J. Mitali, S. Dhinakaran and A.A.
Mohamad
Fig. 28. Schematic diagram of hydrogen energy storage system. Hydrogen is produced from water via electrolysis and stored in a storage tank during the charging
cycle. During the discharging cycle, electricity is generated using a fuel cell from the stored hydrogen.
Table 18
Characteristics of different types of fuel cells [260].
Fuel cell Fuel Temperature (°C)
PEMFC Pure H2 60–140
AFC Pure H2 150–200
PAFC Pure H2 150–200
MCFC H2 , CO3 600–700
SOFC H2 200–700
DMFC CH3 OH 30–80
research laboratory. In 2015, the Energiepark Mainz project began in
Mainz, Germany, as a collaboration between Stadtwerke Mainz, Linde,
Siemens and the RheinMain University of Applied Sciences. The en-
ergy park converts excess wind power from neighbouring wind parks
into hydrogen fuel, which is then used to generate energy. In 2018,
Enbridge Gas Distribution and FCHEA member Hydrogenics collabo-
rated to open the Markham Energy Storage Facility, a 2.5 MW - first
multi-megawatt power-to-gas facility in Ontario, Canada. This facil-
ity uses renewably-sourced hydrogen and currently provides grid reg-
ulation services to Ontario’s Independent Electricity System Operator
(IESO). Apart from that, Orsted, Denmark’s largest energy company,
plans to build a 700 MW facility that will use excess energy from
its North Sea wind farms to power electrolysis and generate renew-
able hydrogen energy. Mitsubishi Hitachi Power Systems and Magnum
Developer are planning to build a 1000 MW power plant in Millard
County, Utah, to store renewable hydrogen. Xcel Energy, a large util-
ity provider, is planning a 110 kW wind-to-hydrogen project in collab-
oration with the National Renewable Energy Laboratory (NREL), which
would use excess wind energy to generate hydrogen. This hydrogen
could be stored for later use or could be converted back to the elec-
tricity grid during peak demand hours. As a result, it is clear that the
world is embracing hydrogen energy storage on a larger scale in order to
account for the energy supply and demand imbalances [271,272]. Fol-
lowing are the various FCs that have been developed: proton exchange
membrane FC (PEMFC), alkaline FC (AFC), phosphoric acid FC (PAFC),
molten carbonate FC (MCFC), solid oxide FC (SOFC), direct methanol FC
(DMFC).
186
Energy Storage and Saving 1 (2022) 166–216
Efficiency (%) Application
55 Backup power
60 Spacecrafts, military applications
>40 Distributed generation
45 Power utility storage
40 Power utility storage
30 Electric transportation vehicle
2.3.2. Synthetic natural gas (SNG)
Natural gas is the most widely used and clean energy source among
the fossil fuels that currently dominate the energy supply. The concept
of coal-to-synthetic natural gas (SNG) conversion has been proven to be
a viable energy production alternative [17]. Another intriguing concept
is the use of biomass for the production of SNG, as biomass is found to
be carbon neutral. The methanation process was used to produce SNG
from coal in the 1960s and 1970s (primarily in Germany and the USA).
Recently, new thermal gasification processes for producing SNG from
coal and dry biomass have been developed. The production of SNG from
coal and solid dry biomass (e.g., wood and straw) via a thermo-chemical
process requires several conversion steps (drying, gasification followed
by gas cleaning, methanation of the producer gas, and subsequent gas
upgrading), as shown in Fig. 29 [273]. SNG can be stored in pressurised
tanks, underground caverns or fed directly into the gas grid. The Great
Plains Synfuels Plant (GPSP), near Beulah, North Dakota, the USA is the
world’s only SNG gasification plant, operating since 1984 and produc-
ing approximately 4.1 million m3 /day of SNG from lignite coal [274].
Table 19 [275−279] summarises some of the largest plants ever built
based on SNG technology around the world.
2.3.3. Solar fuels
The goal of solar energy storage is to harvest the sun’s abundant en-
ergy, convert it to usable forms, store it in the chemical bonds of fuel,
and then consume it as needed. Solar fuels are chemical fuels that store
energy received from th sun. Scientists are currently exploring three
J. Mitali, S. Dhinakaran and A.A. Mohamad
Table 19
A list of major plants built using synthetic natural gas technology around the world [275–279].
Year Project Location
2009 Biomass CHP Plant Güssing, Austria
2010 Gaya - -
2011 Dong Pyroneer Plant Denmark
2012 Waste-to-energy gasifier Lahti, Finland
2013 GoBiGas Sweden
2013 Birmingham Bio Power Plant Tyseley, Birmingham, UK
2016 WoodRoll Sweden
Test Plant
Fig. 29. General procedures for producing synthetic natural gas (SNG) from
coal and solid dry biomass.
main approaches to producing solar fuel production: natural photosyn-
thesis, artificial photosynthesis, and thermochemical production [280].
Nature has devised a well-thought-out system for converting solar
energy into fuel, known as photosynthesis. It is a chemical process that
allows plants, algae and some bacteria to store solar energy in car-
bohydrates. These carbohydrates function as fuels that the plant uses
for growth and maintenance. Water and CO2 are the raw materials re-
quired for natural photosynthesis [281]. The term “artificial photosyn-
thesis”, also known as the “artificial leaf”, refers to a process that ex-
plicitly mimics natural photosynthesis. The sunlight is captured, and the
stored energy is used to chemically convert water and carbon dioxide
into fuels. The process is artificial photosynthesis. The ultimate prod-
ucts are solar fuels (Fig. 30). The thermochemical method uses sun-
light to heat materials to extremely high temperatures, where they re-
act with steam or CO2 to produce carbon monoxide (CO) or hydrogen
(H2 ) [282].
Since the 1950s, scientists and engineers have been collaborating to
effectively scale up the laboratory prototypes of solar fuels to a com-
mercial scale. The reviews by Mustafa et al. [283] and Ezugwu et al.
[284] summarise several old and modern thermal technologies utilised
in CO2 conversion, including thorough information on their working
principle, types, various methods, developments, conversion rates, prod-
ucts created, catalysts and operating parameters. Xiao et al. [285] re-
view recent progress, accomplishments, and working principles of three
typical hybrid systems including photovoltaic-driven biological inor-
ganic system, microbial photo electrochemical system, and photosensi-
tized biological inorganic system for the production of organic fuels and
chemicals from CO2 . A comprehensive review by Gong et al. [286] high-
lights the recent advances in CO2 photo-reduction, critical challenges
such as light-harvesting, charge separation, and the activation of CO2
molecules, and prospective solutions for increasing photocatalytic ac-
tivity. The recent progress in synthesis and regulation of few-layer car-
bon nitride (FLCN) based photocatalysts, and their applications in the
conversion of sunlight into fuels and chemicals is briefly summarised in
the work of Chen et al. [287]. Several dedicated research programmes
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Energy Storage and Saving 1 (2022) 166–216
Storage capacity Fuel Status
(MW)
1 Wood chips Demonstration
Wood, straw Demonstration
6 Wood mass Demonstration
160 Shredded textiles, wood, paper, card Industrial scale
and plastics
20 Forestry feedstock, which consists of Industrial scale
pulpwood and forest residues
10.3 Woodwaste Commercial
6 Forestry feedstock, waste from Commercial
industry, agricultural waste
on solar fuels have begun in the USA, Australia and South Korea, and
several renewable energy research centres have been established in In-
dia, China and Japan. Table 20 [281,288] describes the programmes
undertaken globally for research and innovation in solar fuels.
2.4. Electrochemical energy storage (EcES) system
EcES is the most widely used energy storage system, which operates
primarily on three major processes, as illustrated in Fig. 31. It is mainly
categorized into two types: (a) battery energy storage (BES) systems, in
which charge is stored within the electrodes, and (b) flow battery energy
storage (FBES) systems, in which charge is first stored within the fuel
and then externally fed on to the surface of the electrodes [7] (Fig. 32).
Apart from these two traditional energy storage technologies, extensive
research is being conducted in electrochemical storage capabilities to
meet the growing demand for lightweight, compact, and flexible elec-
tronic devices.
2.4.1. Battery energy storage (BES) system
Batteries are electrochemical devices that convert chemical energy
into electrical energy, as illustrated in Fig. 33. They are composed of a
number of cells, each of which has three basic components: two elec-
trodes, namely, an anode and a cathode, and an electrolyte. They are
broadly categorised into two groups: primary and secondary. Primary
batteries are intended to be single-use batteries, with the chemical, once
consumed, cannot be recharged. Secondary batteries, on the other hand,
are designed to be recharged [257]. Secondary batteries are classified
as lead-acid (LA), lithium-ion, nickel-cadmium (Ni-Cd), sodium sulphur
(NaS), sodium-ion (Na-ion), and metal air batteries, depending on the
material of the electrodes and electrolyte. Their specifics are covered in
the sections that follow.
2.4.1.1. Lead-acid (LA) batteries. LA batteries are the most popular and
oldest electrochemical energy storage device (invented in 1859). It is
made up of two electrodes (a metallic sponge lead anode and a lead
dioxide as a cathode, as shown in Fig. 34) immersed in an electrolyte
made up of 37% sulphuric acid and 63% water. Both the electrodes are
separated by a porous separator, which prevents electrons from flowing
directly from anode to cathode [289]. During the discharge cycle, lead
sulphate covers both the electrodes, and the electrolyte is reduced to
water. While charging, both the electrodes return to their initial state. LA
batteries are classified into two types: flooded lead‐acid (FLA) and valve-
regulated lead‐acid (VRLA). Both batteries work on the same principle.
However, VRLA batteries are built differently. They are generally sealed
with a pressure regulating valve, which prevents air from entering the
cells [259].
Over 150 years ago, the main ingredients of the lead acid battery
were established. Gaston Plante, a French physicist, demonstrated the
world’s first rechargeable LA battery in 1859, consisting of nine parallel-
connected cells [290]. Later, in 1880, Camille Alphonse Faure advo-
J. Mitali, S. Dhinakaran and A.A. Mohamad Energy Storage and Saving 1 (2022) 166–216

Fig. 30. Artificial photosynthesis: pathway from sunlight to fuels.

