engineering or structural design. For example, incorpo-
rating functional film in LIBs or increasing the polymer surface
roughness can effectively improve the interfacial adhesive force,
while thickening metal layer, reducing defects, and adding con-
ductive layers can reduce resistance.

Adv. Energy Mater. 2023, 2302134 2302134 (15 of 20) © 2023 Wiley-VCH GmbH
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advenergymat.de

Figure 9. Perspectives on the mechanism and applications of metallized plastic current collectors (MPCCs). a) Research on chemical and electrochemical
stability and corrosion mechanism, such as the effects of metal crystal structure and defects on electrochemical properties, and corrosion mechanisms;
b,c) Enhancing thermal conductivity and electrical conductivity. d–f) The development of functions and novel applications of MPCCs, such as bipolar
electrodes, self-healing MPCCs, and wearable devices. In-depth investigations of the chemical and electrochemical stability and the kinetics of MPCCs
during cycling of LIBs in depth are crucial. In addition, simplifying the production process and improving consistency can accelerate the commercialized
production of MPCCs in batteries. The advancements of MPCCs will contribute to the development of practical, lightweight, ultrathin, and flexible LIBs
with high energy density and safety.

However, there is currently a lack of studies on stability-related
mechanisms of MPCCs, including chemical stability, electro-
chemical stability, fatigue resistance and cycling stability. To meet
the demands of its practical applications, further researches need
to focus specifically on the susceptible solubilization and swelling
properties of PET in some electrolytes, weak adhesive force be-
tween PP and Cu layer as well as the development of modifi-
cation methods to enhance the thermal, electrical conductivities
and weldability of MPCCs. Additionally, it makes sense to further
functionalize the MPCC and the cost control. Here, we provide
valuable insights and novel directions for the rational design of
MPCCs and their practical application in high-energy LIBs as fol-
lowing.
trolyte by-products and the polymer substrate or the corrosion of
the thin metal layer would increase the internal resistance and
reduce cycle stability of LIBs. The weight variation of MPCCs in
cycles can provide direct evidence of their stability, however, it has
been paid less attention and not been reported yet. Additionally,
the related mechanisms (Figure 9a) underlying the stability and
corrosion of MPCC remain unclear. These issues need to be tack-
led and provide significant insights into selecting more effective
polymers and optimizing preparation methods for the long-term
use of MPCCs in LIBs.
5.2. Increasing Chemical Stability of Polymer
Substrate—Reducing Swelling

5.1. Exploration of Stability and Corrosion Mechanism of MPCCs
The chemical and electrochemical stability of MPCCs is a critical
prerequisite for their electrochemical properties and practical ap-
plications in high-energy LIBs. The interactions between the elec-
PET, PVDF, and certain polymers tend to swell upon immersion
in electrolytes, leading to variation in stress distribution and a
mismatch between the active electrode materials and the metal
layer. The issue can be addressed through cross-linking low-
swelling polymers, and changing the electrolyte composition.

