CHAPTER

Introduction, Electrochemical cells and redox

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 Introduction and Fundamentals of Batteries Chapter 1

Abstract: In the first chapter, we have discussed about the importance of

electrochemical energy storage system along with the conversion devices in daily life

and also highlighted the advantages of low cost, simple, eco-friendly, less expensive

and safe battery systems for the present situation. Herein, gave highlighted introduction

about batteries which includes development, basic components, classification, basic

principles involved in the working of batteries and some important parameters of

batteries. This is followed by general introduction of secondary rechargeable battery

system. The basics of rechargeable lithium-ion batteries, electrode materials for RLIBs

and the advantages and limitations of RLIBs have also been discussed. The application

of organic electrode materials in RLIBs, challenges faced by the organic electrode

materials, merits and demerits of organic compounds, have been discussed along with

the advantages and limitations over non-aqueous RLIBs, development and working

principle.

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 Introduction and Fundamentals of Batteries Chapter 1

1.1 General Introduction

The demand for the constant energy supply in the world is expected to increase by

50 % from 2015 to 2040 [1]. At the same time, dealing with man-made climate change is an

irrefutable importance. The fading supply of fossil fuels, the increase in global warming and

the contamination of the environment have led to increased renewable energy practices. Since

then, green energy feeds have oscillated over the season and time of year [2]. Admirably,

energy supply would be both economically sustainable and cost-effective. The increase in the

living standards of today's population contributes to the demand for greater power output [3].

However, a growing awareness of human impacts on the environment and limited energy

sources on planet leads to increased energy production, which should ideally be more

sustainable and less polluting. The "cleaner world" is not only a priority for future

generations, but also a means of avoiding the exhaustion of greenhouse gasses caused by

climate change [4] and of controlling the problems of smog formation in industrial areas and

large cities [5]. The conventional development of current methods is replaced by renewable

sources of energy including wind, tidal solar and geothermal energy. At present, the

accelerated development of energy needs, fossil fuels such as natural gas, coal and petroleum

are being exploited on a massive scale, while gas emissions, on the other hand, cause serious

environmental pollution due to the consumption of these energy resources [6, 7]. The limit on

non-renewable resources will cause serious energy supply concerns in the future. Renewable

energy sources are the promising candidates for non-renewable resources [8]. Although these

renewable resources could be accomplished on the basis of natural circumstances. For the

further implementation of sustainable energy, parallel flexibility is desirable and therefore the

growth of flexible storage is crucial [5].

In future power supply systems and smart grids, progress is needed in order to make

efficient use of renewable energies. Several energy storage systems, such as chemical,
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magnetic, mechanical, electrochemical, etc., have currently been explored [9]. Among these

storage systems, the electrochemical storage process is the most attractive system in which

the distribution of a carrier electron converts chemical energy into electrical energy [10].

Since there are still some transitions between the electrochemical storage systems between

the fuel cells and the batteries that occur reverbly or in a solitary way.

RLIB is one and only one of the major efficient aspirants for the renewable energy

transfer and storage. It was first marketed by Sony in the 1990s. While the LIB was

technologically advanced by the Asahi Kasei Corporation in Japan, it was then marketed by

Sony in 1991. LIBs have major remuneration, such as good performance, high energy

density, and no memory effects lead customers to accept it as the best. Although the basic

features of lithium are the lightest metal element, the best electropositive material with -3.04

V vs. NHE and high gravimetric density allows for good electrochemical storage and high

energy density [11, 12]. LiCoO2 and graphite have initially made a significant breakthrough

as the first generation of LIBs for power source applications and devices like notebook,

computers as well as cell phones [13]. Although the requirement for clean energy sources has

been further developed in collaboration with innovative sources of energy. In the automotive

industry, the desire to replace internal combustion engines with zero emission vehicles has

been developed to reduce CO2 emissions. LIB was developed as an effective tool for

understanding both plug-in EVs as well as HEVs. High-capacity power storage systems,

including self-supporting power plants, would be more significant in this sense in the future

as renewable sources of energy expand around the globe [14]. The amount of electrical

energy of the battery shall be either represented by unit of weight (W h kg -1) or by unit of

volume (W h-1), that is a function of both the capacity (A h kg -1) and the cell potential (V).

Table 1.1 demonstrates the aids of the LIB as opposed to other recognized types of batteries

[15, 10].

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 Introduction and Fundamentals of Batteries Chapter 1

Table1.1: Comparision of various properties and types [15, 10].

The type and the quantity of active materials used are the main factors that derive the

battery cell's maximum capacity. In fact, only a fraction of the battery's theoretical energy

was obtained in the meantime. This is owing to the necessity of non-reactive materials such

as casings and containers, as well as for reactive components such as electrolytes, current

collectors and separators. The relationship of the constituents is shown in figure 1. 1.

Important cost and safety reduction criteria need to be improved for commercialization.

Cyclazability, amplified power density and energy, and refining of the temperature range of

the operating cells must be carried out along with these factors [12, 16].

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 Introduction and Fundamentals of Batteries Chapter 1

Figure 1.1: Battery cell apparatus, left pie chart is cost-dependent, and right

pie chart is mass-% dependent (Dillon et al.)[17].

1.2. Electrochemical cells and redox reactions.

An electrochemical cell is an apparatus that generates electrical energy via spontaneous

chemical reactions or triggers non-spontaneous chemical reactions via electrical

energy consumption. The main cell formed is a galvanic cell; later, the electrolyte cell joins

the line [18]. An electrochemical cell comprised of 2 electrodes that are immersed in an

electrolyte. Whereas the electrolyte is an ionic conductor and the electrodes are electronic

conductors. The redox (oxidation-reduction) reaction generates electrical current at the

electrode-electrolyte interface. The oxidation process takes place in anode, while the

reduction occurs in cathode respectively. The chemical reaction involving electron transfer to

the chemical species is referred to as the redox reaction. Redox species required to be capable

of altering their oxidation status. Two species that are active in the reaction are usually both

an oxidant (oxidizing agent) as well as a reductant (reducing agent). The reductant transports

the electrons to the oxidant throughout the reaction. Therefore an oxidant increases with the

number of electrons and decreases (the oxidation number decreases) whereas a reduction

loses electrons and becomes oxidized (the oxidation number increases). Half reactions

traditionally represent the redox reaction of the certain element and are grouped into

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reductions. The redox pair contains an oxidized and a reduced species of a particular element

(Table 1.2). Both of these half-reactions can be connected to a standard electrode potential, E

°. Conversely, each half-reaction must be connected through a standard reference electrode

without being able to estimate the potential for half-reaction in absolute logic. The SHE

electrode consists of a platinum hydrogen-flushed platinum electrode with a water solution

solution of 1 mol / l HCl water solution (T = 25 ° C, p = 1 bar, all active species at unit

activity). The electrode is also used as a reference electrode and its potential is estimated to

be 0.0 V. [19].

