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Energy storage systems: A review
J. Mitali , S. Dhinakaran , A.A. Mohamad
PII: S2772-6835(22)00022-X
DOI: https://doi.org/10.1016/j.enss.2022.07.002
Reference: ENSS 17
To appear in: Energy Storage and Saving
Received date: 25 November 2021

Revised date: 26 June 2022
Accepted date: 9 July 2022
Please cite this article as: J. Mitali , S. Dhinakaran , A.A. Mohamad , Energy storage systems: A
review, Energy Storage and Saving (2022), doi: https://doi.org/10.1016/j.enss.2022.07.002
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(http://creativecommons.org/licenses/by-nc-nd/4.0/)
Energy storage systems: A review
J. Mitali1, S. Dhinakaran2,*, A.A. Mohamad3
1
Department of Aerospace Engineering, Defence Institute of Advanced Technology, (Deemed to be University), Girinagar, Pune
- 411 025, India
2
The Centre for Fluid Dynamics, Department of Mechanical Engineering, Indian Institute of Technology Indore, Khandwa Road,
Simrol, Indore - 453 552, India
3,*
Department of Mechanical and Manufacturing Engineering, Schulich School of Engineering, University of Calgary, Calgary, AB
T2N 1N4, Canada
efence Institute of
Abstract
________________________________________________________________________
The world is rapidly adopting renewable energy alternatives at a remarkable rate to address
the ever-increasing environmental crisis of CO2 emissions. Renewable Energy Systems
(RES) offers enormous potential to decarbonize the environment because they produce no
greenhouse gases or other polluting emissions. However, the RES relies on natural
resources for energy generation, such as sunlight, wind, water, geothermal, which are
generally unpredictable and reliant on weather, season, and year. To account for these
intermittencies, renewable energy can be stored using various techniques and then used in a
consistent and controlled manner as needed. Several researchers from around the world
have made substantial contributions over the last century to developing novel methods of
energy storage that are efficient enough to meet increasing energy demand and
technological breakthroughs. This review attempts to provide a critical review of the
advancements in the Energy Storage System (ESS) from 1850 – 2022, including its
evolution, classification, operating principles and comparison.
Keywords: Energy storage systems, history, classification, technology readiness level;

thermal, mechanical, chemical, electrochemical, electrical, and smart energy storage;
application
_______________________________________________________________________
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Corresponding Author: Dr. S. Dhinakaran, sdhina@iiti.ac.in
Nomenclature
A-CAES Adiabatic Compressed Air Energy Storage LHS Latent Heat Storage
AFC Alkaline fuel cell LA Lead-acid
ALTES Aquiferous low-temperature TES Li-ion Lithium-ion
ATES Aquifer thermal energy storage LTES Low temperature Energy Storage
BES Battery energy storage MES Mechanical Energy Storage
CAES Compressed Air Energy Storage MCFC Molten carbonate fuel cell
CES Chemical Energy Storage MWNT Multiwalled nanotubes
CFD Computational Fluid Dynamics NaS Sodium Sulphur
CNT Carbon Nanotubes Na-ion Sodium Ion
D-CAES Diabatic Compressed Air Energy Storage Ni-Cd Nickel Cadmium
DMFC Direct methanol fuel cell PAFC Phosphoric acid fuel cell
EcES Electrochemical Energy Storage PCM Phase Change Material
EES Electrical Energy Storage PEMFC Proton exchange membrane fuel cell
EDLC Electric Double Layer Capacitors PHES Pumped Hydro Energy Storage
ESS Energy Storage System PSB Polysulfide bromide
FBES Flow Battery energy storage PTES Pumped Thermal Energy Storage
FES Flywheel Energy Storage RES Renewable Energy Systems
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FC Fuel Cell SPHES Seawater pumped hydro energy
storage
FLA Flooded lead‐acid SHS Sensible Heat Storage
GES Gravity Energy Storage SMES Superconducting Magnetic Energy

Storage
GFRP Glass fiber reinforced plastics SNG Synthetic Natural Gas
HES Hybrid Energy Storage SOFC Solid oxide fuel cell
HTES High temperature Energy Storage TES Thermal Energy Storage
HTF Heat transfer fluid TCES Thermochemical Energy Storage
HTM Heat transfer medium TRL Technology Readiness Level
I-CAES Isothermal Compressed Air Energy Storage UPHES Underground pumped hydro energy
storage
IEA International Energy Agency UTES Underground Thermal Energy

Storage
IRENA International Renewable Energy Agency VRB Vanadium redox batteries
ITES Ice-cool thermal energy storage VRLA Valve-regulated lead‐acid
LAES Liquid Air Energy Storage ZnBr Zinc‐bromine
1. Introduction
Global energy consumption has increased dramatically as a result of increasing
industrialization, excessive technological breakthroughs, and economic growth in developing
countries. According to a recent International Energy Agency (IEA) survey, worldwide energy
demand will increase by 4.5%, or over 1000 TWh (terawatt-hours) in 2021. The rise in global
energy demand also boosted CO2 emissions by over 5% in 2021. Given the current scenario,
renewable energy systems are being employed at an astonishing rate to mitigate the ever-
growing global environmental issue of CO2 emissions, as no greenhouse gases or other
polluting emissions are produced during the process. According to a recent International
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Energy Agency (IEA) survey, electricity generation from renewable resources is on track to
set new records with a more than 8% rise, reaching up to 8300 TWh in 2021. Also, according
to the International Renewable Energy Agency (IRENA), the share of non-fossil fuel-based
generation sources, i.e., renewable energy sources should increase to 57% globally by 2030
in order to meet the Paris Agreement’s target of keeping the average global temperature rise
well below 2°C. The share of renewable sources in the power generation mix had hit an all-
time high of 30% in 2021. Renewable sources, notably solar photovoltaic and wind, are
estimated to contribute to two-thirds of renewable growth, with an increase in renewable
electricity generation of roughly 18% and 17%, respectively [1]. However, these renewable
sources are intermittent; for example, solar panels may be inefficient in cloudy weather, wind
turbines may be inefficient in calm weather, and renewable energy sources may produce
excess energy, causing the system to overload at times. Thus to account for these
intermittencies and to ensure a proper balance between energy generation and demand,
ESSs are regarded as the most realistic and effective choice, which has great potential to
optimise energy management and control energy spillage. ESSs are primarily designed to
harvest energy from various sources, transforming and storing the energy as needed for
diverse uses.
Because of the large variety of available ESSs with various applications, numerous
authors have reviewed ESSs from various angles in the literature. However, the types of
ESSs addressed in the reviews are often limited. Some assessments, for example, focus
solely on electrical energy storage systems, with no mention of thermal or chemical energy
storage systems. There are only a few reviews in the literature that cover all the major ESSs.
Luo et al. [2] provided an overview of several electrical energy storage technologies, as well
as a detailed comparison based on technical and economic data. Rahman et al. [3]
presented technological, economic, and environmental assessments of mechanical,
electrochemical, chemical, and thermal energy storage systems. Koohi-Fayegh and Rosen
[4] explored numerous ESS categorizations, comparisons, applications, and current
advances. Guney and Tepe [5] provided a description of ESSs, including classifications,
features, benefits, environmental implications, applications, and implementation options.
Begdouri and Fadar [6] reviewed the widely utilised renewable energy storage technologies
and provided extensive comparisons of various technologies in terms of benefits, drawbacks,
and application. Gür [7] discussed the current status of mechanical, thermal, electrochemical,
and chemical storage technologies.
More general reviews of all the available energy storage systems is needed to provide
better insights into their differences, potential applications and current status. This review is a
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modest attempt to assemble all the available information on ESSs developed in 1850-2022 to
benefit novice researchers in this field. This paper attempts to cover all the core concepts of
ESSs, including their evolution, detailed classification, the current status, characteristics, and
applications. This extensive compilation of information on energy storage systems will act as
a reliable reference for future developments in this field. Any future developments regarding
ESSs will find this paper a helpful source wherein all the necessary information has been
assembled.
2. Techniques of Energy storage

With the recent breakthroughs in the Electric Vehicle sector and the economy's shift towards
greener energy, the demand for ESS has skyrocketed. The requirements for energy storage
are expected to triple the present values by 2030 [8]. The demand drove researchers to
develop novel methods of energy storage that are more efficient and capable of delivering
consistent and controlled power as needed. Fig. 1 depicts the classification of major energy
storage systems. The evolution of ESS in chronological order is presented in Table 1. It
should be mentioned that the deployment of ESSs began nearly in the 19th century and they
have come a long way since then to reach the point they are at now. ESSs can be classified
according to the form of energy stored, their uses, storage duration, storage efficiency, and
so on. This article focuses on the categorisation of ESS based on the form of energy stored.
Energy can be stored in the form of thermal, mechanical, chemical, electrochemical,
electrical, and magnetic fields. Energy can also be stored in a hybrid form, which is a blend of
two separate forms. Table 2 lists the many ESSs discussed in this paper, followed by in-
depth discussions of each kind.
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Fig. 1. Classification of major Energy Storage Systems.
Table 1: Evolution of ESS
Year ESS Description Reference
1839 Fuel Cell In 1839, Sir William Robert Grove invented the first [9]
simple fuel cell. He mixed hydrogen and oxygen in the
presence of an electrolyte and produced electricity
and water
1859 Lead acid battery French physicist Gaston Planté invented the first [10]
practical version of a rechargeable battery based on
lead-acid chemistry
1883 Flywheel Energy The first FES was developed by John A. Howell in [11]
Storage 1883 for military applications.
1899 Nickel-Cadmium Waldemar Jungner, a Swedish scientist, invented the [12]

battery nickel-cadmium battery, a rechargeable battery that
has nickel and cadmium electrodes in a potassium
hydroxide solution
1907 Pumped Hydro The first use of pumped storage was in 1907 at the [13]
Energy Storage Engeweiher pumped storage facility near
Schaffhausen, Switzerland
1960 Sodium sulphur The first Sodium sulphur battery was originally [14]
battery developed by the Ford Motor Company in the 1960's
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1969 Superconducting In 1969, Ferrier originally introduced the [15]
Magnetic Energy superconducting magnetic energy storage system as a
Storage source of energy to accommodate the diurnal
variations of power demands
1977 Borehole Thermal In 1977, a 42 borehole thermal energy storage was [16]
Energy Storage constructed in Sigtuna, Sweden.
1978 Compressed Air The world's first utility-scale CAES plant with a [17]
Energy Storage capacity of 290 MW was installed in Germany in
1978.
1982 Supercapacitor The Pinnacle Research Institute (PRI) developed the [18]
first supercapacitor with low internal resistance in
1982 for military applications
1983 Vanadium redox flow The vanadium redox flow battery was pioneered [19]
battery mainly by M. Skyllas-Kazacos and coworkers in 1983
at the University of New South Wales, Australia
1983 Polysulfide Bromide A bromine-polysulfide flow battery was first reported [20]
flow battery by Remick et al. in 1983
1991 Li‐ion battery In 1991, Sony released the first commercial lithium- [21]
ion battery
2007 Paper Battery Dr. Robert Linhardt, Dr.Omkaram Nalamasu and [22]
Dr.Pulickel Ajayan from Rensselaer Polytechnic
Institute, New York first invented the concept of paper
batteries.
Table 2: Classification of ESS based on the form of energy stored
Sensible Heat Storage (SHS)

● Liquid
● Solid
Thermal Energy Storage (TES)
Latent Heat Storage (LES) or Phase change
materials (PCM)
Thermochemical Energy Storage (TCES)
Pumped Thermal Energy Storage (PTES)
Pumped Hydro Energy Storage (PHES)

Mechanical Energy Storage (MES) Gravity Energy Storage (GES)
Compressed Air Energy Storage (CAES)
Flywheel Energy Storage (FES)
Hydrogen Energy Storage

Chemical Energy Storage (CES) Synthetic natural gas (SNG) Storage
Solar Fuel
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Battery Energy Storage (BES)
● Lead-acid
● Lithium-ion
● Nickel-Cadmium
● Sodium-sulphur
● Sodium ion
Electrochemical Energy Storage (EcES)
● Metal Air
● Solid-state batteries
Flow Battery Energy Storage (FBES)

● Vanadium redox battery (VRB)
● Polysulfide bromide battery (PSB)
● Zinc‐bromine (ZnBr) battery
Paper Battery
Flexible Battery
Electrostatic Energy Storage

● Capacitors
● Supercapacitors
Electrical Energy Storage (ESS)
Magnetic Energy Storage
● Superconducting Magnetic Energy Storage
(SMES)
Others Hybrid Energy Storage
2.1 Thermal Energy Storage
TES systems are specially designed to store heat energy by cooling, heating, melting,
condensing, or vaporising a substance. Depending on the operating temperature range, the
materials are stored at high or low temperatures in an insulated repository; later, the energy
recovered from these materials is used for various residential and industrial applications,
such as space heating or cooling, hot water production, or electricity generation, depending
on the operating temperature range. TES systems are utilised for a variety of purposes,
including industrial cooling below –18°C, building cooling between 0°C – 12°C, heating
buildings between 25°C - 50°C and industrial heat storage over 175 °C [17]. TES systems
are divided into two categories: low temperature (LTES) and high temperature (HTES),
based on the operating temperature of the energy storage material in relation to the ambient
temperature [17,23]. LTES is made up of two components: Aquiferous low-temperature TES
(ALTES) and Cryogenic Energy Storage. In ALTES, water is cooled/iced using a refrigerator
during low-energy demand periods and is later used to provide the cooling requirements
during peak energy demand periods. In Cryogenic Energy Storage, the cryogen, which is
primarily liquid nitrogen or liquid air, is boiled using heat from the surrounding environment
and then used to generate electricity using a cryogenic heat engine. LTES are better suited
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for high power density applications such as load shaving, industrial cooling and future grid
power management [24]. As illustrated in Fig. 2, there are three main types of TES systems
in use. Following sections provide a quick overview of these systems.
Fig. 2. Classification of thermal energy storage system.
2.1.1 Sensible Heat Storage (SHS) system
SHS is the most widely deployed TES system. It stores heat energy by raising the
temperature of a solid or liquid by ΔT without affecting its phase. The specific heat of the
medium governs the heat storage capacity, temperature change (rise or fall) and the mass of
storage material [25]. The classification of SHS, depending on the state of the energy storage
materials used, are briefly reviewed by Socaciu [26]. As illustrated in Fig. 3 the SHS is
classified into two types based on the state of the energy storage material: sensible solid
storage and sensible liquid storage.
Sensible liquid storage includes aquifer TES, hot water TES, gravel-water TES, cavern
TES, and molten-salt TES. Sensible solid storage includes borehole TES and packed-bed
TES. The gravel-water TES is a combination of sensible solid and sensible liquid storage
system. Among these, aquifer TES, borehole TES and cavern TES are all classified as
Underground Thermal Energy Storage (UTES) as they use the underground as a storage
medium. The primary benefit of SHS is that charging and discharging of the storage material
is completely reversible and has unlimited life cycles. However, the major drawbacks of SHS
systems are their massive storage space requirements and hefty initial capital investment.
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Fig. 3. Classification of thermal energy storage technology based on the energy storage
material.
2.1.1.1 Aquifer thermal energy storage
An aquifer is a body of permeable rock that can hold or convey groundwater. Aquifer TES is
a sort of sensible seasonal storage that is used to heat and cool buildings during the winter
and summer seasons, respectively. ATES is made up of at least two hydraulically connected
wells and a heat pump that are utilised for ground water extraction and injection (Fig. 4). One
well holds hot water (at approximately 14-16 °C) while the other stores cold water (at
approximately 5 - 10 °C). These wells can be divided horizontally, which is known as doublet,
or vertically in a single borehole, which is known as monowell [27]. The wells are separated
by a critical distance to keep warm and cold storage remain separate. This critical distance is
a function of well production rates, the aquifer thickness, and the hydraulic and thermal
properties that govern the storage volume. Large scale Aquifer TES system consists of
multiple wells instead of just two wells called multi-well configuration [28]. Groundwater is
taken from the cold well and used for cooling purposes throughout the summer. The residual
warm water is fed into the warm well to recharge the warm storage. In the winter, the process
is reversed, and the groundwater from the warm well, which is at 14 - 16 °C, is heated to
approximately 40 - 50 °C and utilised for heating purposes. Following the heat transfer, the
cold water is injected back into the cold well, replenishing the cold storage which will be used
in the following summer [29]. Due to the flow of water in both directions, both wells are
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frequently equipped with heat pumps. The amount of energy saved with ATES is highly
dependent on the geological location of the site [30,31].
The concept of exploiting aquifers to store thermal energy in the form of heated water
dates back to the mid-1960s [32]. Several laboratory experiments and field testing have since
been conducted to investigate the aquifer storage concept. Kazmann [33], Rabbimov et al.
[34], Meyer and Todd [35] and Sauty et al. [36] are regarded as early theoretical researchers.
In 1965, the first Aquifer TES was reported in Shanghai, China. There were three interrelated
problems in Shanghai that led to the development of ATES – ground subsidence,
groundwater pollution, and the lack of summer cooling in factories. Industries began to use
cold water collected during winter for summer cooling [37]. As the demand for industrial
cooling expanded, so did the number of ATES applications, and by 1984, more than 400
wells were employed for both injection and extraction. While Shanghai’s industry primarily
used ATES for industrial cooling, the requirement to store both warm and cold energy at
various periods of the year necessitated technology development and research. The first
application of a combined heating and cooling ATES was started at the Scarborough Centre
building of the Government of Canada [38]. A few issues were encountered while storing
both warm and cold energy, such as well corrosion, buoyancy flow and an imbalance
between stored heat and cold. However, research revealed that an adequate operational
design of ATES might prevent the majority of the difficulties [39].
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Fig. 4. Schematic diagram of Aquifer Thermal Energy storage system. During summer
groundwater from cold well is extracted for cooling purposes and residual warm water is
injected back into the hot well for recharging the warm storage. In winter, groundwater is
extracted from the hot well for heating purposes and residual cold water is injected back into
the cold well, which is later utilised in the following summer.
Fleuchaus et al. [40] assessed the technical performance of ATES using data collected
from 73 Dutch ATES systems. The data analysis demonstrated that over the storage period,
only minor thermal imbalances and temperature losses occurred. However, because the
temperature difference between the abstraction and injection temperatures is 3 to 4 K smaller
than the optimal design value, the operation must still be optimised. Guo et al. [41] reviewed
selected theoretical and numerical modelling studies, as well as field testing, to assess the
viability of an emerging technology called compressed air energy storage in aquifers, which is
gaining interest as a potential way to deal with the intermittent nature of solar or wind energy
sources. Matos et al. [42] reviewed particular site screening criteria that can be used to
determine the feasibility of both the reservoir and the technology for that site in order to find
appropriate technology-reservoir couples. The most significant developments and the major
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impediments to ATES development, as well as the operational performance and economic
viability, have been summarised in the literature [43,44,45,46,47,48]
ATES facilities are currently operational in Sweden, Germany, the Netherlands,

