GENERAL INTRODUCTION AND

LITERATURE SURVEY
 CHAPTER 1

General Introduction and Literature Survey

Sr. Title Page

No. No.
1.1 General Introduction 1
1.1.1 Need of Supercapacitor 1
1.1.2 Historical Background and Current Status of 5
Supercapacitors
1.1.3 Modern Tendency of Research in Supercapacitors 8
1.1.4 Working Principle of Supercapacitor 10
1.1.5 Types of Supercapacitor and Electrode Materials 12
1.1.5.1 Electric Double Layer Capacitors 13
(EDLCs)
1.1.5.2 Pseudocapacitors 18
1.1.5.3 Hybrid Capacitors 21
1.1.6 Basics of Metal Phosphate Materials 22
1.2 A Review of Literature 24
1.2.1 Literature Survey on Cobalt Phosphate 25
1.2.2 Literature Survey on Manganese Phosphate 30
1.2.3 Literature Survey on Cobalt Manganese 34
Phosphate
1.3 Orientation and Purpose of the Dissertation 46
1.4 References 49
 General Introduction And Literature Survey

1.1 General Introduction:

1.1.1 Need of Supercapacitor:
Air-pollution, global warming, diminishing sources of fossil fuel and rising

oil prices, limited availability of natural resources in the global ecosystem has been

increasingly driving the world towards the progress of eco-friendly high power

energy resources [1]. To overcome these issues, there is a need to develop safe,

clean and green renewable energy resources [2, 3]. Nowadays, the alteration of

natural energy into sustainable and renewable resources, such as the sun, wind and

sea tides, can produce high electric energy. But, humans have been limited control

over natural phenomena because renewable sources depend on geographical and

environmental factors such as climate, location, or gravitational forces on earth by

sun or moon. Utilizing these renewable energy resources like fossil fuel

substitution, their implementation for continuous energy production is more

important. Moreover, energy storage in different forms is an essential factor, which

can solve the problems. The electrical energy storage systems perform a crucial

role in a lot of practical application [4, 5]. The role of advanced technologies in the

area of renewable energy storage and electric vehicles become an important one.

To meet future energy demands, the development of lightweight, flexible, high-

performance, and low-cost energy storage devices are essential. This situation has

inspired researchers to investigate superior energy storage technologies, [6, 7]

such as sodium-ion batteries, lithium-ion batteries (LIBs), and supercapacitors

(SCs), etc. Nowadays, the SCs has been attracted much attention, because they

embrace the great potential in an extensive range of applications [8-10].

Supercapacitors with their fast charge/discharge efficiency, good cycling

life (> 500,000) and high power density (>10 kW kg-1) offer remarkable properties

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as energy storage devices compared to conventional energy storage systems. The

most trustworthy carbon-based supercapacitor achieved a power density of 8500

W kg-1, with hardly 20 % capacitance decay after 1,000,000 cycles, [11] but the

energy density is restricted to less than 7.4 Wh kg-1. A supercapacitor consists of

positive and negative electrodes, and they are electrically isolated using a

separator (like an aqueous and non-aqueous electrolyte, porous membrane, etc.).

The working procedure of supercapacitors (Figure 1.1) is based on collecting ions

from the electrolyte on electrode surface known as an electrical double layer (EDL).

Supercapacitors are widely used in hybrid vehicles, telecommunication devices

(remote communication, cell phones, walkie-talkies, satellites, etc.), memory

backup systems, pace-maker, portable electronic devices, etc. [12, 13].

Figure 1.1: Schematic presentation of supercapacitor working procedure and

related parameters [11].

Supercapacitors can store electrical energy like batteries and deliver like

conventional capacitors, but they utilize different storage mechanisms. Electricity

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in the batteries is chemically stored, while supercapacitors are storing physically

via separating positive and negative charges, therefore, they are highly reversible

and can be repeated for several charge-discharge cycles. Also, they can be operated

at a broad temperature scale (-40 to +50°C). The superior performance of energy

storage devices can be described in terms of their ability to deliver power as well

as energy densities [14, 15].

Figure 1.2: Comparative Ragone plot of several energy storage devices with their

respective energy and power density.

Figure 1.2 shows the simplified Ragone plot which compares available

energy storage devices, such as conventional capacitor, fuel cell, supercapacitor

and battery in terms of their energy and power density. In comparison, a

supercapacitor is situated between the conventional capacitor and batteries. The

energy density of battery is extremely high as compared to capacitor and

supercapacitor [16]. However, the conventional capacitor gives a low energy

density but offers high power density. Supercapacitors maintain an important area

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in the Ragone plot, they fulfilled the gap amongst batteries as well as fuel cells and

conventional capacitors. However, supercapacitors deliver higher power than a

battery and store high energy than the conventional capacitor. In addition,

supercapacitors have long term cyclic stability as compared to batteries, high

capacitance and low internal resistance than the conventional capacitors [17, 18].

Moreover, a recent application in low emission hybrid electric vehicles has shown

that supercapacitors are equally important as batteries for future electrical energy

storage systems [16].

Table 1.1: Comparative table of basic characteristics of batteries, conventional

capacitors and supercapacitors. [19-23].

Sr. Factors Batteries Conventional Supercapacitors

No. Capacitors
1. Charging time h ps - ms ms to s
2. Discharging time h ps - ms ms to s
3. Specific power ~50 - 200 >10,000 ~1000 - 2000
-1
(W kg )
4. Specific energy ~20 - 100 < 0.1 ~1 - 10
-1
(Wh kg )
5. Cycle life (cycles) ~500 - 2000 Almost infinite > 5,00,000
6. Charge-discharge ~70 - 85 ~ 100 Up to 99
efficiency (%)

Note: ps: picosecond, ms: millisecond, s: second, h: hours.

Table 1.1 reveals the detailed performance variations of different energy

storage (battery, conventional capacitor and supercapacitor) devices. In available

energy storage devices, batteries have the most attention of researchers, because

they can store a great amount of energy and provide proper levels of power for

many applications [14]. However, the charge-discharge processes in batteries

usually include irreversible redox reactions at the electrode-electrolyte interfaces,

which change the molecular structure of active materials. For this reason, the

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durability of batteries is normally restricted to only several hundred/thousand

charge-discharge cycles and so it possesses less cyclic performance [24]. On the

contrary, active materials in supercapacitors do not participate in redox reactions;

therefore there are no significant chemical changes in electrode materials during

cycling. As a result, an almost unlimited cyclability is frequently obtained in this

highly reversible storage mechanism [25]. Moreover, much higher power

distribution can be achieved for short times in supercapacitors. However, because

of the faradaic processes in batteries, charge-discharge mechanisms are much

slower than supercapacitors [26]. Furthermore, supercapacitors can be charged-

discharged in few seconds whereas batteries require at least several hours or more

to release their energy and recharge [27]. Nevertheless, the main adequacy of

supercapacitors is their analogously less energy compared to batteries [28]. Due

to high power, supercapacitors have been confirmed to be a budding approach to

overcome the growing power interest of multi-functional devices in the twenty-

first century.

1.1.2 Historical Background and Current Status of Supercapacitors:

The history of supercapacitors began with the first practical use of double

layer capacitors was reported in 1957 by General Electric Company for electrolytic

capacitor by applying porous carbon electrodes [29]. It is known that, this

capacitor exhibited a surprisingly high capacitance and believed that the energy

stored in pores of carbon, but the mechanism of charge storage of supercapacitor

was anonymous at that time. So, this device was not marketed because of its

impracticable design and flooded battery market, in which both the electrodes

required to be immersed in an electrolyte vessel. Besides, in 1966 the Standard Oil

Company of Ohio (SOHIO) was achieved development in energy storage devices by

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manipulating the high surface area of carbon materials in tetra-alkyl ammonium

electrolytes [30]. But SOHIO failed to commercialize their invention, so Nippon

Electric Company (NEC), which after marketed all outcomes (supercapacitors) to

provide backup power for maintaining computer memory and various consumer

appliances under the license of SOHIO in 1978. In 1975, B. E. Conway formed a new

scheme of charge storage mechanisms based on fast and reversible redox reactions

arising near surface of electrode material. The development of first

pseudocapacitor (a supercapacitor is also known as pseudocapacitor) is composed

of ruthenium oxide (RuO2) films as an electrode [31-33]. At present, the capacitors

available in the market contain both carbon material with high surface area

(activated carbon) in addition to highly redox active RuO2 [34]. Many companies

ventured in the 1980’s manufacturing electrochemical capacitors. Panasonic

(previously known as Matsushita Electric Industrial Co.) invented “Gold capacitor”

[35]. The main difference between Panasonic and NEC devices was the electrolyte,

NEC used an aqueous electrolyte while Panasonic used a non-aqueous electrolyte.

In 1987, ELNA begun to produce double-layer capacitor by the name of “Dyna

capacitor” [36]. In 1982, “PRI Ultracapacitors” developed first high power double-

layer capacitors utilizing metal-oxide electrodes [37]. In 1990, the entire research

field in supercapacitor become more concerned to develop supercapacitor devices

with high performance. The revelation of supercapacitor devices generated

curiosity, so the United States Department of Energy (DoE) started a study in the

context of hybrid electric vehicles, and by 1992, a development program of

ultracapacitor was started at Maxwell Laboratories [36]. There were four

companies representing the supercapacitor’s market until 1998 and they are NEC-

Token, Maxwell Technologies, Panasonic, and Elena Capacitors. Further, several

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vendors were providing supercapacitors as per global demand from 1999 to 2013,

which was much higher than the market growth value. In year 2013, forty

companies were competing in the carbon dielectric supercapacitor market

worldwide (according to Paomanok's analysis data, the usage of EDLC

supercapacitors worldwide has grown by 275 %, while the several vendors

providing the market has risen by 1000 %) [38]. Composite based hybrid

supercapacitor commercially manufactured by several companies are summarised

in Table 1.2.

Table 1.2: Summary of world-wide commercially available supercapacitor [39].

