Chapter 1

Introduction

“Basic introduction of rechargeable battery technology, sodium-ion battery technology, its

components, working principle, literature review, objective and scope of the thesis.”
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1.1 Motivation

From the beginning of civilization, energy is the main concern to mankind. We need more and
more energy in the form of electricity to fulfill our requirements and to develop our civilization.
Our country, India is one the most energy consuming country (after China and USA) in the world.1
Till now, this energy is mainly supplied from fossil fuel mainly; wood, coal, oil (petrol, diesel,
kerosene, etc.) and natural gases. But, the burning of these fossil fuels created a bigger problem by
the emission of greenhouse gases. Furthermore, India has limited resources, almost 50% of foreign
purchase are going to purchase this fossil fuel.2 To solve this problem, scientists and researchers
have a keen interest in environmentally clean renewable energy like solar, hydrothermal, wind,
tide, geothermal, etc. But one of the major problems of this renewable energy is the localized based
sources and cannot get all time throughout the year. So, we need to store this energy to fulfill our
requirements. The energy can be stored in different forms like chemical, mechanical, thermal,
electrochemical and electrical energy. Electrical energy is the most desired form of energy and
battery can store and release this energy. The battery is the most important devices which convert
chemical energy into electrochemical energy through redox reaction and by this process, it
effectively stores and releases energy in the form of electricity. There are mainly two types of
battery are available, primary battery (single use) and secondary battery (rechargeable). Lead acid,
nickel cadmium, nickel metal hydride and lithium-ion batteries are the most widely used
rechargeable battery systems, due to its unique property and cyclability. However, the lithium-ion
battery is the most popular to the portable electronic devices and electric vehicles due to its light
weight, high energy density, and better cyclability. Recently, sodium-ion battery has attracted great
attention to the research community for its low cost, huge abundant resources and similar
electrochemical behavior to the lithium-ion battery system.

Figure 1.1 Schematic representation of the trends of energy resources used.

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1.2 History of Battery

Late in 1748, Benjamin Franklin introduced battery in the form of Leyden jars which were used in
military applications.3 After 50 years, in the year of 1800, Alessandro Volta described first
electrochemical battery known as a voltaic pile.4 It was a nice combination of copper and zinc
plates. They used the brine-soaked paper disk as a separator between copper and zinc. Then British
chemist John Frederic Daniell developed the first modern type battery in 1836 by the using of a
copper pot filled with copper sulfate solution.5 This was the first time; the battery was used as an
electrical source (for electrical telegraph). After that, the lead-acid battery was invented by Gaston
Plante in 1859 which was the first rechargeable battery (secondary battery). First, the alkaline
battery was invented in the form of Nickel-cadmium battery in 1899. In 1912 scientists tried for
the lithium-ion battery but they didn’t succeed.6 After a long time, in 1980 nickel metal hydride
batteries was indroduced. In the same time, Sony introduced lithium-ion battery in 1980. In the
parallel manganese battery, sodium-ion battery and the alkaline battery were invented but alkaline
and the lead-acid battery was most popular. First rechargeable sodium-ion battery was sold by
Sony in 1991 which was the most stable and high capacity secondary battery. Although sodium
and lithium-ion battery was investigated from 1970 to 1980 in parallel, the sodium-ion battery
technology remains behind the picture due to the huge success of commercializing lithium-ion
battery by SONY in 1991.5 As day by day our basic requirement is increasing exponentially and
the rapid development of electronics devices; we need more and more high-energy/power density,
super stable rechargeable battery. To get high energy density secondary battery, we require highly
positive redox potential as well as highly negative redox potential. From the last few decades, the
lithium-ion secondary battery has been extensively used in almost all the portable
electronic/electrical devices and automobiles (electrical/hybrid electrical vehicles) industry due to
its capability to store and release electrochemical energy efficaciously. However, the ability of
accessible lithium resources is politically sensitive and are not well distributed throughout the
world. Moreover, our country, India doesn’t have any known lithium resources throughout the
country, shown in Figure 1.2. So, we need an alternative energy system which can be easily
available and compete with lithium-ion technology. Table 1.1 shows the basic property of different
battery technology.

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Recently, a lot of efforts have been given to find out the suitable long-term and large-scale storage
system which can satisfy our energy/power demand and can also fit in our economy. Sodium-ion
battery (SIB), one such kind of technology, has been attracting great interest for its low cost and
huge abundant resources in the earth crust all over the world.7 Sodium metal has high negative
redox potential - 2.71 V vs. RHE. It has comparatively low atomic weight 22.99 g mol-1, high
theoretical energy density 1166 Ah kg-1, has a huge abundance resource (2.64%) and it has
comparatively low cost, 20 times cheaper than lithium and here, sodium-ion technology brought
into the light again. Although the sodium-ion battery has lots of advantages, till now it is not
commercialized.7,8 So, there is a lot of scope to the researchers on sodium-ion technology to make
it commercialize.

Figure 1. 2 Lithium resources available on the earth.9

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Table 1.1 Comparison of different battery metal as an anode6

Metal Charge Atomic Electrode Potential Theoretical Specific Terrestrial

weight (vs RHE) Energy density Abundance
(g mol-1) (V) (Ah kg-1) (%)

Li +1 6.94 -3.05 3862 0.006

Na +1 22.99 -2.71 1166 2.64

Mg +2 24.31 -2.38 2205 1.94

Zn +2 65.38 -0.76 820 0.012

Cd +2 112.41 -0.40 477 0.00003

Pb +2 207.20 -0.13 259 0.0018

1.3 Components of Sodium-ion Battery

SIB has similar structures like all other batteries system. The main components of the battery are
an anode, cathode, electrolyte, current collector and separator. Anode and cathode are separated
by a separator which is soaked with the liquid/polymer electrolyte. The current collector is used to
provide the continuous flow of electron from the electrode to the outer circuit. Generally,
aluminum is used as a current collector for both cathode and anode. There are some basic selection
criteria for good cathode material in SIB as follows;

• The electrode material should contain a redox ion in its matrix.