Fig. 31. The fundamental operational procedures in an electrochemical energy
storage (EcES) system.
Fig. 32. Classification of electrochemical energy storage system.
cated coating the lead sheets with a paste of lead oxides, sulfuric acid,
and water, which led to the development of the contemporary pasted-
plate battery, which is the most commonly used LA battery today [291].
Toward the end of the 19th century, LA batteries were used to power
electric cars, as well as stand-by batteries to give emergency power to
essential equipment in electricity-generating stations and other critical
facilities. In the early 1920s, a more acid-resistant, hard rubber case was
developed and used. Simultaneously significant developments were also
made in plate design and production techniques that resulted in more ef-
ficient LA batteries with high specific power. In the late 1960s, injection-
moulded polypropylene case and cover were introduced, which resulted
in durable, compact and lightweight containers for LA batteries. Later,
the VRLA battery was developed and the commercial units were man-
ufactured in German company Sonnenschein in the late 1960s and by
Gates Corporation in the USA in the early 1970s [292–294]. Today, LA
batteries are widely employed in a variety of projects worldwide. Sev-
eral industrial and academic research initiatives to increase the perfor-
mance of LA batteries have been ongoing for several decades. Zhang
et al. [295] reviewed the main shortcomings of current research sta-
tus of LA batteries in terms of grid composition and structure, lead
paste formula, additives, curing and formation process. Pradhan and
Chakraborty [296] reviewed recent advances as well as past inventions
of bipolar LA batteries with respect to substrate material, designs, fab-
rication and sealing techniques. Researchers have also reviewed appli-
cations of different forms of elemental carbon in LA batteries, such as
in Hao et al. [297], Lach et al. [298] and Mandal et al. [299]. Car-
bon materials when used as an additive to the negative active mass
can improve the cycle life and charge acceptance of batteries. Table 21
[300−307] summarises various LA battery storage systems employed
across the world, whereas Table 22 [308,309] discusses the benefits and
drawbacks of LA batteries.

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Fig. 33. Schematic diagram of battery energy storage system. The key components in this case are batteries, which are used to store electrical energy in the form of
chemical energy.

larly in power grid applications and plug-in hybrid electric vehicles,

owing to their higher charge density than other rechargeable batter-
ies [11,310]. The Li‐ion batteries are made up of lithium metal oxide
as the cathode, graphitic carbon as the anode, and inorganic dissolved
lithium salt as the electrolyte. A current flows when lithium ions mi-
grate between the anode and cathode. During the charging cycle, the
lithium cations migrate to the carbon anode via the electrolyte. They
combine with external electrons and are deposited as lithium atoms be-
tween the carbon layers. During the discharge process, this process is
reversed [23]. Fig. 35 depicts the working principle of Li-ion batteries.
In the 1970s, Stanley Whittingham, an English chemist working for
Exxonmobil, proposed the concept of Li-ion batteries. He discovered
Fig. 34. Principal components of a lead-acid battery. It is made up of an anode
the concept of intercalation electrodes, which use titanium disulfide as
made of metallic sponge lead, a cathode made of lead dioxide and an electrolyte
cathode and lithium metal as the anode [311]. In 1981, Goodenough
consisting of 37% sulphuric acid and 63% water.
experimented with lithium cobalt oxide as the cathode instead of tita-
nium disulfide, which doubled the battery’s energy potential [312]. In
2.4.1.2. Lithium-ion (Li-ion) batteries. Currently, Li‐ion batteries are
1987, Yoshino et al. [313] of Japan developed a new cell design us-
profoundly used in electronics and transportation industries, particu-

Fig. 35. Principle components and operation of a lithium-ion battery. It is made up of a cathode made of lithium metal oxide, an anode made of graphitic carbon,
and electrolytes made of lithium salt. During the charging cycle, the lithium cations migrate to the carbon anode via the electrolyte. They combine with external
electrons and are deposited as lithium atoms between the carbon layers. During the discharge cycle, the process is reversed.

189
J. Mitali, S. Dhinakaran and A.A. Mohamad
Table 20
Programmes undertaken globally for research and innovation in solar fuels
[281,288].
Country Research programmes
USA In 2010, a Joint Centre for Artificial Photosynthesis (JCAP) - a
Department of Energy Innovation Hub was established between
the California Institute of Technology and the Lawrence
Berkeley National Laboratory in California. It is primarily
focused on developing a cost-effective method to produce fuels
using only sunlight, water, and carbon-dioxide. In 2012, the
Solar Fuels Institute (SOFI), based at Northwestern University,
was launched to support the development of an efficient and
cost-effective system that uses sunlight to produce a liquid fuel.
This institute is a research collaboration of universities,
government labs, and industry united together with the goal of
developing and commercialising liquid solar fuel within 10
years.
Europe The largest single national investment in a solar fuels research
project has been started by the Dutch government together
with six universities. A collaborative research is being
undertaken to produce solar fuels by both natural and artificial
photosynthesis.
Australia Australia is leading the world in solar research. Researchers in
Canberra, Sydney and Melbourne are developing novel
methods, applications and products that will represent the
future of solar energy. The University of New South Wales is
well-known for some of the world’s most advanced solar
research. It is developing a hydrogen trapping technology to
create a new form of wafer that could contribute to low cost
solar cells. Monash University in Melbourne is developing
highly efficient, semi-transparent photovoltaics (PV) that could
be utilised in the construction of integrated photovoltaic
(BIPV) windows. The Commonwealth Scientific and Industrial
Research Organization (CSIRO) in Melbourne is aiming to
translate the laboratory-scale highly efficient perovskite cells to
the much larger commercial-scale PV modules.
India Solar PV Hub - a joint initiative by Department of Science &
Technology (DST), Government of India and Centre of
Excellence for Green Energy and Sensor Systems (CEGESS),
Indian Institute of Engineering Science and Technology (IIEST)
was established to develop a state-of-the-art facility of
fabrication and characterization of Industry compatible solar
cell and solar photovoltaic system. Also, the Solar Energy
Harnessing Centre – a collaboration between Department of
Science & Technology (DST) and Indian Institute of
Technology, Madras is a first of its kind centre to undertake
research and technology development in multi-disciplinary
domain including highly efficient solar photovoltaics, cutting
edge research for production of solar fuels and storage of solar
energy using indigenous resources.
South Korea The Korean Centre for Artificial Photosynthesis (KCAP) was
established in 2009 at Sogang University and in 2011, it made
a cooperation agreement with POSCO, a steel company to
conduct joint research on the commercialization of artificial
photosynthesis.
China The world’s first thousand-ton scale demonstration project for
direct solar fuel synthesis started operation in Lanzhou, China
in 2020. This project converts carbon dioxide, water and solar
energy into transportable liquid fuels such as methanol by
utilising three technological units: solar photovoltaics to
generate electricity, electrolyzer to produce hydrogen by
splitting water, and CO2 hydrogenation to produce methanol at
the end.
Table 21
Overview of Lead-acid battery energy storage systems installed worldwide.
Location Year Service area References
Indonesia 2013 Small village in west Indonesia [300]
Türkiye 2013 50 residential houses [301]
Saudi-Arabia 2015 Remote area [302]
Tamil-Nadu, India 2016 Household load [303]
Estrella, Colombia 2016 Off-grid village in Colombia [304]
Kohmak Island, Thailand 2017 Hotel [305]
Bangladesh 2017 Village [306]
New Delhi, India 2017 Electrical faculty load, New Delhi [307]
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Energy Storage and Saving 1 (2022) 166–216
Table 22
Benefits and drawbacks of lead-acid battery energy storage systems [308,309].
Benefits Drawbacks
• Low capital cost • Limited life cycle
• Good performance at low and high • Slow charging
temperatures
• Low maintenance • High self-discharge rate
• High specific power • Not environmentally friendly
• Available in large quantities and in a variety • Limited energy density
of sizes and designs
ing petroleum coke, a carbonaceous material. This improved the per-
formance of Li-ion batteries significantly. In 1991, Sony Energytec Inc.
began to produce commercial lithium-ion cells under the leadership of a
persona named Yoshio et al. [314–315] and Hideto et al. [316]. Soon af-
ter commercialization, the Li-ion battery storage system quickly gained
popularity because of its high-energy density and good performance.
The vast majority of the Li-ion battery manufacturing industries are in
China, the USA, Asia, and Europe. While Li-ion batteries have been the
dominant choice, numerous emerging applications demand for high en-
ergy density, higher capacity, better safety, improved performance and
lower costs. Gao et al. [317] reviewed state-of-the-art solutions for im-
proving the performance and lowering the cost of Li-ion batteries. The
reviews of the developments of electrode materials for next-generation
energy-density and low-temperature Li-ion batteries are presented by
Shen et al. [318] and Zhang et al. [319]. The review articles [320–
322] attempted to assess the safety issues associated with key materials
and cell design techniques, as well as to summarise the effects of carbon
materials as electrodes on battery safety performance and electrochem-
ical properties. Table 23 [323−329] provides a detailed overview of
Li-ion battery energy storage technologies and battery energy systems
around the world. The majority of analysts predict that Li-ion batteries
will dominate the energy storage markets in the next 10 years [330].
In Table 24 [308,309,331], the advantages and disadvantages of Li-ion
batteries are presented.
2.4.1.3. Nickel-cadmium (Ni-Cd) batteries. Ni-Cd batteries, invented in
1899 by Waldemar Jungner of Sweden, are one of the most mature
and widely used technologies. Jungner established a factory in Sweden
in 1906 to manufacture industrial Ni-Cd batteries [12]. In 1946, the
first Ni-Cd batteries were manufactured in the USA. The batteries pro-
duced at that time were “pocket type”, with nickel and cadmium active
materials [332]. Around the middle of the twentieth century, sintered
plate Ni-Cd batteries became popular because the sintered plates were
much thinner than pocket batteries, allowing for higher current flow.
The plates are made by infusing nickel powder under high pressures
at temperatures lower than the melting point. This technique produces
highly porous plates with approximately 80% pore volume [333]. Since
the early 2000s, all the Ni-Cd batteries have been available in jelly form.
Table 25 [332,334−340] summarises the evolution of the Ni-Cd BES sys-
tem.
The positive electrode of the Ni-Cd battery is spongy nickel oxyhy-
droxide, the negative electrode is metallic cadmium, and the electrolyte
is potassium hydroxide (Fig. 36). Both electrodes are separated by a
nylon divider, which prevents direct charge transfer between the elec-
trodes [289]. During the discharge cycle, nickel oxyhydroxide at the
positive plate reacts with water to form nickel hydroxide, whereas cad-
mium at the negative plate reacts to produce cadmium hydroxide [23].
The whole process is reversed during the charging phase. Ni‐Cd batteries
are extensively used in electrical power applications because they have
a longer life cycle than LA batteries. The advantages and disadvantages
of Ni-Cd batteries are listed in Table 26 [198 308,309,341].
2.4.1.4. Sodium sulphur (NaS) batteries. NaS batteries are typically
cylindrical electrochemical cells with molten sulphur at the positive
J. Mitali, S. Dhinakaran and A.A. Mohamad Energy Storage and Saving 1 (2022) 166–216

Table 23
Summary of lithium-ion battery energy storage technologies and battery energy systems around the world.