Company Country Product Name Voltage Capacitance

Range (V) Range (F)
Cooper US Powerstor 2.5-5.5 0.07-100
Bussmann
Evans US Capattery 5.5, 11 0.47-1.5
AVX US Bestcap 3.6-16 0.010-1
Maxwell US Boostcap 2.2-125 1-3000
IOXUS US Ultracapacitor 2.3-16 58-5000
Cell
IOXUS US Hybrid 1-2.3 220-1000
Capacitor
Tarvima Canada ESCap 14-300 2-160
Cornell UK CDE 2.1-5.5 0.022-70
Dubilier
SAFT-ESMA France Saft Nickel 7-29 500-1200
Capacitor
WIMA Germany Supercap 2.5, 2.7 110-6500
Cap-xx Australia Cap-xx 2.3-5.5 0.09-120
Cellergy Israel Cellery 2.1-12 0.01-0.12
Panasonic Japan Gold Capacitor 2.1-5.5 0.015-70
NEC-Tokin Japan Supercapacitor 2.7-12 0.01-100
Elna Japan Dynacap 2.5-5.5 0.047-100
Nichicon Japan Evercap 2.5, 2.7 0.47-4000
Nesscap Korea EDLC 2.3-2.7 5-60
Nesscap Korea Pseudocapacitor 2.3 50-300
VINATECH Korea HY-CAP 2.3-5.4 0.75-800

Currently, products from Japan, US, and Russia occupy almost the entire

supercapacitor market. Every nation’s supercapacitor products have their own

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features and benefits like capacity, power, price and so on. According to Bosch’s

(2007–2022 research report on the current status and investment prospects of

china’s supercapacitor market), the international supercapacitor market has

reached $16 × 109 USD in 2015, and analysts predict that the supercapacitor

market will exceed $92.3 × 109 USD by 2020. Currently, the market addresses a

large majority of symmetric supercapacitors using activated carbon as material for

electrodes [40, 41]. Currently, IOXUS and Soft-ESMA are trying to commercialize

asymmetric hybrid capacitors, exhibiting their capability to compete with the

currently available lithium-ion hybrids and asymmetric nickel-carbon based

supercapacitors [42].

1.1.3 Modern Tendency of Research in Supercapacitors:

One of the new emerging energy storage technology is a supercapacitor,

which is going to play a significant role in the future of energy systems. The main

feature of supercapacitors is the high energy storage capacities, which makes it an

essential option for different manufacturers [43]. With constant improvement in

research, supercapacitors are achieving more attention in markets all over the

world. For example, rail sections and automobiles are opening new possibilities in

emerging sections such as grid energy storage. Hybrid vehicles are in demand,

because of strict government rules concerning carbon emissions which inspire the

growth of supercapacitors market [44]. The new consumer’s electronic devices

like cell phones and sensors required different power demands because of their

various functionalities. Batteries react very slowly due to their chemical reactions.

As a result, in most cases, the batteries do not supply the full energy requirement

for all electronic devices. The increase in interest of supercapacitors at the industry

level due to their benefits over battery in terms of power density and durability.

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Supercapacitors can deliver large amounts of energy at high power and fast charge-

discharge rates, making them fit for supplying high power to multifunctional

electronic devices. Even, with these great features of supercapacitors, the

industrial practicability of supercapacitors is limited by low energy density.

Currently, researchers are trying to enhance the energy density by applying

various approaches without interrupting the other features of supercapacitors.

In last few decades, carbon based materials are generally used in

commercial supercapacitors [45]. But, carbon-based materials limit commercial

use because of its low specific capacitance. Contemporary research suggests that,

pseudocapacitive transition metal oxides are more promising electrode materials

for supercapacitors because of their cost-effectiveness, lower resistance, and

environmental friendly nature [46]. Furthermore, reversible and fast surface redox

reactions of pseudocapacitive materials remarkably improved energy storage

capacity of supercapacitors. However, the cycling life time of pseudocapacitive

material is less due to the decomposition of active material in the liquid electrolyte

during cyclic stability. Therefore, solid-state supercapacitors are investigated with

a greater interest in which solid polymer (gel-type) electrolyte is used. Solid-state

supercapacitors have several benefits over aqueous capacitors, as they overcome

the problem of electrolyte leakage, flexibility, and ease of handling [47]. Moreover,

the present research has focused on the improvement of supercapacitors using

various ionic liquid electrolytes. These electrolytes are more beneficial, since they

are non-toxic and thermally stable. Further, the voltage range of supercapacitors

with these ionic liquid electrolytes can be increased up to 4 to 6 V [48]. The

electrochemical performance of supercapacitor is not only subject to the electrode

material, but also to the electrolyte, separator and current collector. The choice of

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proper electrode material (non-toxic and low-cost) with corresponding electrolyte

increases specific capacitance and energy density of a supercapacitor [49].

1.1.4 Working Principle of Supercapacitor:

The conventional capacitor and electrochemical capacitor have same charge

storage mechanisms but the difference is in separating medium (dielectric and

electrolyte). The conventional capacitors store electrical energy in dielectric

separator material that is carried by two metal plates work as terminals for the

device. Similarly, electrochemical capacitors store energy in an electric double-

layer formed at electrode-electrolyte interface. Formed an electric double-layer

separated by a distance order of few Angstrom is depends on the used electrolytes.

The schematic diagram of the energy storage mechanism of an electrochemical

capacitor is shown in Figure 1.3. An electrochemical capacitor is composed of two

electrodes coated with electroactive materials separated by an electrolyte.

Figure 1.3: Schematic diagram of electrochemical capacitor.

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When electrode surface is exposed to the electrolyte, the layers of charges

formed at both sides of electrode-electrolyte interface. The total charge stored

regarding the operating potential is called capacitance (Eqn. 1.1) [50].

𝑄
𝐶= 1.1
𝑉

where, ‘C’ is the specific capacitance (F g-1), ‘Q’ is the stored charges (coulomb) and

‘V’ is the operating potential (V). In case of an electrochemical capacitor, ‘C’ is

inversely proportional to the thickness of a double layer and directly proportional

to the electroactive surface area of each electrode; [14]

𝜀𝑟
𝐶= 𝐴 1.2
𝑑

where, ‘ɛr’ is the relative permittivity, ‘A’ is specific surface area of electrode and ‘d’

is thickness of electric double layer.

Also, the energy and power density of electrochemical capacitor is

measured by the following equations: [51]

𝐸 = 1⁄2 𝐶𝑉 2 and 1.3

𝐸
𝑃= 1.4
∆𝑡

where, E - energy density (Wh Kg-1), C - specific capacitance, V - operating voltage,

P - power density (W kg-1) and Δt - discharging time.

Capacitance is a determination of the energy storing ability of capacitor

which can be assessed using the above mentioned Eqn. (1.1). The energy delivered

per unit time is known as power density. Generally, the resistance of physical

elements (e.g., auxiliary substrate, electrode material, and electrolyte, etc.) in a

supercapacitor needs to be considered while determining the energy density of the

supercapacitor. Supercapacitors (electrochemical capacitors) have a similar

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fundamental principle as conventional capacitors. Nevertheless, they include

electrodes with an effective thickness of electric double layer (d) and larger surface

areas (A) and resulted in enhanced capacitance and energy density (Eqn. (1.2) and

(1.3)). Also, the power density is calculated by the above Eqn. (1.4).

1.1.5 Types of Supercapacitor and Electrode Materials:

Chart 1.1 describes the classification of electrochemical supercapacitors

with various types and subtypes. Depend on the charge storage mechanism,

supercapacitors mainly classified into three categories namely, electrochemical

double-layer capacitors (EDLCs), pseudocapacitors and hybrid capacitors. The

charge storage mechanism includes faradic, non-faradic and composition of these

two processes. In the faradic process, redox reaction occurs between electrode-

electrolyte interfaces facilitated by transfer of charge. Conversely, chemical

reactions do not happen in the non-faradic process, the charges are collected on

the electrode surface by a physical process that does not involve breaking or

forming a chemical bond. EDLCs based electrodes store charges electrostatically

into a Helmholtz double-layer created by carbon-based materials using a non-

faradic mechanism [52-54]. Pseudocapacitors store charges using a faradaic

mechanism occurring close to the surface and in bulk of existing materials [55].

Usually, pseudocapacitors are comprised of metal oxides/hydroxides, sulfides,

phosphates, and conducting polymers [56-58].

The hybrid capacitors are operating on faradaic and non-faradaic (both)

mechanisms. Hybrid capacitors are constructed by including carbon-based

materials with conducting polymers or metal oxides or both [59-61]. It is known

that, electrode material plays a vital role to reach the superior electrochemical

performance of supercapacitors. So, supercapacitor electrode needs properties like

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large specific area, high thermal and chemical stability, higher porosity and

electrical conductivity. Several materials are applied as electrodes for

supercapacitor and they have widely categorized in the below section.

Chart 1.1: Classification of supercapacitors.

1.1.5.1 Electric Double Layer Capacitors (EDLCs):

The energy storage mechanism in EDLCs is non-faradic, there is no charge

transfer at the electrode-electrolyte interface, and which is equivalent to a

conventional capacitor. This indicates that, the electrolyte concentration remains

constant after charging-discharging process [62]. Using voltage across

electrochemical capacitor, both electrodes in the capacitor produce an electrical

double-layer. These double-layers consist of two layers of charge: one electronic

layer is in lattice structure at electrode surface and second with opposite polarity

arises from solvated ions dissolved in the electrolyte. Both layers are differentiated

by a single layer of the solvent (water as solvent) molecule, termed the inner

Helmholtz plane. So in this process, charge transfer in electrode-electrolyte is

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restricted and forces that cause adhesion are electrostatic forces (not chemical

bonds) [62, 63]. The schematic representation of energy storage mechanism in

EDLCs is displayed in Figure 1.4 (a). A highly reversible EDLC capacitor delivers

high cycling stability. EDLCs achieve higher capacitance due to the higher surface

area of electrodes. Moreover, EDLCs can also provide higher specific power density

due to faster discharge rate, and superior cycle life due to the absence of charge

transfer chemical reactions [64].

For carbon-based electrodes, all operating potentials are electrochemically

inert. The decomposition potential (1-5 V) of electrolyte is very essential for

determining the operating voltage range of EDLC. Accordingly, the electrical energy

storage ability of EDLC depends on electrolytes (aqueous or non-aqueous). The

ionic conductivity of the aqueous electrolyte is high as compared with a non-

aqueous electrolyte which enhances the specific power density of a capacitor.

Carbon based materials such as graphene, activated carbon, carbon aerogel, and

carbon nanotubes are generally utilized as EDLC materials.