• It should be air chemically and thermally stable.
• The electrode should have enough space (inter-layer space or gallery space) in its matrix
so that during the large size sodium-ions insertion/extraction, there should be no change
or least change in the structure to have good cycle life.
• The electrode materials should have well electronic and ionic (sodium-ion) conductivity.
• The redox reaction should occur between the electrolyte stable potential window (bellow
electrolyte stable window for cathode and above for anode).
• Several sodium-ions can be inserted to achieve high energy density SIB.
• It should have low cost and environmentally acceptable.

The components of the SIB are discussed in details in the following sections.

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1.3.1 Cathode
The cathode is the positive electrode of a cell which under goes reduction reaction during the
discharge process and gain electrons from the external circuit. The cathode is the deterministic
component of the battery which decides crucial factors like cost, safety, energy and power density
of the battery. Most of the cathode materials are typically intercalations compounds containing
lithium source. Generally, cathode materials of SIB are noted as NaxMyXz, where M is a transition
metal, and X is the anion (oxides or polyanions (XO4)n-).

Generally, layer transition metal oxides were used as cathode material for SIB. From 1970 to 1980,
Whittingham and Hagenmuller investigated several intercalation materials like MoS2, TaS2, TiS2
and NaxMO2 (M = Co, Mn etc.) as an electrode for sodium-ion battery.10–13 In 1980, Delmas and
his research group used layer transition metal oxide as a cathode material for a sodium-ion
battery.11,12 Besides, transition metal salts with oxoanions like phosphate, sulphate, fluro-
phosphate, fluorides, and some hexa-cyanoferrates were also used as a cathode material for
SIBs.11,12 The development of cathode materials will be discussed in details in the later sections.

1.3.2 Anode
The negative electrode is known as anode where the oxidation reaction happened during the
spontaneous discharge process and release electron into the external circuit. Sodium metal is an
ideal candidate as an anode material for SIB. However, due to very low redox potential, it creates
dendrite formation by reacting with an electrolyte which causes short-circuit of the cell.14 It leads
to the thermal runway and possible explosion, prompt researchers are searching for better anode
material for SIB. Carbonous materials are another choice as anode materials SIBs.

In the cathode section, we have been discussed that cathodes are basically based on intercalation
materials (transition metal oxides). However, the reaction mechanism is more diverse for anode
materials and classified into three categories

1. Intercalation materials: Hard carbon, TiO2, Na2Ti3O7

2. Conversion-based material: Fe2O3, MoS2, MoSe2
3. Alloy-based material: SnS, SnO2 etc.

Doeff et al. first investigated different carbon materials for sodium-ion battery with PEO-
NaCF3SO3 polymer as the electrolyte in 1993.15 They used different compositions of graphite-like

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NaC70, NaC30 and NaC15, petroleum coke and Shawinigan black. After huge success in LIBs,
Graphite was considered as an anode for SIBs. However, it can intercalate very little amount of
sodium into its layer and it was well supported by thermodynamic properties of hard carbon. Wang
et al. showed that the graphite intercalating compounds NaC6 was not energetically favorable from
the DFT calculations.16 As the interlayer spacing is small to intercalate the big size Na+, researchers
have tried to expand the graphite interlayers.17 Wen et al. expanded the graphite interlayer spacing
to 0.43 nm which provide a reversible specific capacity of 300 mAh g-1 at 20 mA g-1 current
density.18 Stevens and Dahn in the year of 2000 introduced glucose-derived hard carbon in SIBs.
They prepared hard carbon by pyrolysis process at two different temperature and check their
electrochemical behavior for both Li and Na system.19 Hard carbon showed similar
electrochemical characteristics (metal insertion process) in both systems. However, the plateau at
lower potential region was a little bit higher (potential) in Na system and showed relatively less
storage capacity in sodium system. This material delivered 300 mAh g-1 reversible discharge
capacity vs. Na+/Na but initial Coulombic efficiency was very low (35%) and reproducibility
(getting same specific capacity) for both LIBs and SIBs was an issue. After that many researchers
work on hard carbon and enhance its storage capacity by adopting different strategies, modifying
the morphology, introducing nano porosity or reducing the surface area etc.17 However, there is a
change of sodium plating on hard carbon as the reduction potential is very low, close to sodium
plating voltage.20 Other types of anode materials have also been studied in SIBs in the last few
years, like transition metal oxides (NaxVO2, Na2Ti3O7), metal alloys, metal oxides (TiO2), metal
sulfides (MoS2, SnS) etc.17 Sun et al. reported a high reversible capacity of 896 mAh g-1 at the
very low current rate (C/70) in Sb2O4 thin film for SIB in a voltage range 0 - 3.5 V but suffered
from a large polarization loss.21 Komaba’s group showed nanocrystalline Fe2O3 and Fe3O4 exhibits
a reversible capacity of 160-189 mAh g-1 in a voltage range 1 - 4 V.22 Na2Ti3O7 has also attracted
great attention as anode materials for a sodium-ion battery like Li. Balaya and Jiao et al. reported
that it showed high reversible capacity.23,24 FeS2 also deliver a high reversible capacity of 447 mAh
g-1 in a voltage range 0 - 2.6 V but all this type of materials have the stability issues.25

Detailed discussion on the anode materials is beyond our interest of the present thesis; recently
some excellent reviews have been published in the anode materials for SIB. For simplicity, the
main focus is limited to cathode material which will be discussed in detailed in successive sections.

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1.3.3 Electrolyte
Electrolyte, an essential part of batteries, acts as the ionic transport medium between cathode and
anode. The chemical nature of the electrolyte has an important role in electrochemical performance
and safety of a battery. The redox reaction of electrolyte species is generally close to the electrode,
leads to possible decomposition of the electrolyte and decomposes at the electrode/electrolyte
interface which is essential for long cycle life. An ideal electrolyte should have the following
property.