Table 1.2: Standard electrode potential for some

At equilibrium, equation 1.1[19] provides the Nernst equation for the assessment of the half-

reaction potential for non-standard conditions.

E=E0+RTnFlnaiυi……………………………………………………………………………….. 1.1

Where E refers to the electrode potential in ‘V’, whereas E 0 refers to the standard electrode

potential in ‘V’, R refers to the ideal gas constant in ‘J K -1mol-1’, T to the absolute

temperature in ‘K’, n to the number of electrons exchanged, F to the Faraday constant in

‘Cmol-1’, υi to the species I to the activity and the stoichiometric coefficient i.

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For an electrochemical cell the cell voltage is enumerated from the electrode potential of the

half reactions. The variance among the reduction potential of the half cell (cathode) and the

oxidation (anode) defined in equation1.2 generally defines the theoretical cell voltage of an

electrochemical cell.

ΔE=Ered−Eox=Ecat− Ean……………………………………………………………………………..1.2

The 'Volta cell' is recognized as the first galvanic cell consisting of an electrode made of a

copper wire and a fragment of zinc metal dipped into an electrolyte of sulphuric acid denoted

as Zn | H2SO4 | Cu. Each interface is categorized as a vertical stroke because of the custom,

and because the electrochemical chain involves several successive electrolyte media, | |

notation is generally used at that time for the dividing zone of two electrolytes.

One more galvanic cell is a 'Daniel cell' composed of two parts enclosing a zinc metal in

contact with a ZnSO4 aqueous solution along with a copper metal in contact with CuSO 4

aqueous solution which in effect is electrically connected with a third aqueous solution, such

as a conc. KNO3 solution described as a salt bridge and referred to as Zn | ZnSO4 || CuSO4 |Cu.

Galvanic cells are commonly classified as batteries divided into two battery types, primary

and secondary. Primary batteries provide energy for a short time and must be disposed of

immediately once they completely discharged (for example, Alkaline batteries) are based on

permanent electrochemical reactions. Although reversible electro-chemical reactions are

driving secondary batteries, they can be reloaded and converted into chemical energy by

recharging the batteries (e.g. lead acid, Ni-Cd and Li-ion batteries). From the time the

invention of the "Volta cell" battery relies on a number of chemistries; the common industrial

batteries are shown in table 1.3 along with their basic capacity, voltage and redox reaction,

and the precise and volumetric measurement of energy is as shown in figure 1.2.

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Table 1.3: Comparison of diverse batteries with their electrochemical reactions

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 Introduction and Fundamentals of Batteries Chapter 1

Figure 1.2: Battery chemistry over the years (left) [20] and comparison

batteries technologies (right) [21].

1.3. Fundamentals along with electrochemical principles of lithium-ion battery

Batteries are a collection of cells, which generate a stream of electrons within the

circuit through chemical reactions. All batteries are manufactured with three fundamental

components: an anode (a negative fin), a cathode (a positive end) called electrodes and some

sort of electrolyte (a chemically reacting material with anode and cathode). A porous

electronic insulator separator is located between the two electrodes to avoid short circuit as it

allows ions to pass through it liberally. It is an energy storage system consisting of a

collection of electrochemical cells arranged either in parallel or in series or in both customs in

order to make accessible the required voltage and power.

In fact two types of batteries are in use, primary and secondary. The primary works on

the theory of only trend of discharge, in which the electrodes cannot be retrieved once after

using it is worn out. Zinc manganese batteries and alkaline batteries are the primary batteries

of interest to be used from the past few decades [22]. In comparison, secondary batteries can

recover their structural integrity regarding the deliberation of electrical energy even after

being charged / discharged for several cycles. As a result, the recharging process is shown

under practical conditions. At present, the commercially available rechargeable batteries are

nickel-metal hydride, lead-acid batteries, nickel-cadmium as well as LIBs, etc.

When discussed earlier, the LIB consists of two electrodes; a anode as well as a

cathode submerged in a water-based electrolyte consisting of lithium salts. Lithium ions pass

between negative and positive electrodes. A porous electronic insulator separator is located

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 Introduction and Fundamentals of Batteries Chapter 1

between the two electrodes to avoid short circuits but allows ions to pass through it freely.

More specifically, lithium ions are introduced on the bulk material without interruption, while

electrons extracted from one electrode inserted in the other, thereby storing as well

as transmitting the electrical energy continues throughout the battery. The name "rocking

chair" was given for this transport of lithium-ions [12, 14]. Fig. 1.2 illustrates a stereotypical

graphical illustration of the lithium-ion battery. The battery consists of LiCoO 2 cathode

lithium metal oxide along with the graphite anode and the battery operation as explained

below.

During discharge: the positive electrode (cathode) is reduced in the rechargeable

battery and the negative electrode (anode) is oxidized during the discharge phase. The

electron flow starts through the external circuit of the anode to the cathode during this stage,

and activates our laptop, smart phone and more. Through the transfer of negative ions and

positive ions, the electrical circuit can be completed in the electrolyte.

(a)

(b)

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Figure 1.2: Battery operation upon (a) charging and (b) discharging.

During charging: The reaction is reversed during the charging process, and a

corresponding amount of energy desires to be supplied to the entire battery system. Oxidation

takes place at the cathode during the charging or recharging of a cell and reduction takes

place at the anode and electron transfer arise at the same time from the cathode via external

load to the anode. Generally speaking, electrodes with reduction are called cathode and one

whose oxidation occurs is called anode, here the positive electrode is assumed as anode, and

the negative is cathode material. When all the mobile ions (ex., Li +, Na+, K+, Mg2+, Zn2+) stop

flowing, the battery is likely to be fully charged and ready to use. The diagram figure.1.2 has

shown above depict the basic operation of a battery under discharge and charge conditions

The overall cell reaction can be seen below.