A) Activated Carbon (AC):

Generally, activated carbon is used as electrode materials in EDLCs due to

its well-known characteristics such as low cost, feasible and scalable synthesis,

higher surface area (>1000 m2g-1), excellent electrical conductivity and chemical

stability [65]. Activated carbons are obtained from various carbon-based organic

precursors, such as coal, wood, peat, nutshells, leaves, and charcoal. Normally, the

process of AC activation can be achieved by chemical, physical (also called thermal)

and hybrid activation methods, and it improves specific surface area along with

capacitive performance [22]. Enhanced performance of supercapacitors using

activated carbon depends on the surface area, distribution of pores, pore length as

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well as pore size. Even though capacitance depends on surface area, the

experimental result implies that all surface area of activated carbon does not

contribute in capacitance of device. Mostly, activated carbon in the organic

electrolyte shows capacitive performance in range of 50 to 150 F g-1, and 100 to

200 F g-1 in aqueous electrolytes. The high capacitive performance (energy density

of 10 Wh kg-1 and power density of 1.0 kW kg-1) in aqueous electrolytes is

associated with smaller size of solvated ions [16, 66].

B) Carbon Nanotubes (CNTs)

Current research trends imply that, there is an expanding interest in the use

of CNTs as EDLCs electrode material. The development of CNTs electrodes due to

their excellent properties including higher porosity, excellent electrical

conductivity, good mechanical integrity, high thermal and chemical stability,

unique open tubular structure, a high aspect ratio of CNTs make them good

electrode than other materials. Therefore, it has led to being widely researched for

supercapacitor applications. CNTs have been studied to offer new opportunities for

carbon electrodes in several applications like a supercapacitor, hydrogen storage,

batteries, sensors, etc. CNTs are nothing but an allotrope of carbon arranged in a

cylindrical hollow nanostructure. CNTs are generally observed in three forms,

multi-walled (MWNTs), single-walled (SWNTs) and double-walled (DWNTs)

nanotubes. CNTs are widely used as electrode material for supercapacitor devices

because of their lower ESR (equivalent series resistance) than AC electrodes and

show the enhanced power and energy density of a supercapacitor [67, 68].

Current progress for the utilization of CNTs in supercapacitor application as

conductivity enhancers and that can replace carbon black. The investigation on

replacing carbon black with CNTs in EDLC electrodes showed a 90 % decrease in

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ESR [24]. The novel structure of stuck nanotube electrodes achieves a range of

specific capacitance between 80 and 130 F g-1 [69].

C) Graphene:

Geim and Novoselov won the Nobel Prize (Physics) for their ground

breaking research on graphene. Graphene is a promising candidate for the EDLCs

electrode material and it is a two-dimensional (2D) single layer sheet

arrangements of sp2 carbon atoms in a hexagonal lattice, which shows superior

electrical conductivity, large surface area, high carrier mobility, suitable pore size

distribution, chemical and thermal stability, mechanical strength, etc. [70]. It is

quite promising that, in near future it would draw a revolution in electrical,

semiconductor, and biochemical research. Graphene-based electrochemical

capacitors are highly demanded in energy storage device applications based on

their superior mechanical, chemical and electrical properties.

Up to date, several methods have been employed for the preparation of

graphene which can be widely categorized as a top-down and bottom-up approach.

Among them, the effective approaches include mechanical exfoliation [70],

chemical vapor deposition (CVD) [71], epitaxial growth [72], thermal reduction

and so on. The modified Hummers method is generally used for preparation of

graphene oxide (GO) [73], it can provide a higher level of oxidation in presence of

strong acids and oxidants to form graphitic layered structure functionalized with

covalently connected oxygen-containing groups such as hydroxyl, epoxide,

carboxyl groups [74]. The modified Hummers method has been employed in

present work for preparation of a GO based electrode. The prepared GO is

hydrophilic in nature [75] and one important advantage is that, GO can be simply

dispersed in various solutions like water, ethylene glycol, ethanol, tetrahydrofuran,

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n-methyl-2-pyrrolidone (NMP), dimethylformamide, etc [76]. Graphene has

extensively studied as electrode material in various electrolytes including organic

electrolyte (TEATFB), inorganic electrolyte (H2SO4, KOH, Na2SO4) [77, 78], and

ionic liquid (N-butyl-N-methylpyrrolidiniumbis (trifluoromethanesulfonyl) imide

(PYR14TFSI), IMIMTFB) [79, 80].

Normally, reduced graphene oxide (rGO) is another option for graphene in

practical application. In rGO, carbon planes are restored by carbon atoms except

for few defects at the edges. The structure of rGO alters because of small variations

in the adopted reduction paths. Nevertheless, GO sheets commonly represent a

lower electrical conductivity owing to the effect of higher disorder [81] and

remaining oxygen-containing groups. Theoretically, a monolayer of sp2 bonded

carbon atoms can exhibit theoretical specific capacitance up to ~550 F g-1, high

intrinsic mobility of 200,000 cm2 Vs-1, large surface area of 2675 m2 g-1, and optical

transmittance around 97.7 % [82], and they are essentially fixed the higher limit

for all carbon materials. Compared to the other carbon-based material such as

carbon nanotubes and activated carbon, graphene is a highly interesting material

due to its quick electron-transfer kinetics, large surface area, and longer stability

[83]. Hence, specific attention has been dedicated to the improvement of highly

efficient synthesis approaches of graphene for excellent electrochemical

performance.

In recent years, many researchers prepared graphene by different methods

and obtained high specific capacitance, such as Yin et al. [84] prepared GO sheets

by modified hummer’s method and obtained maximum specific capacitance of 326

F g-1 for activated graphene. Ahmed et al. [85] prepared Nitrogen-doped

mesoporous graphene hydrogel (MGHG) via a hydrothermal method. The as-

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prepared MGHG shows a high 595.7 F g−1 specific capacitance. Moreover, Xian et al.

[86] prepared graphene nanosheets (GSs) from graphite oxide via thermal

exfoliation process and good supercapacitive performance (233.1 F g−1) in a 6 mol

L−1 KOH electrolyte. Therefore, there is particular interest in developing

approaches for more effective synthesis of graphene, to achieve better

electrochemical performance.

As the carbon-based materials (like ACs, carbon aerogel, graphene, CNTs,

etc.) store energy only on surface of an electrode, the specific capacitance of those

materials is relevant to the characteristics of electrode surfaces.

Figure 1.4: Schematic diagram of two different electric charge storage

mechanisms, (a) Electrical double-layer capacitor (EDLCs) and (b)

Pseudocapacitor [87].

1.1.5.2 Pseudocapacitors:

In converse with EDLCs supercapacitor, the energy storage mechanism of

pseudocapacitors is based on a transfer of charges by reversible faradaic reactions

between electrode and electrolyte. The schematic illustration of a pseudocapacitor

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with an oxidation/reduction reaction is exhibited in Figure 1.4 (b). Generally, the

metal oxides, sulphides, conducting polymers, and phosphates are used as

pseudocapacitor materials [88-92]. The charge storing capacity of the

pseudocapacitors electrode surface is higher than EDLCs, which means that it

produces 10 times more capacitance and higher energy density than the EDLCs.

However, several factors are affecting the pseudocapacitors like surface area of

electrode, conductivity and porosity of materials, particle sizes, etc. Also,

pseudocapacitors suffer from a lower life cycle span than EDLCs due to

delamination of active material through electrochemical redox reactions. However,

the pseudocapacitive materials are growing interest, because of their high specific

capacitance, high energy density with fast and reversible redox reactions [93, 94].

A) Conducting Polymer:

Conducting polymers are gaining much attention as an electrode material

to improve the performance of supercapacitors. They give relatively higher specific

capacitance, as redox reactions have not only the surface but also bulk material is

involved in the charge storage mechanism and further, they have high porosity,

better electric conductivity and broad potential window than carbon-based

materials [95, 96]. The conducting polymers electrode materials like polyaniline

(PANI), polypyrrole (PPy), and polythiophene (PTh) are the most usually studied

materials for supercapacitors. Furthermore, the highest capacitances of PANI, PPy,

and PTh are 750, 620 and 485 F g-1, respectively [97]. Interestingly, electrolytic

ions get absorbed to the surface of polymers during charging and released while

discharging. However, the reduction of the polymer during an electrochemical

reaction is a major issue resulting in disintegration of nanostructure and

consequently decrease specific capacitance. The conducting polymers are charged

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positively or negatively during oxidation or reduction (also called doping)

reactions. The conducting polymer electrodes were investigated using ionic liquid

electrolytes, and it shows better electrochemical performance [98] but, much

lower cycle life than carbon electrodes, since redox sites in conducting polymer are

not adequately stable. The proper operating potential window is a very crucial

factor for polymers. Conducting polymers degrade and lose their conductivity by

operating in an improper potential window. Accordingly, the potential range is

very important for the excellent supercapacitive performance of conducting

polymers.

Recently, many scientists prepared different polymers by different

methods, such as Deshmukh et al. [99] prepared polyaniline (PANI) electrode via

microwave-assisted chemical bath deposition method (CBD) and obtained

maximum 753 F g-1 specific capacitance at a scan rate of 5 mV s-1. Hryniewicz et al.

[100] synthesized polypyrrole nanotubes by direct electro-synthesis method on

flexible mesh electrode and obtained a maximum specific capacitance of 423 F g−1

at a current density of 0.5 A g−1. Patil et al. [101] prepared polythiophene thin films

at room temperature using CBD method. Polythiophene thin film showed a

maximum specific capacitance of 300 F g−1 at 5 mV s−1. It is known that, conducting

polymers are less stable, therefore the composites can save mechanical breaking of

polymers during long cycle life.

B) Metal Oxides:

Metal oxide materials are attractive electrode material for

pseudocapacitors, because of their good cyclic stability as compared to conducting

polymers along with high theoretical specific capacitance, high energy and power

density. Pseudocapacitance obtained because of reversible redox reaction at

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interface of metal oxide materials and electrolytes. Charging/discharging

processes of metal oxides are able to convert into different oxidation states and

ions can be inserted/deserted in the active electrode material. The different

transition metal oxides could give high possibilities to manipulate the physical as

well as chemical properties. Different metal oxides like TiO2 [102], RuO2 [103],

MnO2 [104], Fe2O3 [105], Co3O4 [106], and NiO [107] are extensively studied as

electrode materials for pseudocapacitors. Among these transition metal oxides,

RuO2 is the most popular active material as supercapacitor electrodes because of

its higher specific capacitance (2192 F g-1 at 2 mV s-1 scan rate) with low ESR, good

electrical conductivity, and broad potential window (0.0-1.0 V) [108, 109].

However, RuO2 electrode material utilization has restricted by its toxicity and high

cost.