• Large stable electrochemical potential window.

• High ionic conductivity and low electronic conductivity.
• Chemically stable towards all cell components.
• Low viscosity, high thermal stability, low cost and low toxicity.
• Should be able to form a stable passivation layer at the surface of the electrode.

Different type of liquid electrolyte has been analyzed by several research groups for SIB.
Tarascon’s group reported three different kinds of salt (NaClO4, NaTFSI, and NaPF6) combined
with different solvents (PC, EC, DMC, DME, DEC, THF, triglyme and their mixture).26 Major
group used NaClO4 or NaPF6 salt in either EC:PC, EC:DEC, PC, EC:DMC solvents.27 Some
researchers tried to short out good electrolyte combination among all. Ponrouch et al. investigated
different parameters like thermal stability, electrochemical stability at different potential windows,
cycling feasibility of different type of solvent that can be used in SIBs. They concluded that EC:
PC is a good solvent in either NaClO4 or NaPF6 salt for hard carbon anode.26 Later on the same
group showed that EC0.45:PC0.45DMC0.1 solvent with 1M Na-salt performed best electrochemical
performances for hard carbon as this ternary mixture has low ion paring, high ionic conductivity,
low viscosity and able to from more stable SEI layer.28 Kamath et al. concluded from both
theoretical and experimental analysis that the EC:EMC and EC:DMC solvents showed better
cycling stability than EC:DEC in NaClO4 salt for TiO2 nanotubes.29 Hu et al. reported NaFSI salt
in PC solvent act as an excellent electrolyte for Na3V2(PO4)3 cathode and Na2C8H4O8 anode,
operated at both high and low temperature.30 A new type of electrolyte, NaFSA-C1C3pyroFSA
can act at high oxidation window up to 5.2 V.31 Ong et al. used fluoroethylene carbonate (FEC) as
an effective functional additive to improve reversibility of Na+ insertion for both hard carbon and
NaNi0.5Mn0.5O2 electrode in non-aqueous sodium batteries.32 Several groups also tried ionic liquid
(IL) as a safe and high potential range electrolyte in SIBs.33 So proper choice of solvent (mixture),

9
salt and additive are required for optimum electrochemical performances for a particular sodium-
ion battery system.

1.3.4 Current Collector and Separator

The current collector is used to collect the electron and passed it to the outer circuit. Generally,
aluminum (Al) is used for the positive electrode whereas copper (Cu) used for the negative
electrode.34 Most important, these current collectors are of low cost and have good electronic
conductivity due to the high purity of Al/Cu metal. Though, Al is the current collector for high
voltage cathode SIBs; however, have experience problem associated with corrosion after
prolonged cycling at high potential. Further, decomposition of the NaClO4 salt at high potential
results in the formation of HF in the electrolyte solution which leads to corrosion of Al current
collector. Initially, for all anodes, Cu used as a current collector for SIBs. However, after the
successful use of Al as a current collector for anode (as it is cheaper and lighter than Cu), Cu is
not considering as a current collector. The reason behind the stability of Al against sodium at lower
potential was not understood yet.35 The use of an Al current collector in both electrodes further
reduces the cost of the battery and minimizes the weight of the battery (as Al is cheaper and lighter
than Cu).

The separator is used to separate the anode and cathode electrode and also act as an electrolyte
reservoir. It does not participate in any electrochemical reaction but its structure and physical
property have a strong impact on battery performance especially in safety and cycle life. Separators
are shocked with liquid/polymer electrolyte and then sandwiched between the anode and cathode
so that it prevents the direct contact (electronic) between them but provide a pathway to transport
ions (Na+). The ideal separator should be electronically insulator and have enough porosity (40 –
60%) to transport the ions (pore size should be less than 1 μm).36 It should have good wettability
property so that it can easily wet by the electrolyte and make proper channels for Na + transport.
Besides, it should possess good physical strength and thermal resistance to withstand (stress
generated during gas evolution, volume expansion-contraction) during cell operation. In the
sodium-ion battery, borosilicate glass fiber, polypropylene (PP) or polyethylene (PE) are the most
popular choice in SIBs.

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1.3.5 Other Important Components of Sodium-ion Battery
In the above section shows cathode, anode, electrolyte, current collector and separator are the
primary components of the battery. However, there are many more components (like conductive
additives, binder, solvents) are used to construct the battery and have a definite role in battery
performances.

The conductive additives are incorporated into active materials to enhance the electronic
conductivity of the electrode. Usually, carbonaceous materials like carbon black (CB), super C-
65, activated carbon (AC) and more recently carbon nanotubes (CNT), multiwall carbon nanotubes
(MCNT), carbon nanofiber or graphene are also worked as good conductive additives.37,38 Use of
these type of conductive carbon help to maintain the electronic connectivity during cycling process
and help to enhance the cyclability of the system. Besides, this (graphene, RGO) also act as a
buffer zone which maintain integrity of the cell during volume expansion or contraction. 39
Generally 10-20% conductive additive used in SIB (it should be as less as possible as it increases
the dead mass of the battery).40 Sometimes, this additives also contributes the capacity to the
system (mainly for anode). Dutta et al. showed the super C-65 showed a discharge capacity of 461
and 281 mAh g-1 in the 1st and 2nd cycle at 50 mA g-1 current rate and after 100 cycles it was able
to sustain its 70% initial capacity.41 However, not much work has done on conductive in details in
SIBs.