Accessible energy in a battery primarily depends on the electrochemical reactions at

the electrodes, even if a lot of other stuff, such as separator properties, electrode design, and

electrolyte conductivity, has also influenced the performance or rate capacity of the cell. This

affect the diffusion speeds, the sum of energy loss and the reaction of charge transfer [17].

The kinetics for overall polarization is shown in figure 3. When kinetic charge-transfer

reactions occur mainly on the electrode / electrolyte interface, this is referred to as activation

polarization. The resistance of the individual cell components as well as the resistance of the

cell components due to contact problems are related to ohms polarisation. Finally, the

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drawbacks of the mass transport during cell operations are due to the concentration

polarisation [10]. The current-voltage discharge characteristics (figure.1.3) provide a specific

electrochemical effect of the discharge-charge rate to establish the cell capacity and the

general characteristics of the battery condition.

Figure 1.3: Typical discharge curve of a battery showing the influence of different

polarization types, adapted from winter and Linden et al. [10, 17].

Where possible losses (as shown in figure.1.3) are to be avoided, certain advice must be

given to all batteries in order to reduce these losses of polarization and are as follows;

 An electrolyte with a higher ohmic polarization will offer a lower conductivity.

 It would be chemically stable to avoid undesirable reactions within the range of

cells between electrode materials and electrolytes, consisting of both salts and

solvents.

 Activation polarization can be minimized by increasing the rate of anode as well as

cathode electrode reaction. A porous electrode design has a high electrode surface that

decreases the charge-transfer polarization.

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 In order to assist in the transfer of mass, the cell should have sufficient electrolyte and

thus avoid unnecessary polarization of the concentration. The reactants will be

dispersed or extracted from the electrode surface in most battery systems.

Considerations influencing the mass transfer are the reactant concentration, pore size,

porosity and separator properties.

 Present collectors should be compatible with electrolyte and electrode material that

does not cause corrosion problems.

 Reaction products should support reversible reactions during charging /

discharging and be both chemically and mechanically compatible with electrolytes.

Anode materials: The metallic lithium used as an anode material was rapidly replaced by the

carbonaceous material in RLIB because of safety problems. During the first point of the

marketing, the anode material used was coke [23], and then the mesocarbon microbeads

(MCMB) became an admired anode material owing to a high specific capacity of 300

milliamp hour per gram with enhanced safety properties [17]. Owing to their low price,

abundance, low as well as flat working potential and their long cycle life, the most demanded

anode material is graphite at the present situation. Compared with MCMB, graphite yields a

good electric discharge of 372 milliamp hour per gram [24]. Various varieties of carbon

materials are available in the industry; the structure has the greatest effect on the

electrochemical properties of carbon materials, including lithium intercalation /

deintercalation capacity and potential.

The basic building block, a flat carbon sheet organized in a hexagonal array, as shown

on the left in Figure 1.4. If the planar sheets are stacked, numerous graphite structures occur.

The most common hexagonal graphite is ABAB stacking, while ABCABC stacking order

gives

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rhombohedral graphite [17]. LiC6 graphite stoichiometry has the highest Li-enriched

intercalation, indicating six carbon atoms per lithium-ion intercalate, achieving a theoretical

efficiency of 372 milliamp hour per gram. This capacity is in contrast to other intercalation

compounds (such as Si / C composites) but is below the required as well as low practical

energy density [26, 11].

Figure 1.4: A carbon layer, hexagonal and rhombohedral graphite structure [17].

Two forms of carbons are present; soft and hard carbon. The soft carbons are materials which

can be graphitized by treating at high temperatures; whereas hard carbons cannot be easily

graphitized [23]. Hard and soft carbons have a broad range of capacity based on conditions of

processing and starting materials; but higher capacities are offered by hard carbons compared

to graphite, in addition to a faster rate capability [26].

Cathode materials: cathodes in the RLIB are categorized into two varieties. First variety

involves layered complexes with transition metal cations found in alternative layers within

the anion-close-packed lattice, as well as lithium ions and anion sheets are introduced into the

rest of the empty layers. Within this class are also included the spinels with transition metal

cations well-arranged in the entire layers. Also incorporated in this grouping are cathodes

such as LiCoO2, LiMn2O4, LiNiO2 and LiNi1-xCoxO2 and have a higher energy density due to

the extra compact lattice and their topology allows easily available ion-diffusion pathways

[27, 28] as they enter the second group of cathode materials. Wherever there is a very

compact lattice in the first group of cathode materials, the next category of cathode materials

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has open structures, like vanadium oxides and metal phosphates ( LiMnPO 4 or LiFePO4) [29].

As mentioned earlier, LiCoO2 as well as graphite is the first generation of LIBs. Owing to the

suitability, high operating voltage as well as the ease of preparation LiCoO 2 has recognized a

widely held cathode material [29]. At RT, Li xCoO2 shows an impressive 1 > x>0.5 cycling

capability. LiCoO2 found its theoretical capacity to be 274 milliamp hour per gram. LiMn 2O4

is another common cathode source because it has advantages of abundance and less toxicity

[29], while it also has a plane operating voltage of 3.95 - 4.1 V vs. Li / Li + with a theoretical

output of 148 milliamp hour per gram [13] for the spine structure system.

Electrolytes: The third main part of the battery containing salt and solvent solution is called

an electrolyte [12]. The main role of aqueous electrolytes [11] is the action of the ion

conductor to transfer the Li-ions back and forth among the anode as well as the cathode when

the cells are charged / discharged. In general, the performance of each electrolyte is different

from the other; hence each electrolyte is intended for a specific use of the battery, so

numerous electrolyte varieties are used in LIBs.

Advancement of electrode material is only the first stage in a cell, since the structural or

electronic activities of the electrode material indicates the capacity of the cell, but the

poor life span of the cell is also embedded in the side reactions at the interface of the

electrode and electrolyte. The ideal electrolyte must have certain properties, such as;

 Lithium-ion cells would have a wide electrochemical window of at least 4.5 V along

with a high voltage cathode.

 Over a wide temperature range it should possess high Li+ conductivity.

 During cycling, as electrode particles modify their electrode / electrolyte interface

volume preservation should be accomplished

 Capable of thermal and chemical resistance.

