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Graphene Applications in the Energy Field: State-of- the-Art and Impact

Conference Paper · July 2018

DOI: 10.18687/LACCEI2018.1.1.444

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 Graphene Applications in the Energy Field: State-of-
the-Art and Impact
Juan Prieto Vivanco, MSc,1 and Carlos Rodríguez-Monroy, PhD2
1
INDRA Corporation, Spain, [email protected]
2
Universidad Politécnica de Madrid, Spain, [email protected]

Abstract– Graphene with its unique properties combining multiply by 10 the power density of current lithium ion
mechanical resistance 200 times superior to steel, exceptional batteries with load times of the order of few hours, super
electrical, thermal, quantum and optical properties apart from an capacitors or new cheaper photovoltaic cells with better use of
enormous versatility to modify its properties, has become a
solar energy. If these projections were to be fulfiled, the world
"technological catalyst" that allows the drastic evolution of a series
of devices and systems existing until now limited in their capacities. of energy, transport and electronic devices with autonomous
At the same time, it opens new barely explored application fields power supply, would be radically transformed. Despite the
related to nanomaterials science. Its mono atomic thickness and the enthusiasm in the scientific community, it is not yet clear what
need for precise control in its composition and structure to exploit will be the real impact of graphene in this domain or what the
its properties are posing a fundamental challenge for its real implications of this application would be for the different
manufacture and application, which is requiring enormous efforts markets.
by the scientific community and the industry. Without having yet
achieved precise and complete control of the manufacturing chain,
there are already small-scale graphene production chains II. GRAPHENE PRODUCTION. TECHNICAL AND
exploiting different production methods and producing graphene ECONOMIC STUDY
worldwide to feed a first generation of graphene-based devices. The
energy sector in a fundamental process of transformation towards The properties of Graphene vary drastically depending on the
the generation, and massive and sustainable supply of energy to purity, size and shape of the crystals and the way in which the
supply an exponentially growing demand, is one of the sectors in graphene sheets are arranged with each other and with other
which a more immediate impact of this first generation of systems materials. Graphene series production is economically the
based on graphene is foreseen. The imminent commercial great challenge that once solved will allow the development of
appearance of a new generation of storage technologies based on
graphene, will significantly break the technical-economic viability
the hundreds of applications.
thresholds that were limiting applications such as mass storage of
energy in electricity networks or transport applications. In
subsequent waves (2020-2025), new cheaper and more efficient
hydrogen and electric generation devices will increase the
availability of cheap, sustainable and distributed energy. As can be
seen from the increase in the number of patents in recent years in
graphene-based technologies and the gradual emergence of
commercial publications from the private sector, the market is in
the commercial testing phase prior to commercial exploitation.
Numerous private companies have been set up to capitalize on the Fig. 1: Evolution in the size of the graphene crystals produced, from 1-
value of this first generation of graphene commercial applications micrometer graphene flakes produced by exfoliation to reel processing [1]
and large corporations and niche companies are accelerating their
machinery to position themselves first in this market. The next At present, there are different methods of graphene
wave of applications with substantially more disruptive impact is production, each with different costs, degrees of purity, crystal
still in the conceptualization and proof of concept phase in sizes and chemical modifications that fundamentally condition
laboratories and universities, requiring levels of technological
its application. At present, 8 basic blocks of processes for the
maturity that are not expected before 2025.
Keywords— Graphene, Energy applications, Technological synthesis of graphene and its derivatives are distinguished.
maturity Despite the progress made in recent years in the production of
I. INTRODUCTION graphene, the production of large graphene crystals of
monatomic uniform thickness on any type of substrate
Since its identification in 2004, graphene has become the remains a challenge in the production of graphene, as is the
'holy grail' of materials science. Its electrical and mechanical cost of production.
properties have led to the opening of hundreds of research
projects and development initiatives seeking to solve both its
serial production and its application in fields as diverse as the
development of high frequency electronic devices, advanced
filters for desalination or neuronal interfaces. Among the
multiple affected areas is the world of energy storage devices,
with promises of new generations of batteries that can