Binder is another important component in SIBs. Binder is applied to bind the active materials and
carbon additives with the current collector and ensure good electronic conductivity. It also helps
to accumulate the volume change during sodiation/de-sodiation process. There are several types
of the polymeric binder which were implemented in SIBs; however, carboxy methylcellulose
(CMC), poly-vinylidene fluoride (PVdF) and alginate (sodium), polyacrylic acid (PAA) are more
popular.27,42 Typically, 5-10 wt% binder is used to prepare the electrode. PVDF is mostly used as
a binder in SIBs.27 However, Dahbi et al. showed the use of CMC binder provided much more
cycling stability than PVDF.43 Moreover, water is used as a solvent for CMC binder which makes
it cheaper, easier and safer to process than PVDF which need toxic and costlier N-methyl-2-
pyrrolidone (NMP). Fang et al. used PAA binder to prepare the electrode with tin anode which
also displayed better electrochemical performances than PVDF.43 However, CMC did not provide
better electrochemical performance in terms of cycling stability than PVDF for carbon anodes.27
They concluded that the PAA exhibited improved cycling performances was due to the formation

11
of better stable passivation layers and also for lower internal resistance. But this PAA binder is not
good for all electrode materials. Valvo and their groups found PAA binder was not good for co-
intercalating anodes.44 So, proper selection of the binder is important for better electrochemical
performances.

1.4 Working Principle of Sodium-ion Battery

The working principle of the sodium-ion battery is similar to any kind of secondary battery (like
Lithium-ion battery). The working principle is based on the conversion of chemical energy into
electrical energy through a redox reaction. This conversion reaction is also known as rocking-chair
mechanism and here a reversible exchange of sodium-ion and electron are happening between the
positive and negative electrode. During the charging process, the positive electrode (NaFePO4) is
oxidised and the anode material (graphite) is reduced simultaneously, known as de-intercalation
of sodium-ion from cathode material and intercalation into the negative electrode, (hard carbon,
HC), reverse phenomena is happening during discharging process (Figure 1.3).

Figure 1.3 Schematic diagram of a sodium-ion battery.

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The charge-discharge reaction mechanisms are shown as follows:
Cathode half-cell reaction: NaFePO4 ↔ Na1-xFePO4 + xe- + xNa+
Anode half-cell reaction: xNa+ + HC + xe- ↔ NaxHC
Overall reaction can be written as: NaFePO4 + HC ↔ Na1-xFePO4 + NaxHC

1.5 Electrochemical Aspects and Evaluations of Battery Performances

Cell Voltage (V)

The most important parameter in an electrochemical experiment is the cell voltage. Cell voltage is
defined as the potential difference between the two electrodes.

V = ∆µ

Cell voltage is also denoted as open circuit voltage (OCV) when no net current is applied to the
battery. Cell voltage calculated as

Ecell = Ecathode - Eanode

Capacity (Q)

The capacity is defined as the total amount of charge can be store in a battery and denoted as
𝑡
Q = ∫0 𝐼𝑑𝑡

where I is the current applied trough the battery (in Ampere), t is the time (in seconds) and Q is
the capacity (in Coulombs).

The theoretical capacity is calculated from the number of electron exchange from the formula unit
of the host matrix by the using of the following equation:
𝑛.𝑚.𝐹 𝑛.𝐹
Q (C) = or Q (mAh) = 3.6𝑀
𝑀

where n is no. of electron exchanged per formula unit (equivalent to number of Na+
inserted/extracted into/from the host), m is the weight of the active materials (g), F is Faraday’s
constant (96485 C.mol-1) and M is the molecular weight of the active material (g. mol-1).

Generally, the specific capacity is defined as the capacity per unit weight of the active materials
(mAh g-1).

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Energy (W)

The amount of energy can be delivered from a battery known as energy density and denoted as
𝑡
W = ∫0 𝑉. 𝐼𝑑𝑡 = Q.V

Energy is basically expressed per unit of weight known as specific energy density (Wh kg-1) or per
unit of volume (volumetric energy density Wh L-1)

Energy efficiency is the ratio of useful energy to the energy supplied to get this output energy.

Power (P)

The power (W) is the ability to how fast it can deliver electron and sodium-ion to the system and
it depends on the kinetic of the redox reaction. It is defined as the energy per unit time.

P = V.I

In battery system specific power density (W kg-1) and volumetric power density (W L-1) generally
used.

Power efficiency (η%) is the ratio of the output power to the input power:

η = Pout / Pin * 100%

Cycle life or Cyclability

Cycle life or cyclability is the number of complete charge-discharge cycles that can be carried out
before a lower limit of capacity (80% initial capacity).

Coulombic Efficiency

Coulombic efficiency is defined as the ratio of output capacity to the input capacity and it has to
be as close as possible to 100%. If we did discharge first then coulombic efficiency is defined as
𝑄𝑐ℎ
Coulombic efficiency = (𝑄 ) ∗ 100
𝑑𝑖𝑠𝑐ℎ

and if we do charge process first, then it is defined as

𝑄𝑑𝑖𝑠𝑐ℎ
Coulombic efficiency = ( ) ∗ 100
𝑄𝑐ℎ

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Round Trip Efficiency

Round trip efficiency is defined as the ration of energy input (in MWh) into energy retrieved from
storage (in MWh) means the fraction of energy that can be recovered from the system. It is noted
in percentage (%) and typically its value is about 80%.

1.6 Development of Cathode Materials in SIBs

The structure of this transition metal oxide is like NaxTMO2+y (where, T = transition metal).
Typically, the layered structure is built by sheets of edge-shared TMO6 octahedral, wherein alkali
ions are located between TMO6 sheets. Sodium layer oxides can be classified into three categories;
O3-, P2- and P3- types depending upon oxide layers arrangements with the surrounding sodium
atoms. If the Na is located in an octahedral position called as O-type and is known as P-type when
Na attach in the prismatic site and how much unique interlayers are surrounded by oxide layers,
present the number whereas, prime (/) signify a disordered phase. So, in O3-phase, the oxide layers
are stack in ABCABC pattern and all the Na (0.7 ≤ x ≤ 1) shares alternatively edge and face
positions as shown in Figure 1.4a. P2-phase form when x ≤ 0.7 and oxide layers decorate in
ABBA manner and all the Na share either face or edge Figure 1.4b.