 Low toxicity and inexpensive.

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 Nontoxic materials, if possible non-explosive as well as non-flammable.

Assembling all these necessities proves to be a major challenge, and numerous desires

contradict each other. Various forms of electrolytes, for example ion liquids, hybrid

electrolytes, organic liquid electrolytes, polymer electrolytes and inorganic solid electrolytes

have been used in LIBs [17]. Organic liquid electrolytes, consisting of a combination of

organic solvents and lithium salt, are the most widely used and readily available

comprehensive electrolytes, typically carbonates described as the strongest solvents for

lithium salts with an oxidation potential at ca. 4.7. Because ionic liquids enclose several

advantages over carbonate-based electrolytes and have no flammability, high oxidation

capacity and increased thermal stability, they are considered an alternative route for

traditional organic liquid electrolytes, to date no ionic liquids on larger batteries have been

developed [30]. Polymer electrolytes provide an additional compensation to their liquid

counterparts, usually in security matters. A solid electrolyte often as well serves as an

electrode separator.

Separators: A porous membrane that exists between reverse polarity electrodes is

considered to be a separator. It is penetrable to the ion flow, but avoids electrical interaction

between the electrodes [11, 31]. The separator would basically be electrochemically as well

as chemically stable to the materials of the electrolyte and the electrodes. For high

conductivity, the structure of the separator must have enough porosity to captivate liquid

electrolyte. Yet the battery performance is affected by the limited space inside the battery

which is due to the electrical resistance offered by the separator [32]. Slight scientific

attention has been paid to the separator as a passive element of the battery system and little

research is centred on characterising and advancing new separators [15].

 A separator should have certain properties which should be used in LIBs:

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 Electronic insulator. The effective electronic insulation must be achieved over a

wide range of temperatures and should be long-lasting over many years and in

highly aggressive media [15, 31].

 Chemical stability. The separator must be stable, as well as compatible with both

electrode and electrolyte materials [11]

 Mechanical strength. During battery assembly, the separator has to be

mechanically strong to bear the tension of the winding operation [17, 32].

 Size of the pores and porosity. A suitable porosity is essential to embrace enough

liquid electrolytes for ionic conductivity among the electrodes, although the pore

size of the electrode components must be smaller than the particle size [32].

 Wettability: The separator must be quickly wetted in the electrolyte and the

electrolyte should be retained indefinitely [17, 32].

 Shutdown. For battery protection, when overheating happens, the separator needs

to be able to shut the battery down in order to prevent a thermal extinction. A

multi-layer configuration of the separator will achieve shutdown feature in which

at least one layer melts to close the pores to provide mechanical strength in the

other layer so as to protect against interaction between physical electrodes [32].

 Symmetry in the thickness and pore distribution .[11, 31]

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Figure 1.5: Diagrammatic representation with the shape and components of different LIB

configurations (A) cylindrical, (b) prismatic, (c) slim, and (d) flat [12].

There are three varieties of separators, namely non-woven fabric mats, micro-porous polymer

membranes and inorganic composite membranes. The most commonly used separator in the

liquid electrolyte battery is the micro porous polymer membrane due to its cost, safety and

performance advantages. As shown in figure.1.5, there are several commercial types of

batteries, each requiring a unique interest in the choice of separators, electrolytes and current

collectors.

1.4. The Battery Parameters

The main parameters of the general system of batteries [16] are discussed below.

 Capacity: Capacity is measured in an ampere-hour battery system and refers to how

much energy the battery or cell holds in Ah or how much charge the battery or cell can

deliver at the rated voltage. The theoretical capacity (in mA h g -1) of an electrochemical

cell can be determined on the basis of the active components which participate in a cell

reaction and their equivalent weights [16]. Hypothetically, 1 gram-equivalent weight of

substance would hold 96,487 C or 26.8 Ah (i.e., a gram-equivalent weight is the atomic

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or molecular weight of the active element in grams determined by the number of

electrons involved in the reaction).

Theoretical capacity = n×F/M×3.6……………………………………………1.3

Where F refers to the Faraday constant (96485.3329 A / mol), n refers to the number

of electrons engaged in electrochemical reactions (exchangeable electrons) and M

refers to the molar mass of the insertion compound. The theoretical capacity was

considered only for the weight of the anode or cathode, but the weight of the electrode

additives (binders and conductors), the electrolytes, the separators; the current

collectors, the battery case, the connections, the circuit of protection, etc. are not

included in the theoretical capacity calculation.

 Cell or Battery Voltage (V): In general, the battery or cell produces a voltage potential

when electrodes with different affinities are dipped into an electrolyte solution. The

type of active substance will provide the standard potential of the cell. Free

experimental approach or Free Energy data may be deliberated on. For example, the

standard potential of the Daniel cell can be determined as follows from the standard

electrode potential. At Zn (negative electrode or anode);

ZnZn2++2e-, Eanode=-0.76 V………………………………………………….1.4

At Cu electrode (positive electrode or cathode);

Cu2++2e-Cu, Ecathode=0.34 V…………………………………………..…...1.5

The standard cell voltage is provided by

Ecell= (Ecathode-Eanode) =1.1 V ………………………………………….…..... 1.6

Apart from the nature of the active material, the cell voltage also depends on the

concentration of the electrolytic medium as well as the temperature at which the

electrode reaction to be performed, such properties depend on the cell system's

intrinsic voltage, which could be monitored in equilibrium by the Nernst equation.

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For any reaction; aA+bB=cC+dD…………………………………………….. 1.7

The voltage of the system can be expressed by

Where Eo refers to standard electrode potential, R is the gas constant, T is the

temperature in ‘K’, F is the faradays constant, n is the number of electrons involved in

the oxidation/reduction reaction and [A], [B], [C] and [D] refers to the concentration

of each species.

 C-rate: Various C-rates also reflect the discharge and charging capacity of the

batteries. For example, the charging capacity of a cell or battery is measured at 1 C,

which would mean a fully charged battery device valued at 1 A h would provide 1 A

for 1 h. Correspondingly, 500 mA at 0.5 C for 2 h and 2 A for 30 min at 2 C will have

the same discharging battery. Or put it another way, C-rate is a quantity of the rate of

charging or discharging of a battery compared to its full power. For example, 1 C-rate

means permitting the battery to discharge within 1 h, C/2 or 0.5 C means letting the

battery to charge / discharge within 2 h, and allowing the battery to charge / discharge

within 5 h and so on.