Adv. Energy Mater. 2023, 2302134 2302134 (16 of 20) © 2023 Wiley-VCH GmbH

www.advancedsciencenews.com
5.3. Modification of MPCCs—Improving Basic Performance
5.3.1. Improving Thermal Conductivity of MPCCs
Exploring alternative polymers, blending or polymerizing mate-
rials with high thermal conductivities and cost-effectiveness are
highly desirable. An MPCC with high thermal conductivity can
effectively dissipate heat (Figure 9b), preventing heat accumu-
lation and enhancing LIBs safety, which also influences their
electrochemical performance. Additionally, minimizing the co-
efficient of thermal expansion of MPCC can reduce the volume
changes within the operating temperature range, further con-
tributing to improved battery stability.
5.3.2. Improving Electrical Conductivity of MPCCs for Fast Charging
of LIBs
As shown in the Figure 9c and the simulated circuits, the incor-
poration of conductive materials into the polymer resulted in a
significant reduction in the resistance of MPCCs. This reduction
facilitates fast charging of high-energy LIBs.
5.3.3. Improving Weldability of MPCCs
As favorable materials for substituting CCs and battery tabs, Ni-
coating CCs or Ni-metal alloys are advantageous to prevent break-
age during ultrasonic welding, due to their high weldability, high
mechanical strength, in combination with high toughness. Be-
sides, they enhance welding joint strength and maintain low-
electrical resistance, which are also effective in MPCCs applica-
tion .[69]
5.3.4. Innovative Applications
From an application perspective, the flexibility and insulating
properties of polymer substrate offer opportunities for innova-
tive applications of MPCCs. For instance, a MPCC-based bipo-
lar electrode (Figure 9d) utilizes a polymer substrate coated with
cathode and anode electrode materials. Self-healing MPCCs has
an ability to repair itself (Figure 9e). MPCCs also enable the de-
velopment of flexible energy storage devices, such as wearable
devices (Figure 9f) and all-solid-state batteries.
5.3.5. Cost Control—Continuous Utilization of Equipment in the
Production Line
To reduce the manufacturing cost of MPCCs, it is important
to ensure that the welding speed of the equipment of MPCC
matches the production line speed of LIBs, while maintaining re-
liable welding quality. Thus, the development and optimization
of the equipment related to the MPCC, including rolling, adapter
sheet incorporation, and unwinding, should be considered in de-
tail for successful integration into the production line.
Acknowledgements
The authors would like to show gratitude to the National Natural Science
Foundation of China (no. 22279070, 52206263, U21A20170), and the Min-
istry of Science and Technology of China (no. 2019YFA0705703) and the
Adv. Energy Mater. 2023, 2302134 2302134 (17 of 20)
16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advenergymat.de
Postdoctoral Research Foundation of China (no. 2023M731917). The au-
thors also would like to thank the “Explorer 100” cluster system of Ts-
inghua National Laboratory for Information Science and Technology for
facility support.
Conflict of Interest
The authors declare no conflict of interest.
Author Contributions
Z.Z. contributed in writing—original draft—investigation. L.W. con-
tributed in methodology, conceptualization, writing—review and editing.
Y.S. and B.Z. contributed in writing—review and editing. X.H. contributed
in conceptualization, investigation, formal analysis, supervision, project
administration, and funding acquisition.
Keywords
battery safety, current collectors, high energy density, lithium-ion batteries,
metal-polymer-metal multilayer composite structure
Received: July 5, 2023
Published online:
[1] a) Q. Wang, M. Zhu, G. Chen, N. Dudko, Y. Li, H. Liu, L. Shi, G. Wu,
D. Zhang, Adv. Mater. 2022, 34, 2109658; b) B. Han, D. Xu, S. S. Chi,
D. He, Z. Zhang, L. Du, M. Gu, C. Wang, H. Meng, K. Xu, Z. Zheng,
Y. Deng, Adv. Mater. 2020, 32, 2004793.
[2] P. Zhu, D. Gastol, J. Marshall, R. Sommerville, V. Goodship, E.
Kendrick, J. Power Sources 2021, 485, 229321.
[3] H. Jeong, J. Jang, C. Jo, Chem. Eng. J. 2022, 446, 136860.
[4] Y. Ye, L.-Y. Chou, Y. Liu, H. Wang, H. K. Lee, W. Huang, J. Wan, K. Liu,
G. Zhou, Y. Yang, A. Yang, X. Xiao, X. Gao, D. T. Boyle, H. Chen, W.
Zhang, S. C. Kim, Y. Cui, Nat. Energy 2020, 5, 786.
[5] R. Choudhury, J. Wild, Y. Yang, Joule 2021, 5, 1301.
[6] W. Lu, J.-B. Baek, L. Dai, John Wiley & Sons 2015.
[7] S. G. Woo, S. Yoo, S. H. Lim, J. S. Yu, K. Kim, J. Lee, D. Lee, J. H. Kim,
S. Y. Lee, Adv. Funct. Mater. 2020, 30, 1908633.
[8] M. Yazici, D. Krassowski, J. Prakash, J. Power Sources 2005, 141, 171.
[9] S. W. Kim, K. Y. Cho, J. Electrochem. Sci. Technol. 2015, 6, 1.
[10] L. Wang, X. He, J. Li, J. Gao, M. Fang, G. Tian, J. Wang, S. Fan, J. Power
Sources 2013, 239, 623.
[11] J. H. Yun, G.-B. Han, Y. M. Lee, Y.-G. Lee, K. M. Kim, J.-K. Park, K. Y.
Cho, Electrochem. Solid-State Lett. 2011, 14, A116.
[12] S. Xu, Y. Zhang, J. Cho, J. Lee, X. Huang, L. Jia, J. A. Fan, Y. Su, J. Su,
H. Zhang, H. Cheng, B. Lu, C. Yu, C. Chuang, T. I. Kim, T. Song, K.
Shigeta, S. Kang, C. Dagdeviren, I. Petrov, P. V. Braun, Y. Huang, U.
Paik, J. A. Rogers, Nat. Commun. 2013, 4, 1543.
[13] M.-S. Jung, J.-H. Seo, M.-W. Moon, J. W. Choi, Y.-C. Joo, I.-S. Choi,
Adv. Energy Mater. 2015, 5, 1400611.
[14] P. Jindal, J. Bhattacharya, J. Electrochem. Soc. 2019, 166, A2165.
[15] X. Feng, M. Ouyang, X. Liu, L. Lu, Y. Xia, X. He, Energy Storage Mater.
2018, 10, 246.
[16] a) W. Yao, Z. Zheng, G. Zhong, Y. Lin, D. Liu, J. Song, Y. Zhu, J. Alloys
Compd. 2023, 941, 168937; b) Z. Liu, Y. Dong, X. Qi, R. Wang, Z. Zhu,
C. Yan, X. Jiao, S. Li, L. Qie, J. Li, Y. Huang, Energy Environ. Sci. 2022,
15, 5313.
[17] L. L. Chen, W. L. Song, N. Li, H. Jiao, X. Han, Y. Luo, M. Wang, H.
Chen, S. Jiao, D. Fang, Adv. Mater. 2020, 32, 2001212.
© 2023 Wiley-VCH GmbH