16th LACCEI International Multi-Conference for Engineering, Education, and Technology: “Innovation in Education and
Inclusion”, 19-21 July 2018, Lima, Peru. 1
 a. Massive reduction of emissions of carbon dioxide to
the atmosphere, forcing the substitution of energy
sources based on fossil fuels for other energy sources that
do not emit greenhouse gases.
b. Efficient storage. The presence of non-manageable
energy sources in systems that depend on a continuous
and reliable supply over time, as well as the need to
replace fossil fuels as a source of energy storage for
transport, require storage and storage elements, in order
to convert rapidly large volumes of energy either in a
fixed or in a mobile way (electric vehicles and other
mobile devices).
c. Maintain the supply of increasing amounts of
energy cheaply, that sustain the growing energy needs of
a world population increasingly developed industrially
and with growing energy needs.

Fig. 2: Relative price and quality of graphene depending on the production The transformation of the energy sector is being supported on
method [1]
technological storage and generation solutions that after a very
intense development during the last decades begin to show
Given the different qualities, production efficiency and
signs of depletion, facing three basic challenges:
substrates, of the different synthesis methods identified to
1. Efficiency increase in energy storage and conversion
date, the following methods have been identified as the most
processes.
promising for the production of graphene for energy
2. Reduction of production costs.
applications:
3. Decrease in size / weight of the conversion and
storage devices in relation to the storage capacity /
• Liquid phase exfoliation.
energy conversion, reducing the needs of materials
• Chemical vapor deposition.
and favoring their mobility.
• Growth on silicon carbide.
The Ragone diagram allows the different energy storage /
III. THE APPLICATION OF GRAPHENE TO ENERGY conversion devices to be classified according to their peak
STORAGE AND PRODUCTION power and their energy storage capacity per unit mass.
A. Current reality and challenges of the energy sector

Production / conversion, transport and storage are the

essential functions of any energy system. Electricity due to its
versatility in the conversion to and from other energy sources
and its ease of transportation has become the main energy
vector of our society, being at the base of almost all sectors of
activity. Hydrocarbons in the form of gas and petroleum
derivatives are other energy vectors with great development
and wide use throughout the planet, mainly for thermal uses
and transportation. The abundant and cheap availability of
these two energetic vectors has constituted the base of the
industrial revolution, and the technological revolution that our
society has experienced in the last three centuries.

Problems associated with sustainability over time and the

availability of resources force the energy sector to address
three major, intimately related fundamental challenges: Fig. 3: Ragone diagram corresponding to the different commercial
energy storage technologies