Table 1.4: Different C-rates and service times when charging and discharging

batteries of 1Ah (1,000 mA h).

C-rate Time

1C 1h

2C 30 min

5C 12 min

0.5 C or C/2 2h

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0.2 C or C/5 5h

0.1 C or C/10 10 h

0.05 C or C/20 20 h

 Conductivity: Generally, electrode materials conduct electrons as well as lithium ions

during the charging and discharging process. But most lithium-ion insertion materials

are semiconductor, and composite formation, doping and surface coating, etc., with

high conductivity materials, will further increase the conductivity of these materials.

 Cycle life: Cycle life is one indicator of the materials' electrochemical stability.

Higher electrochemical stability (high materials for electrochemical stability are

considered top tactical materials) higher cycle life. Typical LIB has a cycle life of

4000-10000 cycles and even more, while lead acid battery life is as short as 800-1000

cycles. The battery life depends on so many factors, such as temperature, compound

composition, stability, morphology, discharge depth etc.

 Columbic efficiency: Columbic efficiency is the fraction of a number of charges that

extracted during the discharge to the number of charges enters during the charge or in

other words, battery efficiency can be obtained by using the energy used and

produced during charge/discharge.

[Columbic efficiency = Specific energy during discharge/Specific energy during

charge × 100]………………………………………………………………….. 1.9

Generally, lithium-ion battery has 99 % charge efficiency, and the discharge is small

and varies, depending up on the electrode materials. Generally, electrode materials

with more than 90 % columbic efficiency are considered as highly reversible

electrode materials.

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 Specific energy (W h/kg) and Energy Density (W h/L): Gravimetric energy density or

specific energy describes the battery capacity in weight (W h/kg) and energy density

or volumetric energy density represents volume in liters (W h/L).

 Power density: Power density is measured in W / kg or W / L is the battery capacity

per unit weight and speed at which the electricity can be supplied to the load.

Power density or Energy density/time= Current (A/kg or A/L) × Voltage (V)

Power density depends on impedance of the cells or batteries, ion-diffusion kinetics

through the electrode, electrolyte and other components

 Battery thermodynamics and Kinetics: for a reversible electrochemical process the

essential thermodynamic equation is specified as; ΔG= ΔH-TΔS………………1.10

Where Gibbs free energy ΔG is in J, enthalpy ΔH is in J, entropy ΔS is in J K-1, and

Temperature T in K. Hereby it can be observed that the state functions of a given cell

depend on the existence of the active cell substance. ΔG’s negative value defines the

reaction's spontaneity [10]. Through definition, it can be estimated that the required

net energy for the electrochemical reaction will be agreed as part of a rechargeable

cell system.

1.5 Benefits and drawbacks of lithium-ion batteries

Benefits: LIBs have their own advantages and limitations, like other technologies. Below are

the general advantages and limitations of traditional RLIB.

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 High energy density: it is well known that RLIBs have high energy capacity, and are

useful for driving various electronic equipment including laptops and mobile

telephones, other electrical applications, etc.

 Comparatively low self-discharge: in comparison to nickel based batteries, LIBs are

substantially smaller.

 The Substantial maintenance: LIB's do not need any maintenance, i.e. no frequency

charge. No memory impact is needed.

 A number of potential categories: various types of lithium-ion cells with specific

energy requirements can be obtained.

 The slim and light: Li-ion batteries are compact and lightweight compared to other

batteries. With that, car makers are using these batteries for driving smaller vehicles,

electric cars, aerospace applications, etc.

Limitations: There are many disadvantages as well, such as the use of some technology,

which involve balance along with advantages.

 Price: the LIB's expense is a big constraint. The LIB's are usually more expensive to

produce than other secondary battery systems, but due to the tremendous demand in

different applications, they are of limited resources and flexibility in air and water.

 Limited resources: Because of increased demand for lithium resources eventually

increase the cost and availability in the market. Most accessible global lithium

reserves are in remote areas.

 Concerns about safety: RLIBs may explode when overcharged or overheated. Internal

short circuit or overheating might ignite the electrolyte and causes combustion and

gases produced by electrolyte decomposition amplify the interior pressure of the

24
 Introduction and Fundamentals of Batteries Chapter 1

battery. For this reason, Li-ion batteries are avoided for transport especially when they

are transported in larger measures.

 Required protection: RLIBs are not as reliable as other rechargeable battery systems.

During over charging, they require adequate protection as well as discharge and, more

importantly, they need to be kept under reasonable limits.

 High temperature sensitivity: RLIBs are more vulnerable to additional heat generated

by overheating or overloading and, more importantly, the heat causes the battery to

degrade more rapidly.

 Aging: One of the chief disadvantages of LIBs for customer electronics is those LIBs

experiences aging i.e. LIB will obviously degrade once they depart from the factory.

Storage in a cool place which causes 30-40 % reduces the charge due to aging effect.

1.6. Lithium-ion Battery

It is well known that rechargeable LIBs have been an incomparable amalgamation of high

energy density, high performance and superior life cycle [33] and is one of the most widely

used technologies in electronic markets where high energy density and light weight are of

fundamental importance.

Using layered TiS2 cathode and metallic lithium as an anode, Whittingham announced the

first RLIB in 1976 [34, 35] and tried to market the battery, but unfortunately they did not

succeed owing to the formation of lithium dendrite and the short circuit that occurred during

the cycling [36].