Belgium, and a few other European nations [28,49]. Around 3000 ATES systems have been
installed worldwide, with more than 90% of them functioning in the Netherlands alone. Table
3 summarises the technical parameters of some global ATES systems including the largest
Aquifer TES in the world, located on the campus of the University of Technology in
Eindhoven, which saves around 13x103 tonnes of CO2 per year, equivalent to the average
yearly CO2 footprint of 800 Americans or 1300 German citizens [50]. The benefits and
drawbacks of ATES are outlined in Table 4.
Table 3: Summary of technical parameters of some ATES in the world.
Year Location Purpose Numbe Flow Maximu Capacit Reference

r of Depth of Distanc rate m y (MW)
wells wells (m) e (m3/h) Temper
betwee ature
n wells (°C)
(m)
1991 University of Heating 2 210 - - 50 - 90 2.6 - 6 [51]

Utrecht, and 260 100
Netherlands Cooling
1996 Anova Heating 2 240 - 2 [52]

Verzekering Co. and
Building, Cooling
Amersfoort,
Netherlands
1997 Gas and Steam Heating 2 1200 1300 200 80 77 [53]

Turbine Power
Plant in
Neubrandenburg
Deutschland
1998 Hooge Burch, Heating 2 135-151 67 200 0.6 [54]

Zwammerdam and
near Cooling
Gouda,
Netherlands
1999 Reichstag, Heating 12 60-320 - 100- - [55]

Berlin, Germany and 300
Cooling
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1999 Rostock (DE) Heating 2 15-20 55 20 50 - [53]
1999 IKEA store Heating 2 - - 200 1.4 [56]

Amersfoort, and
Netherlands Cooling
2000 Klina hospital, Heating 2 65 100 100 1.2 [57]

Belgium and
Cooling
2001 West Harbour, Heating 10 70-80 - 120 1.3 [58]

Malmö and
Cooling
2001 Mersin, Turkey Cooling 2 100 - 0.194 [59]
2002 Agassiz, British Heating 5 60 90 40 0.563 [60]

Columbia, and
Canada Cooling
2002 University of Heating 36 28-30 - 3000 20 [61]

Technology in and
Eindhoven, Cooling
Netherlands
2003 Malle ETAP, Cooling 2 67 - 90 0.57 [62]

Belgium
2008 Richard Stockton Cooling 6 35-60 1300 272 2 [63]

College, New
Jersey (US)
2009 Stockholm Heating 11 20 - 720 10 [64]

Arlanda airport, and
Sweden Cooling
2009 IKEA Store in Heating 11 90 - 180 1.3 [65]

Malmö, Sweden and
Cooling
2010 Widex Heating 10 100 - 250 2.5 [50]

headquarters, and
Copenhagen, Cooling
Denmark
2011 National Heating 2 60 - 45 0.4 [50]

Maritime and
Museum, Cooling
Greenwich, UK
2015 Copenhagen Heating 10 110 - - 5 [66]

Airport, and
Denmark Cooling
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Table 4: Benefits and drawbacks of Aquifer Thermal Energy Storage
Benefits of ATES ● Large storage capacities

● Low construction costs
● Low risk of contamination
● Flexibility to expand for increased storage capacity
Drawbacks of ATES ● Clogging

● Corrosion
● Environmental impact such as effect of increasing and decreasing
temperature on biological communities around the hot/cold well,
effect on varied temperatures on geological structures of the soil;
effect of temperature variation of chemistry composition and
properties of the aquifer water.
2.1.1.2 Hot water thermal energy storage
A hot water TES system is often a concrete structure that is wholly or partially buried in the
ground depending on storage volume requirements and space available. Some high volume
storage tanks are also erected as free-standing structures on the ground (Figs. 5 and 6).
Water is commonly used as a storage material because it has a large specific heat capacity
and high power rates for charging and discharging. Concrete, on the other hand, can
withstand higher temperatures of up to 1200°C. The energy storage capacity is determined
by the hot water temperature and tank volume. Thermal losses and energy storage duration
are determined by tank insulation. Hot water TES is an established technology that is widely
used on a large scale for seasonal storage of solar thermal heat in conjunction with modest
district heating systems. These systems have a storage volume in thousands of cubic metres
and charging temperatures of 80-90°C [67].
The hot water TES in Friedrichshafen–Wiggenhausen, Germany has been

operational since 1996, with the hot water storage tank partially buried in the ground to
reduce heat losses in the winter. The storage is constructed with a reinforced concrete tank,
that is only heat insulated on the roof and side walls and is lined with 1.2 mm stainless-steel
sheets to ensure water tightness, protect the heat insulation on the outer side and to reduce
heat losses caused by steam diffusion through the concrete wall. The inside stainless steel
liner was later discovered to be a very pricey component of the tank. Following the
development of new construction techniques, a heat storage tank was erected at Hannover-
Kronsberg, Germany without the need of a liner and instead using a high density reinforced
concrete [68]. Glass fibre reinforced polymers (GFRP) are now being explored as a novel
wall material at the Technical University of Ilmenau in Germany. Omer et al. [69] reviewed a
wide variety of thermal insulation materials for use in hot water storage cylinders, including
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organic foams, inorganic insulations, composite insulations and vacuum insulation panels. A
few research [70,71,72] found that installing PCMs inside hot water tanks can increase their
energy density and discharge time. Hot water tanks equipped with Phase change materials
(PCMs) have also been designed for household applications [73,74]. Seddegh et al. [75],
Abokersh et al. [76], Douvi et al. [77], Sharma and Chauhan [78] reviewed TES technologies
for solar water heating systems with integrated PCMs like integrated PCM storage vessels,
integrated PCM solar collectors, and integrated PCM unit inside the solar hot water circuit.
Yang et al. [47], Chandra and Matuska [79], Dahash et al. [80], Jodeiri et al. [81] present
reviews of state-of-the-art methods and best practises such as geometrical construction,
structural design incorporation, wall material specification, operational parameters and
system performance to ascertain improved performance of larges cale hot water TES. From
a thermodynamic standpoint, hot water TES has proven to be the most advantageous among
other systems [26,82]. Table 5 summarises the geometrical parameters of hot water TES
systems installed in Germany.
Fig. 5. Various types of large scale hot water tanks: (1) tank above the ground (2) tank
partially buried in the ground and (3) tank completely buried inside the ground.
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Fig. 6. Schematic representation of hot water TES. During the charging cycle, a heating unit
generates hot water inside the insulated tank, where it is stored for a short period of time.
During the discharging cycle, thermal energy (heat) is extracted from the tank's bottom and
used for heating purposes.
Table 5: Summary of geometrical parameters of some hot water TES systems installed in
Germany [52,68,80,82,83].
Year Location Storage Area of Height Depth of Service Area Solar

Volume solar of tank tank (m) Fraction
(m3) collectors (m) (%)
(m2)
1996 Hamburg-Bramfeld 4500 1650 10.7 25.7 124 row 49

houses
1996 Friedrichshafen- 1.2X 104 5600 20 33 570 47

Wiggenhausen apartments
1998 Ilmenau 300 262 8 7.2 - -
2000 Hanover-Kronsberg 2750 1350 11 19 106 39

apartments
2002 Attenkirchen 9850 800 8 8.9 30 Single 55

Family
houses
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2006 Crailsheim-Hirt. 480 362 14.5 6.3 260 50
apartments
2007 Munich-Acker 5700 2900 16.1 24.6 300 47

apartments
2.1.1.3 Cavern thermal energy storage
A cavern is a type of underground cave. Cavern TES makes use of Cavern, which are natural
or man-made structures. These systems are uncommon due to the scarcity of suitable
caverns. Mostly abandoned mines, tunnels and natural karsts structures are used as
prospective structures for cavern TES. For artificial caverns, large underground water
reservoirs must be built to act as the thermal energy storage. This leads to more expensive
construction and installation, limiting the practical applicability of the cavern TES, which is
rarely employed these days. Fig. 7 displays a basic Cavern TES set-up. Thermal energy is
added to or removed from the insulated tank/store buried underground by pumping water into
or out of the storage unit. Excess heat is used to heat up water inside the storage tank during
the charging cycle. Hot water is taken from the top of the insulated tank/store and used for
heating purpose during the discharging cycle. When warm heat transfer fluid (HTF) is stored
in the cavern at first, substantial heat losses to the surrounding rocks occur. However, after
one to two years of installation, the cavern develops a stable thermal halo around itself, with
temperature progressively falling away from the warm central point. Even though there is
some heat loss, because the thermal conductivity of dry rock is so low, the heat loss during
one operational cycle is limited to less than 10% under ideal conditions.
The benefit of rock cavern TES is its exceptionally high injection and extraction rates,
whereas the disadvantage is its extremely high construction cost [84,85]. Although full scale
heat storages have been demonstrated, the higher installation cost prevents large scale
commercialization. However, reconstructing existing caverns or abandoned mines may make
them economically viable. In the world, there are very few examples of rock cavern thermal
energy storage systems. Several researchers, however, have conducted numerous
experimental studies on cavern TES. Park, Dohyun, et al. [86], Park, Jung-Wook, et al. [87],
Böttcher et al. [88] used numerical analyses to evaluate the cavern’s structural stability and
thermal performance. Park, Dohyun, et al. [89], Park, Jung-Wook, et al. [90], Kim et al. [91]
have investigated the effect of aspect ratio on the thermal stratification and amount of heat
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loss in rock caverns for underground TES. In the early 1980s, Sweden built the first two
cavern thermal energy storages. The Avesta cavern TES with a capacity of 1.5X104 m3 was
built in 1981 to store heat from an incineration plant for a limited period of time. The Lyckebo
TES system with a storage volume of 1.15X105 m3 and maximum temperature of 90°Chas
been in operation since 1983 [92, 93]. There are few other instances of cavern TES systems
that have been constructed and are being used as thermal storage for district heating [94,95].
Fig. 7. Representation of Cavern Thermal Energy storage system. Thermal energy is added
to or removed from the natural insulated tank/store buried underground by pumping water in
or out of the storage unit. During the charging cycle, excess heat is used to heat up water
inside the storage tank. While during discharging cycle, hot water is extracted from the top of
the insulated tank/store and used for heating purpose
2.1.1.4 Gravel-water thermal energy storage
Gravel-water thermal energy storage is an underground heat storage system. Here, instead
of constructing a huge and costly hot water storage tank, an excavated pit buried in the
ground closer to the ground surface in the range of 5-15 m is used [96]. The storage pit is
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usually waterproof and insulated at the sidewalls and on the top (Fig. 8). Insulation is also
provided at the bottom at the bottom of the storage, depending on its shape and size. The
storage medium is usually a gravel and water mixture, although it can also be sand and water
or soil and water. Depending on the insulating material, a maximum storage temperature of
90°C can be obtained. Heat is charged and discharged into and out of the storage occurs
either by direct water exchange or through plastic pipes installed at different layers inside the
storage. Because the gravel-water mixture has a lower specific heat capacity than water
alone, the storage must be 50% larger than water-based TES to attain the same heat storage
capacity at the same temperature levels [26,97]. The review article by Pfeil and Koch [98]
showed the technical improvements of the new third generation type gravel-water thermal
energy and proved the novel storage technique’s strong cost-cutting potential as well as the
ecological compatibility of the materials utilised. Novo et al. [99] reviewed the technological
advances and issues encountered during the construction and operation of Gravel-water
thermal energy storage. Table 6 summarises the characteristics of some gravel-water and
sand/soil-water thermal storage systems.
Fig. 8. Schematic diagram of Gravel-water Thermal Energy Storage system. A mixture of

gravel and water is placed in an underground storage tank, and heat exchange happens
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through pipelines built at different layers within the tank. Excess heat from solar heating is
used to heat the water during the charging cycle, and this hot water is then pumped through
the pipelines. The tubes carry thermal energy from the hot water to the gravel-water
combination inside the storage tank. The heat from the gravel-water mixture is removed
during the discharging cycle by flowing cold water through the pipelines.
Table 6: Some features of gravel-water and sand/soil-water thermal storage systems

[80,98,99,100,101,102].
Year Location Storage Area of Height Diameter Tempe Heat

Volume solar of tank of tank rature Storage
(m3) collector (m) (m) Range Capacit
s (m2) (°C) y
(MWh)
1984 Institute for 1050 - - -

Thermodynamics and
Thermal Engineering of
Stuttgart University
1995 Chemnitz, Germany 8000 540 7 39 30-85 -
1997 Eggenhausen, Germany 300 115 4 8.7 - -
1999 Steinfurt-B, Denmark 1500 1305 4 24.25 - -
2008 Eggenstein, Germany 4500 1600 - - - -
2011 Marstal, Denmark 7.5X104 1850 16 21.2 17-88 6000
2013 Dronninglund, Denmark 6X104 3.75X104 - - 10-89 5400
2014 Gram pit storage, Denmark 1.25X105 4.4X104 15 - 20-90 1.21x1

04
2016 Toftlund pit storage, 8.5X104 - - - 20-90 6885

Denmark
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2.1.1.5 Molten salt thermal energy storage
Molten salts are suitable candidates for liquid sensible heat storage at temperatures
exceeding 100°C. The term "molten salt" refers to a liquid formed by the fusing of an
inorganic salt. Molten salts have many advantages, including high boiling temperatures, low
viscosity, low vapour pressure, and large volumetric heat capacities. Because of the low
vapour pressure, storage solutions without pressurised vessels are possible, and better
volumetric heat capacity corresponds to a smaller storage tank space [103]. Molten salt is
commonly utilised in concentrated solar facilities that include parabolic mirrors (troughs) or
sun-tracking mirrors (heliostats). Because of the high demand for molten salt in the
concentrated solar plant industry, the research for suitable molten salt mixtures for HTFs and
thermal energy storage materials has been intense in recent years. The market for molten
salt thermal energy is expected to grow during the forecast period (2021-2026).
Solar salts, Hitec, and Hitec XL are the most often utilised molten salt fluids. Table 7
compares the key features of these three molten salt mixtures. The molten salt energy
storage system is available in two configurations: two-tank direct and indirect storage
systems. A direct storage system uses molten salt as both the heat transfer fluid (absorbing
heat from the reactor or heat exchanger) and the heat storage fluid, whereas an indirect
system uses a separate medium to store the heat. Two tanks are used: one for cold storage
and another for hot storage. Cold temperatures typically range between 280°C and 290°C,
while hot temperatures range between 380°C and 550°C. Tank size and quantity are
determined by storage capacity and fluctuate according to salt inventory. Tanks with heights
of 12–14m and diameters greater than 35m are commonly utilised in commercial operations
[104].
Table 7: Properties of various molten salt mixtures [105,106,107]
Solar salt HITEC HITEC XL
Composition by weight 60% NaNO3 and 40% 7% NaNO3, 53% KNO3 45% KNO3, 7% NaNO2
KNO3 and and 48% Ca(NaNO3)2
40% NaNO2
Maximum operating 585 450-538 480-505

Temperature (°C)
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Melting Point (°C) 220 142 120
Density (kg/m3) 1899 1860 1992
Viscosity [cp] 3.26 3.16 6.37
The direct molten salt storage system (illustrated in Fig. 9) works on the following
principle: the concentrated sunlight reflected from the heliostats heats the 'cold' molten salt
(at 290°C) entering the tower receiver. Heated salt (at 550°C) is pumped downward into a hot
storage tank. When energy is needed, hot salt from the tank travels through the heat
exchanger to produce superheated steam, which powers the turbine and generates
electricity. This sort of plant has the advantage of being able to achieve greater temperatures
of around 535°C. Because molten solar salt has a relatively high freezing point, there is a
substantial risk of storage medium solidification [103,107,108].
Fig. 9. Schematic representation of direct molten salt storage system. Molten salt serves as
heat transfer fluid (HTF) as well as a storage material. During the charging cycle, intense
sunlight reflected from the heliostats heats cold molten salt, which is then stored in a hot
storage tank. During the discharging cycle, hot molten salt from the storage is transferred
through the heat exchanger to produce superheated steam, which powers the turbine to
produce electricity.
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In an indirect molten salt storage system (as shown in Fig. 10), during the charging
cycle, the HTF i.e. synthetic oil, circulates through the solar field and is heated to 390°C. A
portion of the synthetic oil from the solar field is routed to the oil-to-salt heat exchanger,
where the synthetic it cools down from around 390°C to approximately 295°C.
Simultaneously, molten salt from the cold storage flows through this heat exchanger, where it
is heated from 290°C to 380°C by the high-temperature HTF. This heated salt is stored in a
hot storage tank. During the discharging cycle, the heat is transported from the salt to the
synthetic oil in the oil-to-salt heat exchanger to produce enough thermal energy for the power
block [103,107]
Fig. 10. Schematic of indirect molten salt thermal energy storage system. In the solar field,
synthetic oil is employed as heat transfer fluid (HTF), while molten salt is used as a storage
material. During the charging cycle, the synthetic oil is heated by circulating it through the
solar field. A part of the heated synthetic oil is directed to the oil-to-salt heat exchanger,
where it cools down by exchanging thermal energy with the molten salt. This heated salt is
stored in a hot storage tank. During the discharge cycle, the heat is transferred from the
heated salt to the synthetic oil in the heat exchanger, generating enough thermal energy to
generate superheated steam, which powers the turbine and generates electricity.
There are several molten salt energy storage demo plants worldwide. Table 8 outlines
characteristics of some prominent systems. All these demo plants have laid the ground for
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commercialization of indirect and direct molten salt storage systems. Recently, Israeli and
French scientists have proposed a PV-plus-thermal-storage (PV-TS) concept that might be
used in areas with low direct solar beam radiation but significant levels of global solar
radiation. They presented a model for integrating solar power generation from utility scale
facilities with high-temperature molten-salt storage and calculated that when paired with
molten salt storage, the grid penetration rate of a large scale PV facility may increase from
roughly 30% to up to 95% [109]. Roper et al. [110] has briefly discussed the advanced
energy applications of molten salts. Caraballo et al. [111] assessed the performance of
various molten salts using certain performance metrics.
Table 8: Characteristics of some molten salt storage systems [107,112,113]
Plant/study Location HTF Storage Temperature Temperature Tank Capacity

material of cold tank of cold tank Volume (MW)
(°C) (°C) (m )
3
CESA-1 Spain Steam HITEC 220 340 200 12
Thermis France HITEC HITEC 250 450 310 40
CRTF USA Solar Salt Solar 288 566 53 7

Salt
Solar Two USA Solar Salt Solar 290 565 875 105
Salt
Archimede Italy Solar Salt Solar 290 550 25 4