Figure 1.4 Typical crystal structure of (a) O3-, (b) P2-, and (c) P3-phase layered oxides.45

Whereas, ABBCCA arrangements of the oxide layers are noticed in P3-phase where Na (x ≤ 0.5)
share one face with a TMO6 octahedron and their edge with three TMO6 octahedra as shown in
Figure 1.4c. The crystal structure has a strong influence on electrochemical performances of

15
different phase’s oxide materials due to its different Na amount in the pristine phase, the stability
and kinetics of each layer depend on the surrounding Na environment. Generally, O3-phase have
poor cycling stability as it experiences a series of phase transitions due to the layer-sliding during
electrochemical performances. However, P2-phase shows higher specific capacity due to faster
diffusion and higher Na contents than O3-type and also exhibit better stability. However, if sodium
extracted deeply during the charging process, the phase transition may occur from P2 to O2.

1.6.1 Mono and Multi Layered Transition Metal Oxides:

Hagenmuller et al.46 reported that NaxMnO2 exist in several phases within the range of x = 0 to 1.
The P2 type Na0.7MnO2 gives the reversible discharge capacity of 100 mAh g-1. Whereas P2 type
Na0.6MnO2 showed discharge capacity around 140 mAh g-1 for the first few cycles, shown in
Caballero et al.47 Monoclinic α-NaMnO2 gives a higher capacity of around 185 mAh g-1 for the
initial cycle.48 All the three types of sodium manganese oxide are not stable, after few cycles, rapid
reduction of capacity was observed. NaFeO2 also has attracted great attention due to inexpensive
and nontoxic. Thorne et al.49 demonstrated that NaxFexMn1-xO2 was able to deliver a reversible
capacity of ~ 90 mAh g-1 in the voltage range 2.5 to 4.2 V, whereas P2-Na0.67Fe0.5O2 showed better
first cycle discharge capacity about 190 mAh g-1.50 Gonzalo et al. prepared both the O3 and P2
phase Na2/3Fe2/3Mn1/3O2 solid state route.51 Both O3 and P2 phase exhibited a discharge capacity
of ~ 151 mAh g-1 at C/10 rate in the first cycle, however after 10 cycles it declined to 122 mAh g-
1
, however, P2 phase showed better cycling stability. The other transition metal chromium also
investigated by Komaba and their group.52 They showed that NaCrO2 displayed a reversible
capacity of 120 mAh g-1. Some researcher also examined the NaNiO2 cathode material, it delivered
a capacity of 123 mAh g-1 within the voltage range of 1.25 to 3.75 V.53 O3 type NaNi0.5Mn0.5O2
transition metal oxide was reported by Komaba’s group which exhibits a capacity of 105–125 mAh
g-1 in a voltage range of 2.2 – 3.8 V. All the transition metal oxide described above as positive
electrode for sodium-ion battery showed poor cyclic performance and some of the materials have
limited discharge capacity.

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Figure 1.5 (a) Schematic P3- and (b) O3-structures of Na–Fe–Mn–O layered compounds (yellow
and red color indicated sodium and oxygen respectively).

Tunnel type oxides are generally orthorhombic and noted as NaxTMO2. In this structure, all TM4+
and TM3+ ions are occupied in the octahedral site (TMO6). The s-shaped tunnel is formed by the
edge sharing of TMO5 units which is joined with one triple and two double octahedral chains. The
s-tunnel is favors the sodium diffusion one direction (c-axis).38 Baudrin et al. examined the
insertion de-insertion mechanism of Na0.44MnO2 for sodium-ion battery between 2 V to 3.8 V.54
Cao and coworkers,55 another Chicness group reported orthorhombic Na0.44MnO2 which provided
a discharge capacity of 130 mAh g-1 at the rate of 0.1 C. These materials showed super stable
performance up to 1000 cycles. A higher amount of Na+ is expected to be further extracted if it is
charged to a higher voltage; however, it was very difficult to find a stable electrolyte with a wider
voltage window. This result is consistent with the chemically desodiation results that 0.44 Na+ can
be extracted from Na0.875Fe0.875Ti1.125O4 by using NO2BF4 as oxidation agent.56

17
Figure 1.6 Crystal structure tunnel type transition metal oxide. (Reproduce57).

1.6.2 Phosphates:
Different types of phosphates like NASICON, olivine, pyrophosphate, and mixed polyanion and
alluaudite were investigated as cathode materials for sodium-ion battery. Olivine-type phosphate
has NaMPO4 (M = Fe, Mn, Co etc.) structure. Hammond and Jaghib et al. reported that if NaMPO4
is prepared by normal chemical route then it produce maricite structure, not olivine and this
material is chemically inactive due to lack of cationic transport through the channels.58,59 The
maricite structure exhibited a very poor storage capacity as it does not has a proper Na+ diffusion
channel. Whereas olivine structured showed a high discharge capacity of 147 mAh g-1 at C/20
current rate. However, both the phase had suffered from stability issue. The olivine NaFePO4
showed good storage capacity of 100 mAh g-1 in voltage range 2 to 4 V with good cyclic
performance.60 However, making of NaFePO4 was little bit hepatic; first, they delithiated the
LiFePO4 and again sodiated this to make olivine NaFePO4. NASSICON type phosphate
(NaXM2(PO4)3) are first introduced by Hong and Goodenough with high Na+ conductivity.61,62
NASICON type NaTi2(PO4)3 exhibited a good storage capacity of 120 mAh g-1 with Ti4+/Ti3+
redox center.63

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Figure 1.7 Crustal structure of (a) NaFePO4 maricite phase, (b) Olivine NaFePO4 (Yellow: Na,
Red: O).