1.1.5.3 Hybrid Capacitors:

A new third type of capacitor, developed by the co-operation of EDLC and

pseudocapacitors is known as a hybrid capacitor and it accumulates charge

through both faradic and non-faradic reaction mechanisms. EDLC provides a quite

higher surface area by employing carbon-based materials as compared to

pseudocapacitive materials. Moreover, EDLCs show comparatively less capacitive

performance which hinders energy densities and further application in

supercapacitors. The energy density of pseudocapacitors is more than EDLCs, but

they have restrictions for the long life cycles, electrical conductivity, and power

densities [110-114]. Researchers are trying to develop hybrid materials as

supercapacitor electrodes which have higher specific capacitance, high energy with

high power density without sacrificing the cyclic stability and life of the device.

Asymmetric hybrid capacitors consist of EDLC and pseudocapacitor electrodes in

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the same cell [115]. The hybrid electrode system consists of a combination of

carbon-based materials with metal oxides/conducting polymers that lead to

benefit of EDLC and pseudocapacitive charge storage mechanisms collectively in a

single electrode. Usually, a high surface area of carbon materials improves the

interaction amongst pseudocapacitive materials and electrolyte, whereas faradaic

reactions enhance the charge storing ability of composite electrodes. Therefore, the

coupling of carbon-based electrode materials and pseudocapacitive materials has

obtained huge importance due to a large enhancement in the capacitance of devices

[116].

1.1.6 Basics of Metal Phosphate Materials:

The phosphate (also called orthophosphate) ion [PO4]3- is obtained from

phosphoric acid by the elimination of three protons (H+). Phosphate is a salt of

phosphoric acid. Phosphorus can react with many elements in the periodic table

and produce different phosphates and phosphides [117]. A functional group

contains one phosphorus atom bonded with four oxygen atoms in a tetrahedral

structure (one double and three single bonds). Metal phosphate-based materials

exhibit enormous potential as favorable electrode materials for the utilization of

energy storage devices. Several lithium-based metal phosphate materials have

been previously reported for commercialization in battery production, [118, 119]

while nickel and cobalt phosphates are widely studied as a cathode material in

energy storage devices. Metal phosphates provide excellent charge storage

capacity and ionic conductivity due to their wide channels and open structure with

cavities and high chemical stability according to strong P-O covalent bonds [117].

The phosphate-based materials show a pseudocapacitive type behaviour almost

similar to the oxide-based materials.

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Moreover, a lot of research on polymers, metal oxides/hydroxides and

sulfides have been done and found out limitations of these pseudocapacitive

materials. Metal oxides are much stable than metal hydroxides, sulfides and

conducting polymers, but suffers from poor conductivity. Now a day’s peoples are

in a thrust of new emerging materials to overcome deficiencies of metal oxides,

hydroxides and polymers applicable for supercapacitor, which can be completed

by metal phosphate materials [120]. Metal phosphates are new emerging

materials in supercapacitor application and show better electrochemical

performance, conductivity more than metal oxides, hydroxides and sulfide

materials. Therefore, transition metal phosphate attracted great attention in many

fields such as an electrochemical supercapacitor, solar cell, Li-ion batteries, as

catalysts, etc., because of their distinctive morphology, excellent mechanical and

electrical properties.

To date, several efforts have been carried out to produce metal phosphate

(transition metal phosphates) based electrodes for energy storage devices [121].

Moreover, transition metal phosphates are favorable electrode materials for

supercapacitors, because of their rich redox behavior and open structure

framework [122]. Generally, various types of monometallic phosphates are

produced by different chemical methods for supercapacitor applications. However,

recently researcher's attention has been focused on the production of bimetallic

phosphates, such as Ni-Co phosphates, Co-Mn phosphates [123, 124], which have

given improved electrochemical performance compared to monometallic

phosphates, due to synergy between different metal ions.

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1.2 A Review of Literature:

Transition metal phosphate such as cobalt phosphate and manganese

phosphate have been studied for supercapacitor applications because of good

conductivity, redox behavior and open frame structure. In addition, the

supercapacitor performance depends on the surface morphology of electrode

material, also a potential window playing a vital role in increasing specific

capacitance as well as the energy density of electrode material.

Hereafter, the earlier published different types of monometallic and

bimetallic phosphate-based electrode materials are summarized, such as Wang et

al. [125] prepared cobalt hydrogen phosphate nanosheets via a facile and eco-

friendly, low-temperature hydrothermal method and achieved maximum specific

capacitance of 411.2 F g-1 at a current density of 1 A g-1. Marje et al. [126]

synthesized nickel phosphate by CBD method and exhibited highest specific

capacitance of 1031 F g−1 at 0.5 mA cm−2 current density. Furthermore, Xiao et al.

[127] synthesized Co-Ni phosphate nanocages by metal-organic frameworks as a

template. Due to the synergistic effect of Co and Ni species, prepared Co-Ni

phosphate electrode showed a high specific capacitance of 1616 F g−1 at 1 A g−1 and

excellent capacitance retention of 72.46 % after 2000 GCD cycles. Mirghni et al.

[128] have been recently published a research paper on the preparation of

NiMn(PO4)2/GF cubic rods by facile hydrothermal method and achieved a

maximum specific capacity of 97 mAh g-1 at 0.5 A g−1. Moreover, Mao et al. [124]

successfully synthesized Co2Mn(PO4)2 nanorods via a mild temperature method,

which showed a specific capacitance of 525 F g-1 at 1.0 A g-1. Also, Wang et al. [129]

synthesized BaxNi3−x(PO4)2 nanofibers and reported maximum specific

capacitances of 1058 F g−1 at 0.5 A g−1. In these reported works, compared to

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monometallic phosphate, bimetallic phosphate-based electrode materials

exhibited maximum specific capacitance, high cyclic stability, and better

electrochemical performance, because of the synergy between different metal ions.

Table 1.3, 1.4, 1.5, 1.6 and 1.7 displays electrochemical properties (literature

review) of cobalt phosphate, manganese phosphate, and cobalt manganese

phosphate, respectively.

1.2.1 Literature Survey on Cobalt Phosphate:

Cobalt phosphate is the most important and attractive electrode material

for supercapacitors due to its high specific capacitance, multiple oxidation states,

natural abundance, non-toxic nature, and environmental compatibility [51, 130].

The structural parameters are important to optimize electrochemical performance

of cobalt phosphate electrode. Cobalt phosphate thin films are used for

supercapacitor applications, synthesized by various chemical methods, such as

solvothermal [131], hydrothermal [132], chemical precipitation [130], etc.

Theerthagiri et al. [120] synthesized hierarchical nanoflakes of Co3(PO4)2

by simple co-precipitation method and reported a specific capacitance of 188 F g-1

at 3 Ag-1. Also, Pang et al. [122] investigated the electrochemical supercapacitor

properties of K2Co3(P2O7)2·2H2O nanocrystalline whiskers and obtained specific

capacitance of 1100 mF cm-2 at a current density of 0.001 A cm-2. Wang et al. [125]

studied the capacitive performance of flowers-like Co(H2PO4)2 electrodes prepared

via a hydrothermal method. The Co(H2PO4)2 exhibits a maximum capacitance of

411.2 F g-1 at 1 A g-1. Pang et al. [130] successfully synthesized different

morphologies from nano-microflowers/plates-like of NH4CoPO4.H2O via co-

precipitation method and achieved specific capacitance of 369.4 F g-1 at 0.6 A g-1. Xi

et al. [131] synthesized Co3(PO4)2 nanowires which shows a high specific

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capacitance of 1174 F g−1 at 2 A g−1. Recently, Sankar et al. [132] reported 15,687

mF cm−2 specific capacitance for Co3(PO4)2 electrode synthesized via hydrothermal

method. The flower-like morphology of Co3(PO4)2.8H2O synthesized via green-

precipitation method, which shows specific capacitance of 350 F g-1 at 1 A g-1

current density and better cycle life (102 % cyclic stability over 1000 cycles) [133].

Pang et al. [134] prepared the CoHPO4.3H2O electrode and reported a specific

capacitance of 413 F g-1 at 1.5 A g-1. The Co3P2O8.8H2O onto nickel foam substrate

has been prepared via chemical precipitation method by Liu et al. [135] and

demonstrated high cyclic stability (106 %) of the electrode. Li et al. [136]

synthesized Co3P2O8.8H2O nanoparticles by chemical co-precipitation method and

electrochemical properties were tested. Cobalt phosphate hydrate nanoflakes were

directly grown on nickel foam using a hydrothermal method and utilized as binder

less electrode for high-performing supercapacitors (1578.7 F g-1 at 5 A g-1) by Shao

et al. [137]. The uniform ultralong nano-ribbons like Co11(HPO3)8(OH)6

architecture have been synthesized via hydrothermal method without any additive

and reported specific capacitance of 321 F g-1 by Pang et al. [138]. Lee et al. [139]

prepared dumbbell-shaped Co11(HPO3)8(OH)6 on Ni foam by a one-pot

hydrothermal route and specific capacitance of 226 F g-1 at 1 A g-1 was obtained.

Wang et al. [140] reported chemical precipitation of NH4CoPO4.H2O microflowers

and it exhibits high cyclic durability of 99.4 % over 400 cycles. Cobalt phosphate

(Co3(PO4)2) material was successfully prepared using the hydrothermal method by

Tang et al. [141] and reported a specific capacitance of 247.7 F g-1 at 0.25 A g-1.