Salt
TES-PS10 Spain Synthetic Solar 288 388 220 8.1

Oil Salt
NOOR I Morocco - - - - - 150
2.1.1.6 Borehole thermal energy storage
The Borehole TES system is an underground structure that stores enormous amounts of
solar heat captured in summer for later use in the winter. The schematic diagram of a U-
shape borehole TES is shown in Fig. 11. Here, heat is transferred to the underground mostly
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through conductive flow through a series of closely spaced boreholes. Heat is charged or
discharged by vertical borehole heat exchangers (BHE), which are typically 100 -150 mm in
diameter and deployed 30–200 m below the ground surface [85,114]. The borehole houses
some type of heat exchange pipe, which is often in the shape of a U-shaped tube. High
density polyethylene (HDPE) or cross-linked polyethylene (PEX) is typically used to make
this U-tube. A heat transfer fluid based on an antifreeze solution (ethanol, ethylene or
propylene glycol) and additives such as biocides and corrosion inhibitors is commonly
circulated (by pumping) around the BHE [115]. To guarantee adequate contact between the
pipe and the ground and to reduce heat resistance, the area between the pipe and the hole is
filled with a suitable material. Instead of ordinary materials, phase change materials (PCMs)
such as mixture of n-decanoic acid and lauric acid (DLC) are used as grout [116].The
system’s top surface is appropriately insulated to decrease heat losses over the surface.
During charging, the flow direction is from the borehole’s centre to the storage boundaries,
resulting in high temperatures in the centre and lower temperatures at the boundaries. The
flow direction is reversed during the discharging phase. In the summer, the hot HTF
circulates through borehole heat exchangers (BHE), transferring excess heat to the soil for
long-term storage. In the winter, the stored heat is recovered through the reverse circulation
of HTF and used to heat the buildings.
The parameters that govern the performance of borehole TES are thermal conductivity
of storage material, which is usually water, the number of pipes, and the material of pipes.
Due to high construction costs associated with drilling multiple deep boreholes, borehole TES
is the most expensive alternative among the natural Underground TES applications. In some
borehole TES applications, the ambient ground temperature is directly used for free natural
cooling. Such systems are referred to as passive systems because they are naturally
recharged. In most applications, cold must be actively stored in the soil and rock, to provide
the required temperature. These systems are known as actively recharged systems, and they
are considered true borehole TES applications. This system is highly adaptable to almost any
ground conditions, making it one of the most popular forms of TES [26,96]. There have been
a number of successful large-scale borehole TES installations around the world. In the
archival literature, several researchers have briefly reviewed BTES. Shah et al. [117]
investigated the potential seasonal TES systems for space heating using various parameters
such as heating demand, climate conditions, availability of solar resources, storage
temperature, energy efficiency, and life cycle cost. The analysis indicated that the double U-
tube borehole thermal energy storage (BTES) integrated with ground coupled heat pump
(GCHP) and evacuated tube solar collector (ETSC) system was the best choice for space
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heating in cold climate zones. Amara et al. [45] reviewed the potential and benefits of using
BTES technology in hard-climate buildings. The most significant developments and the major
barriers to the development of aquifer thermal energy storage as well as the operational
performance and economic viability have been summarised in the literature [47,48]. Further,
reviews of the state of the art in BTES have been extensively published by [97,114,118,119]
Table 9 summarises the characteristics of some prominent borehole TES systems.
Fig. 11. Schematic diagram of Borehole TES. Heat exchange to the underground storage
occurs here via vertical boreholes with U-shaped heat exchangers. During summer, excess
heat is used to heat the fluid that circulates through the boreholes, where heat exchangers
transfer the excess heat to the underground for long-term storage. In the winter, this stored
heat is recovered by reverse circulation of cold fluid through boreholes and used for heating.
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Table 9: Characteristics of some prominent Borehole TES systems.
Year Location No. of Storage Area of Service Area Storage Reference
Boreholes Volume solar Capacity
(m3) collector (MWh)
s (m2)
1980 Kungsbacka, 8.5X104 1500 School 8.6X104 [120]

Sunclay, Sweden Building
1982 Vaulruz Project, Horizontal 3500 Maintenance 90 [121]

Switzerland tubes Center
1983 Innsbruck, Horizontal 6X104 100 [121]

Kranebitten, Austria tubes
1985 Kerava solar 54 1.1X104 1100 44 terraced 320 [122]

village, Finland houses
1997 Neckarsulm, 528 6.34X104 5670 300 flats, a 1000 [123]

Germany shopping
centre, a
school with
gymnasium
and two
residential
homes
2000 Attenkirchen, 90 104 836 25 houses 77 [124]
Germany
2001 Anneberg, 99 6X104 3000 50 houses 550 [125]
Stockholm
2004 University of 370 1.4X106 7000 Four 9700 [126]

Ontario, Canada University
Buildings
2007 Akreshus 228 3X105 Hospital [127]
University Hospital,
Norway
2007 Crailshem, 80 3.9X104 School & 1135 [128]
Germany Gymnasium
2007 Drake Landing 144 3.4X104 2293 52 houses 780 [129]

Solar Community
(DLSC) in Okotoks,
Canada
2013 Brædstrup District 48 1.9X104 1.86X104 1500 houses 616 [130]
Heating, Denmark
2.1.1.7 Packed-bed thermal energy storage
In the packed-bed TES system, the rock materials are loosely packed in a bed-like structure.
Heat transfer to the packed-bed system takes place through inlet and outlet tubes installed in
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the storage system (Fig. 12). During the charging cycle, hot air from the solar collector enters
the upper portion of the storage through an inlet tube and transfers the thermal energy to the
rock bed. Hot air loses heat to the packed rock-bed storage due to density differences, and
then flows back to the collector for the next charging cycle. During the discharging cycle i.e.,
at night time, cool air from the room/space enters the packed-bed storage from the bottom
tube and retrieves the stored heat energy from the rock bed. Again, due to density difference,
the cold air is heated and used for space-heating. After the heat stored in the packed bed
storage is removed completely, the storage system is ready for the next charging cycle
during the day [131].
The first commercial high temperature packed-bed TES system was built in Ait Baha,
Morocco, based on pilot-scale thermal model test results that concluded that air can be
successfully used as heat transfer fluid [132]. Kröger [133] patented a design and layout
concept of a thermal packed bed storage system in 2013. In this case, hot air was introduced
into the top section of the packed-bed, while cold air was introduced from the bottom, forming
a thermocline with the hot air section at the top and the cold section at the bottom of the
packed-bed. The packed rock-bed is surrounded by a solid structure that insulates it from
ambient conditions. One disadvantage of this concept was the cost of insulation. Gauché
[134] created a second concept primarily to simplify the previous concept and make it a more
cost-effective option. During charging, hot air was introduced at the centre of the rock-bed
and allowed to flow towards the outer surfaces. This concept had the advantage of not
requiring any thermal insulation. It also included an optional cover to protect the rockpile from
the elements such as rain and wind. This concept did have one flaw. During long-term
thermal energy storage, the buoyancy effect caused hot air to rise and dissipate into the
atmosphere. The discharge of the hot air would cause flow reversal, sucking the air back into
the duct and out into the pipe that had previously supplied the hot air into the rock bed.
Based on the second concept, a facility was built at the Stellenbosch University Renewable
Energy (SUNREC) site outside of Stellenbosch, Western Cape, South Africa. However, after
the facility was commissioned, it was recommended that insulation be added to ensure
proper heat recovery. Many experimental studies and CFD simulations are being conducted
to confirm the concept’s adaptation [135,136]. Trevisan et al. [137] investigated the thermo-
economic performance of a packed-bed TES and proposed a complete methodology for
designing packed-bed thermal energy storage systems. He et al. [138] reviewed the
numerical research on the heat transfer performance of packed bed TES systems with
spherical PCM capsules along with some practical applications. Alami et al. [139] conducted
an exhaustive comparative study of three different Moroccan rock types in order to identify
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the most promising rocks for use as high-temperature thermal storage materials. Further
reviews on various design parameters, economic feasibility, operation and performance of
packed bed TES have been extensively documented by several researchers
[140,141,142,143]. Table 10 summarises some packed-bed storage system characteristics.
The efficiency of a packed-bed TES system is governed by various parameters like the
shape and size of storage materials, the porosity of the storage system and rate of heat
transfer, etc. The heat storage capacity of a packed-bed storage system is approximately
60% lower than water-based TES. Unlike water-based TES, which allows for simultaneous
heat addition and removal from storage, a packed-bed TES system does not allow for
simultaneous heat addition and removal [144]. However, installation and operational costs of
the packed-bed TES system are lower than those of the water-based storage system.
Furthermore, packed bed systems can be used at high temperatures, whereas water storage
systems have temperature differential limitations.
Fig. 12. Schematic diagram of Packed-bed Thermal Energy Storage system. The storage
tank consists of loosely packed rock materials that are arranged in a bed-like structure.
During the charging cycle, hot air from the solar air collector enters the top section of the
storage tank and transfers thermal energy to the rock bed. During the discharging cycle, heat
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energy stored in the rock-bed is retrieved for space-heating and the residual cold air is
directed back into the solar air collector which is then used for the next charging cycle.
Table 10: Characteristics of some packed-bed TES systems
Plant/study Solid Fluid Diamete Diameter Length Tempe Capa Reference

r of of solids of the rature city
whole (mm) packed (°C) (MW
packed- bed (m) )
bed (m)
10-MWe Rock Caloria 3.2 25/1.5 12.4 232- 10 [145]

solar-thermal mixture of HT43 316
central- river
receiver pilot gravel
plant, and No. 6
Daggett, silica
California sand
Numerical Rocks Air 0.57 18-30 0.84 - - [146]

study of rock
beds
Full-scale River Air 1.8 18.1 0.38 – 20-60 - [147]

rock-bed gravel 1.82
experiment
Analytical Crushed Air 1 18-45 2.45 30–75 - [148]

study of a quarry
rock-bed rocks
thermal
storage
system
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Experimental Soda lime Air 0.375 12.6 0.6191 25-70 - [149]
study of
packed-bed glass
thermal spheres,
storage
system
Pilot plant of Rocks Hindustan 2.2 50 2 230- 0.1 [150]

100kWh Petroleum 250
pebble-bed Hytherm
thermal 500
storage
system
Experimental Porcelain Air 0.15 20 1.2 25-550 - [151]

and spheres
analytical
study of high
temperature
rock bed
storage
Molten-Salt Quartzite Hitec XL 3 19 6.1 290- - [152]

Thermocline rocks and nitrate salt 390
Thermal silica
Storage sand
System
Experimental Sandy oil 0.29 5 0.3 20-240 - [153]

simulates of stones
oil-pebble
bed thermal
energy
storage
system
Pilot-scale Rocks Air 2.5-4 20-30 2.9 20–650 6.5 [132]

packed-bed
thermal
storage
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Laboratory- Solid Air 0.508 x 50.8 x 1.07 20- - [154]
scale TES bricks 0.203 203 x 527.8
prototype 178
system
Experimental Ceramic Flue gas 0.4 19 0.62 25-900 - [155]

study of pebbles
packed-bed
thermal
storage
Experimental Crushed Air 0.4 14.6 0.4 20-350 - [156]

study of rocks
packed-bed
thermal
storage
Experimental Ceramic Mixed 0.263 30 0.55 250- - [157]

investigation spheres nitrate 355
of a molten molten salt
salt
thermocline
storage tank
Experimental Alumina Air 0.58 8 1.8 38-239 - [158]

and CFD beads
study of
packed-bed
thermal
storage
Laboratory- Quartzite Rapeseed 0.4 40 1.8 160- - [159]

scale rock oil 210
experiment
at PROMES-
CNRS
laboratory,
France
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Experimental Rock and Therminol 1 30/3 3 20-250 - [160]
study of sand 66
pilot-scale
thermal oil
packed bed
thermal
storage
system
2.1.2 Latent Heat Storage (LHS) System
Latent heat storage system utilises the amount of heat absorbed or released when the
storage material undergoes a phase change. The ability of storage material to undergo phase
change at a constant temperature is critical to the performance of LHS systems. Fig. 13
depicts the phase transition profile for a storage material when heat is added/removed from
it. It can be observed that as the energy in the form of heat is added to the material, the
consequence is an increase in temperature (sensible heating) or a change of phase (latent
heating). The material in the solid phase is represented by point O. Heat addition causes
sensible heating of the solid (region O-A), further melting occurs and the material is
converted from a solid phase to the liquid phase (region A-B). The heat absorbed during this
transition is known as latent heat of fusion. Region B-C represents sensible heating of liquid,
followed by a liquid-to vapour phase change (region C-D). The absorbed heat is referred to
as latent heat of vaporisation and regions D-E represents sensible heating of the vapour
[161].
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Fig. 13. Temperature-Energy diagram for heating and cooling of a substance. Point O :
Material in the solid phase, Region O-A : Sensible heating of material due to heat addition,
Region A-B : Conversion of material from solid phase to liquid phase due to melting, Region
B-C : Sensible heating of liquid, Region C-D : Liquid-to vapour phase change Region D-E :
Sensible heating of the vapour
The classification of LHS systems (see Fig. 14), based on the type of phase change and
energy storage material used, are detailed in the review by Sharma et al. [25] and
Kalaiselvam and Parameshwaran [162]. LHS can take the following forms depending on the
phase change type: solid-solid, solid-liquid, solid-gas, and liquid-gas and vice versa. In solid-
solid transition, energy is stored as the storage material changes from one crystalline to
another. This type of phase change has very little latent heat and produces very small
volume changes. Solid-gas and liquid-gas phase transitions have higher latent heat but their
phase transitions result in large volume changes, which are not feasible due to containment
issues. When compared to liquid–gas transitions, solid–liquid transitions have a lower latent
heat. However, these transformations only result in a minor volume change (of an order of
10% or less). As a result, solid-liquid transitions are commonly used in TES systems [25].
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Fig. 14. Classification of latent heat storage technology based on type of phase change and
storage material
2.1.2.1 Ice-cool thermal energy storage (ITES)
The use of ice or solid water in the form of crystals or slurries as an energy storage material
is referred to as Ice-cool thermal energy storage system (ITES) [162]. Tables 11 and 12
summarise the primary characteristics of the two media (chilled water and ice) and compare
them. The cool thermal energy is stored (charging) during the phase transition from water to
ice, and the same energy is released (discharging) at the cost of the latent heat of fusion
during the phase transition of solid ice to water. The heat transfer medium (HTM) or
refrigerant circulating through the cooling coils embedded in the storage tank activates the
charging and the discharging processes (Fig. 15). During the charging cycle, the HTM
passes through the heat exchanger coil. The water in the tank extracts cool thermal energy
from the flowing HTM due to heat transfer between the HTM and the water in the tank, and
the phase transition of water to ice occurs. The cool thermal energy stored in formed ice is
exchanged with the warm water during the discharge period to meet the building cooling
requirements. To effectively meet cooling and energy redistribution requirements in buildings,
the ITES system is dependent on the mode of operation, type of storage medium, and
charging and discharging characteristics [163]. Yau and Rismanchi [164] summarised the
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research and analysis of the TES systems used for space cooling applications in terms of
various types of storage technologies and operating strategies. Liu et al. [165] simulated the
optimal operation of an electric-thermal integrated energy system with various cool storage
subsystems, and results revealed that the integrated energy system with dynamic ice storage
technology was more energy efficient than other systems. Hunt et al. [166] investigated the
use of swimming pools as a long-term cold energy storage system, in which a small building
can store solar energy for cooling purposes in a yearly cycle by filling the pool with ice slurry
in winter and using that ice to cool the house in the summer. The authors also conducted a
case study in Phoenix, Arizona, USA, using the proposed system and found that the cost of
energy storage was significantly lower than that of batteries.
Furthermore, ITES has emerged as one of the primary solutions to the electrical power
imbalance that exists between daytime demand and night time abundance. During the night,
it creates a reservoir of cold storage using refrigeration equipment. During the day, the cold
storage reservoir is tapped to provide cooling capacity. Lower night time temperatures allow
refrigeration equipment to operate more efficiently than during the day, resulting in lower
energy consumption and load. This reduces the required chiller capacity, lowering the capital
equipment costs [167].
Fig. 15. Schematic diagram of Ice-cool Thermal Energy Storage system. During the charging
cycle, cool thermal energy released during the phase transition from water to ice is stored in
a storage tank. During the discharge cycle, as per demand, the same stored energy is
released during the phase transformation from solid ice to water
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Table 11: Primary features of two common storage media used in old thermal energy storage
systems, namely ice and chilled water [168].
Features Chilled water Ice
Specific heat (kJ/kg K) 4.19 2.04
Latent heat of fusion (kJ/kg) - 334
Tank volume (m3/kWh) 0.089-0169 0.019-0.023
Charging Temperature (̊C) 4-6 -6 to -3
Discharging Temperature (̊C) 5-10 1.-3
Table 12: Comparison of two commonly used storage in old thermal energy storage systems:
ice and chilled water [169].
Ice Water
Large load capacity for a given volume Higher chiller charging efficiency
Less space required for delivering same amount of The refrigeration design is the
cooling load same as the non-storage system
Lower maintenance Lower initial cost
Lower storage temperature
2.1.2.2 Phase Change Material thermal energy storage (PCM-TES)
PCM-TES refers to the use of various phase change materials depending on the required
temperature range. It is an effective way of storing thermal energy and has the advantages of
high thermal energy storage density and the isothermal nature of the storage process. There
are large numbers of PCMs that melt and solidify at a wide range of temperatures, making
them suitable for a wide range of applications [25]. To be considered for commercial
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applications, a PCM should satisfy the properties listed in Table 13. PCMs are typically
divided into two categories (see Fig. 16): Organic PCMs and Inorganic PCMs. Organic
PCMs have high storage density with small melting and freezing temperature differences.
They are classified primarily as paraffin wax and fatty acids. Paraffin wax is a combination of
hydrogen and carbon molecules (CnH2n+2), where n ranges from 20 to 40. As the chain length
increases, there is an increase in the melting temperature and latent heat of fusion. Because
paraffins have a high specific heat of fusion, they have a higher energy storing capacity [170].
Fatty acids are carboxylic acids having a long aliphatic tail with the general formula
CH3(CH2)2nCOOH, where n is an even number ranging from 12 to 28. They can withstand a
large number of thermal (freezing and melting) cycles with no loss. Fatty acids have better
phase transition properties than paraffin wax but are more expensive [171]. Inorganic PCMs,
on the other hand, have sharp melting points with high heat of fusion, high latent heat storage
capacity per unit mass, and high thermal conductivity. Inorganic PCMs are classified as Salt
hydrates and Metallics [172]. Salt hydrates are inorganic salts that contain water of
crystallisation. The salt hydrate is dried here to store thermal energy, and the dry salt and
water are stored separately. Salt hydrates are known to have the highest storage density with
little to no heat loss during storage [173]. Metals with low melting temperatures and metal
eutectics are examples of metallic PCMs. Metallics have high latent heat of fusion, high
thermal conductivity, low specific heat, and low vapour pressure. Apart from these PCMs,
eutectic materials have recently piqued the interest of researchers as phase change
materials due to their fixed freezing/melting point. Eutectics are mixtures of two or more
components that do not interact to form a new chemical compound; rather, when these
compounds are mixed in specific proportions, they inhibit crystallisation process, resulting in
a system with lower melting temperature than its constituents [25]. Melting point and latent
heat of fusion of some organic and inorganic PCMs are listed in Table 14 [172].
When heat is supplied to the PCM (during the charging cycle), it continues to absorb
heat without significantly increasing its temperature until it undergoes a phase transition from
solid to liquid. During the discharging period, as the ambient temperature around the liquid
PCM falls, it again undergoes a phase change from liquid to the solid phase, releasing the
stored latent heat [174]. PCMs can store 5-14 times more energy per unit volume than the
traditional sensible storage materials such as water, rocks and other solids. Apart from that,
PCMs can store and release heat energy at a nearly constant temperature, which is another
benefit. However, the low thermal conductivities of phase change materials pose a significant
barrier to their use in large scale applications. A lot of research is being done to overcome
this limitation, and new methodologies are being developed. Xu et al. [175] reviewed
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methods for increasing the thermal conductivity of PCMs. Among the various methods, PCMs
with carbon-based materials and metal-based materials demonstrate superior thermal
properties. Mishra et al. [176] provided a brief review of various carbon based PCMs and
their applications in Textiles, heat therapy packs, electronics and packaging. Hu [177]
reviewed recent advances, challenges and new application opportunities of high performance
polymeric phase change composites for thermal energy storage. Several other review articles
(Nie et al. [178], Zhang et al. [179]) summarised the recent progress of PCM in cold TES
applications. Panchal et al. [180] summarised the development of multiple-phase change
materials in cascaded latent heat TES, which is primarily used for low-grade thermal energy
storage applications (cold: below 20°C and for low-temperature heat: between 20°C and
100°C). The authors also reviewed the selection criteria,PCM stacking, operating and
geometric parameters that influence the performance of cascaded latent heat TES. Shoeibi
et al. [181] reviewed the most recent studies conducted on nano-enhanced PCMs in various
solar technologies. Because of their increased thermal conductivities and lower melting
points, these materials facilitate the charging and discharging processes of heat storage
units.
Table 13: Important properties of phase change materials [16,162,182]
Thermal Physical Chemical Economics
● Fusion temperature in the ● Minimal change in the ● Completely reversible ● Cost-effective
desired operating range volumetric capacity ● Charging and ● Available in
● High latent heat of fusion during phase transition discharging cycles large‐quantity
with respect to unit ● Small vapour pressure ● Chemical and thermal
volume of the material stability to withstand
● High thermal conductivity ● High density heat at high
in both solid and liquid temperatures
phases ● No phase separation
● Non-flammable, non-
toxic, non-polluting
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Fig. 16. Classification of PCM's.
Table 14: Melting points and heat of fusions of some organic and inorganic PCM’s
[16,25,31,172,183,184,185].
Compounds Melting Points (°C) Heat of fusion (kJ/kg)
Paraffins
Paraffin 14-Carbons 5.5 228
Paraffin 15-Carbons 10 205
Paraffin 16-Carbons 18.2 237.1
Paraffin 18-Carbons 27.7 243.5
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Metallics
Mercury 38.87 11.4
Cesium 28.65 16.4
Gallium 30 80.3
Rubidium 38.85 25.74
Cerrolow eutectic 59 91
Inorganic Substances
H2O 0 333
LiClO3· 3H2O 8.3 253
KF· 4H2O 18.7 231
Mn(NO3)2· 6H2O 26 125.9
CaCl2· 6H2O 29.2 190.8
LiNO3· 3H2O 30.2 296
Na2SO4· 10H2O 32.6 254
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Zn(NO3)2 6H2O 36.2 246.5
Na2CO3· 10H2O 34.2 146.9
CaBr2· 6H2O 30.2 115.5
Na2HPO4· 12H2O 35.7 265
Na2S2O3· 5H2O 48.2 201
Na(CH3COO)· 3H2O 58.2 264
Na2P2O7· 10H2O 70.2 184
Ba(OH)2· 8H2O 78.2 265.7
Mg(NO3)2· 6H2O 89.2 162.8
(NH4)Al(SO4)· 6H2O 95.2 269
MgCl2·6H2O 117.2 168.6
NaNO3 307.2 172
KNO3 333.2 266
KOH 380.2 149.7
MgCl2 714.2 452
NaCl 800.2 492
Na2CO3 854.2 275.7
KF 857.2 452
K2CO3 897.2 235.8
Inorganic eutectics
58.7% Mg(NO3)・6H2O + 41.3% MgCl2・6H2O 59.2 132.2
66.6% CaCl2・6H2O + 33.3% MgCl2・6H2O 25.2 127
48% CaCl2 + 4.3% NaCl + 0.4% KCl + 47.3% H2O 27 188
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47% Ca(NO3)2・4H2O + 33% Mg(NO3)2・6H2O 29.2 190.8
60% Na(CH3COO)・3H2O + 40% CO(NH2)2 30.2 136
66.6% Urea + 33.4% NH4Br 76.2 161
14% LiNO3 + 86% Mg(NO2)2 ・6H2O 72 180
2.1.3. Thermochemical Energy Storage (TCES) System
Thermochemical storage (TCES) is a method of indirectly storing heat energy. Heat is not
directly stored as in SHS or LHS, but is absorbed and released during
dissociation/association of molecular bonds in an entirely reversible chemical reaction [5]. It
stores heat energy by utilising the enthalpy of reaction ΔH. The amount of heat stored
depends on the type and amount of storage material, the enthalpy of the reaction, and the
degree of conversion [25]. During an endothermic reaction i.e., a positive change of ΔH, heat
is stored by the dissociation of reactive components into individual components and the
stored energy is released through exothermic reactions (ΔH < 0) by combining the individual
components (Fig. 17). Several parameters must be considered while choosing a
thermochemical material, as they have a significant impact on the TES system. Some
promising thermochemical storage material candidates have been listed in Table 15, along
with their energy density and reaction temperature values, as these two factors, among
others, are important for application in thermochemical TES systems. Few review articles
[186,187,188] attempted to assess and summarise the realistic potential application of TCES.
They have also identified several issues that are impeding this technology’s maturity. Han et
al. [189] evaluated the technical properties of cobalt, manganese, and copper oxide-based
TCES systems in terms of energy density and cycle life. The reviews of recent developments
and applications of hydrated salt based TCES are presented in references [190],[191] and
[192].
Thermochemical energy storage systems are primarily of two types: open and closed
systems (Fig. 18). In an open system, the working fluid, which is primarily gaseous, is directly
released into the environment, thereby releasing entropy. In contrast, in a closed system, the
working fluid is not released directly. Nonetheless, entropy is released into the environment
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via a heat exchanger interface [193,194]. TCES systems have a lot of potential in the future
energy economy. TCES system, among the available TES systems, offers promising
advantages, including (i) higher energy densities compared to sensible or phase change
materials storage, (ii) a wide operating temperature range (iii) no heat leakage, and (iv) long-
term storage. The major drawback of this system is its increased complexity. As a result, new
integration strategies are being developed to account for these complexities [195].
Fig. 17. Schematic diagram of thermochemical energy storage system based on reversible
chemical reactions.
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Fig. 18. Classification of thermochemical energy storage systems.
Table 15: Promising materials for Thermochemical Energy Storage [196]
Thermochemical Solid Reactant Working Fluid Energy Storage Charging