www.advancedsciencenews.com
[18] C. Wang, X. Li, G. Zhang, CN114864953A 2022.
[19] L. B. P. A. Barbic, S. Voss, F. Hofer, W. Grogger, J. Power Sources 1999,
79, 271.
[20] H. Yim, S.-H. Yu, S. H. Baek, Y.-E. Sung, J.-W. Choi, J. Power Sources
2020, 455, 227978.
[21] a) S. Wang, K. V. Kravchyk, A. N. Filippin, U. Muller, A. N. Tiwari,
S. Buecheler, M. I. Bodnarchuk, M. V. Kovalenko, Adv. Sci. 2018, 5,
1700712; b) Y. Ye, W. Huang, R. Xu, X. Xiao, W. Zhang, H. Chen, J.
Wan, F. Liu, H. K. Lee, J. Xu, Z. Zhang, Y. Peng, H. Wang, X. Gao, Y.
Wu, G. Zhou, Y. Cui, Adv. Mater. 2022, 34, 2202848.
[22] J.-Q. Hu, Y.-Z. Li, S.-Y. Liao, X.-W. Huang, Y.-Z. Chen, X.-K. Peng, Y.-B.
Yang, Y.-G. Min, ACS Appl. Energy Mater. 2021, 4, 9721.
[23] E. Cohen, S. Menkin, M. Lifshits, Y. Kamir, A. Gladkich, G. Kosa, D.
Golodnitsky, Electrochim. Acta 2018, 265, 690.
[24] K. Sarakinos, J. Alami, S. Konstantinidis, Surf. Coat. Technol. 2010,
204, 1661.
[25] Y. Ma, L. Li, J. Qian, W. Qu, R. Luo, F. Wu, R. Chen, Energy Storage
Mater. 2021, 39, 203.
[26] a) Z. W. Zhong, J. H. Wang, Surf. Eng. 2013, 21, 119; b) M. Z.
Pakhuruddin, K. Ibrahim, A. A. Aziz, Int J Polym Mater 2012, 61, 669.
[27] T. S. V. Zaporojtchenko, K. Behnke, C. v. Bechtolsheim, A. Thran, F.
Faupel, Microelectron. Eng. 2000, 50, 465.
[28] F. Muench, ChemElectroChem 2021, 8, 2993.
[29] M. Zhou, W. Zhang, D. Ding, M. Li, Appl. Surf. Sci. 2012, 258, 2643.
[30] Y. C. Ee, Z. Chen, L. Chan, A. K. H. See, S. B. Law, K. C. Tee, K. Y. Zeng,
L. Shen, Thin Solid Films 2004, 462, 197.
[31] E. R. Mamleyev, F. Falk, P. G. Weidler, S. Heissler, S. Wadhwa, O.
Nassar, C. N. Shyam Kumar, C. Kubel, C. Woll, M. Islam, D. Mager,
J. G. Korvink, ACS Appl. Mater. Interfaces 2020, 12, 53193.
[32] Y. Wang, L.-J. Ni, F. Yang, F.-Q. Gu, K. Liang, K. Marcus, Y.-D. Wan,
J.-J. Chen, Z.-S. Feng, J. Mater. Chem. C 2017, 5, 12769.
[33] K. I. M. G. Faraj, Int. J. Thin Film Sci. Technol. 2015, 4, 27.
[34] M. M. Hamasha, K. Alzoubi, J. C. Switzer, S. Lu, S. B. Desu, M. Poliks,
Thin Solid Films 2011, 519, 7918.
[35] J. Duan, X. Tang, H. Dai, Y. Yang, W. Wu, X. Wei, Y. Huang, Elec-
trochem. Energy Rev. 2019, 3, 1.
[36] X. Wang, W. Zeng, L. Hong, W. Xu, H. Yang, F. Wang, H. Duan, M.
Tang, H. Jiang, Nat. Energy 2018, 3, 227.
[37] M. T. M. Pham, J. J. Darst, W. Q. Walker, T. M. M. Heenan, D. Patel, F.
Iacoviello, A. Rack, M. P. Olbinado, G. Hinds, D. J. L. Brett, E. Darcy,
D. P. Finegan, P. R. Shearing, Cell Rep Phys Scif 2021, 2, 100360.
[38] H. Li, H. Wang, Z. Xu, K. Wang, M. Ge, L. Gan, Y. Zhang, Y. Tang, S.
Chen, Small 2021, 17, 2103679.
[39] Z. Zhuang, G. Shi, L. Xiong, S. Yu, L. Liu, Q. Yang, Z. Yao, Y. Chen, H.
Fei, X. Yan, Y. Cheng, CN114361461A 2022.
[40] C. Wang, X. Li, G. Zhang, CN114744213A 2022.
[41] Y. Liu, R. Ren, CN114497568A 2021.
[42] Z. Chen, P.-C. Hsu, J. Lopez, Y. Li, J. W. F. To, N. Liu, C. Wang, S. C.
Andrews, J. Liu, Y. Cui, Z. Bao, Nat. Energy 2016, 1, 15009.
[43] J. Jia, H. Liu, S. Liao, K. Liu, Y. Wang, Nano Lett. 2022, 22, 9122.