Wang et al. [142] synthesized NH4CoPO4.H2O electrode by hydrothermal method

and 662 F g-1 specific capacitance was achieved at 1.5 A g-1. The cobalt phosphate

nanoflakes were deposited onto nickel foam substrate by facile hydrothermal

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method without using any surfactant and 410 F g-1 specific capacitance was

achieved by Mao et al. [143]. The flake-like Co3(PO4)2.4H2O/GF was synthesized by

a single-step hydrothermal process by Mirghni et al. [144] and reported a specific

capacity of 39.8 mAh g-1 in 6 M KOH. The rod-shaped Co7(PO4)2(HPO4)4 treated by

N-Methyl-2-Pyrrolidone (NMP) on nickel foam was fabricated using an ultrasonic

treatment route by Wang et al. [145] and obtained specific capacitance of 345 F g-

1 at a current density of 1 A g-1. Patil et al. [146] synthesized cobalt

cyclotetraphosphate (Co2P4O12) nanoparticles on carbon cloth substrate via solid-

state sintering method. The achieved specific capacitance for cobalt

cyclotetraphosphate is 437 F g-1 at 2.5 A g-1 current density. The preparation of Ni-

doped Co11(HPO3)8(OH)6 nanowire arrays by Hydro(solvo)thermal method on

nickel foam substrate and specific capacity of 159 mAh g-1 at 0.5 A g-1 current

density was reported by Dan et al. [147]. Duraisamy et al. [148] obtained a specific

capacitance of 203.4 C g-1 at 2 A g-1 for amorphous Co3(PO4)2 anisotropic

nano/micro rectangular architecture. Furthermore, Hou et al. [149] prepared the

one-dimensional (1D) Co2P2O7 using a temperature treatment method which gives

specific capacitance of 483 F g-1 in 3 M KOH. Khan et al. [150] reported the

synthesis of Co2P2O7 on carbon paper by hydrothermal method and 580 F g-1

specific capacitance was achieved for the nanosheets structured surface. The

nanoflakes like Co3(PO4)2 synthesized by Shao et al. [151] for pseudocapacitor

applications. It exhibits a specific capacitance of 1990 F g−1 at 5 mA. Moreover,

Liang et al. [152] reported the synthesis of KCoPO4·H2O electrode by hydrothermal

method and achieved a specific capacitance of 229 F g-1. Liu et al. [153] prepared

NaCoPO4.H2O by microwave-heated deposition method on nickel foam substrate

and obtained a specific capacitance of 154.8 F g-1 at 1 A g-1. Mahmoud et al. [154]

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synthesized agglomerated grains of Co3(PO4)2/GF by co-precipitation synthesis

method. Tian et al. [155] synthesized Co11(HPO3)8(OH)6 flower-like

microstructure on nickel foam substrate via a solvothermal method. The specific

capacitance of 1532.2 F g−1 is obtained for Co11(HPO3)8(OH)6 at 1 A g-1 current

density.

Moreover, a literature study of cobalt phosphate-based symmetric and

asymmetric devices is summarized in Table 1.4, such as Pang et al. [122]

manufactured solid-state micro-supercapacitors of K2Co3(P2O7)2·2H2O//Graphene

device and it exhibits specific capacitance of 6.0 F cm-3 at 10 mA cm-3 in PVA-KOH

electrolyte. The cyclic stability of micro-supercapacitor device was 94.4 % over

5000 cycles. Xi et al. [131] manufactured Co3(PO4)2//AC asymmetric device and

obtained specific capacitance of 169.35 F g-1 at 2 A g-1 and also it exhibits superior

cycling stability (85.8 % over 4000 cycles) with a little deterioration. Sankar et al.

[132] fabricated Co3(PO4)2//AC asymmetric device and achieved specific

capacitance of 85 F g-1 at 1 A g-1 and energy (26.66 Wh kg-1) and power (750 W kg-

1) density. Li et al. [136] assembled Co3P2O8.8H2O//AC asymmetric device and

achieved a specific capacitance of 55 F g-1 at a current density of 0.5 A g-1.

Furthermore, the device offers high energy (11.9 Wh kg-1) and power (3.59 kW kg-

1) density. Moreover, Shao et al. [137] fabricated Co3(PO4)2.8H2O//AC asymmetric

device and it delivers a gravimetric capacitance of 111.2 F g-1 at 5 mA cm-2. Wang

et al. [142] assembled NH4CoPO4.H2O//graphene asymmetric device and achieved

energy and power density of 26.6 Wh kg-1 and 852 W kg-1, respectively.

Furthermore, Mao et al. [143] fabricated a flexible symmetric

[Co3(PO4)2//Co3(PO4)2] device with PVA-KOH electrolyte and it exhibited a specific

capacitance of 165 F g-1 at 0.5 A g-1 with cyclic stability of 96.1 % over 2000 cycles.

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Also, Mirghni et al. [144] assembled Co3(PO4)2.4H2O/GF//C-FP hybrid asymmetric

cell consist of Co3(PO4)2.4H2O on graphene foam (GF) as positive and carbonized

Fe adsorbed polyaniline (PANI) as a negative electrode. The

Co3(PO4)2.4H2O/GF//C-FP hybrid device displayed excellent cycling stability of

~99 % with less distortion up to 10,000 cycles and energy density of 24 Wh kg-1 at

a power density of 468 W kg-1 was achieved for device. Moreover, Wang et al. [145]

fabricated Co7(PO4)2(HPO4)4//AC asymmetric device and exhibited specific

capacitance of 84.34 F g-1 at 0.5 A g-1 with better cycling stability of 93.08 % over

2500 cycles in 3 M KOH. Patil et al. [146] fabricated a Co2P4O12//AC cell with an

extended potential window (1.8 V). The reported specific capacitance of 156 F g-1

at 2.5 A g-1 and the cell deliver battery-level energy of 70 Wh kg-1 at 2300 W kg-1

power density. Dan et al. [147] fabricated Ni-doped Co11(HPO3)8(OH)6//AC

asymmetrical supercapacitor and displays a specific capacity of 55 mAh g-1 at a

current density of 0.5 A g-1 and good cycling stability of 90.5 % after 10,000 cycles.

Duraisamy et al. [148] assembled supercapattery device combining Co3(PO4)2 and

activated carbon (AC) as a cathode and anode electrode, respectively and exhibited

174 C g-1 specific capacity at 0.4 A g-1 current density with specific energy (35.5 Wh

kg-1) and power (293.9 W kg-1) density. Also, Shao et al. [151] developed a low cost

and scalable prototype supercapattery of Co3(PO4)2//AC and it delivers high

energy (43.2 Wh kg−1) and power density (5.8 W kg−1) with excellent cyclic stability

(68 % retention over 1,00,000 cycles). Mahmoud et al. [154] made an asymmetric

device using Co3(PO4)2/GF and biomass-derived activated carbon from pepper

seed (ppAC) as a cathode and anode, respectively, which provided energy density

of 52 Wh kg-1. The Co3(PO4)2/GF//ppAC asymmetric device exhibited capacity

retention of 80 % over 10,000 cycles. Tian et al. [155] fabricated asymmetric

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supercapacitor of Co11(HPO3)8(OH)6//AC and exhibits specific capacitance of 65.3

C g-1 at 1 A g-1. The asymmetric device shows cycling stability of 83.5 % over 7800

cycles.

Electrochemical performance of cobalt phosphate-based single electrodes

and symmetric as well as asymmetric devices with their specific capacitance,

energy and power density, and the synthesis method are summarized in Tables

1.3 and 1.4. Also, some articles on cobalt phosphide-based single electrode

materials and devices are summarized in Tables 1.3 and 1.4, respectively [156-

166]. A literature survey indicates that, cobalt phosphate electrodes have low

energy density than current battery technology. Hence, some extra efforts are

needed to enhance the electrochemical performance of cobalt phosphate-based

electrodes.

1.2.2 Literature Survey on Manganese Phosphate:

In recent years, manganese phosphate has got a significant technical and

scientific importance, due to its electrochemical properties, such as long-term

cyclic stability, energy density, and wide potential window, in energy storage

devices [167]. Several deposition methods have been summarized for the

preparation of manganese phosphate materials as an electrode for

supercapacitors, such as hydrothermal method [168], sol-gel technique [169],

electrodeposition [170], solvothermal method [171], chemical precipitation

[167], etc. Most of these studies focused on synthesis methods with the purpose of

achieving enhanced specific capacitance and long-term cycling behavior. The

electrochemical properties of manganese phosphate-based single electrodes and

symmetric and asymmetric devices are summarized in Tables 1.5 and 1.6.

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Dai et al. [167] synthesized Mn3(PO4)2·3H2O on Ni foam using co-

precipitation method and it obtained a specific capacitance of 370 F g-1 at 0.5 A g-1.

Mirghni et al. [168] synthesized hexagonal micro-rods like Mn3(PO4)2/GF by a

facile hydrothermal method. This Mn3(PO4)2/GF electrode displays specific

capacitance of 270 F g-1 with excellent cyclic stability (99 % after 1000) retention.

Priyadharsini et al. [169] obtained 516 F g-1 specific capacitance for KMnPO4.H2O

over SS substrate prepared by sol-gel method. Furthermore, Hao et al. [170]

prepared PMn (phosphating manganese oxide) nanosheets array onto indium

doped tin oxide (ITO) substrate by electrodeposition process exhibited specific

capacitance of 6.7 mF cm-2 at 5 mV s-1 in 0.1 M Na2SO4. Xu et al. [171] prepared

LiMnPO4 nano-particles via PVP-assisted solvothermal process and obtained a

specific capacitance of 217 C g-1 at 0.5 A g-1. Moreover, Pang et al. [172] reported

NH4MnPO4.H2O micro-nano structure via heat treatment and 35 F g-1 specific

capacitance at a scan rate of 10 mV s-1. Yan et al. [173] synthesized MnPO4.H2O/GO

on Ni-foam using the hydrothermal method and obtained specific capacitance of

287.9 F g-1. Ma et al. [174] reported long-term cycling (10,000 cycles) behavior

with 91.1 % stable performance and highest specific capacitance (203 F g-1 at 0.5 A

g-1) for Mn3(PO4)2 electrode. Also, Lee et al. [175] prepared Mn3(PO4)2/PANI

nanoparticles using the sonochemical method and specific capacitance of 347 C g-1

at 1 A g-1 discharge rate. Yang et al. [176] reported Mn3(PO4)2.3H2O/graphene

synthesis by exfoliation precipitation based on the chemical reaction of ammonium

phosphate with manganese chloride in an aqueous solution and reported 152 F g-1

specific capacitance. Also, it obtained energy and power density of 0.17 µWh cm-2

and 46 µW cm-2, respectively. Raju et al. [177] prepared NH4MnPO4.H2O

nanosheets by a microwave-assisted method and obtained capacitance of 423 F g-

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1 at scan rate of 5 mV s-1. Also, cyclic stability after 10,000 cycles of electrode is 97

%. Moreover, Senthilkumar et al. [178] synthesized NaMnPO4 microparticles over

graphite sheet by solution combustion synthesis and reported specific capacitance

of 163 F g-1 at 2 mA cm-2 current density. Sharmila et al. [179] prepared manganese

phosphate by hydrothermal method on nickel foam substrate and reported a

specific capacitance of 290 F g-1 in 0.5 V potential window. Also, it obtained energy

and power density of 15 Wh kg−1 and 350 W kg−1, respectively. Also, Raja et al.

[180] prepared NH4MnPO4.H2O-rGO clusters of flake slabs by a microwave-

assisted method and obtained capacitance of 705 F g-1 at a current density of 1 A g-

1. Also, cycling stability over 5000 cycles of an electrode is 85 %. Recently, Zhang et

al. [181] prepared Mn(PO3)2 ultrathin porous nanosheets on N, P doped graphene

(NPG) framework by hydrothermal method. The Mn(PO3)2/NPG hybrid electrode

delivers excellent specific capacitance of 2073.4 F g-1 at 1 A g-1 and good capacity

retention of 92.9 % over 10,000 cycles.