Material Density (GJ/m3) Reaction
Temperature (̊C)
Epsomite Magnesium sulphate 7H2O 2.8 122

(MgSO4·7H2O) (MgSO4)
Ferrous carbonate Ferrous Oxide (FeO) Carbon Dioxide 2.6 180

(FeCO3) (CO2)
Calcium hydroxide Calcium oxide (CaO) H2O 1.9 479

Ca(OH)2
Ferrous Hydroxide Ferrous oxide H2O 2.2 150

Fe(OH)2 (FeO)
Calcium carbonate Calcium oxide (CaO) Carbon Dioxide 3.3 837

CaCO3 (CO2)
Calcium sulfate Calcium sulfate 2H2O 1.4 89

dihydrate CaSO4
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CaSO4·2H2O
2.2 Mechanical Energy Storage (MES) System
In the Mechanical Energy storage system, the energy is stored by transforming between
mechanical and electrical energy forms [24]. When the demand is low during off-peak hours,
the electrical energy consumed by the power source is converted and stored as mechanical
energy in the form of potential or kinetic energy. During peak hours, again, the mechanical
energy is transformed back into electrical power. As indicated in Fig. 19, MES systems are
essentially categorised into three different categories: Pumped hydro energy storage (PHES),
Gravity energy storage (GES), compressed air energy storage (CAES), and flywheel energy
storage (FES). Potential energy is stored in PHES, GES, and CAES systems, whereas
kinetic energy is stored in FES systems [11]. The MES systems key advantage is its
capability to quickly convert and release stored mechanical energy [5].
Fig. 19. Classification of mechanical energy storage systems.
2.2.1 Pumped Hydro Energy Storage (PHES) System
Pumped Hydro Energy Storage system is the most widely implemented MES system with a
huge energy capacity, long storage period and high efficiency [197]. A typical PHES system
(Fig. 20) consists of (i) two large reservoirs located at various elevations, (ii) a unit to pump
water from the lower reservoir to the higher reservoir, and (iii) a turbine to generate electricity
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as water flows downwards from the upper reservoir to the lower reservoir. During off-peak
hours (during the charging process, Fig. 21), the electrical energy from the power source is
turned into mechanical energy, which is then converted into potential energy by pumping and
storing water from lower reservoir to higher reservoir through pump. During peak hours
(when discharging, Fig. 21), the stored water from the upper reservoir is released back into
the lower reservoir, rotating the turbines and generating electricity through generators [198].
By transferring water between two reservoirs at different elevations, it stores and generates
energy in the form of potential energy. The volume of water stored in the reservoirs and the
difference in elevation between them determine the amount of energy stored [17].
Underground pumped hydro energy storage (UPHES) and Seawater PHES (SPHES) are
new technologies with similar working principles to conventional PHES systems, with the only
difference being the kind of lower reservoir. In the case of UPHES, abandoned quarries or
mines are used as lower reservoirs, however in the case of SPHES, the sea is used as the
lower reservoir which helps to save construction cost and time. These two technologies have
the potential to reduce the construction cost with minimal adverse impact on the environment
as compared to the conventional PHES. Another technology that is already in use in a
number of operating plants in Japan is variable speed PHES. It employs asynchronous
motor-generators, which allow for control of the rotational speed of the pump/turbine unit,
allowing for regulation of the amount of energy absorbed during the pumping cycle.
[199,200].
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Fig. 20. Schematic diagram of Pumped Hydro Energy Storage system. The potential energy is stored
and extracted by transferring water between two reservoirs located at different elevations. During the
charging cycle, excess electrical energy from the grid or renewable energy sources is transformed into
mechanical energy, which is then converted into potential energy by pumping and storing water from
the lower reservoir to the higher reservoir. The stored water from the higher reservoir is released back
into the lower reservoir during the discharging cycle, which drives the turbines and generates
electricity via generators.
The earliest PHES plants were erected in the Alpine regions of Switzerland, Austria, and
Italy in the 1890s. In initial PHES plants, separate pump impellers and turbine generators
were employed. In the 1950s, a new design was implemented that used a single reversible
pump-turbine unit. Since then this has become the preferred design for PHES plants [201].
The development of PHES was somewhat slow until the 1960s, but from the 1960s to the
late 1980s, a tremendous development was witnessed, owing mostly to the deployment of
nuclear power plants, the inertia of which was largely compensated for by the flexibility of
PHES. During the 1990s, global PHES development slowed dramatically, owing mostly to the
scarcity and saturation of suitable and cost-effective geographical locations, as well as a
slowing of nuclear development growth [199]. Since the year 2000, many PHES plants have
been erected across Europe, particularly in Germany and Austria. PHES were created to
improve the way major thermal and nuclear power plants dealt with substantially fluctuating
electricity demand at different times of the day. Initially, PHES plants were built to serve as a
system tool, supplying energy during peak demand and assisting baseload power plants in
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operating at high efficiencies during times of low demand. However, PHES plants have
recently been installed to function as an integrator for variable wind power generation [202].
On a global scale, the United States and Japan now have the highest installed capacities of
PHES. In India, the first PHES plant, Nagarjunasagar Pumped Storage Plant, was
operational between 1980 and 1985. Currently, the country has 11 active PHES plants with a
total installed capacity of 4804 MW [203]. A plant is being built in the Hatta region of United
Arab Emirates (UAE) with a water reservoir suitable for PHES uses. When completed in
2024, the project is expected to supply 2.06 TWh per year, assisting the UAE in meeting its
objective of depending on 25% renewable energy resources in their energy mix by 2030
[204]. A comprehensive review by Evans et al. [205], Vilanova et al. [206], Blakers et al. [207]
covered the technology, cost, environmental impacts, siting opportunities and market
prospects of PHES. A vast number of off-river pumped hydro sites have been located in most
regions of the world as they have low environmental impact and low water consumption. Ruiz
et al. [208], Hoffstaedt et al. [209] reviewed the state of the art of the components and
viability of low-head and seawater pumped hydro storage systems in terms of design, grid
integration, control, and modelling. Vasudevan et al. [210] provided a critical review of
different levels of control and energy management strategies needed for variable speed
PHES, which is emerging as a feasible alternative for PHES with existing infrastructure. One
limitation of PHES is that it requires suitable natural geological locations as well as an
adequate supply of water.
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Fig. 21. Working principle of pumped hydro energy storage system.
2.2.2 Gravity Energy Storage (GES) System
Due to the geological limitations and water requirements encountered with PHES, there has
been inclinations towards a new concept which depends on gravity and is called Gravity
Energy storage (GES) system [211]. It stores energy by using water to lift a piston or any
other object with the requisite mass, and then dropping the piston to push the water back
through hydroelectric generators when the power is required. This storage concept i.e. the
Gravity Power module was proposed by Gravity Power, LLC [212]. A sketch of this storage
technology is presented in Fig. 22. It is made up of a large piston suspended in a deep,
water-filled shaft and a return pipe connected to the powerhouse that permits the water to
flow. A pump, turbine, and motor/generator make up the powerhouse. During the charging
cycle, the off peak electricity is used to drive the motor/generator that spins the pump and
converts electrical energy into mechanical energy. By forcing water down the return pipe and
into the shaft, the pump transforms mechanical energy to kinetic flow energy, elevating the
piston. The piston is held in the same high position till the power is required. During the
discharging cycle, the energy is produced by the downward motion of the piston. When the
piston is dropped, high pressure is applied to the water flowing clockwise through the return
pipe. The kinetic energy of the flow is converted to mechanical energy by the turbine, which
spins the generator and produces energy [213,214]. This technology's energy storage
capacity varies with piston size and shaft height. The sizes under consideration range from
30-100 m piston diameter, 500-1000 m shaft depth, and a piston length that is exactly half
the shaft length. The purpose of gravity power is to provide power in the 40 MW to 1.6 GW
range [212].
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Fig. 22. Working Principle of Gravity Power Module. Surplus energy is stored during the
charging cycle by pumping water to elevate the piston, and excess energy is released during
the discharging cycle by pushing water through the turbine, which spins the generator and
provides required energy.
Several researchers have investigated various features of the GES system. Berrada et al.
[215] proposed GES system dynamic modelling. The proposed model could estimate
container size as well as piston motion during the storage system's charging and discharging
cycles. The same author also conducted an economic analysis to calculate the system's
levelized cost of energy. They demonstrated that the GES system outperforms alternative
storage technologies such as pumped hydro energy storage (PHES) and compressed air
energy storage in terms of operational and economic performance (CAES) [216]. Berrada
and Loudiyi [217] evaluated the acceptable materials that can be applied to the various
components of the storage system. Botha and Kamper [214] reviewed current storage
strategies based on the gravitational potential energy principle. Botha et al. [218] investigated
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a novel gravity energy storage system which utilises the inherent ropeless operation of linear
electric machines to vertically move multiple solid masses to store and discharge energy.
When employed in applications with high power and a high number of annual cycles, the
proposed storage technology proved to be cost-competitive.
2.2.3 Compressed Air Energy Storage (CAES) System
CAES is an energy storage technology that stores energy by compressing the air. The
amount of stored energy depends on the volume of the storage container as well as the
pressure and temperature at which the air is stored [219]. The reliance of PHES on specific
geological formations, as well as the associated environmental concerns make new
development difficult. Compressed air energy storage (CAES) was developed as an
alternative to PHES and has proven to be a promising method of energy storage due to its
high reliability, economic feasibility, and low environmental impacts [220]. A typical CAES
system consists of the following five major components as illustrated in Fig. 23: (i) a motor
that drives a compressor, (ii) a multi-stage compressor that compresses the air, (iii) a
container or cavity for storing compressed air, which can be underground caverns or porous
reservoirs, (iv) a turbine train that includes both high and low-pressure turbines, and (v) a
generator which returns electrical energy to the grid. During off-peak hours, surplus electricity
is used to drive the motor, generating mechanical energy and driving the multi-stage
compressor. The compressor raises atmospheric air pressure, which is then stored in the
underground cavern. During peak hours, the compressed air stored in the cavern is used to
drive the pressure turbines, which convert compressed air energy into mechanical energy,
which is then used to drive a generator that generates electricity [221].
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Fig. 23. Schematic diagram of Compressed Air Energy Storage (CAES) system. During the
charging cycle, excess electrical energy from the grid is used to power the motor, which
generates mechanical energy and drives the multi-stage compressor. The compressed
atmospheric air is stored in the underground cavern. The stored compressed air in the cavern
is then used to drive the pressure turbines, which in turn drive the generator to produce
required electricity during the discharging cycle.
Depending on the procedure adapted to deal with heat generated after compressing the
air, CAES technologies are separated into Diabatic (D-CAES), Adiabatic (A-CAES),
Isothermal (I-CAES) and Liquid Air Energy Storage (LAES). In the diabatic CAES (D-CAES)
system, the air is compressed and heated as it passes through the compressor. The heat is
removed with the help of an air cooler, and the compressed air is then stored in the cavern.
During the discharging cycle, the cooled compressed air is heated in the combustion
chamber. The heated air is used to drive the pressure turbine, which drives the generator to
produce electricity [222]. The schematic diagram of D-CAES is demonstrated in Fig. 24.
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Fig. 24. Schematic diagram of Diabatic Compressed Air Energy Storage (D-CAES) system.
During the charging cycle, excess electricity from the grid is used to power the motor, which
generates mechanical energy and drives the multi-stage compressor. After removing the heat
with the help of an air cooler, the compressed atmospheric air is stored in the underground
cavern. The stored cooled compressed air in the cavern is then heated in a combustion
chamber and expanded to release the energy as needed during the discharging cycle.
An A‐CAES makes use of the heat released during the compression stage by storing it in
a separate thermal energy storage system (TES). The stored heat energy is used to raise the
temperature of compressed air before it enters the turbine, increasing system efficiency
significantly [223]. Figure 25 shows the schematic diagram of A-CAES..
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Fig. 25. Schematic diagram of Adiabatic Compressed Air Energy Storage (A-CAES). During
the charging cycle, excess electrical energy from the grid is used to power the motor, which
generates mechanical energy and drives the multi-stage compressor. The compressed
atmospheric air is stored in the underground cavern, while the heat released during the
compression stage is stored in a heat storage. During the discharging cycle, the stored
compressed air is heated by utilising the surplus heat and then expanded to release the
required energy.
An I‐CAES is an emerging energy storage system that does not require multiple stages
of compression, cooling, heating, and expansion of air, compared to conventional CAES. It
also does not use compressors and turbines like traditional CAES; instead, liquid piston
machinery is utilised to compress the air, increasing the compression efficiency by up to
95%. In I-CAES, the entire charging and discharging cycle occurs at a constant or near-
constant temperature, which lowers the losses caused due to temperature difference [224].
For lower power requirements, isothermal and adiabatic storage systems are typically
employed. Diabatic storage systems are commercially used to enable flexible energy storage
and regeneration. Liquid air energy storage system is often considered a type of TES system
and referred to as cryogenic energy storage. In LAES, the air is stored in the liquefied state in
special cryogenic containers, unlike conventional CAES where the air is stored in a
compressed gaseous state in underground caverns. The schematic diagram of LAES is
demonstrated in Fig. 26. During the charging cycle, excess electrical energy is used to
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liquefy the air or nitrogen. Later this liquefied air is stored in an insulated tank. While during
the discharging cycle, this liquefied air or nitrogen from the storage tank is reheated and
expanded to generate a high-pressure stream of gas which drives the turbine and generator
to produce electricity [225,226]. The key limitations of the CAES system are the need for a
favourable geography, fossil fuel for combustion, and emission of pollutants.
CAES technology is not widespread yet, since there are just 11 operational CAES
projects in the world, with a total installed capacity of 406.690 MW. The Kraftwerk Huntorf
plant, Germany’s first commercial D-CAES plant, was installed on January 12, 1978, with a
capacity of 290 MW to provide peaking power service for the utility Nordwestdeutsche
Kraftwerke AG [227]. The second plant, with a capacity of 110 MW, was built at McIntosh,
Alabama in 1991. This plant was integrated with recuperators that use heat from the exhaust.
No commercial CAES facilities were built in the two decades succeeding McIntosh [228].
Later, in 2012, the world's third CAES project, a 2MW near I-CAES facility, was erected in
Gaines, Texas [229]. A 1.5 MW SustainX I-CAES facility was installed in Seabrook, New
Hampshire. It stored the compressed air in pressure vessels at constant temperature coupled
with staged hydraulic compression and expansion to improve the efficiency of the system
[230]. The first commercial A-CAES system, the Hydrostor, was installed in Goderich, Ontario
in 2019 providing service to the Ontario Grid [231]. Other plants with capacities less than 1
MW have been installed in Canada, Switzerland, China, United Kingdom, and the United
States [232]. Venkataramani et al. [233] provided a detailed review on various aspects of a
CAES system including thermodynamic analysis, modelling and simulation analysis,
experimental investigation, various control strategies, a few case studies, and an economic
evaluation of the role of CAES system’s role in smart grid. Saidur et al. [234], Budt et al.
[235], Zhou et al. [236], Olabi et al. [237] in their review, conducted a thorough evaluation of
the components, operational parameters, selection criteria, benefits, drawbacks, economic
impacts, and current research status for various CAES Systems. Gouda et al. [238] reviewed
the current state-of-the-art in Liquid Piston (LP) technology for CAES. By surveying Liquid
Piston projects all over the world, different strategies for improving heat transmission and
flow patterns are presented.
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Fig. 26. Schematic diagram of Liquid Air Energy Storage (LAES). During the charging cycle,
excess electricity from the grid is used to power the motor which generates mechanical
energy and drives the multi-stage compressor. The compressed atmospheric air is stored in
liquefied form at low temperature in the liquid air storage. The stored liquified compressed air
is then expanded into gaseous form at high temperature during the discharging cycle to
extract the required energy.
2.2.4 Flywheel Energy Storage (FES) System
The Flywheel energy storage system is a mechanical energy storage device that stores the
energy in the form of mechanical energy by utilising the kinetic energy, i.e., the rotational
energy of a massive rotating cylinder [11]. A flywheel, magnetic bearings, an electrical
motor/generator, a power conditioning unit, and a vacuum chamber are the five essential
components of a modern flywheel system (see in Fig. 27). The integrated reversible electrical
machine acts as a motor during the charging cycle. It draws power from the grid to rotate the
flywheel system at high speeds and stores kinetic energy. While in discharging mode, with
the rotor decelerating, the reversible machine operates as a generator, converting the kinetic
energy stored in the flywheel back to electrical energy [239]. Thus, in a FES system,
electricity is used to accelerate or decelerate the flywheel, and the stored kinetic energy is
transferred to or from the flywheel via an integrated motor/generator [24]. FES are generally
classified into two groups: (a) low-speed FES, where the flywheel is made up of steel and
rotates at less than 6x103 rpm; (b) high-speed FES, which uses advanced composite
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materials for the flywheel and usually rotates at speeds of up to 105. Table 16 shows the
benefits and drawbacks of the FES system.
The term ‘flywheel’ first appeared in print in 1784, at the start of the industrial revolution.
Flywheels were mostly employed on steam engine boats and trains during those periods, as
well as as energy accumulators in factories [240]. Later, the drop in price of cast iron and
cast steel led to the production of flywheels in one complete piece. Very large flywheels with
curved spokes were also built in the middle of the 19th century. Flywheels were initially
employed for transportation in a Gyrobus manufactured in Switzerland in the 1950s. These
flywheels weighed around 1500 kg and measured 1.6 metres in diameter [241]. FESS were
proposed in the 1960s and 1970s for electric vehicles, stationary power back up, and space
missions. Olabi et al. [242] provided a complete account of the latest technologies, the
materials used in the production of FESS, and an overview of applications in various sectors.
Zhang et al. [243] reviewed the control strategies as well as different power converters and
machine types used in FESS. The reviews of the advances, components, characteristics,
applications and prospective future directions of FESS are described in [244], [245] and
[246]. Table 17 summarises some of the world’s major FESS. Despite substantial
developments in their early stages, commercialization of flywheels has been minimal.
However, thanks to the recent advancements in materials, magnetic bearings and the
introduction of high speed electric machines, FESS have become a solid alternative for
energy storage applications [247].
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Fig. 27. Schematic diagram of Flywheel Energy Storage (FES). During the charging cycle,
excess electrical energy from the grid is used to rotate the flywheel system using a reversible
electrical machine that functions as a motor. The rotational energy of a rotating cylinder is
stored in the form of mechanical energy. In the discharging cycle, the reversible machine acts
as a generator, converting the kinetic energy stored in the flywheel back to electrical energy.
Table 16. Advantages and disadvantages of the flywheel [232,242,248].
Advantages Disadvantages
High energy and power density High self-discharge
High cycle life Low storage capacity
Very fast response High capital cost
High cycle efficiency (90–95%)
Very short discharge duration
Table 17: Summary of some major FES systems around the world.
Year Project/Company Location Storage Power Application References