Project Location Storage capacity (MW) Status References

AES Alamitos Energy Storage Array Long Beach, California, USA 100 Contracted [323]
Magdeberg-SK Innovation – BESS Magdeberg, Saxony-Anhalt, Germany 30 Announced in 2014 [324]
Grand Ridge Energy Storage Marseilles, Illinois, USA 31.5 Commissioned in 2015 [325]
Nishi-Sendai Substation - Tohoku Electric/Toshiba Sendai, Miyagi Prefecture, Japan 40 Operational since 2015 [326]
Kingfisher Project Roxby Downs, South Australia, Australia 100 Announced in 2016 [327]
Gyeongsan Substation South Korea 49 Operational since 2016 [328]
Minami-Soma Substation - Tohoku Electric/Toshiba Minamisoma, Fukushima Prefecture, Japan 40 Operational since 2016 [329]

Table 24 der to keep the sodium and sulphur in a molten state and ensure ade-
Advantage and disadvantages of lithium-ion battery energy storage systems quate conductivity in the electrolyte, all the components are housed in-
[308,309,331]. side a thermally insulated enclosure maintained at a temperature above
Advantages Disadvantages 270 °C [342,343]. NaS batteries have three times the higher energy
density than LABs. Apart from that, they also have a longer life span
• Light weight • Higher production cost
• High energy density • Requires special charging circuit
and require less maintenance. NaS batteries were first developed by
• High efficiency • Sensitive to high temperatures Ford Motor Company in the 1960s, but modern sodium sulphur tech-
• Longer life-cycle • Involves risk of bursting nology was developed and commercialised in Japan by the Tokyo Elec-
• High specific power • Complete discharge damages the battery tric Power and NGK insulators [344]. Table 27[2,250,345–348] sum-
marises major NaS BESS demonstration projects and plants. Since this
technology is complex, small-scale NaS batteries are less economical
[349]. The advantages and disadvantages of NaS batteries are listed in
Table 28 [308,309,350].

Fig. 36. Principal components of a nickel-cadmium battery. It consists of nickel
oxyhydroxide in a spongy form as anode, metallic cadmium as cathode and
potassium hydroxide as the electrolyte.
Fig. 37. The main components and operation of a sodium sulphur battery. It
consists of molten sulphur as anode, molten sodium as cathode and solid beta
alumina as electrolyte. During the discharge cycle, molten sodium at the core
donates electrons, which pass through the electrolyte and combine with sulphur
to form sodium polysulpides. This process is reversed during the charging cycle.
electrode and molten sodium at the negative electrode separated by a
solid beta alumina electrolyte (Fig. 37).
In NaS batteries, molten sodium at the core donates electrons to
the external circuit, causing sodium ions to migrate through the elec-
trolyte toward the positive electrode compartment. The free electrons
are captured by the molten sulphur and transformed into polysulphide.
This process is reversed during the charging cycle, wherein sodium
polysulfides are decomposed to release the positive sodium ions back
through the electrolyte to recombine as elemental sodium [17]. In or-
2.4.1.5. Sodium ion (Na-ion) batteries. Among the batteries, Li‐ion bat-
teries have proven to be popular in numerous areas of energy storage
systems. Since their first commercialization in 1991 by Sony in Ener-
gytec Inc., this technology has undergone extensive research and de-
velopment. However, due to its low power density, poor cycle life, and
safety concerns, scientists are looking for an alternative material that
can store and dispense energy in a manner similar to lithium. Among
the many available anode candidates, sodium (Na) based anodes have
piqued the interest of researchers. Development of the Na-ion battery
began along with that of the Li-ion battery in early 1980s. However, af-
ter the commercialization of Li-ion batteries in 1991, research interest
in Na-ion batteries began to wane. However, in the early 2010s, re-
searchers became interested in Na-ion batteries, owing to the increasing
demand and cost of Li-ion battery raw materials [351]. Because sodium
is abundant and cheap, Na-ion battery technology has the potential to
overcome the limitations of Li-ion batteries and provide a low-cost al-
ternative that is less vulnerable to raw material supply risks [352,353].
A typical Na-ion battery consists of an anode, a cathode, an elec-
trolyte (can be non-aqueous or aqueous), and a separator as shown
in Fig. 38. The operation is similar to that of Li-ion batteries. During
the charging process, the sodium ions from cathode are extracted and
inserted into the anode. The reverse is true for the discharge process
[354,355].
Recent advancements in the anode and cathode materials used in Na-
ion batteries have been made. Cathode materials such as sodiated layer
transition metal oxides, phosphates, and organic compounds have been
developed, along with carbonaceous materials, transition metal oxides
(or sulphides), and intermetallic and organic compounds as anodes. In
addition to electrode materials, appropriate electrolytes, additives, and
binders are being developed [356]. In addition, similar to Li-ion batter-
ies, aqueous Na-ion batteries are also found to be suitable as stationary
power sources for sustainable energies such as wind and solar power.
During the past decades, many efforts have been made to improve the
performance of the aqueous Na-ion batteries [357].
2.4.1.6. Metal-air batteries. With the advancement of portable elec-
tronic devices and electrification of transportation, the demand for more
advanced battery storage systems to meet the high energy storage re-
quirements has increased. Because of their higher specific capacity and

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Table 25
Advances of nickel-cadmium (Ni-Cd) battery energy storage system.

Year Advancement References

1899 Pocket-plate technology [332]

• Reliable, sturdy and have long life

• Effective operation over a wide temperature range
• Good charge retention
• Withstand both severe mechanical and electrical maltreatment such as overcharging, reversal, and
short circuiting

1908 Tubular-plate batteries [334,335]

• To restrict the deformation caused by swelling of the positive active mass in pocket-plate batteries
• To extend the cycle life of batteries in deep-discharge cycling applications

1940 Sintered-plate Ni-Cd batteries [335]

• Thinner than pocket-plate batteries

• Exhibit lower internal resistance
• Superior high rate and low-temperature performance
• Suitable for high-power applications

1983 Fibre-structured Ni-Cd cells [336]

• Two negative electrodes are arranged back-to-back with a porous fibre-nickel structure between two
positive plates
• Use mechanically impregnated fibre electrodes for both negative and positive plates

1989 Super Ni-Cd cells [337]

• Loading of positive and negative active materials into the porous sintered nickel structure is carried
out electrochemically
• Inert polymer-impregnated Zircar cloth replaces the polyamide separator
• Extended life

1991 Sealed Ni-Cd cells [338]

• Able to withstand extreme environmental conditions

• No maintenance requirements
• Low cost
• Higher discharge

1993 Ultra-low-maintenance Ni-Cd batteries [339]

• Thermally welded cells ensure leak tightness

• Seam-welded plate tabs along with copper cell links and terminals provide lower resistance and
minimize voltage drop
• A gas barrier membrane prevents recombination and material migration
• A flooded gas barrier design ensures that the battery survives critical conditions that would destroy
starved-electrolyte sealed cells

2000s Jelly–roll Ni-Cd battery [340]

• Cathode and anode layers are rolled into a cylindrical shape

• Mostly used in portable devices such as mobile phones, digital cameras, and power tools
• Uses cadmium metal as anode, a nickel oxide hydroxide or nickel oxide as cathode, and a potassium
hydroxide as electrolyte solution

Table 26 early 1970’s for a variety of applications [360]. However, these battery
Advantages and disadvantages of nickel-cadmium (Ni-Cd) batteries [198,308, systems have gained impressive progress over the last few years.
309,341]. Metal-air batteries differ from conventional batteries in that they are
Advantages Disadvantages connected to the atmosphere and run on oxygen. Unlike conventional
batteries, which have both anode and cathode within the battery case,
Long shelf life and can be stored in a • Relatively low specific energy
discharged state compared to systems
a metal-air battery has a solid anode within the case (like a battery),
Good low-temperature performance • High self-discharge rates and the cathode fuel is brought into the cell from the outer atmosphere
Economical: Ni–Cd has the lowest • Cadmium is a toxic metal, thus [361]. The main internal components of a metal-air battery are oxy-
cost per cycle cannot be disposed in landfills gen, a metal anode, an air cathode, a separator, and an electrolyte as
Ultra-fast-charging with minimal -
shown in Fig. 39. The metal anodes electrochemically react with oxy-
stress
Good load and low temperature - gen gas from the atmospheric air. Based on the nature of the anode, the
performance electrolyte is either an alkaline aqueous solution such as potassium hy-
droxide, a neutral aqueous solution of a salt (such as sodium chloride),
or a non-aqueous solution of a base metal salt, which is determined
based on the nature of the anode. During the charging cycle, the metal
energy density when compared to conventional batteries, metal-air bat-
on the anode changes into ions, while the oxygen on the cathode trans-
teries have emerged as promising candidates for future battery require-
forms into hydroxide ions. Electrons are produced during the transition
ments [358,359]. Metal-air battery research began in the 1960’s and

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Fig. 38. Working principle of sodium-ion battery. During the charging cycle, sodium ions from cathode are extracted and pushed into the anode. During the
discharging cycle, this process is reversed.

Table 27
Summary of major demonstration projects and plants on sodium sulphur battery energy storage system [2,250,345–348].

Year Location/company Power (MW) Storage capacity (MWh) Type/application

1992 Kawasaki Electric Energy 0.05 4 Prototype

Storage Test Facilities, Japan
1995 Tokyo Electric Power Co., Tokyo, Japan 0.05 4 Load levelling
1997 Tsunashima Substation 6 48 Load levelling
1998 Kinugawa Power Station 0.193 0.772 Load levelling and emergency power
supply
1999 Ohito Substation 6 48 Load levelling
2003 Shinagawa Substation 2 14.4 Load levelling
2006 Long Island Bus’s BES System, New York, USA 1 72 Refuelling the fixed route vehicles
2008 Xcel Energy’s wind-to-battery (W2B) storage 1 - Peak shaving, frequency regulation,
project, Minnesota wind smoothing and wind levelling
2017 Graciosa Island, Younicos, Germany 3 18 Wind and solar power EES for islands
2019 Abu Dhabi Island, UAE 108 648 Load levelling

Table 28
Advantages and disadvantages of sodium sulphur (NaS) batteries
[308,309,350].