Graphene for its exceptional electrical, optical and

physical properties, and abundance and low cost of its raw

16th LACCEI International Multi-Conference for Engineering, Education, and Technology: “Innovation in Education and
Inclusion”, 19-21 July 2018, Lima, Peru. 2
material, has become the focus of the main groups of research Although the peak powers of these batteries are
and marketing of energy storage and conversion solutions. In comparable to those of combustion engines, the power and
the following sections, in order to understand their potential energy density per unit mass is still significantly below. This
impact, graphene applications are analyzed for storage and limitation in the power density leads to excessively long load
conversion of energy that present a higher degree of maturity. times of close to 40 hours for 400 km of battery life with a
normal 220 V socket. The capacity of current lithium-ion
B. Storage devices: batteries and super capacitors. batteries and super capacitors are fundamentally limited in
performance, loading and unloading speed and number of
Challenges cycles for the chemical and physical properties of the
materials used in the anodes and cathodes. The loading and
The use of batteries and super capacitors as energy storage unloading processes produce physical and chemical variations
devices faces three fundamental challenges already identified in the electrodes, which increase with the speed of the process
in the general introduction of the previous section: as the temperature increases and the number of cycles
1. Increased efficiency in storage processes: increases. Table 1 summarizes the current situation of storage
minimization of losses in the charging / discharging solutions in terms of energy density and cost per unit of
process and maintenance during the life of the energy and the target values for the different applications.
battery, measured in the form of number of charge
and discharge cycles. TABLE I
CURRENT VALUES AND FUTURE TARGETS FOR THE
2. Reduction of production costs. Substituting raw APPLICATION OF BATTERIES TO DIFFERENT ENERGY DOMAINS
materials and high cost production processes for
other cheaper materials and processes. Current Target Values
3. Increase in storage density and power, increasing values Transport Electric
the power and maximum power of the battery per
unit mass. Grid
The electrochemical battery is the most widespread storage Specific Energy (Wh/kg) 250-250 600-1000 -
mechanism by degree of maturity and allows higher storage
Cost ($/kWh) 250 100 100
densities at the lowest cost. The capacitors, unlike the
batteries, are characterized by their fast loading and unloading
power, but also by their low energy storage capacity and short Application of graphene.
retention times of stored energy. The density of storage and
power density of electrochemical batteries has been Graphene, due to its high surface / volume ratio, high
increasing, being Lithium ion batteries that achieve maximum load mobility, physical stability and chemical stability, allows
energy density and power per unit mass and volume. The the electrodes to increase the specific power of the batteries,
specific densities reached by this type of batteries have increasing the charge / discharge speed and the number of
allowed the commercial development of electric vehicles, cycles the battery is capable to endure. For hybrid lithium-
evolving from the initial 150 km (100 Wh / kg) of autonomy sulfur (Li-S) batteries and architectural cathodes hybridized
to 400-500 km (250 Wh / kg) of the new generation. with sulfur, graphene and carbon nanotubes, energy densities
of up to 400 Wh / kg and power of 10,000 W / kg are
estimated [80].

Fig.4: Lithium-nickel-manganese-cobalt battery systems of the Renault Fig. 5: Figure of hybrid structures Graphene-carbon nanotubes GSH@APC
ZOE with a range of 403 km [2]

16th LACCEI International Multi-Conference for Engineering, Education, and Technology: “Innovation in Education and
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 Fig. 6 shows on a Ragone diagram, the results obtained in Existing prototypes.
some experimental prototypes.
There are already prototypes that substantially exceed the
performance of current technologies. Currently, they are in the
reduction of costs and commercial production stage and an
imminent appearance of commercial products is expected.
There are some external mobile batteries on the market that
integrate graphene into the electrodes, tripling the charging
and discharging speed of standard Li-ion batteries.

Fig. 6: Ragone diagram for Li-S batteries based on different cathodes

based on hybrid architectures of graphene and carbon nanotubes (and Fig. 8: Commercial lithium ion mobile charging battery and graphene
comparison with other storage technologies [2] electrodes, allowing 3 times faster charges and downloads

Another very interesting application is the hybrid storage Samsung SID reports in 2017 on its website the
systems (Battery-supercapacitor hybrid device BSH) in which manufacture of a new generation of lithium-ion batteries with
a battery anode is combined with a super capacitor cathode, "beads" of graphene (GB) in cathodes and anodes, allowing a
combining the very high power density of the super capacitors 45% increase in the capacity of the batteries (444 Wh/kg at
with the high energy density of Battery. BSH prototypes of 60ºC 800Wh/l) and charging and discharging speeds 5 times
Ion Sodium with graphene anode have achieved power higher, operating at temperatures of 60ºC which reduces the
densities of 16,500 W / kg and energy densities of 285 Wh / cooling needs.
kg [3].
C. Fuel cells and storage of hydrogen.