Figure 1.8 Crystal structure of monoclinic sodium iron pyrophosphates (Na2FeP2O7) normal to
the bc plane, Na+ migration in the tunnel pathways. The FeO6 octahedra (light brown), PO4
tetrahedra (light purple) and Na atoms (yellow) oxygen atoms (red) are shown.

Pyrophosphate has structures like Na2MP2O7 (M = Fe, Mn, Co etc.). Pyrophosphates were first
examined for SIB by Yamada’s group.64 They reported that Na2FeP2O7 pyrophosphate has a
triclinic shape and showed a good reversible capacity of 83 mAh g-1 in the voltage range of 2 - 4
V associated with Fe3+/Fe2+ redox. Homma et al. reported Na2-xFe1+xP2O7 (0<x<0.4) prepared by
the glass ceramic process, exhibited good cyclic performance at a high rate.65 The mixed polyanion
19
compounds were first investigated by Kim et al.66 They reported that the mixed phase
Na4Fe3(PO4)2P2O7 revealed a reversible capacity of 110 mAh g-1 at a current rate C/40. This mixed
phase showed better electrochemical performances than in phosphate and pyrophosphate for SIB.

1.6.3 Progress of Vanadium-based Cathode Materials for Sodium-Ion Battery

Recently, transition metal-based layered oxides became a state of arts for higher energy density
safe cathode materials for sodium-ion battery (SIB).67–71 Among all, vanadium-based oxide
materials have been attracted high attention due to its superior redox behavior (wide range of
oxidation state (+2 to +5), higher specific capacity, better rate capability, and competitive cycling
performance) compare to any other transition metal oxides.72–75 As vanadium oxides have a large
interlayer spacing which accumulates the larger number of sodium-ions (more than 1 sodium-ion
per formula unit of host material) and also facilitates the diffusion process of larger size sodium-
ion into/from the host matrix.76,77 Besides, electronic behavior of most of the vanadium oxides
changes from an insulator to semiconductor or metallic, during the intercalation process at normal
temperature (273 - 333 K) which help to enhance the rate capability of the electrode.35,78 Moreover,
most of the vanadium-based compounds have versatile morphology and crystal structures, which
can be further modified for optimum sodium-ion storage. Various synthesis methods are utilized
such as solid-state calcination process, solvothermal process, hydrothermal technique,
electrochemical depositions methods, microwave-assisted hydrothermal reaction, hydrolysis
process etc. to synthesize various structural and morphological vanadium-based oxides cathode
materials for SIB.79 Lots of vanadium-based cathode materials like V2O5, VO2, VOPO4, NVO,
Na3V2(PO4)3, Na3V2(PO4)3Fx, etc. have extensively studied in recent years.75,80–82 The development
of vanadium- based cathode materials will be discussed in subsequence sections for SIBs.

Vanadium Pentoxide (V2O5):

Vanadium pentoxide (V2O5) has been considered as a promising low-cost cathode for rechargeable
SIBs. V2O5 crystal is formed by the arrangement of a square-pyramidal VO5 unit in parallel. Two
V2O5 units are required to build a unit cell. The four O are surrounded by two V by edge sharing
to form disorder trigonal bipyramidal polyhedral (V2O4)n zigzag double chain along (100)
direction and cross-linked along ((010) direction through corner share.83 This leads to sheets
formation in ab plane and create huge interlayer spacing (4.37 Å) which facilitate the larger Na +
diffusion in the matrix as shown in Figure 1.8.

20
Figure 1.9 Crystal structure of orthorhombic V2O5 (reproduce84).

Su et al. studied bilayered V2O5 nanobelts for high capacity SIB.83 They prepared one-dimensional
V2O5 nanobelts (with an average width of 90 nm and 50 nm thickness) by the simple solvothermal
process. The as-prepared bilayered nanobelts have large interlayer d spacing of 1.153 ((001)
growth directions) which facilitate the sodium-ion insertion/extraction. The V2O5 nanobelts
delivered a high discharge capacity of 231 mAh g-1 at a current density of 80 mA g-1. Tepavecvic
et al. first used nanostructured bilayered V2O5 as a cathode material for the SIB.85 They
synthesized the nanostructured V2O5 by electrochemical deposition method on a nickel substrate.
The bulk orthorhombic V2O5 showed a specific capacity of 150 mAh g-1 at 20 mA g-1 current
density whereas nanostructured layered V2O5 exhibited a high specific discharge capacity of 250
mA g-1 at the same current rate. In this system, more than two sodium-ions (Na2V2O5 ~ 235 mAh
g-1) can intercalate into the V2O5 layer matrix. They found that the orthorhombic and bilayered
V2O5 showed completely different intercalation mechanism. Orthorhombic V2O5 cathode
undergoes two phase transitions (two distinct plateau) during sodium insertion/extraction. The
performance of the orthorhombic V2O5 has been hindered by its low sodium-ion diffusion
coefficient and moderate electrical conductivity. This indicated that change in crystal structure
during intercalation/deintercalation process is associated with the capacity fading of the
orthorhombic phase. Whereas, bilayered V2O5 cathode with larger interlayer d spacing exhibited
single smooth plateau with no phase transitions in its charge-discharge curve. However, when the
aluminum current collector was used instead of nickel substrate, the specific capacity was reduced