Advantages Disadvantages

• High power and energy density • High production cost

• High efficiency • Safety issues
• High cycle life • Stringent operation and
maintenance requirements
• Low-cost potential • Need to be operated above 300 °C
• Insensitivity to ambient conditions -

of the metal into metallic ions, and the metallic ions then dissolve into Fig. 39. Principal components and working of a metal-air battery. It is made
the electrolyte. During the discharging cycle, atmospheric oxygen com- up of a metal anode, an air cathode, a separator, and an electrolyte. During the
bines with the metallic ion to form metal hydroxide, which activates the discharging cycle, a reduction reaction occurs at the air cathode while the metal
anode is oxidised to metal hydroxide which activates the electrolysis process and
electrolysis process and generates current [362].
generates current. During the charging cycle, the metal on the anode converts
The chemical equations of reactions taking place in metal-air battery
to ions, and the oxygen on the cathode converts to hydroxide ions.
with a metal anode M are as follows:
1
Cathode ∶ CO2 + H2 O + 2e− ⇔ 2OH−
2
by the metal anode. Because each metal has its own unique proper-
𝑛 𝑛 ties, each metal anode will produce a voltage with the cathode, and
Anode ∶ M + nOH− ⇔ MO + H O + ne−
2 2 2 each metal will contain a specific amount of energy [361]. Lithium, alu-
minium, magnesium, zinc, potassium, sodium, and iron are all promis-
𝑛 𝑛
Overall chemical reaction ∶ M + O ⇔ MO ing metal anode candidates. Lithium and sodium metal anodes are
4 2 2
used with non-aqueous electrolyte while magnesium, aluminium, iron
The oxygen gas introduced into the battery via an air cathode is and zinc are compatible with aqueous electrolyte. In general, a metal-
an unlimited source. As a result, despite the fact that oxygen is an un- air battery provides the highest energy density of any battery system
limited cathode reactant, the capacity of metal-air batteries is limited [363]. Table 29 [362,364–371] summarises the characteristics of dif-

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Table 29
Characteristics of some metal-air batteries [362,364–371].

Battery type Practical operating voltage (V) Theoretical specific energy (Wh/kg) Actual specific energy (Wh/kg) Actual energy density (Wh/kg)

Aluminium-air 1.35 8,140 350 350

Lithium-air 2.7–2.8 1.14×104 150–6,000 30–1,000
Magnesium-air 2.9 6,800 700 200
Zinc-air 1.65 1,353 400 1,300
Iron-air 1.28 1,000 75 50–75
Sodium-air 2.27 - – 1,600

Table 30
Summary of some anode, cathode, and electrolytes used in solid-state batteries with their optimum conductivity values [377–381].

Anode Cathode Electrolyte Conductivity (seimens per centimeter

(S.cm−1 ))

Lithium metal Carbon composite Lithium doped polyacrylonitrile (PAN) solid polymer -
electrolyte
Potassium Carbon paper doped with iodine Polyethylene oxide (PEO)/KBrO3 7.74 × 10−8 at 30 ◦ C

Graphite based anode Lithium cobalt oxide (LiCoO2 ) Polystyrene doped with varying 9.78 × 10−5 for 10 wt.% Al2 O3 at room
quantities of aluminium oxide (Al2 O3 ) temperature
Silver Graphite coupled with iodine (Ag2 O-P2 O5 -LiCl) glass ceramic composites containing 2.88 × 10−2 for 25 wt.% Al2 O3
silver components

Lithium Lithium Tri-ethyl sulfonium bisimide, 10−2 at 45 ◦ C

LiTFSI (Lithium bis(trifluoromethanesulfonyl)imide),
polyethylene oxide and tetrahydrofuran

ferent metal-air batteries. The primary benefit of a metal-air battery is

its very high theoretical specific energy. Some disadvantages of the sys-
tems include their strong dependency on environmental conditions, and
the aqueous cells may occasionally leak hydrogen gas due to anode cor-
rosion.

2.4.1.7. Solid-state batteries (SSBs). The advancements of portable in-

telligent devices and electric vehicles have raised the energy density and
safety requirements for rechargeable secondary batteries. For the past
30 years, conventional Li-ion batteries have received unprecedented lev-
els of research and industrial attention and have been used to power
portable electrical devices. However, commercial Li-ion batteries with
liquid organic electrolytes cannot meet the demands of scale of battery
applications, particularly in terms of safety, and power density [372].
To overcome these constraints, researchers developed all-solid-state bat-
teries. SSBs have the potential to address not only safety concerns but
also enable operation in hostile environments, such as at temperatures
ranging from −50 to 200 ◦ C or higher, where organic electrolytes fail
due to freezing, boiling or decomposition. Solid electrolytes have higher
thermal stability, energy density, and the power density which makes
SSB one of the best options for next generation batteries [373,374].
Solid electrolytes were first discovered in the 19th century, but the de- Fig. 40. Schematic diagram of conventional liquid battery and all-solid-state
velopments of electric vehicles in the late 20th and early 21st century battery. All-solid-state battery uses a solid electrolyte rather than a liquid elec-
have caused renewed interest in solid-state battery technologies. Several trolyte. However, the cell chemistry of an all-solid-state battery is similar to that
of liquid electrolyte battery.
well-known automakers including Toyota, Volkswagen, General Motors,
Hyundai, and Ford, have already made significant investments in SSB
technology companies with the goal of achieving full commercial de-
they weigh less and require less space than Li-ion batteries for powering
ployment in the first half of the 21st century [375].
electric automobiles. Despite these several advantages, commercializa-
An all-solid-state battery is basically a type of battery that uses a
tion of SSBs remains a challenge due to the underlying material and cell
solid electrolyte rather than a liquid electrolyte, as shown in Fig. 40.
level issues that need to be overcome [382]. Table 31 lists advantages
The cell chemistry of an all-solid-state battery is similar to that of liq-
and disadvantages of all-solid-state Li-ion batteries.
uid electrolyte battery. The main component of all-solid-state batteries
is a solid electrolyte, which can be ceramic, glass, polymer or a mix-
ture [376]. Table 30 [377–381] summarises some anode, cathode, and 2.4.2. Flow battery energy storage (FBES) system
electrolyte used in SSBs along with their optimum conductivity values. Flow batteries consume two electrolytes that are stored in separate
About 20 companies worldwide succeeded in prototype manufac- external tanks (Fig. 41) and there is a microporous membrane that sepa-
turing of SSBs. Since solid systems do not require any cooling system, rates both the electrolytes but allows only selected ions to pass through

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Fig. 41. Schematic diagram of flow battery energy storage (FBES) system. The energy is stored in two liquid electrolytes which are stored in separate tanks. When
these electrolytes are pumped through the electrochemical cells, they convert chemical energy into electrical energy.

Table 31
Advantages and disadvantages of all-solid-state Li-ion batteries.

Advantages Disadvantages

• High thermal stability • High production cost

• High ionic conductivity over a broad • Growth of lithium dendrites in
range of temperatures all-solid-state lithium-based
batteries
• Non-flammable electrolytes • No solid electrolyte interphase
layer formation
• High energy density • Low Specific power density
• Less self-discharge -
• Smaller in size -
• Withstand more number of cycles. -

Fig. 43. Schematic diagram of vanadium redox battery (VRB). During the
charging cycle, vanadium ions accept electrons at the anode (V3+ to V2+ ) and de-
posit electrons at the cathode (V4+ to V5+ ). These reactions are reversed during
the discharging cycle.

Fig. 42. Classification of flow battery energy storage (FBES) system.

it, producing current [219]. FBES systems are classified into two types
(Fig. 42): reduction‐oxidation (redox) flow battery and hybrid flow bat-
tery. In redox flow batteries, all the electroactive materials are dissolved
in a liquid electrolyte, whereas in hybrid flow batteries, one or more
electroactive materials are deposited in the electrolyte [198]. There are
primarily three types of large‐scale FBES that are used, as summarised
in the following subsections:
2.4.2.1. Vanadium redox batteries (VRBs). VRBs store electrochemical
energy by electron transfer between different ionic vanadium materials.
A proton exchange membrane (PEM) separates the two electrolytes here.
Fig. 43 shows the schematic diagram of VRBs. During the charging cycle,
V3+ is converted to V2+ at the anode by ‘accepting an electron’; during
the discharge phase, V2+ ions are converted back to V3+ , resulting in the
release of one electron. A similar process of electron transfer mechanism
takes place between V5+ and V4+ ions at the cathode [23]. Because VRBs
can store energy for a long duration, they are widely employed in utility-
scale applications such as load levelling and peak shaving.
The all-VRB was invented in 1986 by Maria Skyllas-Kazacos, a chem-
ical engineer at the University of New South Wales [383]. Since then,
the all-vanadium redox flow battery has proven the greatest potential
for large-scale energy storage applications with capacities ranging from
1 MW to 100 MW [384]. Table 32 [385−392] depicts the development
history of VRBs. Since the 1990s, a number of vanadium battery field
trials have been conducted in Thailand and Japan [392,393]. Recently,
VRBs have been installed for a variety of purposes like uninterruptible
power supply (UPS), frequency regulation and load shifting applica-
tions. Tsushima and Suzuki [394] performed numerical simulations to
optimise the electrode architecture in vanadium redox flow batteries
with interdigitated flow fields. The results showed that using electrodes
made of finer fibres could considerably improve cell performance. Ara-
mendia et al. [395] provided a comprehensive review of the numerical

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Table 32
Evolution of vanadium redox flow battery.

Year Type Electrodes Electrolyte References

1986 Laboratory scale test cell Graphite Negative and positive half-cell electrolytes are [385]
plates made of 0.1 M V3+ and 0.1 M V4+ in 2 M H2 SO4
respectively

1987 Redox flow cell Graphite plates as cathode and iridium Vanadyl sulphate in sulphuric acid [386]
oxide-coated as anode
1989 Redox flow cell Graphite felt/carbon Vanadium sulphate in sulphuric acid [387]
plastic electrodes
1991 Redox flow cell Graphite fibre 2 M vanadium sulphate in 2 M [388]
sulphuric acid
2002 Membraneless redox fuel cell Carbon-on-gold 1 M solution of [392]
VOSO4 in 25% H2 SO4
2008 Redox flow cell Graphite felt 2 M V4+ in 2.5 M H2 SO4 catholyte and 2 M V3+ [389]
in 2.5 M H2 SO4 anolyte

2011 Single redox flow cell Graphite/graphite oxide (GO) composite 2.0 M H2 SO4 + 0.1 M VOSO4 solution [390]
2019 Three-electrode Carbon nanofiber (CNF) and ZrO2 /CNF 1.6 M V3+ + 3 M H2 SO4 electrolyte [391]
redox flow cell system coated glassy carbon as working
electrode, a saturated calomel electrode
and platinum (Pt) sheet as reference and
counter electrode

Table 33
Summary of major plants ever built based on vanadium redox battery technology around the world [400–403].