Challenges

Fuel cells convert the chemical energy stored in a fuel

into electricity through its oxidation. The electrochemical
process is direct without thermal conversion processes,
intermediate mechanics, achieving efficiencies in the
conversion of fuel energy much higher than that of any 40-
60% conversion engine, and can reach 85-90% with
cogeneration (taking advantage of the residual heat). The main
problem of the current fuel cells in their different
configurations is the high production cost associated with the
need to use noble metals as catalysts of the oxidation reaction
(Pt, Au, Ru). Currently the cost of fuel cells is around $ 53 /
kW and the objective to make them competitive is to reduce it
to $ 30 / kW [DOE 12].

Other challenges faced by fuel cells are:

Fig. 7: Scheme of hybrid super capacitor storage battery system [3] • Temperature management. Maintenance of constant
temperature throughout the cell to avoid its degradation.
The degree of technological maturity is measured by the • Useful life and other specific requirements related to the
technology readiness level (TRL). In the case of batteries and range of operating temperatures.
super capacitators this level is TRL8. • Limited tolerance to CO (carbon monoxide).

16th LACCEI International Multi-Conference for Engineering, Education, and Technology: “Innovation in Education and
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 For fuel cell applications related to the use of hydrogen as Individual prototypes already overcome the properties of
fuel (automotive industry), other challenges arise related to the membranes and catalysts currently in the market. Research is
economic production and safe and efficient storage of being done on the combination of these various functions in
hydrogen, which in gaseous form occupies volumes too high complete commercial fuel cell prototypes.
for automotive applications.
D. Photovoltaic production based on graphene
Application of graphene
Challenges
The high surface ratio, excellent thermal conductivity,
mechanical stability and electronic mobility make graphene an The direct production of electrical energy from solar
ideal candidate to replace the current catalysts based on noble radiation, being an area with a high degree of maturity, faces
metals of high cost (Pt, Au, Rb) in anodes and cathodes of two fundamental challenges:
fuel cells allowing the increase of efficiency, power density,
stability and cost reduction. This catalyst function is 1. The increase in efficiency in the conversion of
maximized by favoring the catalizing activity of graphene solar energy into electrical energy currently
edges, achieving improvements of 70% with respect to Pt around 25% in crystalline silicon panels.
catalysts [4].

Additionally, in fuel cells designed with an exchange

membrane, graphene in combination with Boron Nitride,
forms membranes highly permeable to the passage of protons
and impervious to the passage of any other chemical species,
thus avoiding contaminations that significantly reduce the
efficiency of current fuel cells.

Fig 9: Proton exchange membrane fuel cell. Graphene acts as a catalyst

separating H2 fuel in hydrogen cations and electrons, to combine them later in
the cathode with oxygen, generating water, heat and electric current [4].

Additionally, other applications related to the hydrogen

chain are being studied:
1. Hydrogen storage. Forms derived from graphene allow Fig. 10: Evolution of the efficiency in the conversion of solar into
the absorption and controlled release of hydrogen, allowing its electricity [5]
compact and safe storage.
2. Generation of hydrogen from solar energy. The
permeability of graphene membranes to the passage of protons 2. The reduction of the cost of production. In
could be used to produce hydrogen from water vapor continuous process of reduction by optimizations
molecules at much lower costs than the current hydrolysis in the manufacturing process, but slowing down
methods. in the last ones, due to the cost of the materials.

Current degree of technological maturity: TRL 4-5

16th LACCEI International Multi-Conference for Engineering, Education, and Technology: “Innovation in Education and
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 The application of graphene to photovoltaic production
should allow:
• To reduce costs by minimizing the use of noble metals
such as platinum.
• To increase the mechanical strength and flexibility of
the panels increasing the range of uses.
• To increase the performance in the conversion of light
above the current 25%.
The most promising results have been obtained using
graphene in a new generation of solar cells based on
Perovskite (PSCs), which has aroused great interest in the
rapid evolution in the conversion performance of sunlight
(3.8% in 2009 to 22.1% in 2016 as shown in Figure 12) and
its low production cost and compatibility with flexible plastic
substrates.