[44] C. Jiang, L. Xiang, S. Miao, L. Shi, D. Xie, J. Yan, Z. Zheng, X. Zhang,
Y. Tang, Adv. Mater. 2020, 32, 1908470.
Adv. Energy Mater. 2023, 2302134 2302134 (18 of 20)
16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advenergymat.de
[45] a) P. S. HO, Appl. Surf. Sci. 1989, 42, 559; b) K. W. Paik, A. L. Ruoff, J.
Adhes. Sci. Technol. 1990, 4, 465.
[46] S. H. Kim, S. H. Cho, N. E. Lee, H. M. Kim, Y. W. Nam, Y.-H. Kim,
Surf. Coat. Technol. 2005, 193, 101.
[47] W. Zhao, Z. Wang, Int. J. Adhes. Adhes. 2013, 41, 50.
[48] E. T. K. W. C. Wang, K. G. Neoh, Appl. Surf. Sci. 2002, 199, 52.
[49] Y.-I. Lee, Y.-H. Choa, J. Mater. Chem. 2012, 22, 12517.
[50] Y. Lu, Appl. Surf. Sci. 2010, 256, 3554.
[51] A. T. Megan, J. Cordill, J. Schalko, G. Dehm, Int. J. Mater. Res. 2011,
102, 729.
[52] C. Sun, D. Zhang, L. C. Wadsworth, Adv. Polym. Technol. 1999, 18,
171.
[53] S. K. Nemani, R. K. Annavarapu, B. Mohammadian, A. Raiyan, J. Heil,
M. A. Haque, A. Abdelaal, H. Sojoudi, Adv. Mater. Interfaces 2018, 5,
1801247.
[54] J.-Y. Choi, D. J. Lee, Y. M. Lee, Y.-G. Lee, K. M. Kim, J.-K. Park, K. Y.
Cho, Adv. Funct. Mater. 2013, 23, 2108.
[55] M. M. Kouicem, E. Tomasella, A. Bousquet, N. Batisse, G. Monier, C.
Robert-Goumet, L. Dubost, Appl. Surf. Sci. 2021, 564, 150322.
[56] S. J. Park, T.-J. Ko, J. Yoon, M.-W. Moon, K. H. Oh, J. H. Han, Appl.
Surf. Sci. 2018, 427, 1.
[57] C. Pan, S.-J. Chen, Y.-H. Huang, L. Wang, J.-L. Luo, X.-Z. Fu, J. Power
Sources 2022, 528, 231207.
[58] Z. Wang, A. Furuya, K. Yasuda, H. Ikeda, T. Baba, M. Hagiwara, S.
Toki, S. Shingubara, H. Kubota, T. Ohmi, J. Adhes. Sci. Technol. 2002,
16, 1027.
[59] X. Yang, CN113795954A 2021.
[60] H. Qiu, CN11 2017.
[61] Q. Chen, T. Xu, L. Wang, Y. Wang, CN114015994A 2022.
[62] Z. Zhu, S. Wang, J. Xia, X. Li, G. Zhang, CN115911404A 2023.
[63] A. Zameshin, M. Popov, V. Medvedev, S. Perfilov, R. Lomakin,
S. Buga, V. Denisov, A. Kirichenko, E. Skryleva, E. Tatyanin, V.
Aksenenkov, V. Blank, Appl. Phys. A 2012, 107, 863.
[64] L. Yan, N. Chouw, K. Jayaraman, Composites, Part B 2014, 63,
15.
[65] J. Chen, S. Li, X. Qiao, Y. Wang, L. Lei, Z. Lyu, J. Zhao, Y. Zhang, R.
Liu, Q. Liang, Y. Ma, Small 2022, 18, 2105999.
[66] D. Lepage, L. Savignac, M. Saulnier, S. Gervais, S. B. Schougaard,
Electrochem. Commun. 2019, 102, 1.
[67] N. D. Trinh, M. Saulnier, D. Lepage, S. B. Schougaard, J. Power Sources
2013, 221, 284.
[68] Y. Liu, H. Zhang, H. Porwal, J. J. C. Busfield, T. Peijs, E. Bilotti, Polym.
Int. 2019, 68, 299.
[69] L. N. Trinh, D. Lee, Metals 2020, 10, 842.
[70] E. Yoon, J. Lee, S. Byun, D. Kim, T. Yoon, Adv. Funct. Mater. 2022, 32,
2200026.
[71] J. Cheng, S. Sun, G. Cao, Y. Yang, CN101192669A 2006.
[72] K. Schenzle, A. Moni, CN1271246C 2006.
[73] Y. Wen; Z. Ren; L. Shao; P. Zhao; W. Zhang; G. Cao; Y. Yang,
CN106876716A 2017.
[74] L. Cao, L. Li, Z. Xue, W. Yang, H. Zou, S. Chen, Z. Liu, J. Porous Mater.
2020, 27, 1677.
© 2023 Wiley-VCH GmbH
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advenergymat.de