25
 Introduction and Fundamentals of Batteries Chapter 1

Figure 1.6: Comparison of energy density and specific energy of different rechargeable

battery systems

Besenhard then demonstrated RLIB in 1976 using oxides and graphite as cathode and anode

respectively [37, 38]. In addition, in 1981 [39] Goodenough developed the first LiCoO 2 RLIB

as a high voltage and high energy density material. Again, the same Goodenough research

group came up with another LiMnO2 spinel as a low-cost cathode material [40]. This is

followed by Yazami [41], Basu [42] and Besenhard [43] who, in the 1970s and early 1980s,

discovered and demonstrated the new types of batteries using graphite with the layered

structured cathode. Later, a prototype battery consisting of layered LiCoO2 with the

carbonaceous anode was successfully developed by the Yohsino group in 1987 [43] and the

same Yohsino research group carried out the first safety test on RLIBs [44]. Eventually, in

1991, Sony Corporation released a first marketable LIB with greater safety [45]. With the

introduction of low-cost, environmentally friendly products, and improved electrochemical

properties and efficiency with simple synthetic approaches, after the first marketing, LIB was

extended very quickly. For example, the low-cost LiFePO 4 introduced by Goodenough in

1996 [46], Sony’s high specified capacity anode (C-Sn-Co) in 2005 [47], and Candace’s high

specified capacity nanostructured silicone anode [48] etc. In the 1990's, Dahn and his

colleagues [49] established the C / Si composite as an anode. Likewise, from the past two

decades to the present day, LIBs continuously grew very rapidly with specific

electrochemical characteristics such as high strength, quick charging, high efficiency,

superior performance and long cycle life etc. RLIBs for the portable electronic device, which

is used primarily for mobile phone and laptop computers, are now well dominated in power

source. With the implementation of electric and hybrid vehicles, the rechargeable battery

26
 Introduction and Fundamentals of Batteries Chapter 1

technology, especially the RLIB market, has been expanding very rapidly in recent years to

counter environmental concerns. The performance of the LIB is therefore increased rapidly,

due to different electrical properties as well as high energy and power density, longer cycle

life, faster performance, etc. In addition, the Li-ion battery can also be used in a variety of

applications, such as large power grids and robotics. Small, lightweight and compact RLIBs

thus developed a strong marketplace, especially in applications for portable electronic

devices, EV, and HEV. Therefore, the production of Li-ion batteries has increased rapidly in

the last two decades, following the successful commercialization of LIBs particularly for

portable and electric vehicles.

1.7. Organic electrode materials:

During its electro-activation process, both organic and inorganic cathode and anode

materials can experience reversible electrochemical redox reactions with respect to the

electro-active type. Thus, numerous elementary substances (like Li, Na, Mg, C, O 2, Si, P, S,

Sn I2) [51, 52] are favored in the accumulation of inorganic electrode material [50] which can

participate as electrodes for rechargeable batteries in the accumulation of transition metals.

The electrode reaction is associated with the modification of the valence charge of the

transition metal or atomic ions of inorganic electrodes compounds. The redox reaction relies

on the changes occurring in the charging state of the electroactive organic species in the case

of an organic electrode system. There are three categories of organic electrode materials that

differ on the aspect of the phenomenon, such as organic n-type, p-type, and bipolar organic

electrode materials. In the case of n-type the neutral state reaction as well as the favors of the

negatively charged state, whereas the reaction involving the neutral state as well as the

positively charged state is in the material of p-type organic electrodes. Finally, the bipolar

content displays the neutral state which can be reduced to a negative state or oxidized to a

positive charged state. For the construction of any rechargeable battery, we need a cathode

27
 Introduction and Fundamentals of Batteries Chapter 1

and an anode of interest in accordance with the basic principle. The primary criterion for

electrode selection is that in order to conduct efficient redox reaction it should possess a wide

practical potential difference. The cathode should have greater redox potential for these and

the anode should have less redox potential so we need to learn about the electrode materials'

redox states. For example, when the anode starts in its oxidation state, the cathode has to be

in its state of reduction. In relation to these discussions there are four kinds of cell

configurations for RLIBs as shown in figure.1.7

At the beginning of the electrode reaction, if the anode is in a reduced form and the

cathode in an oxidized form, the cell shows discharge during the electrochemical cycle as in

type a and type c. Unlike this state, the cell undergoes a charging phase at first stage, as in

type b and d. From this we can conclude that, whatever the cell configuration may be, every

organic electrode material can locate its function.

The cell configurations discussed above are not sufficient to select an organic moiety

as an electrode material for rechargeable battery studies, in compliance with the above

aspects. Along with these, one should learn about the structural manifestation of the active

material to serve as an efficient electrode system at experimental condition with its redox

mechanism. Table 1.5 describes the various categories of organic structures, as well as their

redox mechanisms.

28
 Introduction and Fundamentals of Batteries Chapter 1

Figure 1.7 The cell arrangements and charge transfer methods of different types of

rechargeable batteries.

Of these conjugated carbonyls and organodisulfides, n-type organics, conjugated

amines and conjugated thioethers are ideal for p-type organics, while bipolar organics,

conjugated hydrocarbons and nitroxyl radicals are of interest. The thioether group does not

belong to any kind of redox system from the table, but this group is nevertheless known to be

one of the groups showing the chance of multi-electron reactions in organic electroactive

organisms. The table also shows that while nitroxyl radicals are bipolar, they can be used as

organic p-types to achieve a steady electrochemical reaction. In order to demonstrate the

reversible redox reaction, the electrode material should also have a conjugated structure and

atoms with the lone electron pair (N, S and O). Since the conjugated arrangement helps to

transport the electrons during the electrochemical reaction and facilitates to have charge

delocalization.

On the basis of the structure and function as set out in the table, we can aim at the

synthesis route for the high quality of organics. These materialistic findings provide

information on the actual selection criteria for the types of organics to be used for further

studies. In this regard, the investigations examined a number of essential requirements for

these organic substances on the basis of an electrochemical routine. Reversibility of the

reaction including chemical and thermodynamic stability, determines the electrochemical

polarization and the rates of the active component. Redox potential; redox potential can be

determined in Figure.1.8 of some standard organic electrode materials. As already noted,

29
 Introduction and Fundamentals of Batteries Chapter 1

organic electrode materials favor cathode, which is often less than the inorganic cathodes of

intercalation, because their redox potential lies in the midst of 2.0 and 4.0 V vs. Li +/Li.

Table 1.5: Structure and its redox process for different organic electrode materials.

Structure Redox mechanism Example

Conjugated amine

Conjugated

hydrocarbon

Conjugated

thioether

Thioether (4e-)

Organosulfide

Conjugated

carbonyl

Nitroxyl radical

Solubility; the most observable issues in organic battery systems are the dissolution of the

electrode materials into electrolytes (aqueous or organic), leading to a decrease in the cell's
30
 Introduction and Fundamentals of Batteries Chapter 1

cycling capability. Like all electrolytes, small organic molecules typically exhibit a high

dissolution factor and this is inevitable because the discharge efficiency of the electrode

systems is weak with lower cycle output. Whereas the electrolyte is still insoluble in the case

of polymers and makes the cycling process good.