Furthermore, a literature study of manganese phosphate-based symmetric

and asymmetric devices are summarized, such as Dai et al. [167] assembled

Mn3(PO4)2.3H2O//AC asymmetric cell consists of Mn3(PO4)2.3H2O and activated

carbon (AC) as a cathode and anode, respectively. The Mn3(PO4)2.3H2O//AC device

showed better cycling stability of ~65.22 % with small degradation up to 2000

cycles. The energy density of 32.32 Wh kg-1 at a power density of 4250 W kg-1 was

achieved for the device. Mirghni et al. [168] fabricated Mn3(PO4)2/GF//AC

asymmetric cell device within the potential window of 0.0-1.4 V and achieved a

specific capacitance of 28 F g-1 at a current density of 0.5 A g-1 in 6 M KOH. The

energy and power density of Mn3(PO4)2/GF//AC device is 7.6 Wh kg-1 and 3528 W

kg-1, respectively. Xu et al. [171] assembled LiMnPO4/rGO//rGO asymmetric

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device and achieved excellent energy (16.46 Wh kg-1) and power (0.38 kW kg-1)

density. The LiMnPO4/rGO//rGO device maintains 91.2 % of initial capacity over

10,000 cycles and it displays high rate performance and long cycling stability.

Moreover, Yan et al. [173] assembled MnPO4.H2O/GO//MnPO4.H2O/GO symmetric

device. The reported specific capacitance of symmetric device is 115.63 F g-1 at

0.625 A g-1 current density. Furthermore, the device offers high energy (5.78 Wh

kg-1) and power density (150 kW kg-1). Ma et al. [174] fabricated symmetric

(Mn3(PO4)2//Mn3(PO4)2) and asymmetric (Mn3(PO4)2//AC) devices exhibit

specific capacitance of 53.7 F g-1 and 46.8 F g-1 respectively at 0.5 A g-1, in 1 mol L-1

Na2SO4 electrolyte. Also, Lee et al. [175] manufactured Mn3(PO4)2/PANI//AC and

reported specific capacity of 73 C g-1 at 0.5 A g-1 with 80 % capacitive retention

after 3000 charge-discharge cycles. Yang et al. [176] fabricated symmetric

Mn3(PO4)2.3H2O/Graphene//Mn3(PO4)2.3H2O/Graphene device and displayed

specific capacitance of 152 F g-1 (0.5 mV s-1) in PVA-KOH solid polymer electrolyte

with cyclic stability of 100 % over 2000 GCD cycles. Furthermore, Raju et al. [177]

fabricated symmetric (NH4MnPO4.H2O//NH4MnPO4.H2O) and asymmetric

(NH4MnPO4.H2O//AC) devices having a voltage of 1.2 V and 1.8 V, respectively. The

achieved specific capacitance for symmetric and asymmetric device is 48.4 F g-1

and 65.4 F g-1 (at 5 mV s-1 scan rate), respectively. Also, maximum energy and

power density were achieved by symmetric (9.7 Wh kg-1, 262 kW kg-1) and

asymmetric (29.4 Wh kg-1, 133 kW kg-1) devices. Also, Raja et al. [180] fabricated

NH4MnPO4.H2O/rGO//rGO asymmetric cell and reported 336 F g-1 specific

capacitance at 1 A g-1, the cell delivers maximum energy of 151 Wh kg-1 at 448 W

kg-1 power density in 3 M H2SO4. Zhang et al. [181] fabricated an asymmetric

hybrid device using Mn(PO3)2 as positive and MoO2 as negative electrodes (on N, P

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dual-doped graphene (NPG) framework), and revealed specific capacitance of

213.8 F g-1 at 0.8 A g-1 current density with high specific energy (96.2 Wh kg-1) and

power (726.7 W kg-1) density.

1.2.3 Literature Survey on Cobalt Manganese Phosphate:

Nowadays, technology is dedicated to the development of emerging active

materials for supercapacitors that meet specific requirements in terms of their

capacitive efficiency. The design and fabrication of supercapacitor electrodes

require high specific capacitance, high power density, wide potential window, and

fast charging-discharging rate. Therefore, combining advantages of both metal

phosphates (cobalt and manganese phosphate) is a very effective strategy to

optimize each metal phosphate for improving their electrochemical performance.

Accordingly, the cobalt manganese phosphate is the proper electrode material for

construction of supercapacitors, since it has multiple redox sites, good electrolyte

stability and better electron transport/diffusion, so it can give an excellent

electrochemical performance. The reported electrochemical capacitive

performance of cobalt manganese phosphates-based electrodes are summarized in

Table 1.7.

Mao et al. [124] prepared cobalt manganese phosphate (Co2Mn(PO4)2) on a

nickel foam substrate by the mild chemical method. They exhibit significantly

improved electrochemical performance (525 F g-1 at 1 A g-1) and good capacitive

retention (95.3 %) for supercapacitor application. Moreover, Chinnadurai et al.

[182] reported a hydrothermal method for synthesis of MnxCo3−x(PO4)2·8H2O

nanoflowers and it shows 979.9 F g-1 capacitance at a current density of 2 A g-1 in a

3 M KOH.

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A literature study reveals that, only a few reports are available on cobalt

phosphate, manganese phosphate, and cobalt manganese phosphate preparation

by chemical methods. So, our aim is to prepare cobalt manganese phosphate using

simple chemical methods, such as hydrothermal and successive ionic layer

adsorption and reaction (SILAR). These are promising methods for the preparation

of metal phosphate thin films over stainless steel substrate. Those methods are

probably easiest, low cost, and suitable to prepare large-area, binder-free thin film

electrodes for supercapacitor applications.

Chapter 1 Page 35
 General Introduction And Literature Survey

Table 1.3: Comparative literature survey of electrochemical capacitive performance of cobalt phosphate based electrodes.

Sr. Material Sub- Method of Electro- Capacitance Energy Power Cycles Stability Ref.
No. (Nano/Micro strate deposition lyte at current density density
structure) density
1. Co3(PO4)2 Carbon Co-precipitation 3 M KOH 188 F g-1 at 3 32.6 Wh 420 W 800 95 % 120
(Nanoflakes) Paper A g-1 kg-1 kg-1
2. K2Co3(P2O7)2·2H2O Nickel Hydrothermal 3 M KOH 1100 mF cm- -- -- -- -- 122
(Nanocrystal Foam 2 at 1.0 mA

whiskers) cm-2
3. Co(H2PO4)2 Nickel Hydrothermal 2 M KOH 411.2 F g-1 at -- -- 10000 97.6 % 125
(Nanoflower) Foam 1 A g-1
4. NH4CoPO4.H2O Nickel Chemical 3 M KOH 369.4 F g-1 at 10.4 Wh 1407 W 400 99.7 % 130
(Nano/Microflowers/ Foam precipitation 0.625 A g-1 kg-1 kg-1
plates)
5. Co3(PO4)2 Nickel Solvothermal 3 M KOH 1174 F g-1 at -- -- 4000 -- 131
(Nanowires) Foam 2 A g-1
6. Co3(PO4)2 Nickel Hydrothermal 1 M KOH 15,687 mF 0.41 1.065 6000 89 % 132
(Nanograss) Foam cm−2 at 6 A mWh mW cm-
g−1 cm-2 2

7. Co3(PO4)2.8H2O Nickel Green- 3 M KOH 350 F g-1 at 1 -- -- 1000 102 % 133

(Flower like) Foam precipitate A g-1
process
8. CoHPO4.3H2O Nickel Hydrothermal 3 M KOH 413 F g-1 at 8.7 Wh 3225 W 3000 58.1 % 134
(Layered) Foam 1.5 A g-1 kg-1 kg-1
9. Co3P2O8.8H2O (Flakes) Nickel Chemical 6 M KOH 205 F g-1 at 1 -- -- 1000 106 % 135
Foam precipitation A g-1

Chapter 1 Page 36
 General Introduction And Literature Survey

10. Co3P2O8.8H2O Nickel Chemical 3 M KOH 446 F g-1 at -- -- 1000 100 % 136
(Nanoparticles) Foam precipitation 0.5 A g-1
11. Co3(PO4)2.8H2O Nickel Hydrothermal 1M 1578.7 F g-1 -- -- 1000 72.8 % 137
(Nanoflakes) Foam NaOH at 5 A g-1
12. Co11(HPO3)8(OH)6 Nickel Hydrothermal 3 M KOH 321 F g-1 at -- -- 3000 89.4 % 138
(Nano-ribbons) Foam 1.25 A g-1
13. Co11(HPO3)8(OH)6 Nickel Hydrothermal 3 M KOH 226 F g-1 at 1 -- -- 30 76 % 139
(Dumbbell like shape) Foam A g-1
14. NH4CoPO4.H2O Nickel Chemical 1 M KOH 525 F g-1 at 11.9 Wh 1377 W 400 99.4 % 140
(Microflowers) Foam precipitation 0.625 A g-1 kg-1 kg-1
15. Co3(PO4)2 Nickel Hydrothermal 2 M KOH 247.7 F g-1 at -- -- -- -- 141
(Mesoporous) Foam 0.25 A g-1
16. NH4CoPO4.H2O Nickel Hydrothermal 3 M KOH 662 F g-1 at 26.6 Wh 852 W 3000 92.7 % 142
(Microbundles) Foam 1.5 A g-1 kg-1 kg-1
17. Co3(PO4)2 Nickel Hydrothermal 3 M KOH 410 F g-1 at 1 -- -- 2000 96.1 % 143
(Leaf like, Nanoflakes) Foam A g-1
18. Co3(PO4)2.4H2O/GF Nickel Hydrothermal 6 M KOH 39.8 mAh g-1 -- -- -- -- 144
(Flakes) Foam at 10 A g-1
19. Co7(PO4)2(HPO4)4 Nickel Ultrasonic 3 M KOH 345 F g−1 at -- -- 2000 80.14 % 145
/NMP (rod-shaped) Foam treatment 1 A g−1
20. Co2P4O12 Carbon Solid-state 2 M KOH 437 F g-1 at -- -- 3000 90 % 146
(Nanoparticles) Cloth sintering 2.5 A g-1
21. Ni-doped Nickel Hydro(solvo) 2 M KOH 159 mAh g-1 -- -- 8000 71.1 ％ 147
Co11(HPO3)8(OH)6 Foam thermal at 0.5
(nanowire arrays) A g-1