Zhiguo Zhang is currently a postdoctor in Prof. Xiangming He’s group in Insititute of Nuclear and
New Energy Technology, Tsinghua University. She received her Ph.D. from Key Laboratory of Materials
for New Energy Conversion and Storage (Ministry of Industry Technology, Harbin Institute of Tech-
nology). Her current research interests focus on the fields of advanced current collectors, reference
electrodes, and the related mechanisms for lithium-ion batteries of high energy density and safety.

Youzhi Song received his Ph.D. degree under Prof. Baoku Zhu from the Department of Polymer Sci-
ence and Engineering at Zhejiang University in 2018. Currently, he is a postdoctoral in Prof. Xiangming
He’s group in the Institute of Nuclear and New Energy Technology, Tsinghua University. His current
research interests are focused on the rational design of polymeric membrane separators for safe and
endurable lithium-based batteries.

Bo Zhang was born in Shanxi, China, in 1992. He received his Ph.D. in Beijing University of Posts and
Telecommunications (BUPT) in 2021. Now, he continues his research in the Institute of Nuclear and
New Energy Technology, Tsinghua University as a postdoctoral research fellow (working with Prof.
Xiangming He). His research is focused on the theoretical design of cathode materials for lithium-ion
batteries.

Li Wang is an associate professor at the Institute of Nuclear and New Energy Technology, Tsinghua
University, China. She received her B.S. in 1999 and Ph.D. in analytical chemistry in 2004 from the Ts-
inghua University. Her research expertise includes new electrode material preparation technology,
failure mechanism of lithium-ion battery, safety power-battery technology, and fundamental under-
standing of related electrochemical processes.

Adv. Energy Mater. 2023, 2302134 2302134 (19 of 20) © 2023 Wiley-VCH GmbH
 16146840, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202302134 by Hefei University Of Technology, Wiley Online Library on [10/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advenergymat.de

Xiangming He is a professor and the group leader of the Lithium-ion Battery Laboratory at the Institute
of Nuclear and New Energy Technology, Tsinghua University. He received his bachelor’s and mas-
ter’s degrees from the School of Chemical Engineering and Ph.D. from the Institute of Nuclear and
New Energy Technology, Tsinghua University. His research focuses on the design and application of
functional materials for energy storage and conversion and a fundamental under-standing of related
electrochemical processes.

Adv. Energy Mater. 2023, 2302134 2302134 (20 of 20) © 2023 Wiley-VCH GmbH