Year Location Storage capacity Applications

(MWh)

1996 Kashima-Kita Electric Power, Japan 0.8 Load-levelling

1996 Tatsumi Substation, Kansai Electric, Japan 0.9 Peak shaving
2000 Kansai Electric, Japan 1.6 Peak shaving
2001 Hokkaido Electric 1 Wind turbine output power stabilisation
Power Wind Farm, Japan
2001 Tottori Sanyo Electric, Japan 1.5 Peak shaving and emergency back-uppower
200 Stellenbosch University, South Africa 0.5 Peak shaving and UPS back-up power
2001 Gwansei Gakuin University, Japan 5 Peak shaving
2001 Milan, Italy 0.09 Distributed power systems
2003 High-Tech factory in Japan 2 UPS/peak shaving
2003 Huxley Hill Wind Farm on King Island 1 Wind energy storage and diesel fuel replacement
2004 Castle Valley, Moab, USA 2 Voltage support and rural
feeder augmentation
2005 Electric Power Development Co., Ltd. in 6 Wind energy storage and wind power stabilisation
Tomamae, Hokkaido, Japan
2010 Vierakker, Netherlands 0.1 -

models developed to analyse various types of flow fields and patterns,
and to enhance the performance and lifetime of VRBs. Huang et al.
[396] summarised the crucial factors influencing the development of
VRB and detailed the working principle, electrochemical reaction pro-
cess and system model of VRB. Palanisamy and Oh [397] reviewed re-
cent developments in hybrid polymer composite membranes with inor-
ganic TiO2 nanofillers for VRB applications. Researchers have also re-
viewed the critical role of ion exchange membranes and developments
in nanocomposite membranes with reduced vanadium ion permeability
and improved proton conductivity in order to achieve high performance
and extended life of VRB systems such as in references [398] and [399].
Table 33 [400–403] lists the key plants ever built based on VRB tech-
nology around the world. Though VRBs are the most developed among
flow batteries, the capital expense of these systems is a barrier to wider
commercialization. Table 34 [309,404] lists the benefits and drawbacks
of VRBs [15].
2.4.2.2. Polysulfide bromide (PSB) flow batteries. The PSB battery, also
known as Regenesys, is a type of regenerative fuel cell in which a re-
versible electrochemical reaction between two electrolytes, sodium bro-
mide and sodium polysulfide, occurs. Polymer membrane works as a
Table 34
Advantages and disadvantages of vanadium redox batteries [309,404].
Advantages Disadvantages
• High power • High production cost
• Long life-cycle • Large area
• Fast charge and discharge • Low energy density
• Quick response times -
separator, allowing sodium cations to transfer between electrodes. Dur-
ing the charging cycle, three bromide ions are oxidised and combined
to form a tribromide ion at the positive electrode. At the negative elec-
trode, dissolved sodium particles in the polysulfide electrolyte are con-
verted to sulphide ions. This process is reversed during the discharge
process [405]. A schematic diagram of PSB batteries is shown in Fig. 44.
The PSB was first patented by Remick and Ang in 1984 [406]. Re-
genesys Technology Ltd. (formerly Innogy Technology Ventures Ltd.)
conducted considerable research on PSB from 1993 to 2006 [407]. The
reviews of the developments of materials for membrane separators, elec-
trolyte solutions, and electrodes for PSB flow batteries are presented in
references [405,408,409]. Zhang et al. [20] reviewed the various poly-

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Table 35
Development of polysulfide bromide flow battery.

Year Type Electrodes Electrolyte Membrane References

1984 Single PSB flow battery Solid graphite as cathode and Catholyte as 1 M Nafion 125 [405]
porous sulfided nickel as sodium bromide saturated with bromine and
anode anolyte being a 2 M sodium sulfide solution
2001 S-, L-, and XL-series cell Carbon-Polyelfin composite Tribromide/bromide and polysulphide/sulphide Sodium [406]
stacks cation-exchange
membrane
2004 Single flow cell Ni/C and Pt/C catalysts as Catholyte as 2.0 M Na2 S2 solution and anolyte as Nafion [411]
the positive and negative 1.0 M Br2 dissolved in 2.0 M NaBr solution
electrodes
2006 Single flow cell Carbon felt (CF) and 1.3 M Na2 S4 aqueous solution as anolyte and Nafion-117 [412]
activated carbon (AC) 4.0 M NaBr aqueous solution as catholyte

2018 Na-aqueous-redox-flow- Na-metal anode Organic electrolyte as 1 M NaCF3 SO3 in NASICON [413]
battery (NaAqRFB) tetraethylene glycol dimethyl ether (TEGDME) (Na3 Zr2 Si2 PO12 )
cell

Table 36
Advantages and disadvantages of polysulfide bromide flow battery energy stor-
age system [415].

Advantages Disadvantages

• No self-discharge • Hazardous for toxic bromine gas

• Very fast response time of about 20 milliseconds • High preparation cost
• High energy efficiency -
• Capable of rapid charge -
• Adequate power density for most applications -
• Low-environmental-impact -

developed in the 1970s by Exxon, Gould, and the National Aeronau-

Fig. 44. Schematic diagram and working principle of polysulfide bromide (PBS)
battery system. It consists of two electrolytes: sodium bromide and sodium poly-
sulfide. During the charging cycle, sodium tribromide is converted to sodium
bromide at the positive electrode, while sodium disulfide is converted to sodium
polysulfide at the negative electrode. The process is reversed during the dis-
charging cycle.
sulfide flow battery systems that have been developed to date, as well as
their prospects for future development. Chai et al. [410] reviewed the
recent progress in organic redox-active materials in aqueous and non-
aqueous media, ranging from small molecules to polymers. Table 35
[405,406,411−413] displays the development history of PSB flow bat-
teries. In 2002, a 15MW Regenesys PSB flow battery was built at Little
Barford in the UK. Although the construction of the facility was com-
pleted, it was never fully commissioned due to some engineering chal-
lenges linked to scaling up the technology [414]. PSB flow batteries
have certain advantages and disadvantages as listed in Table 36 [415].
Because of their quick response time, they are particularly used for fre-
quency response and voltage control applications. To date, three series
of PSB systems have been developed, including 5, 20, and 100 kW class
systems. Unfortunately, there are still some technical challenges with
the commercialization of the PSB battery, such as the cost of carbon
felt-based electrode preparation and the complex synthesis methods of
sodium polysulfide from molten sodium [15,393].
2.4.2.3. Zinc‐bromine (ZnBr) flow batteries. The ZnBr flow battery is dis-
tinct from VRB and PSB flow batteries. It is a type of hybrid flow battery
tics and Space Administration (NASA) of the USA and first patented by
Thaller [416], Butler et al. [417]. In 1991, prototypes of 1 MW, 4 MWh
batteries were built. Following many years of research and development,
ZnBr flow batteries have now become a mature technology and are being
used by various firms [418]. Table 37 [419−425] depicts the evolution
of ZnBr flow batteries.
It consists of two aqueous electrolyte solutions of zinc and bromine
placed in separate containers, as illustrated in Fig. 45. These electrolytes
are then circulated through the electrolytic cells during charging and
discharging cycles, resulting in reversible electrochemical reactions.
During the charging cycle, solid zinc is deposited on the negative elec-
trode and bromine is deposited on the positive electrode [426]. During
the discharging cycle, the zinc deposited on the negative electrode dis-
solves in the electrolyte and becomes available for the next charging
cycle. Table 38 [308] summarises the benefits and drawbacks of ZnBr
batteries. Currently, integrated ZnBr flow battery systems for utility-
scale applications have been tested on transportable trailers (up to 1
MW). In addition, a new type of ZnBr battery is being developed in
Australia, which is lighter, flexible, safer, and charges faster
[15,198,259]. Lin et al. [427] reviewed the technical features and mate-
rials of the electrolyte, membrane and electrode of ZnBr battery, as well
as the potential for development of ZnBr battery. Khor et al. [426] and
Wang et al. [428] reviewed various types of zinc-based redox flow bat-
teries based on their electrolyte environments, emphasising advance-
ments in electrode and membrane materials. Yuan et al. [429] reviewed
the functions, structures and chemistries of various materials used in
zinc-based flow batteries in relation to battery performance. Jiang et al.
[430] discussed recent advancements in carbon-based material elec-
trodes and carbon nanotube modified electrodes for ZnBr flow batter-
ies. Lee et al. [431] enhanced the electrochemical performance of ZnBr
flow batteries by improving reaction kinetics and suppressing Zn den-
drite growth by replacing a conventional polymer mesh with a titanium-
based mesh interlayer.

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Table 37
Development of zinc bromine flow battery.

Year Type Electrodes Electrolyte References

1991 Single zinc-bromine battery Carbon/polyvinylidene fluoride Polybromide/aqueous [419]

(PVDF) bipolar
2001 Non-aqueous zinc-bromine Glassy carbon electrodes 0.5 M N-methyl-ethyl-morpholinium [420]
battery (MEM)-Br, 0.5 M
N-methyl-ethyl-pyrrolidinium (MEP)-Br, and
3 M ZnBr2
2013 Single flow zinc bromine battery Semi-solid carbon felt positive 2 M ZnBr2 [421]
electrode
2014 Rechargeable zinc bromine Single-walled carbon anotube ZnBr2 [422]
battery (SWCNT) and multiwalled carbon
nanotube (MWCNT)

2017 Single zinc-bromine redox flow Carbon felt electrodes with 2.25 M ZnBr2 , 0.5 M ZnCl2 , 0.8 M MEP [423]
battery ultrathin nafion-filled porous and 5 M Br2
membrane
2018 Single zinc-bromine redox flow Boron-doped graphene (BDG) 0.05 M ZnBr2 and 1 M HClO4 [424]
battery
2019 Aqueous zinc-bromine battery Zinc anode and liquid Br2 Alkaline-acid hybrid electrolytes [425]
cathode

Fig. 45. Schematic diagram and working principle of zinc bromine battery system. Solid zinc is deposited on the anode during the charging cycle, and bromide ions
are oxidised to bromine on the cathode. The zinc metal deposited on the anode during the charging cycle is oxidised to Zn2+ ions during the discharging cycle, and
bromine is converted to bromide ions at the cathode.

Table 38 ditional batteries, with the exception that they are non-corrosive and
Advantages and disadvantages of zinc-bromine batteries [308]. require minimum housing and casing [432]. They have a high amount
Advantages Disadvantages of flexibility, since they can be bent, twisted, or wrapped around things
instead of having to adhere to rigid set-up criteria, and they can be
• High specific energy • Initially high self-discharge rate when
easily fitted or accommodated into tight gaps or spaces, decreasing the
shut down while being charged
• Good energy efficiency • Auxiliary systems are required for system’s overall size and weight [24]. Fig. 46 depicts the basic assem-
circulation and temperature control bly of a paper battery. A sheet of paper coated with an ionic solution is
• Capable of rapid charge • Safety issues smeared with a specially formulated carbon nanotube ink. On the other
• Adequate power density for -
side of the paper, a thin coating of lithium is laminated to operate as
most applications
• Low-environmental-impact -
an anode. To carry the current between the electrodes, two aluminium
rods are linked on each sides [433].
To date, several types of paper batteries have been developed for var-
ious applications. Table 39 [434−444] summarises the advancements in
2.4.3. Paper batteries
paper batteries. It was discovered in 2011 that when a sheet of cellulose
Paper batteries are made mostly of paper/cellulose and carbon nan-
paper is covered with thin layers of opposite electrochemical potential
otubes, and are ultra-thin and flexible. They operate similarly to tra-

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Table 39
Advances in paper batteries.