Fig. 11: Evolution of the cost of solar generation compared to the cost of
electricity supply [13]

Most of the photovoltaic cells manufactured are based on

silicon, its performance in the conversion being conditioned to
the purity of the silicon and the degree of alignment of its
silicon molecules. Based on these parameters, three
fundamental types of photovoltaic cells can be identified:

• Monocrystalline Silicon (Mono-Si). Unique Si crystals

of high purity, high performance in the conversion of energy
between 15-25%, and maximum useful life. They are
substantially more expensive and more susceptible to damage Fig. 12: Performance evolution of Perovskite-based cells (PSC). Yields
by snow and dust than other types. above 18% have been obtained using graphene as a conductive electrode [6]
• Polycrystalline silicon (p-Si / mc-Si). Simpler treatments
and lower purity silicon is used, reducing the final cost of
Current degree of technological maturity: TRL 4-5
production. This reduces its performance to 13-16%.
• Thin Film Cells (Thin Film Solar Cells, TFSC). They
There are already PSC and graphene cells that have
are manufactured by deposition of thin layers of photovoltaic
equivalent yields to those of monocrystalline Si at a
material on a substrate. This type of cells achieve yields
theoretically lower cost. It is necessary to optimize designs
between 7 and 13%, are easy for mass production, flexible and
and serial production processes.
potentially cheaper than crystalline Si. They degrade more
quickly than those of crystalline Si.
F. Impact study of graphene on different energy storage
sectors
Application of graphene
As identified in the previous section, a gradual arrival of
The high transparency of graphene to incident light
commercial applications of graphene in the energy field is
throughout the frequency range, together with its mechanical
expected:
and electrical properties, make graphene an ideal material to
1. Imminent 2018-2019. First wave of applications of
perform different functions in photovoltaic cells:
graphene with the first commercial models of batteries and
1. Photo anodes for their efficiency in the transport of
super capacitors.
charges, preventing recombinations.
2. 2019-2020. Second wave with the first commercial
2. Photosensitive element producing electrons under
models of battery hybrids with super-capacitor cathodes and
irradiation in a greater frequency range,
photovoltaic solar cells that match the performance of current
3. Structural material, providing flexibility and resistance
silicon crystalline cells significantly reducing the cost.
to the photovoltaic cell while maximizing the range of usable
light frequencies.

16th LACCEI International Multi-Conference for Engineering, Education, and Technology: “Innovation in Education and
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 3. 2021-2025. Third wave with the arrival of the second graphene, and it is a clear competitive advantage for China,
generation of low cost hydrogen cells replacing noble metal one of the most active countries in the research of the
catalysts by graphene and hybrid battery systems with super applications of graphene. As identified in Section 2, there are,
capacitors in the cathode. apart from manufacturing methods from graphite, other
4.> 2025. Commercial application of other more methods that start from other carbon sources, such as
disruptive technologies such as a third generation of hydrocarbons (ethane, methane, etc.). This opens up other
photovoltaic cells with yields higher than 30% (based on alternatives for the production of graphene that does not
complex architectures of uncertain graphene), H2 storage in require the use of graphite. The following figures show the
graphene structures, thermoelectric generation devices for distribution of graphene production, by country, still limited
energy collection and nanogenerators, in a new generation of and how this production is shared between top-down methods
self-supplied electric devices. (72%) from graphite and bottom-up methods from other
carbon sources (28%).

Fig. 13: Applications of graphene in the energy field: Impact and

roadmap

G. Analysis of national and international markets.

Raw material and manufacturing capacity. One of the first
elements in the market analysis is the consideration of the Fig. 15: Global distribution of graphene production in 2015 [8]
distribution of the raw material graphite in the world and the
current production capacity of graphene. In Figure 14, we can
see the distribution of global reserves of graphite in the world.

Fig. 14: Global reserves of graphite in 2017 [7]

The main volume of reserves is concentrated in Turkey,

Brazil, China and Mozambique. This concentration of
reserves can be a problem when creating an open market for Figure 16: Distribution of global production of graphene based on the
the supply of graphite for the top-down manufacture of raw material of origin in 2015 [8].