Capacity (MWh)
(MW)
1987 Max Planck Garching, 387 Onsite power [247]

Institute – FESS Bavaria,
Germany
2001 New Energy Japan 10 [249]

Development
Organization
(NEDO)
2005 PowerStore Flores Island, 0.5 Frequency [250]

Portugal regulation, voltage
support
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2006 ABB Ltd Graciosa 0.5 Frequency [250]
island regulation
2006 Utsira project North Sea, 0.2 0.005 Short-term storage [251]
outside
Haugesund
2008 Railway Technical Japan 0.3 0.1 Stabilize power [252]

Research Institute suppliesX
(RTRI)
2015 Beacon Power Massachusett 20 0.1 Grid-scale [253]

Corporation s, USA frequency
regulation and
power backup for
telecommunication
Piller flywheel Dresden, 5 UPS solution and [254]

technology Germany load levelling in
local grid
Flores power Island of 0.35 0.005 Improving [255]

system Flores - system frequency
Azores stability
2.3. Chemical Energy Storage (CES) System
CES systems are best suited for long-term storage of chemical energy. The energy is stored
in the chemical bonds between the materials’ atoms and molecules, and the stored chemical
energy is released during chemical reactions. During energy release, the composition of the
materials changes as the original chemical bonds in the material break and new ones are
formed [256]. Chemical fuels currently dominate both the generation of electricity and the
transportation industry internationally. Coal, gasoline, diesel fuel, natural gas, liquefied
petroleum gas (LPG), propane, butane, ethanol and hydrogen are all common chemical
fuels. These chemicals are first converted into mechanical energy and subsequently into
electrical energy which is utilised to generate electricity [257]. CES systems mainly include
hydrogen, synthetic natural gas and solar fuel storage systems [258].
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2.3.1 Hydrogen Energy Storage System
Hydrogen is regarded as an ideal energy carrier as it is clean, and a carbon-free or zero-

emission chemical energy carrier [256,257]. It can be produced from water via electrolysis or
directly from sunlight using photocatalytic water splitting. A typical hydrogen energy system
comprises three major components as shown in Fig. 28. These are (i) a hydrogen generation
unit such as an electrolyzer to convert the electrical energy input into hydrogen, (ii) a
hydrogen storage system and (iii) a hydrogen energy conversion unit, such as a fuel cell (FC)
or regenerative fuel cell, to convert the stored chemical energy in the hydrogen back to
electrical energy.
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.
When there is excess power during the charging process, hydrogen is produced from
water via electrolysis and stored in a storage tank. During peak hours, when power
availability is limited (during discharging cycle), electricity is generated from stored hydrogen
using fuel cells. An electrolyzer uses electrolysis to break down water into hydrogen and
oxygen. The oxygen is then released into the atmosphere, while the hydrogen is stored in the
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storage tank [259]. Furthermore, a fuel cell has four main parts: an anode, a cathode, an
electrolyte, and an external circuit. At the anode, hydrogen is oxidised into protons (positively
charged hydrogen ions) and electrons to power the fuel cell. Positively charged hydrogen
ions from the anode are collected at the oxygen electrode flowing through the electrolyte. The
reaction of oxygen, hydrogen ions, and electrons at the cathode produces water and heat.
During this process, the electrons flow from anode to cathode via an external circuit, resulting
in current flow and, ultimately, electricity production. The hydrogen fuel cells are classified
into six types [24]. The characteristics of different types of FCs is listed in Table 18.
Abe et al. [260], Yue et al. [261], Tarhan and Çil [262], Hassan et al. [263], Grimaldo
et al. [264] briefly reviewed the uses, limitations, current state of solid-state hydrogen storage
in metal hydrides, as well as recent novel discoveries toward a hydrogen economy. The
review of the developments in materials for hydrogen energy storage and techniques for
safely storing hydrogen fuel for a longer period of time is presented in references [265] and
[266]. Thiyagarajan et al. [267] reviewed the mechanisms involved in underground hydrogen
storage systems along with monitoring techniques and optimization of injection-withdrawal
techniques. Various challenges such as microbial growth, well integrity, and geochemical
reactions encountered while storing in the subsurface are also briefly discussed.
Recent advances in Mg–Li–Al and Mg–Na–Al systems used for solid-state hydrogen
storage have also been reviewed by researchers [268,269]. Since 2000, real-world projects
and demonstrations of hydrogen energy storage have begun to demonstrate its merit beyond
the 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 energy 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 collaborated to open the Markham Energy
Storage Facility, a 2.5 MW - first multi-megawatt power-to-gas facility in Ontario, Canada.
This facility uses renewably-sourced hydrogen and currently provides grid regulation 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 renewable
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 utility provider, is planning a 110 kW wind-to-hydrogen project in
collaboration 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
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could be converted back to the electricity 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 [270,271]. Following are the various
fuel cells that have been developed:
● Proton exchange membrane fuel cell (PEMFC)
● Alkaline fuel cell (AFC)
● Phosphoric acid fuel cell (PAFC)
● Molten carbonate fuel cell (MCFC)
● Solid oxide fuel cell (SOFC)
● Direct methanol fuel cell (DMFC)
Table 18: Characteristics of different types of FCs [272]
Fuel Cell Fuel Temperature (̊C) Efficiency (%) Application
PEMFC Pure H2 60-140 55 Backup Power

AFC Pure H2 150-200 60 Spacecrafts, Military Applications
PAFC Pure H2 150-200 >40 Distributed Generation

MCFC H2. CO, CH4 600-700 45 Power utility storage
SOFC H2. CO, CH4 200-700 40 Power utility storage
DMFC CH3OH 30-80 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 United States). 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.
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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, United
States is the world’s only coal-to-synthetic natural gas (SNG) gasification plant, operating
since 1984 and producing approximately 4.1 million m3/day of SNG from lignite coal [274].
Table 19 summarises some of the largest plants ever built based on SNG technology around
the world.
Fig. 29. General procedures for producing Synthetic Natural Gas from coal and solid dry
biomass.
Table 19: A list of major plants built using SNG technology around the world.
[275,276,277,278,279]
Year Project Location Storage Fuel Status

Capacity
(MW)
2009 Biomass CHP Plant Güssing, Austria 1 Wood Chips Demonstration
2010 Gaya Wood, straw Demonstration
2011 Dong Pyroneer Plant Denmark 6 Wood mass Demonstration
2012 Waste-to-energy Lahti, Finland 160 Shredded textiles, Industrial Scale

gasifier wood, paper, card and
plastics
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2013 GoBiGas Sweden 20 Forestry feedstock, Industrial Scale
which consists of
pulpwood and forest
residues
2013 Birmingham Bio Tyseley, 10.3 Woodwaste Commercial

Power Plant Birmingham, UK
2016 WoodRoll Sweden 6 Forestry feedstock, Commercial

Test plant waste from industry,
agricultural waste
2.3.3 Solar Fuels
The goal of solar energy storage is to harvest the sun’s abundant energy, 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 . Scientists are currently exploring three main
approaches to producing solar fuel production: natural photosynthesis, artificial
photosynthesis, and thermochemical production [280].
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Fig. 30. Artificial photosynthesis: Pathway from sunlight to fuels.
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 carbohydrates. These carbohydrates function as fuels, which the plant uses
for growth and maintenance. Water and CO2 are the raw materials required for natural
photosynthesis [281]. The term “Artificial photosynthesis”, also known as the 'artificial leaf,'
refers to a process that explicitly 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 products are Solar fuels (as shown in Fig.
30). The thermochemical method use sunlight to heat materials to extremely high
temperatures, where they react 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 commercial scale. A review by Mustafa et al.
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[283] and Ezugwu et al. [284] summarises several old and modern thermal technologies
utilised in CO2 conversion, including thorough information on their working principle, types,
various methods, developments, conversion rates, products created, catalysts and operating
parameters. Xiao et al. [285] reviewed recent progress, accomplishments, and working
principles of three typical hybrid systems including photovoltaic-driven biological inorganic
system, microbial photo electrochemical system, and photosensitized biological inorganic
system for the production of organic fuels and chemicals from CO2. A comprehensive review
by Gong et al. [286] highlights 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 activity. The recent progress in
synthesis and regulation of few-layer carbon 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 on solar fuels have begun
in the United States, Australia and South Korea, and several renewable energy research
centres have been established in India, China and Japan. Table 20 describes the
programmes undertaken globally for research and innovation in solar fuels.
Table 20: Programmes undertaken globally for Research and innovation in solar fuels
[281,288]
Country Research Programmes
The United States 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,
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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 CO 2 hydrogenation to
produce methanol at the end.
2.4 Electrochemical Energy Storage (EcES) System
Electrochemical energy storage 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] (See. 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 electronic devices.
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Fig. 31. The fundamental operational procedures in an Electrochemical Energy Storage
(EcES) system.
Fig. 32. Classification of Electrochemical Energy Storage Systems
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2.4.1. Battery Energy Storage (BES) System
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.
Batteries are electrochemical devices that convert chemical energy into electrical energy.
They are composed of a number of cells, each of which has three basic components: two
electrodes, namely an anode and a cathode, and an electrolyte, as illustrated in Fig. 33.
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
Lead-acid 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%
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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].
Overall Chemical Reaction: Pb + 𝑃𝑃𝑃2+ 2𝑃2 𝑃𝑃4 ⇔ 2𝑃𝑃𝑃𝑃4 + 2𝑃2 𝑃
Fig. 34. Principal components of a Lead-Acid battery. It is made up of an anode made of

metallic sponge lead, a cathode made of lead dioxide and an electrolyte made of 37%
sulphuric acid and 63% water.
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 lead-acid
battery in 1859, consisting of nine parallel-connected cells [290]. Later, in 1880, Camille
Alphonse Faure advocated 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 acid 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
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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 efficient 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 valve-regulated lead
acid (VRLA) battery was developed and the commercial units were manufactured in German
company Sonnenschein in the late 1960s and by Gates Corporation in the United States in
the early 1970s [292, 293, 294]. Today, LA batteries are widely employed in a variety of
projects worldwide. Several industrial and academic research initiatives to increase the
performance of LA batteries have been ongoing for several decades. Zhang et al. [295]
reviewed the main shortcomings of current research status of LA batteries LABs 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 lead-acid batteries with respect to substrate material, designs, fabrication and sealing
techniques. Researchers have also reviewed applications of different forms of elemental
carbon in lead-acid batteries, such as in [297], [298] and [299]. Carbon materials when used
as an additive to the negative active mass can improve the cycle life and charge acceptance
of batteries. Table 21 summarises various LA Battery storage systems employed across the
world, whereas Table 22 discusses the benefits and drawbacks of Lead-acid batteries.
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Table 21: Overview of LA battery energy storage systems installed worldwide
Location Year Service area Reference

Indonesia 2013 Small village in west Indonesia [300]
Turkey 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]
Table 22: Benefits and drawbacks of LA battery energy storage systems [308,309]
Benefits Drawbacks
Low capital cost Limited life cycle
Good performance at low and high temperatures. Slow charging
Low maintenance High self-discharge rate
High specific power Not environmentally friendly
Available in large quantities and in a variety of sizes and designs Limited energy density
2.4.1.2 Lithium-ion (Li-ion) batteries
Currently, Li‐ion batteries are profoundly used in electronics and transportation industries,
particularly in power grid applications and plug-in hybrid electric vehicles, owing to their
higher charge density than other rechargeable batteries [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 migrate 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 between the carbon layers. During the discharge process, this process is reversed
[23]. Fig. 35 depicts the working principle of Li-ion batteries.
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Overall Chemical Reaction: 𝑃𝑃𝑃 𝑃+ 𝑃𝑃1−𝑃 𝑃𝑃2 ⇔ 𝑃𝑃𝑃𝑃2+ C
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.
In the 1970s, Stanley Whittingham, an English chemist working for Exxonmobil, proposed
the concept of Li-ion batteries. He discovered the concept of intercalation electrodes, which
use titanium disulfide as cathode and lithium metal as the anode [311]. In 1980, John B.
Goodenough experimented with lithium cobalt oxide as the cathode instead of titanium
disulfide, which doubled the battery’s energy potential [312]. Five years later, in 1985,
Yoshino et al. [313] of Japan developed a new cell design using petroleum coke, a
carbonaceous material. This improved the performance of Li-ion batteries significantly. In
1991, Sony Energytec Inc. began to produce commercial lithium-ion cells under the
leadership of Yoshio Nishi [314, 315, 316]. Soon after 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 United States, Asia, and Europe. While Li-ion batteries have been the dominant choice,
numerous emerging applications demand for high energy density, higher capacity, better
safety, improved performance and lower costs. Gao et al. [317] reviewed state-of-the-art
solutions for improving 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-
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temperature Li-ion batteries are presented in [318] and [319]. The review articles
[320,321,322] 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 electrochemical properties. Table 23 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 [323]. In Table 24, the advantages and disadvantages
of Li-ion batteries are presented.
Table 23: Summary of Li-ion battery energy storage technologies battery energy systems
around the world.
Project Location Storage Status Reference