Figure 1.8: The redox potential and specific capacity of distinctive inorganic and

organic electrode materials for RLIBs.

s and cost; organic moiety is simpler in the structural manifestation than the direct synthesis

of the desired product. There is therefore a long time to follow the optimization and

simplification of the preparation method.

Since the research on organic electrode content is yet to be developed, the cost must not be a

critical constraint for investigations in this respect. Although their potential applications that

carry cost-related concerns, these factors should be evaluated in order to explore certain

organics with uncomplicated structures, inexpensive raw materials as well as simple synthetic

routes. The active applicants for organic electrode materials are relatively equal and even

better than practical inorganic electrode materials such as

31
 Introduction and Fundamentals of Batteries Chapter 1

 High energy density: organic electrode materials have a comparatively lower redox

potential but can be compensated for by their higher theoretical capacity; therefore,

high energy density can be achieved.

 Structural combination and higher power density: organic electrode materials have

massive structural potentials and electroactive properties. Since some organic redox

pathways involve reaction kinetics that is considerably faster than inorganic cathodes,

electroactive organic electrode materials seem to be good components for high-

powered electrodes.

 Flexibility: organic electrode materials are very versatile in their materialistic form;

thus, industrialized smaller, reduced portable flexible devices have been developed in

recent times. In this assessment, organic electrode materials are shown to differ from

inorganic electrode materials.

 Sustainability: organic electrode materials that can be derived and processed from

natural sources that is environmentally safe and highly accessible to inorganic

electrode materials.

Organic electrode materials are confronted with many challenges, such as low mass density

due to their different elements and crystallographic aspects, low electronic conductivity

problems for organic electrode materials, as they are almost electrical insulators critical to the

full consumption and efficient reactions of active materials, the dissolution of organic

materials.

1.8. Rechargeable Li-ion batteries based on aqueous electrolytes

The promising and safer substitutes to conventional RLIBs are aqueous rechargeable batteries

or aqueous rechargeable alkaline metal ion batteries (Li+ and Na + and K+) for many

challenges. This kind of battery utilizes lithium or sodium or potassium-intercalation

compounds as electrode materials and water is used as an electrolyte {alkali salts (e.g.

32
 Introduction and Fundamentals of Batteries Chapter 1

Li2SO4, LiNO3, LiOH, etc.) dissolved in pure water}. All of these aqueous energy storage

systems have several advantages over traditional non-aqueous RLIBs [53, 54]. The key

benefits of the ARLIB over the non-aqueous (organic electrolyte) RLIB are as follows.

 Easy to manufacture (no need for a strict battery assembly in a controlled inert

atmosphere) and low capital investment.

 Aqueous battery gives them favorable safety features, especially with regard to

flammability and thermal runway during charge / discharge.

 Similar to non-aqueous rechargeable battery systems, batteries with aqueous

electrolytes do not need to be sealed tightly because of their environmentally safe,

non-flammable and stable in room atmosphere [55].

 The ionic conductivity of aqueous electrolytes is substantially greater compared to the

non-aqueous electrolytes (organic electrolytes) and high-power density.

 Materials for water decomposition such as hydrogen and oxygen do not contaminate

the battery.

 In fact, water is the most available, the most natural and the most environmentally

friendly [56].

The key downside of aqueous electrolytes is that they have lower voltages of action in cells,

theoretically only < 1.23 V vs. SCE. Therefore, to achieve the overall operating voltages

more cells need to be connected in series. All ARLIBs with voltages above 1.2-1.3 V

however are unstable [56]. A gel polymer electrolyte and LISICON film coated Li metal have

recently been documented by Wu's research group as an anode material for ARLIBs and have

improved the voltage and efficiency of the LiMn 2O4 material by increasing the voltage [57]

window.

33
 Introduction and Fundamentals of Batteries Chapter 1

Figure 1.9: Simple aqueous rechargeable battery.

1.9. Development of the aqueous rechargeable battery system

The first thorough study on the "rechargeable batteries" for the Pb-PbO2 system was

published by the Wade research group in 1902 [58]. Ni-MH and Ni-H batteries with aqueous

electrolytes were subsequently developed and commercialized. Yet both battery systems have

some inconveniences, like low energy capacity, short cycle life as well as lower shelf life

[37-39]. The rechargeable batteries based on lithium-ion subsequently attracted many

researchers who gave massive advantages, for example high energy density, superior cycle

life, high working potential, good performance, etc. For many industrial and research

applications, rechargeable batteries like Ni-MH, Ni-Metal (i.e., zinc , cadmium or cobalt) and

Pb-acid are commonly used, but have their own restrictions. For example, Ni-metal and Pb-

acid batteries are limited by low specific energy capacity and environmental toxicity [59]. Ni-

iron battery is self-discharged due to corrosion and iron electrode poisoning [38] during

operation. Similarly, Ni-MH has a higher energy density but suffers from high self-discharge,

reduced low-temperature capability and limited high-speed capability [49]. In addition, the

Ni-MH battery is very expensive due to its low abundance of precursor molecules. Similarly,

complicated flow-batteries provide lower energy density than portable batteries and

deposition / dissolution occurs in the case of Ni-Cd batteries as the resulting electrodes are

34
 Introduction and Fundamentals of Batteries Chapter 1

not fully reversible [60]. Nevertheless, Sony first commercialized rechargeable Li-ion

batteries based on non-aqueous electrolytes utilizing intercalated compounds in 1990 [61]

and subsequently developed the Li-ion battery quite rapidly and widely used in the various

applications. On the contrary, non-aqueous (organic electrolytes) Li-ion batteries have several

limitations already listed in this chapter.

Based on the above facts, in 1994 [62] Dahn and his colleagues reported a new kind of RLIB

using water as aqueous electrolytes for secondary Li-ion batteries called aqueous

rechargeable li-ion batteries using LiMn2O4 and VO2 as cathodes and anodes in 5 M LiNO 3

aqueous electrolytes, respectively. The new battery device delivers a working voltage of 1.5

V, with an energy density of 75 W h / Kg. Given its short cycle life, the tested new form of

ARLIB has overcome some of the drawbacks associated with the traditional lithium-ion

battery and can compete with other secondary aqueous batteries, including Ni-MH, Ni-Cd

and Pb-acid batteries [62]. Subsequently, a number of ARLIBs have been developed with

improved electrochemical properties and performance.