Chapter 1 Page 37
 General Introduction And Literature Survey

22. Co3(PO4)2 (Anisotropic Nickel Sonochemical 1 M KOH 203.4 C g-1 at -- -- -- -- 148

nano/micro Foam 2 A g-1
rectangular)
23. Co2P2O7 (Nanorods) Nickel Temperature 3 M KOH 483 F g-1 at 1 -- -- 3000 90 % 149
Foam treatment A g-1
24. Co2P2O7 (Nanosheets) Carbon Hydrothermal 3 M KOH 580 F g−1 at -- -- 5000 96 % 150
paper 1 A g−1
25. Co3(PO4)2 Nickel Hydrothermal 3 M KOH 1990 F g−1 -- -- 20000 80.4 % 151
(Nanoflakes/flower) Foam at 5 mA
26. KCoPO4·H2O Nickel Hydrothermal 1 M KOH 229 F g−1 at -- -- 100 123 % 152
(Plate-like) Foam 1.5 A g−1
27. NaCoPO4.H2O Nickel Microwave- 1 M KOH 154.8 F g-1 at -- -- 3000 95.5 % 153
(Particles) Foam heated 1 A g-1
28. Co3(PO4)2/GF Nickel Co-precipitation 1 M KOH 57 mAh g-1 at -- -- 5000 89 % 154
(Agglomerated grains) Foam 0.5 A g-1
29. Co11(HPO3)8(OH)6 Nickel Solvothermal 2 M KOH 1532.2 F g−1 -- -- 1000 64 % 155
(Flower-like Foam at 1 A g-1
microstructure)
30. CoP Carbon Hydrothermal 1 M LiCl 571.3 mF -- -- 5000 82 % 156
(Nanowire arrays) Cloth cm-2 at 1 mA
cm-2
31. CoP (Nanotube arrays) Carbon Hydrothermal 6 M KOH 610 F g-1 at -- -- 10000 99 % 157
Cloth 1.0 A g-1
32. Co2P (Nanoshuttles) Nickel Hydrothermal 6 M KOH 246 F g−1 at -- -- 1000 72 % 158
Foam 1 A g−1
33. Co2P (Nanoflowers) Nickel Thermal 6 M KOH 416 F g-1 at 1 -- -- -- -- 159
Foam decomposition A g-1
Chapter 1 Page 38
 General Introduction And Literature Survey

34. Co2P (Nanoflowers) Nickel Thermal 6 M KOH 412.7 F g-1 at -- -- 10000 124.7 % 160
Foam decomposition 1 A g-1
35. CoP (Nanosheets) Nickel Solvothermal 6 M KOH 416 F g-1 at 2 -- -- 900 97 % 161
Foam A g-1
36. CoP (Microcubes) Nickel Low- 6 M KOH 560 F g−1 at -- -- 10000 91.2 % 162
Foam temperature 1 A g−1
37. CoP (Nanoprism Nickel Hydrothermal 6 mol L-1 1349 F g-1 at -- -- 5000 85 % 163
array) Foam KOH 1 A g-1
38. CoP (Nanowires) Stainle Hydrothermal- 2 M KOH 558 F g-1 at 1 23.4 Wh 274.4 W 5000 98 % 164
ss Steel oxidation- A g-1 Kg-1 Kg-1
Wire phosphidation
39. CoP (Nanoparticles) Stainle Mechanical 6 M KOH 447.5 F g-1 at -- -- 5000 84.3 % 165
ss Steel alloying 1 A g-1
40. Mn-CoP (Nanowire Nickel Hydrothermal 6 M KOH 8.66 F cm-2 at -- -- 2000 82.1 % 166
decorated nanosheets Foam 1 mA cm–2
cluster arrays)

Table 1.4: Literature survey of cobalt phosphate based symmetric and asymmetric devices.

Sr. Material Sub- Electro- Capacitance at a Energy Power Cycles Stability Ref.
No. (Nano/micro- strate lyte current density density density
structure)
1. K2Co3(P2O7)2·2H2O Nickel PVA-KOH 6.0 F cm-3 at 10 0.96 mWh cm-3 54.5 mW cm-3 5000 94.4 % 122
nanocrystalline Foam mA cm-3
whisker//Graphene
nanosheets

Chapter 1 Page 39
 General Introduction And Literature Survey

2. Co3(PO4)2//AC Nickel 3 M KOH 169.35 F g-1 at 2 -- -- 4000 85.8 % 131

(Nanowires) Foam A g-1
3. Co3(PO4)2//AC Nickel 1 M KOH 85 F g-1 at 1 A g-1 26.66 Wh kg-1 750 W kg-1 6000 80 % 132
(Nanograss) Foam
4. Co3P2O8. 8H2O//AC Nickel 3 M KOH 55 F g-1 at 0.5 A g- 11.9 Wh kg-1 3.59 kW kg-1 1000 -- 136
(Nanoparticles) Foam 1

5. Co3(PO4)2.8H2O//AC Nickel 1 M NaOH 111.2 F g-1 at 5 5.33 Wh kg-1 4687 W kg-1 -- -- 137
(Nanoflakes) Foam mA cm-2
6. NH4CoPO4.H2O//grap Nickel 3 M KOH -- 26.6 Wh kg-1 852 W kg-1 -- -- 142
hene (Microbundles// Foam
nanosheets)
7. Co3(PO4)2 //Co3(PO4)2 Nickel PVA-KOH 165 F g-1 at 0.5 A 52.8 Wh kg-1 756 W kg-1 2000 96.1 % 143
(Leaf like, Nanoflakes) Foam g-1
8. Co3(PO4)2.4H2O/GF// Nickel 6 M KOH 24 mAh g-1 at 10 24 Wh kg-1 468 W kg-1 10000 99 % 144
C-FP Foam A g-1
9. Co7(PO4)2(HPO4)4 Nickel 3 M KOH 84.34 F g-1 at 0.5 26.04 Wh kg-1 372.75 W kg-1 2500 93.08 % 145
/NMP//AC Foam A g-1
(rod-shaped)
10. Co2P4O12//AC Carbon KI-added 156 F g-1 at 2.5 A 70 Wh kg-1 2300 W kg-1 5000 94 % 146
(Nanospheres) Cloth KOH g-1
11. Ni-doped Nickel 2 M KOH 55 mAh g-1 at 0.5 58.7 Wh kg-1 532 W kg-1 10000 90.5 % 147
Co11(HPO3)8(OH)6//A Foam A g-1
C (nanowire arrays)
12. Co3(PO4)2//AC Nickel 1 M KOH 174 C g-1 at 0.4 A 35.5 Wh kg-1 293.9 W kg-1 3000 93 % 148
(Anisotropic nano/ Foam g-1
micro rectangular)

Chapter 1 Page 40
 General Introduction And Literature Survey

13. Co3(PO4)2//AC Nickel 3 M KOH 107.7 F g−1 at 5 43.2 Wh kg−1 5.8 W kg−1 100000 68 % 151
(Nanoflakes/Flower) Foam mA
14. Co3(PO4)2/GF//ppAC Nickel 1 M KOH -- 52 Wh kg-1 847 W kg-1 10000 80 % 154
(Agglomerated grains) Foam
15. Co11(HPO3)8(OH)6// Nickel 2 M KOH 65.3 C g-1 at 1 A g- 14.5 Wh kg-1 799.4 W kg-1 7800 83.5 % 155
AC (Flower-like Foam 1

microstructure)
16. CoP//MnO2 Carbon PVA-LiCl 1.94 F cm-3 at 1 0.69 mWh cm-3 10.1 mW cm-3 5000 82 % 156
(Nanowire arrays Cloth mA cm-2
//nanowire)
17. CoP//CoP PVA-LiCl 35.4 mF cm-2 at 1 -- -- 5000 87.05 %
(Nanowire arrays) mA cm-2
18. Co(P,S)/CC//PCP/rGO Nickel 6 M KOH 109.5 F g-1 at 1.0 39 Wh kg-1 0.8 kW kg-1 50000 86.4 % 157
(Nanowires) Foam A g-1
19. Co2P//Graphene Nickel 6 M KOH 76.8 F g-1 at 0.4 A 24 Wh kg-1 300 W kg-1 6000 97 % 159
(Nanoflowers) Foam g-1
20. Co2P//AC (Hollow Nickel 6 M KOH 75.9 F g-1 at 1 A g- 30.5 Wh kg−1 850 W kg−1 10000 108 % 160
nanoflowers) Foam 1

21. CoP//N-doped Nickel 6 M KOH 68.8 F g−1 at 0.5 A 21.4 W h kg−1 373 W kg−1 6000 81.2 % 162
graphene Foam g−1
(Microcubes)
22. CoP//CMK-3 (ordered Nickel 6 mol L-1 -- 24 Wh kg−1 325 W kg−1 5000 93 % 163
mesoporous carbon) Foam KOH
(Nanoprism array)
23. CoP (Nanoparticles) Stainle 6 M KOH 70 F g-1 at 0.5 A g- 19 Wh kg-1 350.8 W kg-1 5000 96.7 % 165
ss Steel 1

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 General Introduction And Literature Survey

24. Mn-CoP//AC Nickel 6 M KOH 98.9 F g-1 at 5 mA 35.21 Wh kg-1 193 W kg-1 4000 88.9% 166
(Nanowire decorated Foam cm-2
nanosheet cluster
arrays)

Table 1.5: Comparative literature survey of electrochemical capacitive performance of manganese phosphate based electrodes.