Capacity
(MW)
AES Alamitos Long Beach, 100 Contracted [324]

Energy Storage California, United
Array States
Magdeberg-SK Magdeberg, Saxony- 30 Announced in 2014 [325]

Innovation – BESS Anhalt, Germany
Grand Ridge Marseilles, Illinois, 31.5 Commissioned in 2015 [326]

Energy Storage United States
Nishi-Sendai Sendai, Miyagi 40 Operational since 2015 [327]

Substation - Prefecture, Japan
Tohoku
Electric/Toshiba
Kingfisher Project Roxby Downs, South 100 Announced in 2016 [328]
Australia, Australia
Gyeongsan Korea, South 49 Operational since 2016 [329]

Substation
Minami-Soma Minamisoma, 40 Operational since 2016 [330]

Substation - Fukushima
Tohoku Prefecture, Japan
Electric/Toshiba
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Table 24: Advantage and disadvantages of Li-ion battery energy storage systems
[308,309,331]
Light weight Higher production cost
High energy density Requires special charging circuit
High efficiency Sensitive to high temperatures
Longer life-cycle Involves risk of bursting
High specific power Complete discharge damages the battery
2.4.1.3 Nickel Cadmium (Ni-Cd) batteries
Nickel cadmium 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 nickel-cadmium batteries [12]. In 1946, the first Ni-Cd batteries
were manufactured in the United States. The batteries produced at that time were "pocket
type”, with nickel and cadmium active materials [332]. Around the middle of the twentieth
century, sintered plate nickel-cadmium 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 summarises the evolution of the Ni-Cd BES system.
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Overall Chemical Reaction: Cd + 2NiOOH + 2𝑃2 𝑃 ⇔ Cd(𝑃𝑃)2+ 2Ni(𝑃𝑃)2
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.
The positive electrode of the Ni-Cd battery is spongy nickel oxyhydroxide, the
negative electrode is metallic cadmium, and the electrolyte is potassium hydroxide (as shown
in Fig. 36). Both electrodes are separated by a nylon divider, which prevents direct charge
transfer between the electrodes [289]. During the discharge cycle, nickel oxyhydroxide at the
positive plate reacts with water to form nickel hydroxide, whereas cadmium 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 lead-acid batteries. The advantages and
disadvantages of Ni-Cd batteries are listed in Table 26 [198,334].
Table 25: Advances of Ni-Cd BES system
Sr No. Year Advancement Reference
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1. 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
2. 1908 Tubular-plate batteries [335,336]

Developed-
● 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
3. 1940 Sintered-plate Ni–Cd Batteries [336]

● Thinner than pocket-plate batteries
● Exhibit lower internal resistance
● Superior high rate and low-temperature
performance
● Suitable for high-power applications
Fibre-structured nickel–cadmium cells

4. 1983 ● Two negative electrodes are arranged back-to-back [337]
with a porous fibre-nickel structure between two
positive plates
● Use mechanically impregnated fibre electrodes for
both negative and positive plates
Super Ni–Cd cells

5. 1989 ● Loading of positive and negative active materials into [338]
the porous sintered nickel structure is carried out
electrochemically,
● Inert polymer-impregnated Zircar cloth replaces the
polyamide separator
● Extended life
Sealed Ni–Cd cells

6. 1991 ● Able to withstand extreme environmental conditions [339]
● No maintenance requirements
● Low cost
● Higher discharge
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7. 1993 Ultra-low-maintenance Ni–Cd batteries [340]
● 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.
8. 2000s Jelly – roll nickel – cadmium battery [341]

● 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: Advantages and Disadvantages of Ni–Cd Batteries [308,309]

Long shelf life and can be stored in a discharged state Relatively low specific energy compared to systems
Good low-temperature performance High self-discharge rates

Economical: Ni–Cd has the lowest cost per cycle Cadmium is a toxic metal, thus cannot be disposed in
landfills
Ultra-fast-charging with minimal stress

Good load and low temperature performance
2.4.1.4 Sodium Sulphur (NaS) batteries
NaS batteries are typically cylindrical electrochemical cells with molten sulphur at the positive
electrode and molten sodium at the negative electrode separated by a solid beta alumina
electrolyte (as shown in Fig. 37).
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Overall Chemical Reaction: 2Na + xS ⇔ 𝑃𝑃2 𝑃𝑃
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.
In NaS Batteries, molten sodium at the core donates electrons to the external circuit,
causing sodium ions to migrate through the electrolyte 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 order to keep the sodium and sulphur in a molten
state and ensure adequate conductivity in the electrolyte, all the components are housed
inside a thermally insulated enclosure maintained at a temperature above 270°C [342,343].
NaS batteries have three times the higher energy density than LA batteries. Apart from that,
they also have a longer life span and require less maintenance. Sodium sulphur batteries
were first developed by Ford Motor Company in the 1960s, but modern sodium sulphur
technology was developed and commercialised in Japan by the Tokyo Electric Power and
NGK insulators [344]. Table 27 summarises major Sodium sulphur BESS demonstration
projects and plants. Since this technology is complex, small-scale NaS batteries are less
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economical [345]. The advantages and disadvantages of NaS batteries are listed in Table
28.
Table 27 : Summary of major demonstration projects and plants on Sodium sulphur BES
[2,250,346,347,348,349]
Year Location/Company Power (MW) Storage Capacity Type/Application

(MWh)
1992 Kawasaki Electric 0.05 4 Prototype

Energy
Storage Test Facilities,
Japan
1995 Tokyo Electric Power 0.05 4 Load levelling

Co, Tokyo,
Japan
1997 Tsunashima Substation 6 48 Load levelling
1998 Kinugawa Power Station 0.193 0.772 Load leveling and

Emergency Power
Supply
1999 Ohito Substation 6 48 Load Leveling
2003 Shinagawa Substation 2 14.4 Load Leveling
2006 Long Island Bus’s BES 1 72 Refueling the fixed

System, New York, US route vehicles
2008 Xcel Energy’s wind-to- 1 Peak shaving,

battery (W2B) storage frequency regulation,
project, Minnesota wind smoothing and
wind leveling
2017 Graciosa Island, 3 18 Wind & solar power

Younicos, Germany EES for islands
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2019 Abu Dhabi Island, UAE 108 648 Load Leveling
Table 28: Advantages and Disadvantages of NaS Batteries [308,309,350]
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
2.4.1.5 Sodium ion (Na-ion) batteries
Among the batteries, lithium‐ ion batteries have proven to be popular in numerous areas of
energy storage systems. Since their first commercialization in 1991 by Sony in Energytec Inc,
this technology has undergone extensive research and development. 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 lithium-ion
battery in early 1980s. However, after the commercialization of Li-ion batteries in 1991,
research interest in Na-ion batteries began to wane. However, in the early 2010s,
researchers became interested in Na-ion, owing to the increasing demand and cost of
lithium-ion battery raw materials [351]. Because sodium is abundant and cheap, sodium ion
battery technology has the potential to overcome the limitations of lithium ion batteries and
provide a low-cost alternative that is less vulnerable to raw material supply risks [352,353].
A typical sodium-ion battery consists of an anode, a cathode, an electrolyte (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].
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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.
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]. Also similar to Li-ion batteries, aqueous sodium-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 electronic devices and electrification of transportation, the
demand for more advanced battery storage systems to meet the high energy storage
requirements has increased. Because of their higher specific capacity and energy density
when compared to conventional batteries, metal-air batteries have emerged as promising
candidates for future battery requirements [358,359]. Metal-air battery research began in the
1960’s and early 1970’s for a variety of applications [360]. However, these battery systems
have gained impressive progress over the last few years.
Metal-air batteries differ from conventional batteries in that they are connected to the
atmosphere and run on oxygen. Unlike conventional batteries, which have both anode and
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cathode within the battery case, a metal-air battery has a solid anode within the case (like a
battery), and the cathode fuel is brought into the cell from the outer atmosphere [361]. The
main internal components of a metal-air battery are oxygen, a metal anode, an air cathode, a
separator, and an electrolyte as shown in Fig. 39. The metal anodes electrochemically react
with oxygen gas from the atmospheric air. Based on the nature of the anode, the electrolyte
is either an alkaline aqueous solution such as potassium hydroxide, 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
on the anode changes into ions, while the oxygen on the cathode transforms into hydroxide
ions. Electrons are produced during the transition of the metal into metallic ions, and the
metallic ions then dissolve into the electrolyte. During the discharging cycle, atmospheric
oxygen combines with the metallic ion to form metal hydroxide, which activates the
electrolysis process and generates current [362].
Fig. 39. Principal components and working of a Metal-air battery. It is made up of a metal
anode, an air cathode, a separator, and an electrolyte. During 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 generates current. During the
charging cycle, the metal on the anode converts to ions, and the oxygen on the cathode
converts to hydroxide ions.
The chemical equations of reactions taking place in metal-air battery with a metal
anode M are as follows:
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1
Cathode: 2CO2 + H2O + 2e- ⇔ 2OH-
𝑛 𝑛
Anode: M + nOH- ⇔ MO2 + 2 H2O + ne-
𝑛 𝑛
Overall Chemical Reaction: M + O2 ⇔ MO
4 2
The oxygen gas introduced into the battery via an air cathode is an unlimited source.
As a result, despite the fact that oxygen is an unlimited cathode reactant, the capacity of
metal-air batteries is limited by the metal anode. Because each metal has its own unique
properties, each metal anode will produce a voltage with the cathode, and each metal will
contain a specific amount of energy [361]. Lithium, aluminium, magnesium, zinc, potassium,
sodium, and iron are all promising metal anode candidates. Lithium and sodium metal
anodes are used with non-aqueous electrolyte while magnesium, aluminium, iron and zinc
are compatible with aqueous electrolyte. In general, a metal-air battery provides the highest
energy density of any battery system [363]. Table 29 summarises the characteristics of
different metal-air batteries. The primary benefit of a metal-air battery is its very high
theoretical specific energy. Some disadvantages of the systems include their strong
dependency on environmental conditions, and the aqueous cells may occasionally leak
hydrogen gas due to anode corrosion.
Table 29: Characteristics of some metal-air batteries

[362,364,365,366,367,368,369,370,371]
Battery Type Practical Theoretical Actual Specific Actual Energy

Operating Specific energy energy density(Wh/kg)
voltage (V) (Wh/kg) (Wh/kg)
Aluminium-air 1.35 8140 350 350
Lithium-air 2.7-2.8 11400 150-6000 30-1000
Magnesium-air 2.9 6800 700 200
Zinc-air 1.65 1353 400 1300
Iron-air 1.28 1000 75 50-75
Sodium-air 2.27 - - 1600
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2.4.1.7 Solid-state batteries
The advancements of portable intelligent devices and electric vehicles have raised the
energy density and safety requirements for rechargeable secondary batteries. For the past
30 years, conventional lithium-ion batteries have received unprecedented levels of research
and industrial attention and have been used to power portable electrical devices. However,
commercial LIBs 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 batteries. Solid-state batteries 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 solid-state battery
(SSB) one of the best options for next generation batteries [373,374]. Solid electrolytes were
first discovered in the 19th century, but the developments of electric vehicles in the late 20th
and early 21st century have caused renewed interest in solid-state battery technologies.
Several 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 deployment in the first half of the 21st century [375].
An all-solid-state battery is basically a type of battery that uses a solid electrolyte

rather than a liquid electrolyte, as shown in Fig. 40. The cell chemistry of an all-solid-state
battery is similar to that of liquid electrolyte battery. The main component of all-solid-state
batteries is a solid electrolyte, which can be ceramic, glass, polymer or a mixture [376].
Table 30 summarises some anode, cathode, and electrolyte used in solid-state batteries
along with their optimum conductivity values.
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Fig. 40. Schematic diagram of conventional liquid battery and all-solid-state battery. An all-
solid state battery uses a solid electrolyte rather than a liquid electrolyte. However the cell
chemistry of an all-solid state battery is similar to that of liquid electrolyte battery.
Table 30: Summary of some anode, cathode, and electrolytes used in solid-state batteries
with their optimum conductivity values [377,378,379,380,381]
Anode Cathode Electrolyte Conductivity
Lithium Metal Carbon composite Li doped polyacrylonitrile (PAN) solid

polymer electrolyte
Potassium Carbon paper Polyethylene oxide (PEO)/KBrO3 7.74 * 10-8 S cm-1

doped at 30 ̊C
with iodine
Graphite based Lithium cobalt Polystyrene doped with varying 9.78 * 10-5 S cm-1
anode oxide (LiCoO2) quantities of Aluminium oxide (Al2O3) for 10 wt% Al2O3
at room
temperature
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Silver Graphite coupled (Ag2O-P2O5-LiCl) glass ceramic 2.88 * 10-2 S cm-1
with composites containing for 25 wt% Al2O3
Iodine silver components
Lithium Lithium Tri-ethyl sulfonium bisimide, lithium 10 mS cm-1 at

TFSI, polyethylene oxide and 45 ̊C
tetrahydrofuran
About 20 companies worldwide succeeded in prototype manufacturing of solid-state

batteries. Since solid systems do not require any cooling system, they weigh less and require
less space than lithium-ion batteries for powering electric automobiles. Despite these several
advantages, commercialization of solid-state batteries remains a challenge due to the
underlying material and cell level issues that need to be overcome [382]. Table 31 lists
advantages and disadvantages of all solid-state lithium ion batteries.
Table 31: Advantages and disadvantages of all solid-state lithium ion batteries.
High thermal stability High production cost
High ionic conductivity over a broad range of Growth of lithium dendrites in all-solid-state lithium-
temperatures 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
2.4.2. Flow Battery energy storage (FBES) system
Flow batteries consume two electrolytes that are stored in separate external tanks and there
is a microporous membrane that separates both the electrolytes (as shown in Fig. 41) but
allows only selected ions to pass through it, producing current [219]. Flow batteries are
classified into two types (as illustrated in Fig. 42): Reduction‐oxidation (redox) flow battery
and Hybrid flow battery. In redox Flow batteries, all the electroactive materials are dissolved
in a liquid electrolyte, whereas in hybrid flow batteries, one or more electroactive materials
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are deposited in the electrolyte [198]. There are primarily three types of large‐scale FBES
that are used, as summarised in the following subsections:
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
Fig. 42. Classification of FBES system
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2.4.2.1 Vanadium redox batteries (VRB)
Vanadium redox batteries 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-vanadium redox battery was invented in 1986 by Maria Skyllas-Kazacos, a

chemical 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 depicts the
development history of VRBs. Since the 1990s, a number of vanadium battery field trials
have been conducted in Thailand and Japan [385,386]. Recently, VRBs have been installed
for a variety of purposes like uninterruptible power supply (UPS), frequency regulation and
load shifting applications. Tsushima and Suzuki [387] 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. Aramendia et al [388] provided a comprehensive review of the
numerical models developed to analyse various types of flow fields and patterns, and to
enhance the performance and lifetime of VRBs. Huang et al. [389] summarised the crucial
factors influencing the development of VRB and detailed the working principle,
electrochemical reaction process and system model of VRB. Palanisamy and Oh [390]
reviewed recent developments in hybrid polymer composite membranes with inorganic TiO2
nanofillers for VRB applications. Researchers have also reviewed 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 [391] and [392]. Table
33 lists the key plants ever built based on VRB technology 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 lists the benefits and drawbacks of VRB’s [15].
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Overall Chemical Reaction: 𝑉𝑂2+ + 𝑉 2++2𝐻 + ⇔ 𝑉𝑂2+ +𝑉 3++𝐻2 𝑂
Fig. 43. Schematic diagram of Vanadium Redox Battery (VRB). During the charging cycle,
vanadium ions accept electrons at the anode (V3+ to V2+) and deposit electrons at the
cathode (V4+ to V5+). These reactions are reversed during the discharging cycle.
Table 32: Evolution of Vanadium redox flow battery
Year Type Electrodes Electrolyte References
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1986 Laboratory scale Graphite Negative and [393]
test cell Plates positive
half-cell electrolytes
are made of 0.1 M V
(III) and 0.1 M V(IV)
in 2 M H2SO4
respectively
1987 Redox flow cell Graphite plates as Vanadyl sulphate in [394]

cathode and iridium sulphuric acid
oxide-coated as
anode
1989 Redox flow cell Graphite felt/carbon Vanadium sulphate [395]

plastic electrodes in sulphuric acid
1991 Redox flow cell Graphite fibre 2M vanadium [396]

sulphate in 2 M
sulphuric acid
2002 Membraneless Carbon-on-gold 1 M solution of [385]

Redox Fuel Cell VOSO4 in 25%
H2SO4
2008 Redox flow cell Graphite felt 2 M V(IV) in 2.5 M [397]

H2SO4 catholyte and
2 M V(III) in 2.5 M
H2SO4 anolyte
2011 Single redox flow Graphite/graphite 2.0 M H2SO4 + 0.1 [398]

cell oxide (GO) M VOSO4 solution
composite
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2019 Three-electrode Carbon nanofiber 1.6 mol L-1 V3+ + 3 [399]
redox flow cell (CNF) and ZrO2/CNF mol L-1 H2SO4
system coated glassy carbon electrolyte
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 VRB technology around the world
[400,401,402,403]
Year Location Storage Application

