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Copper-Graphene Composite Foils via Electro-

Deposition: A Mini Review

Article · January 2018

DOI: 10.1557/adv.2018.28

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DOI: 10.1557/adv.2018.28

Copper-Graphene Composite Foils via

Electro-Deposition: A Mini Review

Gongsheng Song1,2, Qiang Fu2 and Chunxu Pan 1,2, *

1
Suzhou Institute of Wuhan University, Suzhou, 215123, China

2
School of Physics and Technology, Wuhan University, Wuhan, 430072, China

ABSTRACT

As an emerging carbon material with advantages of thinnest, ultrahigh strength, superior

thermal conductivity and electrical conductivity, graphene (Gr) is called the “black gold” and
will have a profound applying potential in the field of materials science and engineering.
Many researches concerning preparation of the Cu-Gr composite via various approaches
have been reported. However, only few works are related to the electrochemical deposition
method. As a simple, low cost, large scale production method, electrodeposition method has
been widely used in industry for manufacturing foils involving copper-clad laminate (CCL),
printed circuit board (PCB) and the negative current collector of lithium ion battery, where
the copper foil not only serve as the carrier of the cathode active material but also play a role
in collecting and conducting electrons. In the present article, we review the research progress
on preparations and mechanical properties of the Cu-Gr composite foils by electrochemical
method, and introduce our recent work in this area. The advancement of the process and the
perspective industrial productions are also discussed.
https://doi.org/10.1557/adv.2018.28
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INTRODUCTION

Due to its excellent electrical conductivity, thermal conductivity and

elongation, metal copper (Cu) has been widely applied in fields of cable and electronic
components. The rapid development in the electronics industry has proposed a high
requirement on comprehensive properties of Cu and its alloys. Developing the novel Cu
alloys and Cu-based composites is very essential. During the past few years, numerous
Cu-matrix composites have been proposed with variant reinforcements, such as Al2O3,
TiO2, graphite, carbon nanotube (CNT), graphene (Gr).
Since discovered by Noble laureates Geim and Novoselov in 2004, graphene
has emerged as a rapid rising star in material field [1]. Graphene consists of a
single-atom-thick planar sheet structure with sp2-bonded carbon atoms arranged in a
honey comb crystal lattice. In the carbon material family, graphene has been making a
crucial impact in many areas of science and technology owing to its remarkable
physical-chemical properties, involving large theoretical specific surface area (~2630
m2/g), strong mechanical strength and excellent thermal and electrical conductivities.
These unique properties render graphene have a profound applying potential in the field
of materials.
Many researches have been reported concerning preparation of the Cu-Gr
composite via various approaches, which demonstrate that Gr possesses incomparable
advantage in enhancing the mechanical and electric conductivity. The main methods for
producing the Cu-Gr composite include powder metallurgy and electrochemical
deposition, in which the former has been intensively investigated. Powder metallurgy
refers to mix up the modified reinforcement (Gr or its derivative) with Cu powders, and
then hot-pressing sinter to obtain the composites [2]. Hwang et al. [3] proposed a
molecular-level mixing modification and spark plasma sintering (SPS) process. The
elastic modulus and the yield strength of the resultant Cu-Gr (2.5 vol%)composite were
131 GPa and 284 MPa, respectively, which were ~30% and ~80% higher than the values
for pure Cu.
Comparatively, studies on electrochemical deposition are relatively few. As a
simple, low cost, large scale production method, electro-deposition is expected to
generate economic benefit in field of industry on preparing the Cu-Gr composite. In this
paper, the recent research progress on preparations and mechanical properties of the
Cu-Gr composite foils via electrochemical method are reviewed and our work in this area
is also introduced. In the end, the perspective industrial productions are discussed.

PERPARATIONS OF CU-GR COMPOSITES BY ELECTROCHEMICAL

PROCESS

In general, preparation of the Cu-Gr composites via electrochemical process is

https://doi.org/10.1557/adv.2018.28

based upon the principle, i.e., adding the Gr precursor into the electrolyte, forming
suspension, and incorporating Gr into the Cu-based composites under applying current,
as shown in Figure 1, where the power supply can be pulse power, direct current power
and other powers.
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Figure 1. Schematic diagram of the electrochemical synthesis method of Cu-Gr composite.

Preparation via pulse reverse electro-deposition (PRED)