Sr. Material Sub- Method of Electro-Capacitance Energy Power cycles stability Ref.
No. (Nano/micro- strate deposition lyte at current density density
structure) density/
scan rate
1. Mn3(PO4)2·3H2O Nickel Chemical 2 M KOH 370 F g-1 at -- -- 2000 74 % 167
(Nanosheets) Foam precipitation 0.5 A g−1
2. Mn3(PO4)2/GF Nickel Hydrothermal 6 M KOH 270 F g-1 at -- -- 1000 99 % 168
(Hexagonal Micro- Foam 0.5 A g-1
rods)
3. KMnPO4.H2O Stainless Sol-Gel method 1 M KOH 516 F g-1 at 2 -- -- 1000 82 % 169
(Submicron sized Steel mV s-1
particles)
4. PMn ITO Electro- 0.1 M 6.7 mF cm-2 -- -- 5000 87.6 % 170
(Nanosheets array) deposition Na2SO4 at 5 mV s-1
5. LiMnPO4 Nickel Solvothermal 1M 217 C g-1 at -- -- -- -- 171
(Nanoparticles) Foam LiOH 0.5 A g-1
6. NH4MnPO4.H2O Nickel Heat Treatment 1 mol L-1 35 F g-1 at 10 -- -- -- -- 172
(Micro-Nano Grid Na2SO4 mV s-1
Structure)

Chapter 1 Page 42
 General Introduction And Literature Survey

7. MnPO4.H2O/GO Nickel Hydrothermal 3 M KOH 287.9 F g-1 at -- -- -- -- 173

(Nanowires) Foam 0.625 Ag-1
8. Mn3(PO4)2 Nickel Hydrothermal 1 mol L-1 203 F g-1 at -- -- 10000 91.1 % 174
(Nanosheets) Foam Na2SO4 0.5 A g -1

9. Mn3(PO4)2/PANI Nickel Sonochemical 1 M KOH 347 C g-1 at 1 -- -- 3000 60 % 175

(Nanoparticle) Foam method Ag -1

10. Mn3(PO4)2.3H2O Nickel Exfoliation 6 M KOH 152 F g-1 at 0.17 46 μW 2000 100 % 176
/Graphene Foam Precipitation 0.5 A g-1 μWh cm- cm-2
(Nanosheets) 2

11. NH4MnPO4.H2O Nickel Microwave 3 M KOH 423 F g-1 at 5 -- -- 10000 97 % 177

(Nanosheets) Foam assisted mV s-1
12. NaMnPO4 Graphite Solution 1M 163 F g-1 at 2 -- -- 1000 93 % 178
(Microparticles) Sheet combustion NaOH mA cm-2
synthesis
13. MnPO4·H2O Nickel Hydrothermal 0.2 M 290 F g-1 at 2 15 Wh 350 W 5000 93.3 % 179
(Nanosheets) Foam KOH A g-1 kg−1 kg−1
14. NH4MnPO4.H2O– Graphite Microwave route 2M 705 F g-1 at 1 -- -- 5000 85 % 180
rGO (Clusters of H2SO4 A g-1
flake slabs)
15. Mn(PO3)2 N, P dual- Hydrothermal 6 M KOH 2073.4 F g-1 -- -- 10000 92.9 % 181
(Ultrathin doped at 1 A g-1
porous nanosheets) Graphene
(NPG)

Chapter 1 Page 43
 General Introduction And Literature Survey

Table 1.6: Comparative literature survey of manganese phosphate based symmetric/asymmetric device.

Sr. Material Substrate Electro- Capacitance at Energy Power cycles stability Ref.
No. (Nano/micro- lyte a current density density
structure) density/scan
rate
1. Mn3(PO4)2.3H2O//AC Nickel 2M -- 32.32 Wh kg-1 4250 W kg-1 2000 65.22 % 167
(Nanosheets) Foam KOH
2. Mn3(PO4)2/GF//AC Nickel 6 M KOH 28 F g-1 at 0.5 A 7.6 Wh kg-1 3528 W kg-1 10000 96 % 168
(Hexagonal Micro-rods) Foam g-1
3. LiMnPO4/rGO//rGO Nickel 1 M LiOH 79 C g-1 at 0.5 A 16.46 Wh kg-1 0.38 kW kg-1 10000 91.2 % 171
(Nanoparticles) Foam g-1
4. MnPO4.H2O/GO// Nickel 3 M KOH 115.63 F g-1 at 5.78 Wh kg-1 150 kW kg-1 1000 85.3 % 173
MnPO4.H2O/GO Foam 0.625 A g-1
(Nanowires)
5. Mn3(PO4)2//AC Nickel 1 mol L-1 46.8 F g-1 at 0.5 16.64 Wh kg-1 7984.48 W 10000 90 % 174
(Nanosheets) Foam Na2SO4 A g-1 kg-1
6. Mn3(PO4)2//Mn3(PO4)2 1 mol L-1 53.7 F g-1 at 0.5 19.09 Wh kg-1 8033 W kg-1 10000 90 %
Na2SO4 A g-1
7. Mn3(PO4)2/PANI//AC Nickel 1 M KOH 73 C g-1 at 0.5 A 14.7 Wh kg-1 2988 W kg-1 3000 80 % 175
(Nanoparticle) Foam g-1
8. Mn3(PO4)2.3H2O/Graph Nickel PVA-KOH 152 F g-1 at 0.5 35.5 Wh kg-1 365 W kg-1 2000 100 % 176
ene//Mn3(PO4)2.3H2O/ Foam mV s-1
Graphene (Nanosheets)
9. NH4MnPO4.H2O// Nickel 3 M KOH 65 F g-1 at 5 mV 9.7 Wh kg-1 262 kW kg-1 10000 98 % 177
NH4MnPO4.H2O Foam s-1
(Nanosheets)

Chapter 1 Page 44
 General Introduction And Literature Survey

10. NH4MnPO4.H2O//AC PVA-KOH 48.4 F g-1 at 5 29.4 Wh kg-1 133 kW kg-1 100000 93 %
(Nanosheets) mV s-1
11. NH4MnPO4.H2O/rGO//r Graphite 3M 336 F g-1 at 1 A 151 Wh 448 W kg-1 5000 80 % 180
GO (Clusters of flake H2SO4 g-1 kg-1
slabs)
12. Mn(PO3)2/NPG-2// N, P dual- 6 M KOH 213.8 F g-1 at 96.2 Wh kg-1 726.7 W kg-1 10000 91.52 % 181
MoO2/NPG (Ultrathin doped 0.8 A g-1
Porous nanosheets graphene
//nanocrystal array) (NPG)

Table 1.7: Comparative literature survey of electrochemical capacitive performance of cobalt manganese phosphate based electrodes.

Sr. Material Sub- Method of Electro-

Capacitance Energy Power Cycles Stability Ref.
No. (Nano/micro- strate deposition lyte at current density density
structure) density
1. Co2Mn(PO4)2 Nickel Mild chemical 3 M KOH 525 F g-1 at 1 -- -- 5000 95.3 % 124
(Nanorods) Foam method A g-1
2. MnxCo3−x(PO4)2·8H2O Nickel Hydrothermal 3 M KOH 979.91 F g-1 -- -- -- -- 182
(Nanoflowers) Foam at 2 A g-1

Chapter 1 Page 45
 General Introduction And Literature Survey

1.3 Orientation and Purpose of the Dissertation:

Modern investigation on supercapacitor provides an idea about advanced

energy storage devices, which are utilized in hybrid electric vehicles, portable

electronic devices, laptops, and power backup, etc. Therefore, supercapacitors

have been considered to be a widespread alternative to batteries. Supercapacitors

offer many potential benefits to their efficiency, including higher energy as well as

power density, better lifetime, and faster charge-discharge rates. Moreover, a

comparatively quick response is necessary for supercapacitor to deliver pulse

power, which can be achieved by lowering equivalent series resistance (ESR).

Therefore, the design and development of active electrode materials to satisfying

the above requirements become an interesting aspect for many electrochemists.

The trend of recent research is focused on producing binary metal

phosphate materials to achieve superior electrochemical efficiency with a high

value of energy and power density. Binary metal phosphate-based supercapacitors

are an important incoming class of electrochemical capacitors, likely to deliver high

energy density at high charging-discharging rates. Improvements in the operating

potential window, specific capacitance and energy density of binary metal

phosphate-based electrodes significantly increase the overall electrochemical

efficiency of the supercapacitor. In addition, the lack of one active (cobalt) material

can be accomplished by another active (manganese) material, and synergy

between both (cobalt manganese phosphate) materials can result in increased

electrochemical performance. The cobalt and manganese with their multiple

oxidation states and high electrical conductivity help to increase working potential

window, capacitance and thereby energy and power density of supercapacitor

devices containing aqueous or neutral electrolytes. In preparation of such

Chapter 1 Page 46
 General Introduction And Literature Survey

electrode materials, a simple, inexpensive and convenient chemical way to

maintain the cost of supercapacitor cells is important. Among various other

deposition methods, hydrothermal and SILAR have many advantages. Chemical

methods produce pinhole-free, well adherent and uniformly deposited thin films.

The nucleation and growth in chemical systems play an important part in the

formation of nanocrystalline materials. Also, these methods are generally used for

large area deposition, which is beneficial for device fabrication.

The literature study clarifies that, a new class of cobalt manganese

phosphate based electrode materials can be synthesized and asymmetric devices

can be fabricated using flexible SS substrates and polymer gel electrolytes. Metal

phosphates (cobalt phosphate, manganese phosphate, cobalt manganese

phosphate) with various types of morphologies could be prepared by simple

chemical methods and utilized as electrode materials in supercapacitors. The

purpose behind construction of asymmetric supercapacitors is to test the

practicability of active electrode material at device level. Our prior aim is that,

synthesis of cobalt manganese phosphate thin films by simple chemical methods

and characterize these thin films with various physico-chemical characterization

techniques. The preparative parameters like pH, concentration, temperature of

solution, and deposition time are optimized. The simple chemical methods

(Hydrothermal and SILAR) can provide binder-free and additive-less thin film

electrodes by improving the interfacial contact of active material and stainless steel

(SS) substrates. Also, corrosion and oxidation of metallic substrates can be

restricted using low temperature deposition methods.

Furthermore, well adherent and uniform cobalt manganese phosphate thin

films are evaluated for phase analysis, structural interpretation, compositional

Chapter 1 Page 47
 General Introduction And Literature Survey

analysis, surface, and microstructural analysis. The X-ray diffraction (XRD)

technique was utilized for phase confirmation of material and chemical bonding in

prepared material was studied by fourier transform infrared spectroscopy analysis

(FTIR). The morphological evaluation of thin film material was carried out using

field emission scanning electron microscopy (FE-SEM) technique. The energy-

dispersive X-ray spectroscopy (EDS) technique is used for confirmation of

elemental composition. The X-ray photoelectron spectroscopy (XPS) technique is

employed for the identification of oxidation states, chemical composition, and

confirmation of material formation. The electrochemical capacitive performances

of the electrodes are investigated by cyclic voltammetry (CV), galvanostatic charge-

discharge measurement (GCD), and electrochemical impedance spectroscopy (EIS)

using an electrochemical workstation. The supercapacitive performance of cobalt

manganese phosphate thin film electrodes and asymmetric device is evaluated

with different electrochemical parameters such as potential window, specific

capacitance, specific power, specific energy, and cycle stability.

Chapter 1 Page 48
 General Introduction And Literature Survey

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