Year Advancement References

1992 Solid paper rechargeable batteries [434]

• It uses polyaniline film as the electrode and nonaqueous gel as electrolyte

2005 Urine-activated laminated paper batteries [435,436]

• The paper batteries are activated by saliva, urine and tap water and produce a maximum voltage
of 1.56 V within 10 s after activation

2007 Organic-based paper batteries [437]

• Cathode-active thin film which was produced by photo-crosslinking a nitroxide radical functional
polymer for the first time without significant side reactions

2007 Paper-based supercapacitors [438]

• All components of the supercapacitor are integrated into nanocomposite papers

• Multiwalled nanotubes (MWNT) as cathode, lithium (Li) as anode and electrolyte are embedded
with nanoporous cellulose paper

2009 Lithium-ion (Li-ion) paper batteries [439]

• Enhanced paper is used as the electrode and as separator which results in a flexible battery with
great performance capabilities
• Carbon nanotube (CNT) as both cathode and anode alongside Li-particle battery segments by
overlaying on to piece of paper
• Using paper as a separator is more effective than using plastic as it improves film adhesion,
simplifies the coating process and significantly lowers the cost
• The conductive paper acts as an excellent lightweight current collector in Li-ion batteries
replacing the existing metallic chemical counterparts

2009 Paper-based electrochemical batteries [440]

• Metal electrode is deposited onto the paper and/or electrolytes are introduced into a whole paper
• e.g., paper-based zinc-air battery, paper-based Al-air battery

2013 Folded paper-based batteries [441]

• Paper folding technique imparts compactness and 3D morphologies to devices

• Folded cells show higher areal energy density compared to the planar cells

2013 Paper-based microbial fuel cell (MFC) [442]

• Ease of use, low production cost, and high portability

• Can be used as an integrated power source in paper-based diagnostic devices for powering
on-chip functions

2014 Aqueous paper batteries [443]

• Cathode and anode slurries made by mixing LiMn2 O4 and carbon coated TiP2 O7 are casted onto
the conductive paper substrates
• Carbon nanotubes coated commercial paper serve as current collectors
• Exhibit excellent rate capability and reasonable cycling life

2018 Paper battery powered by saliva [444]

• It can be used in extreme conditions where normal batteries do not function

• The battery can generate required power from one drop of saliva

materials on both sides, a voltage is generated between both electrodes
of the paper battery. The value of the generated potential depends upon
the materials used for anode and cathode. A circuit voltage of 0.5 V
was obtained for the simple Cu/paper/Al combination [445]. In 2020,
a novel strategy to use paper-based batteries as a sensor for measuring
ionic conductivity was presented [446,447]. Recently a low-cost dispos-
able water-activated paper-based battery was developed using activated
carbon powder loaded on a carbon sheet as the anode. It was noted that
the power output of the battery was proportional to the amount of ac-
tivated carbon loaded on the anode [446]. Yao et al. [448] reviewed
recent breakthroughs in the synthesis of paper-based electrodes, includ-
ing their structural features, electrochemical performances, and imple-
mentation as electrodes for flexible energy storage devices. Sharifi et al.
[449], Thakur and Devi [450] provided a brief overview of the mechan-
ics, emerging novel materials, technological trends, challenges, current
status and future technologies of paper-based devices for the energy sec-
tor. Hou et al. [451] discussed the challenges and future development
prospects of microfluidic paper-based analysis devices (𝜇Pads) for point-
of-care testing (POCT), as well as its applications in disease analysis,
environmental monitoring and food control.
Table 40 [435,436,440,452−458] lists different types of paper bat-
teries along with their characteristics and performances. It is evident
that paper batteries have a great potential to power the next generation
portable and compact electronics, medical devices and hybrid vehicles.
2.4.4. Flexible batteries
The advanced development of flexible, wearable, and multi-
functional electronic devices such as smartwatches, fitness bands, and

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Table 40
Summary of paper batteries.

Type Year Electrolyte Anode Cathode Voltage (V) Device size Applications References

Biofluid- and 2005 Saliva, urine Magnesium Copper 1.56 6 cm × 3 cm Supply high power to [435,436]
water-activated and tap water credit card-sized
paper batteries biosystems on a plastic
chip.
Paper-based, printed 2009 Lithium chloride Zinc/carbon/ Poly (3,4- 12 1 cm × 2 cm - [440]
zinc-air battery polymer composite ethylenedioxythiophene)
(PEDOT)
All-polymer 2009 Sodium chloride Platinum Platinum - 1 cm × 0.5 cm - [452]
paper-based foil foil
batteries
Solid-state paper 2011 Water Copper Aluminium 3 1.2 cm × 3 cm To control paper [453]
batteries transistors
Fluidic batteries 2012 Silver nitrate and Aluminium Silver 1.3 1 cm ×2 cm Power source for on-chip [454]
aluminium assays
chloride
Paper-based 2012 Artificial urine Indium tin oxide Indium tin oxide (ITO) 1.1 2 cm × 1 cm Microelectrochemical [455]
electrochemical (ITO) sensor
sensing platform
Galvanic cell paper 2013 Water Aluminium Carbon 1.53 1 cm × 1cm - [456]
battery
Paper-based Al-air 2019 Cellulose paper Low-grade Al foil Carbon paper 7.7 - Charging portable [457]
battery electronics.
Nano-based paper 2020 - Aluminium foil Cellulose-based 3.38 13.5 cm × 8.5 - [458]
battery paper cm

be bent repeatedly to a radius of 5 mm without structural collapse.

Fig. 46. Schematic diagram of paper battery. Here, the cathode is a specially
manufactured carbon nanotube ink that is dispersed on one side of the paper,
while the anode is a thin layer of lithium laminated on the other side of the
paper.
medical implants necessitates the development of energy storage sys-
tems with high performance and appropriate flexibility [459,460]. Cur-
rent electronic devices are heavy and bulky, making them incapable
of meeting the flexibility requirements. As a result, new battery en-
ergy storage systems are being developed that can withstand continuous
and prolonged mechanical deformation, such as bending, twisting, and
stretching, while also delivering high power and energy over long time
cycles. The primary challenge is to develop and manufacture electrode
materials with high mechanical flexibility, high energy density, power
density, and excellent cycling stability, in conjunction with a compati-
ble electrolyte and separator. Apart from these challenges, another im-
portant factor to consider, particularly for wearable devices, is safety.
Solid-state electrolytes are preferred for flexible batteries to improve
battery safety by preventing the leakage of flammable liquid electrolytes
[461,462].
Many efforts have been made to adapt conventional batteries such
as lithium ion, lithium-sulphur, sodium-ion, zinc-ion while also devel-
oping new materials for electrodes and electrolyte in flexible batteries.
Li et al. [463] developed a graphene-based Li-ion battery that was thin,
lightweight, and flexible using a conductive interconnected network of
graphene foam as a current collector, lithium titanate (Li4 Ti5 O12 ) as
anode and lithium iron phosphate (LiFePO4 ) as cathode. The battery
had a higher performance rate and energy density, as well as the could
Gaikwad et al. [464] discussed the material challenges and mechanical
limits of flexible printed batteries as well as the various printing tech-
niques employed in flexible batteries. Hu et al. [465] fabricated flexible
liquid-free Li-CO2 batteries based on poly(methacrylate)/poly(ethylene
glycol)-LiClO4 with 3 wt.% SiO2 composite polymer electrolyte (CPE)
and multiwall carbon nanotubes (CNTs) cathodes. The pouch-type bat-
teries fabricated were able to bend at various degrees ranging from 0° to
360° while exhibiting remarkable electrochemical performance with a
controlled capacity of 1,000 mA·h·g−1 and a long operation time. Zama-
rayeva et al. [466] developed a flexible Zn/MnO2 battery with polyvinyl
alcohol (PVA)/polyacrylic acid (PAA) gel as a flexible binder for Zn
metal anode and manganese oxide (MnO2 ) cathode. When compared
to conventional batteries, the manufactured battery revealed superior
capacity retention and mechanical qualities when discharged at high
rates. Fu et al. [467], Shi et al. [468], and Xiang et al. [469] reviewed
briefly the mechanics and design concepts, constituent component re-
quirements, emerging new materials, existing issues, current position
and practical applications of flexible batteries, and the future oppor-
tunities for flexible batteries research and development. Despite signifi-
cant advancements, the design, packing and assembly of electrolytes and
electrodes are still required to meet the market application of flexible
batteries [379,470].
2.5. Electrical energy storage (EES) system
The EES systems store energy in an electric field without converting
the electrical energy into other forms of energy. EES systems are clas-
sified into two types (Fig. 47): electrostatic energy storage systems and
magnetic energy storage systems. The capacitors and supercapacitors
are electrostatic energy storage systems. The superconducting magnetic
energy storage (SMES) is a magnetic energy storage system.
2.5.1. Capacitors
When charged, a capacitor stores electrical energy utilising an elec-
trostatic field. It is made up of two closely spaced metal plates separated
by a dielectric layer of non-conducting material (Fig. 48) [471]. During
the operation, as a voltage source is applied across the metal plates,
one plate gets charged with electricity while the opposite sign induces
the other plate. Table 41 lists the specifications of several common ca-
pacitors [472,473]. A capacitor’s energy capacity is determined by the

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Table 41
Summary of some typical kinds of the capacitors [472,473].

Type Dielectric material Electrode material Voltage (kV) Capacitance (𝜇F) Applications

Paper capacitor (1876) Wax-impregnated paper Aluminium sheet 0.001 to 2.000 Radio receivers
Silver mica capacitor (1909) Mica Silver 0.100–1.000 4.7×10−3 In high frequency tuned circuits,
such as filters and oscillators
Ceramic capacitor Ceramic Metal 0.016–15.000 1×10−5 –100 Transmitter stations, induction
furnaces, power circuit breakers,
printed circuit boards
Aluminium electrolytic Aluminium oxide Pure aluminium foil 0.004–0.630 0.1–2.7×106 Flash capacitor for camera
capacitors (1892) flashes, motor start capacitors for
ac motors, energy storage for
airbags, photoflash devices
Film capacitors (1944) Thin plastic film Pure aluminium foil 0.050–2.000 0.001–30.000 Power electronics devices, phase
shifters, X-ray flashes, decoupling
capacitors and filters
Glass capacitors Glass Aluminium 0.025–0.050 2.7×10– 4 –0.1 Critical military and space
programs
Tantalum capacitors (1930) Tantalum oxide Tantalum metal 0.002–0.500 0.001–72.000 Power supply filtering on
computer motherboards and cell
phones

Table 42
Characteristics and performance parameters of capacitor energy storage sys-
tem [474].