21
to 140 mAh g-1 and subsequently decreased upon cycling.85 Raju et al. first time showed carbon
encapsulated orthorhombic V2O5 as a superior cathode material for sodium-ion battery.86 The
uniformly coated orthorhombic V2O5 inside the nano-porous carbon synthesized by an ambient
hydrolysis deposition followed by hydrolysis reaction. The V2O5/C composite showed a high
specific discharge capacity of 170 mAh g-1 at 40 mA g-1 current rate. However, the charge-
discharge curve remained sloppy and they found that a large portion of the sodium-ion storage was
coming from the pseudo-capacitance behavior of V2O5 nanoparticles. G. X. Wang group also
investigated orthorhombic V2O5 as a cathode for SIB.87 They made hierarchical V2O5 hollow
nanosphere by template free polyol-inducted solvothermal method. The hollow nanosphere V2O5
provided a discharge capacity of 150 mAh g-1 (equal to one sodium-ion inserted per V2O5 formula
unit) at 20 mA g-1 current density. They described that the growth of V2O5 was hierarchical in
(001) direction whereas (110) plane act as two-dimensional diffusion path for sodium-ions
intercalation. However, this cathode material had a very low nominal potential below 1.7 V and it
is also facing huge (30%) first cycle irreversible loss which is very unusual for the cathode
material. Sponge-like two-dimensional V2O5 nanosheets were described as a cathode material for
sodium-ion battery by Zhou group.88 The unique sponge like V2O5 was prepared by freeze drying
method which can sustain a high pressure (400 times their own weight). The numerous macropores
V2O5 nanosheets exhibited a high discharge capacity of 216 mAh g-1 at a low current density of
20 mA g-1. They found that (001) plane facile the charge transfer at the electrolyte/electrode
interface due to the shorter diffusion path ways for sodium-ions. But, the sponge like cathode
material was suffering from poor rate capability and had a long-term cycling issue. Recently, Li et
al. shown nanocrystalline V2O5 as an intercalation host for SIB.79 This bilayer nanocrystalline
V2O5 was directly grown on a steel substrate by an electrochemical deposition technique. This
V2O5 had a large interlayer d spacing of 1.16 nm which favored the intercalation process. The
binder free nanocrystalline V2O5 showed a high discharge capacity of 200 mAh g-1 at a low current
rate of 10 mA g-1. However, this material did not show any prominent plateau (charge-discharge
curve is sloppy nature) which suggest the pseudo-capacitance behavior of nanocrystalline V2O5
against Na+/Na.

Recently, Muller-Bouvet et al. showed ’-NaV2O5 as a new sodium intercalation compound.89

The orthorhombic a’-NaV2O5 cathode material was synthesized by an electrochemical deposition
process which was highly stable at high temperature. This material delivered a high discharge

22
capacity of 120 mAh g-1 at C/10 current density. But the average cell potential of this cathode
material was very low (1.6 V), had huge polarization loss and also suffered from poor cycling
stability. NaV6O15 also proposed as electrode materials for SIB. It showed the capacity of 120
mAh g-1 in the voltage range of 1.5 to 1.7 V.90 So, from the above discussion, it was clear that
although V2O5 cathode materials provide a high specific capacity, was suffered from either
stability issue or had a low cell potential which was hindered from its commercial applications.

Vanadium Dioxide (VO2):

Among other known vanadium oxides, metastable vanadium dioxide VO2 (B) attracts the great
interest in the rechargeable battery due to its layered structure and promising properties in the
nanometer domain. The VO2 (B) are built up with distorted VO6 octahedral structure, where both
the corners and edges share each other and forming the V-O tunnels perpendicular to the c-axis.91

Figure 1.10 1 Na insertion in VO2 structure; here blue, red and yellow color sphere represents the
V, O and Na atoms respectively.

Wang et al. first introduced single crystalline VO2 nanosheets cathode materials for the SIB. They
prepared ultrathin VO2 nanosheets by simple hydrothermal process. The length of this cathode
material was hundreds nanometer with 50-60 nm average diameter. From the theoretical
calculation they found that as the number of inserted sodium-ion increases from 0 to 1, NaVO2
phase becomes more stable and very little volume change observed. However, when the inserted
sodium-ion number cross 1.25 (Na1.25VO2), the V-O tunnels were broken and 50% volume
expansion was noticed. This ultrathin semiconducting VO2 cathode provided a high discharge

23
capacity of 214 mAh g-1 at a current rate of 50 mA g-1. However, this showed poor cycling stability
as well as it did not show any straight plateau in its charge-discharge curve.91 Later, Fan and his
group demonstrated graphene quantum dots coated VO2 (VO2@GQD) arrays for both lithium and
sodium-ion batteries.92 Initially, bilayered VO2 was synthesized by solvothermal technique, then,
to prepare VO2@GQD arrays, they adopted the in-situ hydrothermal method followed by a
calcination process. Although this VO2@GQD cathode provided a stable high discharge capacity
of 306 mAh g-1 at C/3 current density, but the sodiation mechanism was controlled by adsorption
phenomena (capacitance behavior).

Vanadyl Phosphate (VOPO4):

Figure 1.11 Crystal structure of β-NaVOPO4 with Na bond valence = 1.5, possible Na+
intercalation sites shows here.

Vanadyl Phosphate (VOPO4) is another promising vanadium-based compound used as a cathode

material for SIB. Although VOPO4 was extremely explored as a cathode material in LIBs due to
its high redox potential, high specific capacity and high rate capability, however, in SIBs it was
rarely studied. First, in the year 2013, monoclinic NaVOPO4 was investigated as a cathode material
for SIB by Goodenough’s group.93 The NaVOPO4 synthesized by a simple sol-gel method has a
monoclinic structure with corner-sharing VO6 octahedra (parallel to the c axis) which are
connected by PO4 tetrahedral. Four equatorial V–O bonds and two axial V–O bonds alternating
along the chains with separations of 1.681 Å and 2.091 Å create disorder VO6 octahedra. The
disorder with chain separation helps to form vanadyl bonds that introduce ferroelectric chains.
Sodium-ions can migrate through the 3D tunnels along (110), (110) and (101) direction. This
24
cathode material exhibited a discharge capacity of 90 mAh g-1 at a current rate of 10 mA g-1 with
an average cell potential of 3.6 V vs. Na+/Na. He at al. demonstrated layered structure VOPO4
cathode for sodium-ion battery.82 Initially, -LiVOPO4 layered material was prepared by the
microwave-assisted solvothermal method and after that, it was delithiated by nitronium
tetrafluoroborate in acetonitrile medium under Ar atmosphere. The delithiated VOPO4 cathode
showed a discharge capacity of 110 mAh g-1 at C/20 current rate with 3.4 V cell voltages. However,
they observed a slow charge transfer due to low electronic conductivity. To overcome this, they
incorporated reduced graphene oxide into it and the specific capacity was further enhanced to 150
mAh g-1 at the same current rate vs. Na+/Na.82 The same group also synthesized -NaVOPO4 by
both electrochemical (as described earlier) and chemical process.94 They added sodium iodate in
VOPO4 to prepare orthorhombic -NaVOPO4 chemically. This -NaVOPO4 cathode delivered a
lower specific capacity of 70 mAh g-1 at C/20 with poor cycling stability. It was suffered from
large irreversible capacity loss, low coulombic efficiency as well as high polarization loss.94