PRED has been widely applied for preparing the Cu-Gr composites. Pavithra et
al. [4] prepared the Cu-Gr composite foils with thickness about 35 μm by using PRED.
The experimental results revealed that the PRED exhibited a uniform distribution of Gr
in Cu matrix, and the optimum GO concentration was found to be 0.5 g/L. After
annealing the composite foils at 300°C, grain size in the pure Cu foil increased up to 10
microns, whereas the Cu-Gr foils did not shown any significant increase, and they
suggested that was due to the presence of Gr as the second phase material at the grain
boundary, which obstructed the motion of grain boundaries and thus retarded the grain
growth. The composite foils exhibiting a high hardness of 2.5 GPa and an increased
elastic modulus of 137 GPa, while exhibiting an electrical conductivity comparable to
that of pure Cu.
In Huang et al.'s work [5], Gr prepared by chemical vapor deposition (CVD)
was served as precursor and the Cu-Gr composite foil was electro-deposited through
pulse electro-deposition under ultrasonic stirring. They used a micromachining
technology to test the thermal conductivity, electrical resistivity and mechanical property
of the composite foils. Compared to pure Cu foils, the mechanical property of the Cu-Gr
composite foils was remarkably increased while the electrical property and thermal
property were comparable. Modification of Gr may affect the composite foil, three
different graphene derivative, i.e., GO, chemically reduced graphene oxide (RGO) and
thermally reduced graphene oxide (TRGO) was investigated, and the wear performance
of the Cu-TRGO composite films was better than that of the Cu-GO and Cu-RGO
composite films [6]. In addition, copper-graphene composite was also synthesized by
electrochemical deposition of copper in graphene quantum dot (GQD, 5% w/v) bath [7].
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The composite resulted in a critical heat flux (CHF) of 216 W/cm 2 and a heat transfer
coefficient (HTC) of 86 kW/m2C, which increased by 66% in CHF over a plain copper
surface. The improved performance has been attributed to the higher thermal
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conductivity of the graphene layers arising from the porous nature of the surface with an
increased surface area.
In general, nanomaterials tend to generate agglomeration in solution due to its
high surface energy. The addition of surfactants somewhat suppresses the agglomeration
of graphene sheets in the plating solutions and leads to the successful co-deposition of
graphene/metal nanocomposite coatings. However, the addition of these capping agents
may introduce heterogeneous impurities, which weaken the interfacial bonding of
graphene sheets and matrix, fading the mechanical and physical properties of the
composite coatings. Therefore, a surfactant-free colloidal solution comprised of copper
(II)-ethylene diamine tetra acetic acid ([CuIIEDTA]2−) complexes and GO sheets is
proposed by Mai et al. [8] to prepare RGO/Cu composite coatings by electrodeposition.
Anionic [CuIIEDTA]2− complexes stably coexist with negatively charged GO sheets due
to the electrostatic repulsion between them, facilitating the electrochemical reduction and
uniform dispersion of GO sheets into the copper matrix.

Preparation via direct current electrodeposition (DCED)

It is well-know that DCED process is widely applied in actual industrial

manufacture for producing important raw foils, such as copper-clad laminate (CCL),
printed circuit board (PCB) and the negative current collector of lithium ion battery,
where the Cu foil not only serve as the carrier of the cathode active material but also play
a role in collecting and conducting electrons. Jagannadham [9-11] prepared a thickness
up to few hundred (~500) microns Cu-Gr composite foils via a DC electro-deposition
method at a low current density of 1.75 mA/cm2. The effective mean field analysis was
used to model the thermal conductivity of the composites, and determined the interfacial
thermal conductance between Cu and Gr, the volume fraction and the resistivity and
temperature coefficient of resistance of the composite foils. The results indicated that the
composite foils with thickness greater than 200 μm showed an improvement in thermal
conductivity over that of electrolytic Cu from 380 W/(m·K) to 460 W/(m·K) at 300 K
(27℃), and the resistivity of electrolytic Cu was reduced by 10-20%with the addition of
8-11% Gr volumes.

Preparation via other electrochemical methods

In general, as for an unknown reaction system, a three-electrode

electrochemical cell with a working electrode, a saturated reference electrode and an a
counter electrode also has been used to investigated the possible reactions. Xie et al.[12]
prepared the Cu-Gr composite films on copper foil, as potential electrical contact
materials, with one-step electrochemical reduction deposition method. Cyclic
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voltammetry (CV) was used to define the deposition conditions, and the stability of
suspension solution was investigated. They found that, within a short deposition period,
the growth of discrete nano-grains in the composite film predominates, whereas
pine-tree-leaf nanostructures are formed in the composite film when the deposition
period is long, due to the chelating role of GO or RGO to regulate the growth rate of
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metallic copper nano-grains. By suitable preparation of the precursor solution and

cathodic deposition conditions, GO could be reduced to Gr during the electrodeposited
process. Compared with the polished Cu foil and the electrodeposited Cu foil, the Cu-Gr
composite foils maintain a lower electrical resistivity. The order of the electroactivity is
polished Cu foil > Cu-Gr composite foils > electrodeposited Cu foils.