Parameter Value

Energy storage W-sec of energy

Method of charging Voltage across terminals
Charge time 10−3 to 10−3 s
Cell voltage 6–800 V/cell
Specific energy (Wh/kg) 0.01–0.05
Specific power (W/kg) < 105
Efficiency (%) > 95
Operating temperature −20 to 100◦ C
Life-time > 105 cycles
Fig. 47. Classification of Electrical energy storage systems. Weight 1 g to 10 kg

pacitors (SICs), as well as recent developments on electrode materials

for SICs, with a particular emphasis on material design strategies and
the relationship between structure and corresponding electrochemical
performances. Liu et al. [482] reviewed the recent advances and future
directions in the development of the next generation electrochemical ca-
pacitors with high energy and power performance. More research and
advancements in capacitor technology are required now, as the world
moves towards electrification. For example, transportation is rapidly
shifting to hybrid electric and toward fully electric. To enable more
power-efficient and compact portable electronic devices for communica-
tions, medical applications, and high-power electronics, advanced low-
voltage capacitors are required. Advanced high-voltage capacitors are
needed for energy storage and distribution related to the interfacing of
renewable energy sources to the power grid, and for pulsed power ap-
plications such as electromagnetic-based pulse power systems [473].

Fig. 48. Different capacitors used in electronic equipments. 2.5.2. Supercapacitors

size and spacing between the conducting plates. Capacitor characteris-
tics and performance metrics are presented in Table 42 [474]. Because
capacitors have a very low energy density, they can only handle high
currents for very short periods of time [5,258]. Han et al. [475], Ra-
makrishnan et al. [476], Su et al. [477], and Han et al. [478] reviewed
the challenges and recent progress in the applications of 2D materials
for high-energy and high-power lithium-ion capacitors and emphasis-
ing the key advantages and critical roles of 2D materials in the con-
struction of lithium-ion, sodium-ion and hybrid capacitors. Yuan et al.
[479], and Zhang et al. [480,481] provided a brief overview of the chal-
lenges and opportunities for the development of sodium-ion hybrid ca-
Supercapacitors, also known as electric double-layer capacitors
(EDLC) or ultracapacitors, are made up of two conductor electrodes,
an electrolyte, and a separator (Fig. 49). They store energy in the form
of an electrostatic field created by a continuous direct current voltage
supplied between two electrodes separated by a thin layer of an insula-
tor or dielectric material [2,483]. The two electrodes made of activated
carbon provide a larger surface area, resulting in higher energy density.
A porous membrane separates the two electrodes, allowing charged ions
to move freely while preventing electronic contact between them. When
the electrodes are charged by an applied direct current (DC) voltage,
ions in the electrolyte diffuse into the pores of the electrode of opposite
charge. These ions accumulate at the interface between the electrodes
and the electrolyte, forming charged double layers with polarity oppo-

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batteries, are made up of two electrodes separated by a porous media

and store energy in the form of an electrostatic field, just like a typical
capacitor [198,484].
The characteristics and performance parameters of supercapacitors
are presented in Table 43 [474]. Although the research and development
on EDLC began in 1950, commercialization of supercapacitors began in
the 1980s [485]. Standard Oil Company Sohio was the first to patent a
method of producing EDLC from carbon materials with high specific sur-
face area in 1968. This invention was then transferred to Nippon Electric
Company (NEC), which began producing supercapacitors in 1979, pri-
marily for electric vehicle starting systems. Simultaneously, Panasonic
developed supercapacitors with activated carbon as the electrode ma-
terial and organic solution as the electrolyte. Since then, numerous su-
percapacitor designs have been introduced. Table 44 [486,487] sum-
marises supercapacitor research and development around the world.
Supercapacitors have evolved over the previous several decades into
high-performance energy storage devices that are widely employed in
electric vehicle energy management, high-power military applications,
consumer electronics, telecommunication applications and other fields
[488,489]. Advances in supercapacitor energy storage technology are
represented in Table 45 [490–501].
Fig. 49. Schematic diagram and working principle of a supercapacitor. A su- Energy storage on board of a railway vehicle was proposed in 2005,
percapacitor comprises of two electrodes submerged in an electrolytic solution and up to 30% energy savings were measured in the light rail vehi-
and separated by a porous membrane separator. It stores energy in the form of cle prototype. Since September 2003, this prototype vehicle has been
an electrostatic field created by the application of a constant direct current (DC) operating as a passenger vehicle [502]. The use of supercapacitors
voltage applied between two electrodes.
for wind energy applications was demonstrated by integrating short-
term energy storage devices with a doubly fed induction generator de-
sign to smooth out quick wind-induced power variations [503]. A re-
Table 43
versibly stretchable supercapacitor with buckled single-walled carbon-
Characteristics and performance parameters of supercapacitor energy storage
nanotube (SWNT) macrofilms as the electrodes was proposed in 2009.
system [474].
Under cyclic stretching and releasing, stretchable supercapacitors with
Parameters Value controlled wavy shape demonstrated exceptionally stable capacitance
Energy storage W-sec of energy [504]. The disadvantages of supercapacitor energy storage systems in-
Method of charging Voltage across terminals clude low energy density, high operational costs, and large voltage vari-
Charge time 1–10 s ation during operation, which will be the subject of future research
Cell voltage 2.3–2.75 V/cell [505]. Some of the reviews in the archival literature [488,506–510] pro-
Specific energy 1–5 Wh/kg
Specific power Up to 104 Wh/kg
vide assessments of recent breakthroughs in supercapacitor research and
Efficiency 85%–98% technology, including charge storage mechanisms, electrode materials,
Life-cycle 3×104 h electrolytes, and production methods. Researchers [511–515] have also
Operating temperature −40 to 85 ◦ C reviewed the recent progress in micro-supercapacitors (MSCs) in fabri-
Life-time > 105 cycles
cation strategies, structural design, electrode materials substrates, elec-
Weight 1 to 2 g
trochemical properties and integrated applications. Uke et al. [516], Wu
et al. [517], Sakib et al. [518], and Das et al. [519] reviewed the recent
advances in the cobalt oxides, cerium oxide, manganese oxides, man-
site to that of the electrode. For example, a positively charged electrode ganese sulphide and their composites as an electrode material for su-
will have two charged layers (double layer) around it - one layer of neg- percapacitor. Supercapacitors are mostly employed in applications that
ative ions at the interface and a second charge, balancing layer of posi- require a high number of rapid charge/discharge cycles, rather than
tive ions adsorbed onto the first negative layer. The opposite is true for long-term compact energy storage. They are utilised for regenerative
the negatively charged electrode. The electrolyte supplies and conducts braking, short-term energy storage, and burst-mode power delivery in
the ions from one electrode to the other. Structurally, a supercapacitor autos, buses, trains, cranes, and elevators [520].
lies somewhere between batteries and capacitors. Supercapacitors, like

Table 44
Research and development around the world on supercapacitors [486,487].

Country Company/lab Year Capacitance (F) Voltage (V) Energy density (Wh/kg) Power density (W/kg)

Japan Panasonic 1978 800–2,000 3 3–4 200–400

NEC 1975 1–2 5–11 0.5 5–10
USA Maxwell 1991 1,000–2,700 3 3–5 400–600
PowerStor - 7.5 3 0.4 250
Los Alamos National Lab 1999 0.8 2.8 1.2 2,000
Pinnacle Research Institute 1982 125 15 0.5–0.6 200
US Army, Fort Monmouth - 1 5 1.5 4,000
Evans - 0.02 28 0.1 30,000
Russia ELIT 1988 0.5 450 1 900–1,000
ESMA 1993 50,000 17 8–10 80–100
Australia Cap XX 1994 120 3 6 300

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Table 45
Advances in supercapacitor technology.

Year Advancement References

1996 Supercapacitors with activated carbon/carbon composite electrodes [490]

2001 Hybrid supercapacitors [491]

• Uses p-doped poly (3-methylthiophene) (pMeT) as the positive electrode and an activated carbon as
the negative electrode
• Exhibit higher average specific power and good cyclability performance

2005 Supercapacitors with nanocomposite hybrid molecular materials [492]

• The organic and inorganic components of hybrid material help to store and release charge in
solid-state supercapacitors
• Exhibit high specific capacitance and good cycle stability

2006 Supercapacitors with multiwalled nanotubes (MWNT) thin film electrodes [493]

• Supercapacitor exhibits superior frequency response

• MWNT thin films serve as a coating layer for current collectors, thereby enhancing the electrode
performance

2010 All-solid-state polymer supercapacitors [494]

• Polyaniline-based electrodes solidified in the H2 SO4 -polyvinyl alcohol gel electrolyte

• The thickness of the entire device is the same as that of a piece of A4 print paper
• High specific capacitance
• Good cycle stability
• Highly flexible

2010 Ultra-high-power micro-supercapacitors [495]

• Onion-like carbon electrodes micrometre-sized supercapacitors

• High specific capacitance
• High energy density and discharge rates
• Applications include wireless sensor networks, biomedical implants, active radio frequency
identification tags and embedded micro sensor

2013 Fibre-like supercapacitors [496]

• Multiwalled nanotubes (MWNT) as cathode, lithium (Li) as anode and electrolyte are embedded with
nanoporous cellulose paper

2015 3D porous supercapacitors [497,498]

• Electrodes with 3D architectures which provide a maximum number of active sites.