16th LACCEI International Multi-Conference for Engineering, Education, and Technology: “Innovation in Education and
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 Research efforts and proximity of marketing. Analysts expect an exponential growth of global graphene
demand from the current $ 40 million to $ 120 million in
Since the discovery of graphene in 1986, the number of 2020, representing uses for energy approximately 30% of total
published academic articles related to graphene has grown demand by 2020 [11].
exponentially. This is a direct measure of the enormous
interest that graphene is raising around the world, as well as
the resources that are turning to make the technological
application of graphene a reality in the different areas of
potential application.

Fig. 18: Ranking of the companies with the largest number of patents
related to graphene [10]
Fig. 17: Evolution of the number of annual publications related to
Graphene (SciFinder Credit: Joseph Meany) [9].
CONCLUSIONS
As has been confirmed by the advanced maturity level of
Graphene in its different forms with its unique properties
the first waves of commercial applications of graphene, the
combining mechanical strength 200 times superior to steel,
interest has transcended in recent years the academic field,
exceptional electrical, thermal, quantum and optical properties
and has spread throughout the world in the form of patents,
apart from an enormous versatility to modify its properties by
annually triggering the number of patents of companies and
functionalization with other chemical species or other
technological institutions which could indicate the imminent
materials through the formation of composite materials, it has
appearance of commercial applications of graphene in the next
become a "technological catalyst" that allows the drastic
two years. If we analyze the distribution of patents by
evolution of a series of devices and systems existing until now
companies / institutions, the number of patents registered by
limited in their capacities while opening new fields of
Samsung and universities in Korea and China stands out.
application hardly explored related to the science of
nanomaterials. Its mono-atomic thickness and the need for
precise control in its composition and structure to exploit its
properties are posing a fundamental challenge for its
manufacture and application, which is requiring enormous
efforts by the scientific community and the industry.

Without having yet achieved precise and complete control

of the manufacturing chain, there are already small-scale
graphene production chains exploiting different production
methods and producing graphene worldwide to feed a first
generation of graphene-based devices. This first generation of
devices, imminent in the different markets (2018-2023)
focuses on improving existing technologies of high demand,
combining graphene with other materials to improve their
performance, their operating ranges and reduce their costs.
The next generations of graphene applications require more
Fig. 18: Ranking of the companies with the largest number of patents fundamental knowledge and exploitation of graphene and the
related to graphene [10] development of theories and architectures of materials barely

16th LACCEI International Multi-Conference for Engineering, Education, and Technology: “Innovation in Education and
Inclusion”, 19-21 July 2018, Lima, Peru. 8
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[10]Sebastian Anthony on May 19, 2014 at 2:34 pm Comment. “The next
As can be seen from the trickle in the number of patents Apple-Samsung battle will be fought over graphene, not in the
in recent years in graphene-based technologies and the gradual courtroom.” ExtremeTech, 19 May 2014,
emergence of commercial publications from the private sector, www.extremetech.com/computing/182657-the-next-apple-samsung-
the market is in the commercial testing phase prior to battle-will-be-fought-over-graphene-not-in-the-courtroom.
[11]Harold Goldmeier Growth, momentum, growth at reasonable
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graphene commercial applications and large corporations and investing-2018.
niche companies are accelerating their machinery to position
themselves first in this market. The next wave of applications
with substantially more disruptive impact is still in the
conceptualization and proof of concept phase in laboratories
and universities, requiring levels of technological maturity
that are not expected before 2025.

This profound technological transformation in successive

waves should not be attributed exclusively to graphene.
Graphene and its derivative forms, due to their exceptional
properties and based in widely accessible carbon, have acted
as a technological catalyst, forcing the scientific community
and technology companies to focus their attention on the
'nano' scale, opening the door to engineering of new materials
and devices with completely new macroscopic properties built
to measure from a fundamental knowledge of the physics
behind the interactions between atoms.

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