OUR GROUP’S CURRENT RESEARCH WORK

Direct determination of Gr amount in the composite foils

For practical applications, the most concerns are the Gr content in the
composite foil and its influence on mechanical and electrical properties. In general, most
researches indirectly determine the relationship between the performance of the Cu-Gr
composite foil and the Gr content through adjusting the Gr or GO concentration in the
electrolyte. In our previous work [13], we firstly propose a direct and accurate approach,
that is, by using an instrumental carbon and sulfur analyzer, to determine the Gr amount
in the direct current electrodeposited Cu-Gr composite foil, and also obtain the
relationship between the Gr amount in the composite foils and GO concentration in the
electrolyte.
Further, mechanical property measurements reveal that: 1) The variations of
mechanical properties (involving elastic modulus, hardness and tensile strength) of the
Cu-Gr foils along with the GO concentration in the electrolyte exhibit the similar
tendency of that along with the Gr content in the Cu-Gr foils, as shown in Figure 2. 2)
According to current experimental conditions, the optimal values of the mechanical
properties and the Gr amount in the foils appear at the GO concentration of 0.5g/L in the
electrolyte; 3) When the GO concentration less than 0.5g/L, the values of mechanical
properties and the Gr amount in the foils present an approximate linear relationships; and
beyond 0.5g/L, the values become unstable and declining, which can be attributed to
agglomeration of excessive GO in the electrolyte and made it difficult to be co-deposited
into the foil. The present approach has many advantages, such as simplicity, rapidity,
high accuracy and good repeatability. It is expected to be employed in other areas of
metal-Gr composites, and shows important significance both in investigation in the
laboratory and in industrial applications.
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(a) (b)

(c) (d)

Figure 2. Effect of GO concentrations in electrolyte on (a) C content in the composite foil, (b) tensile strengh, (c)
hardness and (d) elastic modulus of composite, respectively. Reprinted with permission from Ref 9. Copyright (2017)
Royal Society of Chemistry.

Optimal conditions for preparing thin foils via DC electro-deposition

Nowadays, the DC electrodeposited Cu foils are massively produced in

industry. The major requirements of commercial Cu foils are tensile strength, ductility
and electrical conductivity. At the same time, the foil thickness is also a key factor and is
strictly limited for different applications. The commonly used thickness in industrial
production generally varied from 18μm, to 70μm, and only few companies can achieve
the thickness between 10 μm to 12 μm throughout the world. Besides, it is well
established that many factors, such as concentration of electrolyte, additives, applied
current density, temperature of bath solution, and agitation, etc., will affect the quality of
the electrolytic Cu foils, especially for the thin Cu foils which is more sensitive to
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electrodeposited parameters.
According to the industrial process, we prepared the Cu-Gr composite thin foils
with a thickness of 20±1μm, and studied systematically the effect of the key factors,
involving GO concentration in electrolyte, applied current density and temperature, on
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the foils' mechanical properties, such as hardness, elastic modulus and tensile strength.
The optimal condition was obtained through a series of single factor experiment, and
effect of the three factors on distribution of Gr in the composite thin foils was discussed
in detail [14]. Meanwhile, the relationships between microstructures and mechanical
properties of the composite foils were figured out, which is expected to guide the
practical industrial productions. These results will be a basis of our future work on
achieving the Cu-Gr composite foil with a thickness less than 20μm, and even to 10μm.

MECHANISM FOR CO-DEPOSITION OF GRAPHENE WITH COPPER

In the research of Xie et al., within a short deposition period, the growth of
discrete nanograins in the composite film predominates, whereas pine-tree-leaf
nanostructures are formed in the composite film when the deposition period is long, due
to the chelating role of GO or rGO to regulate the growth rate of metallic copper
nanograins [12]. At present, there is no a general mechanism or model for co-deposition
of Gr with Cu due to many experimental factors were found to influence the
co-deposition process. Herein, we give a preliminary speculation. That is, firstly, two
common processes involved in the incorporation of Gr into Cu matrix can be recognised,
namely physical dispersion and electrophoretic migration of graphene in the electrolyte.
It is essential to investigate in this area.

POTENTIAL APPLICATIONS OF CU-GRAPHENE NANOCOMPOSITES

Cu-graphene nanocomposites are just in the early research stage. Commercial

products for real application in industry fields may be a long way off. However, the
potential applications for the composites exist in many aspects. For the high specific
strength, good thermal and electrical conductivity, good wear resistance and corrosion
resistance, and low coefficient of thermal expansion, Cu-graphene nanocomposites are
suitable for application in the copper-clad laminate (CCL), printed circuit board (PCB)
and the negative current collector of lithium ion battery. Compared with carbon fibres
and carbon nanotubes (CNTs), the production cost for Gr in large quantities will be much
lower, Graphene has better strength and stiffness than carbon fibres and CNTs and also is
easier to disperse in a metal matrix. Therefore, Cu-graphene nanocomposites are
expected to be alternatives in the industry fields where carbon fibre and CNT-reinforced
metal composites are used.

SUMMARY

In recent years, various routes have been proposed for preparing the Cu-Gr
https://doi.org/10.1557/adv.2018.28

composite, in which the electrochemical method will be the promising way in industrial
application, especially for the thin foils less than 20 μm. However, there are still a lot of
deficiencies in the preparation technology, such as instability of Gr suspension and
output current power. From the point view of the instability of Gr suspension, it is very
essential to seek and develop proper surfactants, or properly modify the Gr precursor
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before adding into the electrolyte. In addition, in order to obtain the controllable structure
and desired performance of the Cu-Gr composite foils, the precise control is another
important direction, and more factors affecting the electrochemical process should be
investigated. In the future, any technological progress and innovation in this area will
greatly promote the practical application of the Cu-Gr composite foils.

ACKNOWLEDGMENTS

This work was supported by the Suzhou Science and Technology Project
(Prospective Application Research Program, No. SYG201740).

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