• Electrodes enable: (i) effective contact between active materials and electrolyte ions for chemical
reactions, (ii) easy electron transfer between the current collector and active materials, and (iii)
effective accessibility on the current collector to enhance electrochemical activity

2016 Paper-like supercapacitors [499]

• An energy storage system in the form of a flexible and ultrathin fibre

• Easily moulded into required structures according to the specific individual applications

2018 Flower-like supercapacitors [500]

• A flower-like MnO2 nanocomposite mixed with nitrogen-doped graphene (NG-MnO2 )

• Better specific capacitance
• High-rate capability
• Long-term cycling stability

2018 Ultra-thin and stackable supercapacitors [501]

• Supercapacitors with MnO2 /CNT-web paper electrode

• Ultra-thin, lightweight, all-solid-state symmetric supercapacitors
• High areal capacitance

2.5.3. Superconducting magnetic energy storage (SMES) system
Although the superconductivity principle was first postulated in
1911, the first SMES proposal was made in 1969 by Ferrier, who ad-
vocated the installation of a massive toroidal coil capable of supplying
diurnal storage for France. However, research at the University of Wis-
consin in the USA began in 1971, leading to the building of the first
SMES system [521]. The first commercialised SMES power-grid appli-
cation was in 1981 and was located along the 500 kV Pacific Intertie,
which connects California and the Northwest; it was positioned along
the 500 kV Pacific [522]. The SMES system stores energy in the magnetic
field created by a direct flow current in a coil made of superconducting
material.
SMES is made up of three major components: a superconducting coil,
a control and power conditioning system and a cryogenically cooled re-
frigerator (Fig. 50). To retain its superconducting condition, the super-
conducting coil is cryogenically chilled to a very low temperature using
a refrigeration system. During the charging phase, the flow of current
increases in the superconducting coil while decreasing during the dis-
charging cycle. The control and power conditioning system regulates the
electrical energy of the SMES system during the charging and discharg-

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ing cycle according to the output power requirements and also converts
AC into DC and vice versa as per requirement [2,198]. These systems
have great performance characteristics for applications in power sys-
tems such as rapid response (in milliseconds), high power output (multi-
MW) and high efficiency. Xue et al. [523], Mazurenko et al. [524], Vu-
lusala and Madichetty [525], and Mukherjee and Rao [526] reviewed
the application of SMES systems in electric power grids, power systems
and energy systems. Mukherjee and Rao [527] discussed the advances
of superconducting coils and the design of power electronic convert-
ers for SMES systems used in the power sector. Table 46 [523] sum-
marises SMES applications to power systems. The SMES system con-
cept was created for very big plants that were primarily intended for
diurnal load levelling. However, with the advancement of technol-
ogy, now SMES systems are also used for smaller scale applications.
Table 47 [528−539] represents advancements in SMES technology. De-
spite the fact that SMES systems are commercially available, the number
of SMES sold remains quite low, owing mostly to their high initial cost
in comparison to other mature technologies [540].

Fig. 50. Schematic diagram of superconducting magnetic energy storage

(SMES) system. It stores energy in the form of a magnetic field generated by the 2.6. Hybrid energy storage (HES) systems
flow of direct current (DC) through a superconducting coil which is cryogeni-
cally cooled. The stored energy is released back to the network by discharging The HES system concept is to mix appropriate features of several
the coil. ESSs to obtain the necessary performance. ESSs are divided into two
categories: high power storage systems, and high energy density stor-
Table 46
age systems. High power density systems are typically fast response sys-
Summary of superconducting magnetic energy storage (SMES) system applica- tems, meaning they deliver energy at higher rates but for shorter periods
tions to power systems [523]. of time. High energy density systems, on the other hand, often have a
slower response but can provide power for extended periods of time
Summary Description
[541,542]. A HES system is often built by merging two complementary
storage systems, one with high energy density and the other with high
Improving power quality • Balancing fluctuating load
• Offering spinning reserve power density [543]. Table 48 lists various HES system combinations
• Offering load levelling based on this concept. It should be noted that not all of the combina-
• Defending critical loads tions in the table are viable. Some combinations may be physically and
• Offering backup power supply technically limited. Table 49 [544−548] provides an overview of global
• Balancing voltage and current
asymmetries
HES systems which are mostly used in the power, transportation, and re-
• Enhancing FACTS performance newable energy sectors. Researchers have recently focused on adiabatic
compressed air energy storage (A-CAES) and pumped thermal energy
Improving power system • Improving voltage stability
storage (PTES) systems as power-density solutions. The basic operation
stability • Reduction of system oscillation
of A-CAES is given in Section 2.2.3, and PTES is briefly explained in the
following Section.

Table 47
Advancements in superconducting magnetic energy storage (SMES) system.

Country Company/lab Year Energy Power Coil material Temperature (K) References

USA Bonneville Power 1982 30 MJ 11.16 MW and 9.80 MW Niobium-titanium 4.2 [528,529]
Administration during charge and
(BPA) discharge, respectively
Superconductivity, Inc. 1988 1 MJ 730 kW Niobium-titanium alloy 4.5 [530]
Germany Forschungszentrum 1995 188 kJ 1 MW NbTi/CdCuNi 4.2 [531]
Karlsruhe
USA American 1997 5 kJ - Silver-sheathed 25 [532]
Superconductor BiPb2 Sr2 Ca2 Cu3 o
Corporation (ASC) (BSCCO-2223)
Germany ACCEL Instruments 2003 150 kJ - Silver-sheathed 20 [533]
BiPb2 Sr2 Ca2 Cu3 O
(BSCCO-2223)
Israel Bar-Ilan University 2003 1.2 kJ 20 kW BSCCO coil 64–77 [534]
Korea Seoul National 2007 600 kJ - BSCCO-2223 20 [535]
University wires
France French National Centre 2008 814 kJ 175 kW BSCCO 2212 PIT tape 20 [536]
for Scientific Research
China China Electric Power 2011 6 kJ - BSCCO and Yttrium 65–77 [537]
Research Institute barium copper oxide
(YBCO) tapes
UK University of Bath 2013 60 kJ 10 kW YBCO tape 65 [538]
Italy - 2018 500 kJ 200 kW Cryogen-free magnesium 21 [539]
diboride (MgB2 ) test coil

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Table 48
High power and high energy density energy storage systems.
High power density systems (fast response High energy density systems (slow
systems) response systems)
• Capacitor • Compressed air energ storage
• Supercapacitor • Hydrogen
• Superconducting magnetic energy • Lead-acid
storage
• Flywheel energy storage • Nickel-cadmium
• Lead-acid • Sodium sulphur
• Nickel-cadmium • Lithium-ion
• Lithium-ion • Vanadium redox battery
• Vanadium redox battery • Zinc bromine
2.6.1. Pumped thermal energy storage (PTES) system
Currently, PHES handles more than 99% of large-scale energy stor-
age. PHES stores energy by transferring water between two reservoirs at
different altitudes via a pump or turbine. However, due to geographical
constraints, its installation is restricted. PTES systems are one intrigu-
ing alternative storage solution. This innovative technology has been
around for a few years and is currently being tested in pilot plants
[549,550].
PTES technology includes storing energy as heat, which can be sensi-
ble or latent. It is built on a high-temperature heat pump cycle that con-
verts electrical energy into thermal energy and stores it in two enormous
reservoirs, followed by a thermal engine cycle that converts the stored
thermal energy back into electrical energy [551]. As shown in Fig. 51,
the system comprises a high temperature vessel and a low temperature
vessel, four turbomachines (one compressor/turbine pair utilised dur-
ing the charging cycle and another during the discharging cycle), and
two heat exchangers (one hot and one cold). The tanks are regenerators
composed of refractory material that can store or deliver heat. During
the charging cycle, the working fluid flows clockwise, and during the
discharging cycle, it flows counterclockwise. The basic idea is to use ex-
cess grid electricity during off-peak hours to pump heat from the cold
vessel to the hot vessel. This is accomplished by allowing a cold ther-
mal front to propagate through the low temperature vessel and a hot
thermal front to propagate through the high temperature vessel. The
charging procedure is identical to that of a heat pump. The discharge
process is then analogous to that of a heat engine, in which the temper-
ature difference between the hot and cold storage tanks is employed to
generate work. During the discharging period, a warm front propagates
through cold storage and a cool front propagates through hot storage,
bringing the system temperatures closer together [549].
PTES can be categorised according to their thermodynamic cycle
and working fluid: (i) Brayton PTES systems based on closed/reversible
Brayton cycle using air/argon as working fluid, and equipped with a low
and a high pressure and temperature reservoirs; (ii) transcritical Rank-
ine PTES systems with ice and pressurised water storage tanks that use
CO2 as working fluid; (iii) compressed heat energy storage (CHEST),
which is based on a traditional steam Rankine cycle [550]. Table 50
[551–554] summarises the technical features of various PTES systems.
In the literature, several PTES concepts have been offered. Weis-
senbach [555] proposed PTES based on open cycle in 1979. Air was
compressed to 800–900 °C in that concept, and the heat was stored in
ceramic balls encased in heat-resistant steel tubes. SAIPEM advocated
employing maximum temperatures ranging from 1,000 and 1,500 °C
and storing the thermal energy in refractory bricks such as clay with
a high alumina or magnesia content [556]. Isentropic Ltd. proposed a
PTES design employing argon as the working fluid based on the closed
cycle principle. Magnetite pebbles were utilised to store heat at tem-
peratures close to 500 °C. The system’s rated discharge energy capac-
ity was estimated to be around 16 MWh, with a rated discharge du-
ration of close to 8 h [557]. Newcastle University commissioned the
world’s first grid-scale demonstration plant in 2017, based on the con-
cept of Isentropic Ltd. The PHES research facility employs 150 kW of
surplus grid electricity to power a compression and expansion engine,
which heats (500 °C) and cools (160 °C) argon working fluid streams.
The working fluid is used to heat and cool two thermal storage tanks,
which store a total of 600 kWh of energy. When needed, the process
is reversed to generate 120 kW of electricity for the grid. Table 51
[558] lists the other technical specifications of the demonstration
plant.
Mercangöz et al. [559] described a transcritical CO2 cycle in which
water served as the hot storage and ice slurry served as the cold stor-
age. Koen et al. [560] presented a study in which they investigated
a wide range of working fluids as prospective candidates for trans-
critical PTES cycles. Over 150 working fluids were screened for ther-
modynamic, environmental and safety appropriateness in the study,
and trifluoroiodomethane (R13I1) was determined to be a promising
working fluid, with a high round-trip efficiency of 57%. Frate et al.
[561] examined PTES systems based heat pumps and organic Rankine
cycles from a thermo-economic point of view and found the system suit-
able for large-scale and long-duration energy storage. Thermo-economic
assessments of three distinct PTES system variants based on sensi-
ble heat storage materials was conducted by Zhao et al. [562] taking
into account varied system configurations, working fluids and storage
media.
PTES has various advantages like there are no specific geographi-
cal requirements. It has high energy density than PHES, which means
that it can store more energy in the same volume. This means for a
given amount of energy stored, less space is required. The components
of PTES often survive for decades giving it a long life. However, while
there are numerous factors that make PTES well-suited for large-scale

Table 49
Summary of real-time hybrid energy storage (HES) systems worldwide.

Year Location Combination Capacity (MW) Applications References

2014 Japan Lead-acid batteries and 1.5 Optimal control of current input/output [544]
lithium-ion capacitors
2016 Rankin Substation in Supercapacitor + battery 1.2 Load shifting, extended operational life, [545]
Gaston County, North real-time solar smoothing and extended
Carolina, USA shelf-life
2017 Cerro Pabellon Lithium-ion battery and - Grid stability [546]
geothermal power plant, hydrogen storage
Chile
2018 Varel, Germany Lithium-ion and 11.5 To balance out frequency fluctuations in [547]
sodium-sulphur batteries the regional electricity network
2018 Monash University in Vanadium flow and 1.0 The hybrid system will act as a flexible [548]
Melbourne, Australia lithium-ion batteries platform, integrating with building
management systems and EV charging
stations whilst enabling cutting-edge
“peer-to-pool” energy trading

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