Capacity
(MWh)
1996 Kashima-Kita Electric Power, Japan 0.8 Load-leveling
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-up
power
2001 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, US 2 Voltage support and rural
feeder augmentation
2005 Electric Power Development Co, Ltd in 6 Wind energy storage and wind power
Tomamae, Hokkaido, Japan stabilisation
2010 Vierakker, Netherlands 0.1
Table 34: Advantages and Disadvantages of VRBs [309,404]
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High power High production cost
Long life-cycle Large area
Fast charge and discharge Low energy density
Quick response times
2.4.2.2 Polysulfide bromide (PSB) Flow Batteries
The Polysulfide bromide (PSB) battery, also known as Regenesys, is a type of regenerative
fuel cell in which a reversible electrochemical reaction between two electrolytes, sodium
bromide and sodium polysulfide, occurs. Polymer membrane works as a separator, allowing
sodium cations to transfer between electrodes. During the charging cycle, three bromide ions
are oxidised and combined to form a tribromide ion at the positive electrode. At the negative
electrode, dissolved sodium particles in the polysulfide electrolyte are converted to sulphide
ions. This process is reversed during the discharge process [405]. A schematic diagram of
PSB batteries is shown in Fig. 44.
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Overall Chemical Reaction: 2𝑁𝑎𝐵𝑟+ (x-1)𝑁𝑎2 𝑆𝑥 ⇔ 𝐵𝑟2 + 𝑁𝑎2 𝑆𝑥−1
Fig. 44. Schematic diagram and working principle of Polysulfide Bromide (PBS) System. It
consists of two electrolytes: sodium bromide and sodium polysulfide. 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 discharging cycle.
The PSB was first patented by Remick and Ang in 1983 [406]. Regenesys 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,
electrolyte solutions, and electrodes for PSB flow batteries are presented in references [405],
[408] and [409]. Zhang et al. [20] reviewed the various polysulfide 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 displays the
development history of PSB flow batteries. In 2002, a 15MW Regenesys PSB flow battery
was built at Little Barford in the UK. Although the construction of the facility was completed, it
was never fully commissioned due to some engineering challenges linked to scaling up the
technology [411]. PSB flow batteries have certain advantages and disadvantages as listed in
Table 36. Because of their quick response time, they are particularly used for frequency
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 [15,386].
Table 35: Development of PSB flow battery
Year Type Electrodes Electrolyte Membrane References
1984 Single PSB Solid graphite Catholyte as 1 Molar Nafion 125 [405]
flow battery as cathode (1M)
and porous sodium bromide
sulfided saturated with bromine
nickel as and anolyte being a 2
anode Molar sodium sulfide
solution
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2001 S-, L-, and Carbon- Tribromide/bromide Sodium cation- [406]
XL-series cell Polyelfin and exchange
stacks composite polysulphide/sulphide membrane
2004 Single flow Ni/C and Pt/C Catholyte as 2.0 mol/l Nafion [412]
cell catalysts as Na2S2 solution and
the positive anolyte as s 1.0 mol/l Br2
and negative dissolved in 2.0 mol/l
Electrodes NaBr solution
2006 Single flow Carbon felt 1.3 M Na2S4 aqueous Nafion-117 [413]
cell (CF) and solution as anolyte and
activated 4.0 M NaBr aqueous
carbon (AC) solution as catholyte
2018 Na-aqueous- Na-metal Organic electrolyte as 1 NASICON [414]

redox-flow- anode M NaCF3SO3 in (Na3Zr2Si2PO12)
battery tetraethylene glycol
(NaAqRFB) dimethyl ether
cell (TEGDME)
Table 36: Advantages and Disadvantages of PSB system [415]
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
2.4.2.3 Zinc‐ bromine (ZnBr) Flow Batteries
The zinc-bromine flow battery is distinct from VRB and PSB flow batteries. It is a type of
hybrid flow battery developed in the 1970s by Exxon, Gould, and the National Aeronautics
and Space Administration (NASA) and first patented by Bradley in 1885 [416,417]. In 1991,
prototypes of 1 MW, 4 MWh batteries were built. Following many years of research and
development, Zn-Br flow batteries have now become a mature technology and are being
used by various firms [418]. Table 37 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
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electrolytic cells during charging and discharging cycles, resulting in reversible
electrochemical reactions. During the charging cycle, solid zinc is deposited on the negative
electrode and bromine is deposited on the positive electrode [419]. During the discharging
cycle, the zinc deposited on the negative electrode dissolves in the electrolyte and becomes
available for the next charging cycle. Table 38 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 battery
called ZnBr battery is being developed in Australia that is lighter, flexible, safer, and charges
faster [15,198,259]. Lin et al. [420] reviewed the technical features and materials of the
electrolyte, membrane and electrode of ZnBr battery, as well as the potential for development
of ZnBr battery. Khor et al. [419] and Wang et al. [421] reviewed various types of zinc-based
redox flow batteries based on their electrolyte environments, emphasising advancements in
electrode and membrane materials. Yuan et al. [422] reviewed the functions, structures and
chemistries of various materials used in Zinc-based flow batteries (ZFBs) in relation to battery
performance. Jiang et al. [423] discussed recent advancements in carbon-based material
electrodes and carbon nanotube modified electrodes for ZnBr flow batteries. Lee et al. [424]
enhanced the electrochemical performance of ZnBr flow batteries by improving reaction
kinetics and suppressing Zn dendrite growth by replacing a conventional polymer mesh with
a titanium-based mesh interlayer..
Table 37: Development of Zinc Bromine flow battery
Year Type Electrodes Electrolyte References
1991 Single zinc-bromine Carbon/ Polybromide/aqueous [425]

battery polyvinylidene zmc-bromine
fluoride (PVDF)
bipolar
2001 Non-aqueous zinc- Glassy carbon 0.5 M N-methyl-ethyl- [426]

bromine battery electrodes morpholinium (MEM)-Br, 0.5 M
N-methyl-ethyl-pyrrolidinium
(MEP)-Br, and 3 M ZnBr2
2013 Single flow zinc Semi-solid carbon 2 M ZnBr2 [427]

bromine battery felt positive
electrode
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2014 Rechargeable zinc Single-walled ZnBr2 [428]
bromine battery carbon nanotube
(SWCNT) and
multiwalled carbon
nanotube
(MWCNT)
2017 Single zinc-bromine Carbon felt 2.25M ZnBr2, 0.5M ZnCl2, 0.8M [429]
redox flow battery electrodes with MEP, and
ultrathin nafion- 5 ml L−1
filled porous Br2
membrane
2018 Single zinc-bromine Boron-doped 0.05 M ZnBr2 and 1 M HClO4 [430]

redox flow battery graphene (BDG)
2019 Aqueous zinc- Zinc anode and Alkaline–acid hybrid electrolytes [431]
bromine battery liquid Br2 cathode
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Fig. 45. Schematic diagram and working principle of Zinc Bromine 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: Advantages and Disadvantages of Zn-Br Batteries [308]
High specific energy Initially high self-discharge rate when shut down while being
charged
Good energy efficiency Auxiliary systems are required for circulation and temperature
control
Capable of rapid charge Safety issues
Adequate power density for most applications
Low-environmental-impact
2.4.3. Paper Batteries
Paper batteries are made mostly of paper/cellulose and carbon nanotubes, and are ultra-thin
and flexible. They operate similarly to traditional batteries, with the exception that they are
non-corrosive and require minimum housing and casing [432]. They have a high amount 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 easily fitted or accommodated into tight gaps
or spaces, decreasing the system's overall size and weight [24]. Fig. 46 depicts the basic
assembly of a paper battery. A sheet of paper coated with an ionic solution is smeared with a
specially formulated carbon nanotube ink. On the other side of the paper, a thin coating of
lithium is laminated to operate as an anode. To carry the current between the electrodes, two
aluminium rods are linked on each sides [433].
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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.
To date, several types of paper batteries have been developed for various applications.
Table 39 summarises the advancements in paper batteries. It was discovered in 2011 that
when a sheet of cellulose paper is covered with thin layers of opposite electrochemical
potential 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 0.5V was obtained for the simple Cu/paper/Al
combination [434]. In 2020, a novel strategy to use paper-based batteries as a sensor for
measuring ionic conductivity was presented [435,436]. Recently a low-cost disposable 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 activated carbon loaded on the anode [435]. Yao et al. [437] reviewed
recent breakthroughs in the synthesis of paper-based electrodes, including their structural
features, electrochemical performances, and implementation as electrodes for flexible energy
storage devices. Sharif et al. [438], Thakur and Devi [439] provided a brief overview of the
mechanics, emerging novel materials, technological trends, challenges, current status and
future technologies of paper-based devices for the energy sector. Hou et al. [440] 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.
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Table 40 depicts the published list of paper batteries together 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.
Table 39: Advances in paper batteries
Year Advancement Author
1992 Solid paper rechargeable battery [441]

● It uses polyaniline film as the electrode and nonaqueous
gel as electrolyte
2005 Urine-activated laminated paper batteries [442,443]

● 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 battery [444]

● 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 [445]

● 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 paper batteries [446]

● 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 battery [447]

● 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
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2013 Folded Paper-Based Batteries [448]
● 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) [449]

● 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 [450]

● Cathode and anode slurries made by mixing LiMn2O4 and
carbon coated TiP2O7 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 [451]

● It can be used in extreme conditions where normal
batteries do not function
● The battery can generate required power from one drop of
saliva
Table 40: Summary of paper batteries
Type Year Electrolyt Anode Cathod Voltag Device Applicatio Reference

e e e (V) size n
Biofluid- 2005 Saliva, urine Magnes Copper 1.56 6 cm x 3 Supply high [442,443]
and and tap ium cm power to
water- water credit card-
activated sized
paper biosystems
batteries on a plastic
chip
Paper- 2009 Lithium Zinc/car Poly(3,4- 12 1 cm x 2 [447]

based, chloride bon/pol ethylene cm
printed ymer dioxythio
zinc–air compos phene)
battery ite (PEDOT)
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All- 2009 Sodium Platinu Platinum 1 cm x [452]
Polymer chloride m foil 0.5cm
Paper- foil
Based
Batteries
Solid- 2011 Water Copper Aluminiu 3 1.2 cm x To control [453]

state m 3 cm paper
paper transistors
batteries
Fluidic 2012 Silver Alumini Silver 1.3 1 cm x 2 Power [454]

batteries nitrate and um cm source for
aluminium on-chip
chloride assays
Paper- 2012 Artificial Indium Indium 1.1 2 cm x 1 Microelectro [455]

Based urine tin tin oxide cm chemical
Electroch oxide (ITO) sensor
emical (ITO)
Sensing
Platform
Galvanic 2013 Water Alumini Carbon 1.53 1 cm x [456]

cell paper um 1cm
battery
Paper- 2019 Cellulose Low- Carbon 7.7 Charging [457]

based Al- paper grade paper portable
air battery Al foil electronics
Nano 2020 Alumin Cellulose 3.38 13.5 cm [458]

Based um foil based x 8.5 cm
Paper paper
Battery
2.4.4. Flexible Batteries
The advanced development of flexible, wearable, and multi-functional electronic devices such
as smartwatches, fitness bands, and medical implants necessitates the development of
energy storage systems with high performance and appropriate flexibility [459,460]. Current
electronic devices are heavy and bulky, making them incapable of meeting the flexibility
requirements. As a result, new battery energy storage systems are being developed that can
withstand continuous and prolonged mechanical deformation, such as bending, twisting, and
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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
compatible electrolyte and separator. Apart from these challenges, another important 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–sulfur, sodium-ion, zinc-ion while also developing new materials for electrodes and
electrolyte in flexible batteries. Li et al. [463] developed a graphene-based lithium-ion battery
that was thin, lightweight, and flexible using a conductive interconnected network of graphene
foam as a current collector, Lithium Titanate (Li4Ti5O12) as anode and Lithium iron phosphate
(LiFePO4) as cathode. The battery had a higher performance rate and energy density, as
well as the could be bent repeatedly to a radius of 5 mm without structural collapse. Gaikwad
et al. [464] discussed the material challenges and mechanical limits of flexible printed
batteries as well as the various printing techniques 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
batteries fabricated were able to bend at various degrees ranging from 0° to 360° while
exhibiting remarkable electrochemical performance with a controlled capacity of 1000 mAhg-
1 and a long operation time. Zamarayeva 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], Jingjing et al. [468], Xiang et al. [469] reviewed
briefly the mechanics and design concepts, constituent component requirements, emerging
new materials, existing issues, current position and practical applications of flexible batteries,
and the future opportunities for flexible batteries research and development. Despite
significant 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 classified into two types (as indicated in Fig. 47):
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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.
Fig. 47. Classification of Electrical Energy Storage systems.
2.5.1. Capacitors
When charged, a capacitor stores electrical energy utilising an electrostatic field. It is made
up of two closely spaced metal plates separated by a dielectric layer of non-conducting
material as shown in 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 capacitors
[472,473]. A capacitor’s energy capacity is determined by the size and spacing between the
conducting plates. Capacitor characteristics 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], Ramakrishnan et al. [476], Su
et al. [477], 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 emphasising the
key advantages and critical roles of 2D materials in the construction of lithium-ion, sodium-ion
and hybrid capacitors. Yuan et al. [479], Zhang, Zhihao, et al. [480], Zhang, Taoqiu, et al.
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[481] provided a brief overview of the challenges and opportunities for the development of
sodium-ion hybrid capacitors (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 capacitors 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
communications, 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 energy storage for pulsed power applications such as electromagnetic-based pulse power
systems [473]
Fig. 48. Different capacitors used in electronic equipments
Table 41: Summary of some typical kinds of the capacitor [472,473].
Type Dielectric Electrode Voltage Capacitance (μF) Application

Material material (kV)
Paper Wax- Aluminum 0.001 to 2 Radio receivers

Capacitor impregnated sheet
(1876) paper
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Silver Mica Mica Silver 0.1 – 1 4.7X10-3 In high frequency
Capacitor tuned circuits,
(1909) such as filters and
oscillators
Ceramic Ceramic Metal 0.016-15 1X10-5-100 Transmitter

Capacitor stations, Induction
furnaces, Power
circuit breakers,
Printed circuit
boards
Aluminum Aluminum oxide Pure aluminum 0.004- 0.1 - 2.7X106 Flash capacitor for
electrolytic foil 0.63 camera flashes,
capacitors Motor start
(1892) capacitors for AC
motors, Energy
storage for
airbags,
photoflash
devices
Film Thin plastic film Pure aluminum 0.050-2 0.001 - 30 Power electronics
Capacitors foil devices, phase
(1944) shifters, X-ray
flashes,
decoupling
capacitors and
filters
Glass Glass Aluminum 0.025- 2.7X10-4 – 0.1 Critical military

Capacitors 0.050 and space
programs
Tantalum Tantalum oxide Tantalum 0.002-0.5 0.001 - 72 Power supply

Capacitors metal filtering on
(1930) computer
motherboards and
cell phones
Table 42: Characteristics and performance parameters of Capacitor energy storage system
[474].
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Parameter Value
Energy storage W-sec of energy
Method of charging Voltage across terminals

Charge time 10-3 to 10-3 sec
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

Weight 1 g to 10 kg
2.5.2 Supercapacitors
Supercapacitors, also known as electric double-layer capacitors (EDLC) or ultracapacitors,

are made up of two conductor electrodes, an electrolyte, and a separator (See 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 insulator 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 opposite to that of the electrode. For example, a positively charged electrode will
have two charged layers (double layer) around it - one layer of negative ions at the interface
and a second charge-balancing layer of positive ions adsorbed onto the first negative layer.
The opposite is true for the negatively charged electrode. The electrolyte supplies and
conducts the ions from one electrode to the other. Structurally, a supercapacitor lies
somewhere between batteries and capacitors. Supercapacitors, like 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]
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Fig. 49. Schematic diagram and working principle of supercapacitor. A supercapacitor
comprises of two electrodes submerged in an electrolytic solution and separated by a porous
membrane separator. It stores energy in the form of an electrostatic field created by the
application of a constant direct current (DC) voltage applied between two electrodes.
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
surface area in 1968. This invention was then transferred to Nippon Electric Company (NEC),
which began producing supercapacitors in 1979, primarily for electric vehicle starting
systems. Simultaneously, Panasonic developed supercapacitors with activated carbon as the
electrode material and organic solution as the electrolyte. Since then, numerous
supercapacitor designs have been introduced. Table 44 summarises supercapacitor
research and development around the world. Supercapacitors have evolved over the
previous several decades into high-performance energy storage devices that are widely
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employed in electric vehicle energy management, high-power military applications, consumer
electronics, telecommunication applications and other fields [486,487]. Advances in
supercapacitor energy storage technology are represented in Table 45 [488].
Energy storage on board of a railway vehicle was proposed in 2005, and up to 30%
energy savings were measured in the light rail vehicle prototype. Since September 2003, this
prototype vehicle has been operating as a passenger vehicle [489]. The use of
supercapacitors for wind energy applications was demonstrated by integrating short-term
energy storage devices with a doubly fed induction generator design to smooth out quick
wind-induced power variations [490]. A reversibly stretchable supercapacitor with buckled
single-walled carbon-nanotube (SWNT) macrofilms as the electrodes was proposed in 2009.
Under cyclic stretching and releasing, stretchable supercapacitors with controlled wavy
shape demonstrated exceptionally stable capacitance [491]. The disadvantages of
supercapacitor energy storage systems include low energy density, high operational costs,
and large voltage variation during operation, which will be the subject of future research
[492]. Some of the reviews in the archival literature [488,493,494,495,496] provides
assessments of recent breakthroughs in supercapacitor research and technology, including
charge storage mechanisms, electrode materials, electrolytes, and production methods.
Researchers [497,498,499,500,501] have also reviewed the recent progress in micro-
supercapacitors (MSCs) in fabrication strategies, structural design, electrode materials
substrates, electrochemical properties and integrated applications. Uke et al. [502], Wu et al.
[503], Sakib et al. [504], Das et al. [505] reviewed the recent advances in the cobalt oxides,
cerium oxide, manganese oxides, manganese sulphide and their composites as an electrode
materials for supercapacitor. Supercapacitors are mostly employed in applications that
require a high number of rapid charge/discharge cycles, rather than long-term compact
energy storage. They are utilised for regenerative braking, short-term energy storage, and
burst-mode power delivery in autos, buses, trains, cranes, and elevators [506].
Table 43: Characteristics and performance parameters of Supercapacitor energy storage

system [474].
Parameter Value
Energy storage W-sec of energy

Method of charging Voltage across terminals
Charge time 1-10 sec

Cell voltage 2.3-2.75 V/cell
Specific Energy (Wh/kg) 1–5
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Specific Power (W/kg) Upto 104
Efficiency (%) 85-98

Life-cycle 3X104 h
Operating Temperature -40 to 85 ̊C
Life-time > 105 cycles

Weight 1 to 2 gm
Table 44: Research and development around the world on supercapacitors [507,508]
Country Company/Lab Year Capacitance Voltage Energy Power

(F) (V) Density Density
(Wh/kg) (W/kg)
Japan Panasonic 1978 800-2000 3 3-4 200-400
NEC 1975 1-2 5-11 0.5 5-10
United Maxwell 1991 1000-2700 3 3-5 400-600

States
PowerStor 7.5 3 0.4 250
Los Alamos National 1999 0.8 2.8 1.2 2000

Lab
Pinnacle Research 1982 125 15 0.5-0.6 200

Institute
US Army, Fort 1 5 1.5 4000

Monmouth
Evans 0.02 28 0.1 30000
Russia ELIT 1988 0.5 450 1 900-1000
ESMA 1993 5X104 17 8-10 80-100
Australia Cap XX 1994 120 3 6 300
Table 45: Advances in supercapacitor technology
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Year Advancement References
1996 Supercapacitors with activated carbon/carbon composite [509]

electrodes
2001 Hybrid Supercapacitors [510]

● 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 [511]

● 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 [512]

electrodes
● 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 [513]

● Polyaniline-based electrodes solidified in the H2SO4-polyvinyl
alcohol gel electrolyte.
● The thickness of the entire device is same as that of a A4 print
paper
● High specific capacitance
● Good cycle stability
● Highly flexible
2010 Ultrahigh-power micro-supercapacitors [514]

● 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 Fiber-like supercapacitors [515]

● Multiwalled nanotubes (MWNT) as cathode, lithium (Li) as
anode and electrolyte are embedded with nanoporous cellulose
paper.
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2015 3D porous supercapacitors [516],[517]
● 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 [518]

● 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 [519]

● A flower-like MnO2 nanocomposite mixed with nitrogen-doped
graphene (NG-MnO2)
● Better specific capacitance,
● High-rate capability, and
● Long-term cycling stability
2018 Ultra-thin and stackable supercapacitors [520]