1.10. Working principles of aqueous rechargeable lithium-ion battery system

ARLIB's working theory is similar to the non-aqueous RLIB system, which adopts a

philosophy of "rocking chair" and the ARLIB technology has been adapted from the

technical concept developed by Sony for non-aqueous RLIB system [54]. The process of the

ARLIB method is correlated with the transfer of reversible alkali-metal ions by means of salt

from the electrolytes to / from the host materials and the transfer of electrons between two

electrodes by external circuiting. Therefore, the intercalation / de-intercalation potential of

electrode materials will be within the windows of aqueous electrolyte stability [63].

35
 Introduction and Fundamentals of Batteries Chapter 1

Figure 1.10: Thermodynamic stability window of water together with several electrode

materials in LIBs. The thermodynamic stability window of water with Li-ion battery

electrode materials with respect to pH is illustrated in the Pourbaix diagram. If the potential

window exceeds the thermodynamic stability window, H 2 evolution and O2 evolution takes

place at negative (anodic) and positive (cathodic) side respectively. In case of non-aqueous

electrolytes, the wide electrochemical window could be expected from 0.0 to maximum 5 V

vs. Li/Li+.

ARLIBs were generally produced in full-cell configuration (using two different intercalation

compounds) or in half-cell configurations (one operating electrode vs. reference electrode

usually saturated calomel electrode) and in recent studies, half-cell configuration is

performed in aqueous electrolyte with protected Li (anode or cathode vs. Li) [57] to enhance

voltage as well as specific electrolytes. Note that the electrochemical stability window for

pure water varies from 1.2 to 1.3 V [57]. Therefore, it is very important to select the

appropriate electrode materials to intercalate / de-intercalate Li-ions in the safe potential

window to prevent water decomposition [64-65].

The thermodynamic stability window of water with Li-ion battery electrode materials with

respect to pH is illustrated in the Pourbaix diagram (figure 1.10). If the potential window

exceeds the thermodynamic stability window, H 2 evolution and O2 evolution takes place at

36
 Introduction and Fundamentals of Batteries Chapter 1

negative (anodic) and positive (cathodic) side respectively. In case of non-aqueous

electrolytes, the wide electrochemical window could be expected from 0.0 to maximum 5 V

vs. Li/Li+.

1.11. Outline of the thesis

The thesis' main aims are to study the electrochemical properties and performance of

various organic materials for RLIBs. Microwave assisted reaction, sonication, and traditional

methods were used to synthesize the electrode materials. In Microwave assisted reaction

some electrode materials were synthesized with a heterogeneous catalyst; sulfuric-acid

tungstate. In addition to Amidoalkyl naphthol, Amino-acridine, Calix [4] resorcinarene and

Lithiated methyleneblue electrode materials, Aurin Tricarboxylicacid Copper Metal Organic

frame and Melanin-hybrid type materials for battery applications have also been synthesized.

The structural and morphological characteristics of inorganic materials have been studied

by X-ray crystallography and SEM analysis, etc. Purity and composition were analyzed using

the EDAX technique. Stretching and bending frequency of materials were analyzed in FT-IR

studies. Electrochemical properties and electrode performance have been studied using

electro-analytical techniques such as CV, GCPL, EIS, PITT, etc. Based on the

electrochemical properties, the compounds were classified as anode and cathode, and the

electrochemical characteristics and performance were analyzed in both aqueous and non-

aqueous electrolytes. Most of the pure (bare) electrodes were prepared in the composite form

to improve structural stability and electrochemical performance.

The thesis is set out in the following ten chapters.

Chapter 1 presents an overview to the batteries including the development, basic battery

components, classification, basic theory involved in battery functioning and some essential

parameters. This is followed by the general implementation of the rechargeable battery

system. The basics, the advantages and limitations, importance of organic electrode materials

37
 Introduction and Fundamentals of Batteries Chapter 1

for RLIBs were discussed. Introduction to RLIBs based on aqueous electrolytes has been

discussed and covers the advantages and limitations of non-aqueous RLIBs, as well as their

development and limitations and working principle.

Chapter 2 describes organic literature review as applications for energy storage; followed

by a brief introduction to electrode material synthesis through various synthetic routes.

Chapter 3 consists of experimental details; explains the technique adopted for the synthesis of

the electrode materials, physical characteristics, electrode material preparation, battery

assembly and methods of electrochemical characteristics used in battery studies. Chapter 4

discusses the conventional amino acridine synthesis and evaluates the electrochemical

properties and performance of composite dACD-NH 2 in aqueous electrolytes. Chapter 5

outlines the synthesis of ATC-MOF electrode material aided by the microwave. The

electrochemical properties and efficiency of the composite ATC-MOF were evaluated in both

aqueous and non-aqueous electrolytes. This chapter also presents the comparative

electrochemical performance of the composite electrodes ATA and ATC-MOF in aqueous

and non-aqueous RLIBs. The Amidoalkyl Naphthol material synthesized by microwave

method is discussed in Chapter 6; we evaluated the electrochemical properties and

performance in aqueous electrolyte. The Multiwalled Carbon nanotubes (MWCNTs-COOH)-

encapsulated Melanin (MN-MWCNTs-COOH-OPD) anode material is described in ARLIBs

and RLIBs applications in Chapter 7. Furthermore, we have also demonstrated for

comparison the electrochemical performance and properties of MN-MWCNTs-COOH-OPD

composite in the non-aqueous electrolyte in coin cell. The electrochemical properties and

performance of calix [4] resorcinarene electrode material for ARLIB applications are

described in Chapter 8. Electrochemical properties and performance were studied in aqueous

battery system in half-cell configuration (vs. SCE), while in the case of the ARLIBs,

electrode properties and performance were explored in full-cell configuration using LiCoO 2

38
 Introduction and Fundamentals of Batteries Chapter 1

as cathode material. The electrochemical studies of LiMB electrode in aqueous electrolyte are

discussed in Chapter 9. Chapter 10 ends with a short discussion on the entire study. With

their advantages and limitations, the electrode materials such as dACD-NH 2, ATC-MOF,

HPMU, MN-MWCNTs-COOH-OPD, C-BC and LiMB electrochemical properties and

material performance have been given in brief.

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