● 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 advocated the installation of a massive toroidal coil
capable of supplying diurnal storage for France. However, research at the University of
Wisconsin in the United States began in 1971, leading to the building of the first SMES
system [521]. The first commercialised SMES power-grid application 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 refrigerator (as shown in Fig. 50). To retain
its superconducting condition, the superconducting coil is cryogenically chilled to a very low
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temperature using a refrigeration system. During the charging phase, the flow of current
increases in the superconducting coil while decreasing during the discharging cycle. The
control and power conditioning system regulates the electrical energy of the SMES system
during the charging and discharging 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 systems such as rapid response
(in milliseconds), high power output (multi-MW) and high efficiency. Xue et al. [523],
Mazurenko et al. [524], Vulusala and Madichetty [525], 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 converters for SMES systems used in the power sector. Table 46
summarises SMES applications to power systems. The SMES system concept was created
for very big plants that were primarily intended for diurnal load levelling. However, with the
advancement of technology, now SMES systems are also used for smaller scale
applications. Table 47 represents advancements in SMES technology. Despite 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. [528].
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Fig. 50. Schematic diagram of Superconducting Magnetic Energy Storage (SMES) system. It
stores energy in the form of a magnetic field generated by the flow of direct current (DC)
through a superconducting coil which is cryogenically cooled. The stored energy is released
back to the network by discharging the coil
Table 46: Summary of SMES applications to power systems [523]
Improving Power quality ● Balancing fluctuating load

● Offering spinning reserve
● Offering load levelling
● Defending critical loads
● Offering backup power supply
● Balancing voltage and current asymmetries
● Enhancing FACTS performance
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Improving power system stability ● Improving voltage stability
● Reduction of system oscillation
Table 47: Advancements in SMES technology
Country Company/Lab Year Energ Power Coil Material Temperature Referenc

y (K) e
USA Bonneville Power 198 30 MJ 11.16 Niobium- 4.2 [529,530]

Administration 2 MW and titanium
(BPA) -9.80
MW
during
charge
and
discharg
e
Superconductivity, 198 1 MJ 730 kW Niobium- 4.5 [531]

Inc 8 titanium alloy
German Forschungszentrum 199 188 kJ 1 MW NbTi/CdCuNi 4.2 [532]

y Karlsruhe 5
USA American 199 5 kJ Silver-sheathed 25 [533]

Superconductor 7 BiPb2Sr2Ca2Cu3
Corporation (ASC) 0 (BSCCO-
2223)
German ACCEL Instruments 200 150kJ Silver-sheathed 20 [534]

y 3 BiPb2Sr2Ca2Cu3
O (BSCCO-
2223)
Israel Bar-Ilan University 200 1.2 kJ 20 kW BSCCO coil 64-77 [535]

3
Korea Seoul National 200 600 kJ BSCCO-2223 20 [536]

University 7 wires
France Centre national de 200 814 kJ 175 kW BSCCO 2212 20 [537]

la recherche 8 PIT tape
scientifique, CNRS)
China China Electric 201 6 kJ BSCCO and 65-77 [538]

Power Research 1 Yttrium
Institute Barium Copper
Oxide (YBCO)
tapes
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UK University of Bath 201 60 kJ 10kW Yttrium 65 [539]
3 Barium Copper
Oxide (YBCO)
tape
Italy 201 500 kJ 200 kW Cryogen-free 21 [540]

8 magnesium
diboride (MgB2)
test coil
2.6 Hybrid Energy Storage systems
The HES system concept is to mix appropriate features of several ESSs to obtain the
necessary performance. ESSs are divided into two categories: high power storage systems,
and high energy density storage systems. High power density systems are typically fast
response systems, meaning they deliver energy at higher rates but for shorter periods of
time. High energy density systems, on the other hand, often have a slower response but can
provide power for extended periods of time [541,542]. A HES system is often built by merging
two complementary storage systems, one with high energy density and the other with high
power density [543]. Table 48 lists various HES system combinations based on this concept.
It should be noted that not all of the combinations in the table are viable. Some combinations
may be physically and technically limited. Table 49 provides an overview of global HESS,
which are mostly used in the power, transportation, and renewable energy sectors.
Researchers have recently focused on adiabatic compressed air energy storage (A-CAES)
and pumped thermal energy storage (PTES) systems as power-density solutions. The basic
operation of A-CAES is given in Section 2.2.3, and PTES is briefly explained in the following
section.
Table 48: High power and high energy density ESSs
High power density systems High energy density systems

(Fast response systems) (slow response systems)
Capacitor CAES
Supercapacitor Hydrogen
SMES Lead-Acid
FES Nickel-Cadmium
Lead-Acid Sodium Sulphur
Nickel-Cadmium Lithium-ion
Lithium-ion VRB
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VRB Zn-Br
Table 49: Summary of real-time HES systems worldwide.
Year Location Combination Capacity Application Reference

(MW)
2014 Japan Lead-acid 1.5 Optimal control of current [544]

batteries and input/output
lithium-ion
capacitors
2016 Rankin Supercapacitor 1.2 Load shifting, extended [545]

Substation in + Battery operational life, real-time
Gaston County, solar smoothing and
North Carolina, extended shelf-life
United Stated
2017 Cerro Pabellon Lithium ion Grid stability [546]

geothermal battery and
power plant, hydrogen
Chile storage
2018 Varel, Germany Lithium-ion and 11.5 To balance out frequency [547]
sodium-sulphur fluctuations in the regional
batteries electricity network,
2018 Monash Vanadium flow 1 The hybrid system will act [548]
University in and lithium-ion as a flexible platform,
Melbourne, batteries integrating with building
Australia management systems and
EV charging stations whilst
enabling cutting-edge
“peer-to-pool” energy
trading
2.6.1. Pumped Thermal Energy Storage (PTES) System
Currently, pumped hydro energy storage (PHES) handles more than 99 percent of large-
scale energy storage. 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. Pumped thermal energy storage (PTES) systems are one intriguing
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alternative storage solution. This innovative technology has been around for a few years and
is currently being tested in pilot plants [549,550].
Fig. 51. Schematic diagram of Pumped Thermal Energy Storage system. During the charging
cycle, excess electrical energy from the grid is utilised to pump heat from the low temperature
vessel to the high temperature vessel. This is achieved by propagating a cold thermal front
through the low temperature vessel and a hot thermal front through the high temperature
vessel. The working fluid flows in a clockwise direction during the charging cycle, following an
energy consuming Brayton heat pump cycle. During the discharging cycle, a warm front
propagates through the low temperature vessel and a cool front through the low temperature
vessel. The temperature difference between the two storage vessels is used to generate
required energy.
PTES technology includes storing energy as heat, which can be sensible or latent. It
is built on a high-temperature heat pump cycle that converts 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 during the charging cycle and another
during the discharging cycle), and two heat exchangers (one hot and one cold). The tanks
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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 excess grid electricity during off-peak hours to
pump heat from the cold vessel to the hot vessel. This is accomplished by allowing a cold
thermal 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
temperature 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 Rankine 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 summarises the technical features of various
PTES systems.
Table 50: Technical characteristics of various PTES systems [551,552,553,554].
Variant Discharge Charge Discharge Charge Power Energy Efficiency Life

Power Power Time Time Density Density (%) Year
Range Range (hours) (hours) (kW/m3) (kWh/m3) s
(MW) (MW)
Brayton PTES 10-150 10-150 6-20 6-72 1-15 20-50 50–75 30
Transcritical 10-100 10-100 2-5 3-10 2-8 10-15 50-65 >25

Rankine PTES
Compressed 10-100 10-150 6-72 6-72 0.5-17 40-100 60-70 30

Heat Energy
STorage
(CHEST)
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In the literature, several PTES concepts have been offered. Weissenbach proposed
PTES based on open cycle in 1979. Air was compressed to 800°C-900°C in that concept,
and the heat was stored in ceramic balls encased in heat-resistant steel tubes [555]. SAIPEM
advocated employing maximum temperatures ranging from 1000 °C and 1500 °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 temperatures
close to 500 °C. The system's rated discharge energy capacity was estimated to be around
16 MWh, with a rated discharge duration of close to 8 hours [557]. Newcastle University
commissioned the world's first grid-scale demonstration plant in 2017, based on the concept
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.
Table 51: Technical parameters of the proposed commercial system.
Parameters Value
Rated power during 2 MW

charging
Rated power during 1.6 MW

discharging
Storage capacity 16MWh
Dimensions 17m x 7m
Lifetime 20 years
Mercangöz et al. [559] described a transcritical CO2 cycle in which water served as
the hot storage and ice slurry served as the cold storage. Koen et al. [560] presented a study
in which they investigated a wide range of working fluids as prospective candidates for
transcritical PTES cycles. Over 150 working fluids were screened for thermodynamic,
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
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thermo-economic point of view and found the system suitable for large-scale and long-
duration energy storage. Thermo-economic assessments of three distinct PTES system
variants based on sensible 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 geographical 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 energy storage, it does have
limitations.. Perhaps the most significant problem is its low efficiency. During the discharge
phase, approximately 40-50% of the electricity put into the storage system can be collected
[563,564].
3. Comparison among the Energy storage systems

Because the ESSs discussed above have diverse properties and characteristics, they are
ideal for a variety of applications. Table 52 shows typical properties for various ESSs,
including energy density, power density, power rating, discharge time, efficiency, and lifetime
in both years and cycles. Figs. 52, 53, 54. compare the lifetime, efficiency, and power range
of the selected ESSs based on the average values provided in Table 52.
Table 52: Properties for different ESSs [17,23,24,198]
ESS Power Discharge Power Energy Efficiency Life Cycling

Range Time Density Density Years Capacity
(MW) (Wh/kg) (Wh/kg)
SHS 250 - - - 50-90 10-30 >5000
LHES 5 - - - 75-90 10-30
PHES 10-5000 1-24 hours - 0.5-1.5 70-85 30-60 12x103-
30x103
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GES 40-1600 1-4 hours - - 75-80 - -
CAES 3-300 1-24 hours - 30-60 40-80 20-50 0.5x103-
13x103
FES 0.1-20 Sec-min 400-500 5-80 70-95 15-20 20x103-

100x103
Hydrogen 0.1-50 Secs-24 5-800 600-1200 20-66 10-20 20x103

hours
Lead-Acid 0-20 Secs-hours 75-300 30-75 70-90 5-15 200-2000
Nickel-Cd 0-40 Secs-hours 150-300 40-90 60-90 10-20 3000-4000
Sodium 0.05-8 Secs-hours 90-230 150-240 75-90 10-15 2000-4000

Sulfur
Li-ion 0-0.1 Mins-hours 360 100-200 70-85 5-15 1000-10k
VRB <3 <10 hours 75-150 35-60 70-85 10 >16x103
PSB <15 <20 hours - 15-30 60-75 - 15x103-

20x103
Zn-Br - Secs-10 90-110 75-85 65-75 5-10 >12x103

hours
Capacitor 0-0.05 Millisecs-1 105 0.05-5 60-90 5 >50x103

hour
Supercapacit 0-0.3 Millisecs-1 500- 1.5-2.5 75-95 >20 >105

or hour 5000
SMES 1-10 Millisecs-8 500- 0.5-5 >95 >20 >105

secs 2000
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Fig. 52. Comparison of lifetime for all the ESSs, based on the average data collected in
Table 52
Fig. 53. Comparison of efficiency for all the ESSs, based on the average data collected in
Table 52
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Fig. 54. Comparison of power range for all the ESSs, based on the average data collected in
Table 52
4. Current status of Energy storage systems

The TRL (Technology Readiness Level) scale is a standard way for determining a
technology’s stage of development. It was created by NASA in 1974 and was later adopted
by the new Research Framework Programme (2014-2020). The scale has nine levels,
starting with the most basic technological state and progressing through successful real-
world demonstrations and tests. Table 53 shows how the levels are defined:
Table 53: Technology Readiness Level
Stage TRL Description
Deployment 9 System deployed and operational in a real environment.
8 Complete validation and certification of system in real

environment
7 Prototype validated in real environment
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Research 6 Technology demonstrated in relevant environment
5 Technology validated in relevant environment
Development 4 Technology validated in lab
3 Concept tested
2 Concept/technology formulated
1 Basic idea/concept
Not all of the above-mentioned energy storage technologies have reached the same level of
readiness. Table 54 represents the current state of energy storage technologies based on an
assessment of their commercial maturity and development stages. TRLs for each storage
technology are presented based on data acquired from literature surveys.
Table 54: Current status of energy storage technologies [108,551,565,566]
Storage system Current scenario TRL
Lead-Acid batteries Mature technology, commercially available 9
Lithium-ion batteries Commercial technology 9
Nickel Cadmium batteries Mature technology 9
Sodium Sulphur Large-scale demonstration 8
Vanadium RFB Mature technology 9
PSB 4-5
Zinc Bromine Batteries Demonstration 6
EDLC Early commercial technology 8-9
HESS 7
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Synthetic Natural Gas Prototype testing to large scale demonstration 4-8
PHES Mature technology, commercially available 9
CAES 7-8
Low speed FES 9
High speed FES Prototype testing to small scale demonstration 5-7
Supercapacitors 6
SMES 5-6
Lead-acid, Li-ion batteries, Ni-Cd, VRB flow batteries, PHES, and FES are deployed
technologies that have achieved a mature level, as illustrated in Table 54, despite the fact
that major research on these ideas is still ongoing. EDLC and I-CAES are in an early stage of
development and have tremendous potential for expanded deployment in the next few years.
Hydrogen fuel cells, thermal storages based on phase change materials, and
thermochemical materials are likely to increase in the energy storage market in the near
future.
5. Conclusion
Renewable energy sources such as wind and solar are intermittent. They have a highly
variable output, which means they can produce surplus energy, which can overload the
system, and they can also produce less energy than is required. The energy storage system
is regarded as the most effective method for overcoming these intermittents.
There are a variety of ESSs that store energy in various forms. Some of these
systems have attained maturity, while others are still under development. This paper has
presented a detailed review of various ESSs, including their evolution, operating principles
and characteristics. From the review, it can be noted each system has its own set of benefits
and limitations. Specific storage solutions might be chosen based on the application's
performance needs. For large-scale energy storage applications, pumped-hydro and thermal
energy storage systems are ideal, whereas battery energy storage systems are highly
128/161
recommended for high power and energy requirements. Supercapacitors, SMES and FES
are commonly used for shorter duration and fast response applications. Because of their low
efficiency, hydrogen and methane are not frequently used for energy storage. However,
because they offer excellent storage potential, they are expected to be used on a bigger
scale in the future. Chemical energy storage devices are popular, although they are
expensive. However, much study is being conducted in waste energy management and the
recycling of these batteries. SHS and CAES systems necessitate a large amount of storage
space as well as a significant initial financial expenditure.
Researchers are being drawn to develop new energy storage systems to suit shifting
energy requirements and environmental criteria as the world shifts toward greener energy.
The extensive review offered in this study will serve as a resource for researchers seeking to
create new energy storage technologies while overcoming the constraints of existing systems
and their applications in power systems.
CRedit Author Statement:

A.A. Mohamad and S. Dhinakaran: Conceptualization; A.A. Mohamad, S. Dhinakaran, J. Mitali.:
Methodology, Investigation, Writing - Original draft preparation, reviewing and editing; A.A. Mohamad
and S. Dhinakaran: Supervision
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Energy storage systems: A review

J. Mitali , S. Dhinakaran , A.A. Mohamad

To appear in: Energy Storage and Saving

Received date: 25 November 2021

© 2022 Published by Elsevier B.V. on behalf of Xi’an Jiaotong University.

J. Mitali1, S. Dhinakaran2,*, A.A. Mohamad3

Keywords: Energy storage systems, history, classification, technology readiness level;

AFC Alkaline fuel cell LA Lead-acid

ALTES Aquiferous low-temperature TES Li-ion Lithium-ion

BES Battery energy storage MES Mechanical Energy Storage

CES Chemical Energy Storage MWNT Multiwalled nanotubes

CFD Computational Fluid Dynamics NaS Sodium Sulphur

CNT Carbon Nanotubes Na-ion Sodium Ion

D-CAES Diabatic Compressed Air Energy Storage Ni-Cd Nickel Cadmium

EcES Electrochemical Energy Storage PCM Phase Change Material

ESS Energy Storage System PSB Polysulfide bromide

FES Flywheel Energy Storage RES Renewable Energy Systems

FLA Flooded lead‐acid SHS Sensible Heat Storage

GES Gravity Energy Storage SMES Superconducting Magnetic Energy

GFRP Glass fiber reinforced plastics SNG Synthetic Natural Gas

HES Hybrid Energy Storage SOFC Solid oxide fuel cell

HTES High temperature Energy Storage TES Thermal Energy Storage

HTF Heat transfer fluid TCES Thermochemical Energy Storage

HTM Heat transfer medium TRL Technology Readiness Level

IEA International Energy Agency UTES Underground Thermal Energy

IRENA International Renewable Energy Agency VRB Vanadium redox batteries

ITES Ice-cool thermal energy storage VRLA Valve-regulated lead‐acid

LAES Liquid Air Energy Storage ZnBr Zinc‐bromine

2. Techniques of Energy storage

Table 1: Evolution of ESS

Year ESS Description Reference

1899 Nickel-Cadmium Waldemar Jungner, a Swedish scientist, invented the [12]

Table 2: Classification of ESS based on the form of energy stored

Sensible Heat Storage (SHS)

Pumped Hydro Energy Storage (PHES)

Hydrogen Energy Storage

Flow Battery Energy Storage (FBES)

Electrostatic Energy Storage

Others Hybrid Energy Storage

2.1 Thermal Energy Storage

Fig. 2. Classification of thermal energy storage system.

2.1.1 Sensible Heat Storage (SHS) system

2.1.1.1 Aquifer thermal energy storage

ATES facilities are currently operational in Sweden, Germany, the Netherlands,

Table 3: Summary of technical parameters of some ATES in the world.

Year Location Purpose Numbe Flow Maximu Capacit Reference

1991 University of Heating 2 210 - - 50 - 90 2.6 - 6 [51]

1996 Anova Heating 2 240 - 2 [52]

1997 Gas and Steam Heating 2 1200 1300 200 80 77 [53]

1998 Hooge Burch, Heating 2 135-151 67 200 0.6 [54]

1999 Reichstag, Heating 12 60-320 - 100- - [55]

1999 IKEA store Heating 2 - - 200 1.4 [56]

2000 Klina hospital, Heating 2 65 100 100 1.2 [57]

2001 West Harbour, Heating 10 70-80 - 120 1.3 [58]

2001 Mersin, Turkey Cooling 2 100 - 0.194 [59]

2002 Agassiz, British Heating 5 60 90 40 0.563 [60]

2002 University of Heating 36 28-30 - 3000 20 [61]

2003 Malle ETAP, Cooling 2 67 - 90 0.57 [62]

2008 Richard Stockton Cooling 6 35-60 1300 272 2 [63]

2009 Stockholm Heating 11 20 - 720 10 [64]

2009 IKEA Store in Heating 11 90 - 180 1.3 [65]

2010 Widex Heating 10 100 - 250 2.5 [50]