Sodium Vanadium Polyanion Compounds:

In the polyanionic compounds, the tetrahedral XO4 and trigonal XO3 groups are partially replaced
by VO6 octahedral clusters. Different type of vanadium based polyanionic compounds like
phosphates, fluorophosphates, pyrophosphates etc. were extremely studied as a cathode material
for a secondary battery.38,45,95 It creates a 3D open-framework structure by edge or corner sharing
polyhedrons, to host the larger size sodium-ions. The layered transition vanadium oxides
permeated a straight or tangled channel in polyanionic compounds structure of polyanionic
compounds with relatively low Na+ diffusion energies. Basically, NASICON structured
polyanionic compounds have extensively higher rigidity of a covalent 3D network, shows high
thermal stability and high resistance to oxidation without any phase changes with sodium-ions
insertion (Figure 1.9a).96,97 Further, vanadium based polyanionic compounds offer a higher
operational voltage for SIBs. Yamaki’s group first reported the sodium storage capability of
Na3V2(PO4)3 which were displayed a reversible capacity of 140 mAh g-1 in a voltage range 1.2 to
3.5 V associated with V4+/V3+, V3+/V2+ redox couple.98 Hu et al. introduced the same materials
Na3V2(PO4)3 with carbon coating but the electrochemical performance was not improved, only
showed the reversible capacity of 93 mAh g-1 in NaClO4/PC electrolyte.73 Lim et al. first
investigated NASICON structured Na3V2(PO4)3 as a cathode material for rechargeable SIB.99

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Figure 1.12 Structure of (a) NASICON Na3V2(PO4)3 Yellow Na, Red O and (b) Na3V2(PO4)3F
(upper) and Na3V2(PO4)3F3 (bellow).100

The sol-gel method was used to synthesized this Na3V2(PO4)3 cathode. This cathode material
showed a specific discharge capacity of 84.8 mAh g-1 at C/5 current density which was equivalent
to 1.4 Na per Na3V2(PO4)3. They observed some kind of discrepancy between charging and
discharging capacity after the 1st cycle. However, this NASICON structured cathode displayed
good cycling and rate performance due to a well-defined channel structure. Furthermore, it showed
decent thermal stability up to 450 oC, owing to the stable P-O bonding in a NASICON structure.99
Later on, Shen et al. reported porous Na3V2(PO4)3/C composite as a highly stable cathode material
for SIB.101 The uniform carbon coated porous Na3V2(PO4)3 material was synthesized by sol-gel
method combined with the freeze-drying process. Due to the porous structure, the high specific
surface area of the composite facilitated to increase the connectivity between the electrode and
electrolyte significantly and also open new active sites for sodium-ion storage. The porous
Na3V2(PO4)3/C composite exhibited excellent rate capability and cycling stability. Moreover, it
showed a high specific discharge capacity of 118.9 mAh g-1 at 0.05 current rates with a nominal
potential of 3.4 V. However, a large polarization loss (0.15 V) was experienced in this material.101
Soon, Balaya and his group presented porous 3D NASICON Na3V2(PO4)3/C as a high performance
durable cathode material for SIB.102 This Na3V2(PO4)3/C material was prepared by soft template

26
precipitation technique flowed by a calcination process. This composite provided a specific
capacity of 116 mAh g-1 corresponds to 1.88 mole sodium-ion per mole of Na3V2(PO4)3 at 0.2
current density. It showed excellent rate performance, 92.2% initial capacity (106 mAh g-1) was
retained even at 10 C. It can sustain a prolonged cycle life of 30000 cycles with 50% capacity
retention at 40 C.102 After a few days later, Kajiyama et al. reported Na3V2(PO4)3 nanoparticles
confined in a one-dimensional carbon sheet for enhancing sodium-ion cathode property.103 First
time electrospinning method was used to fabricate one-dimensional Na3V2(PO4)3 nanofibers. The
Na3V2(PO4)3 nanofibers delivered a specific capacity of 94 mAh g-1 in its 1st cycle at 0.1 C.
However, the polarization loss was increased with the current rate and it also suffers from the poor
cycling performance.103 Si et al also used carbon coated sodium vanadium phosphate cathode for
sodium-ion battery.104 One-step solid state reaction (under C2H2 atmosphere) was used to made
uniform carbon coated (average thickness 10 nm) Na3V2(PO4)3 material. Na3V2(PO4)3/C micro-
particle showed a specific discharge capacity of 91.6 mAh g-1 at 1 C current rate and after 300
cycles it sustained its 89.62% initial capacity.104

To enhance the cell potential further, fluorine-ion was introduced into the NASICON structure
(crystal structure with possible sodium-ion diffusion shown in Figure 1.9b). Some
fluorophosphates also reported in SIBs. Kang et al. investigated Na3V2(PO4)2F3 material for
SIB.105 Rojo and his group first used sodium vanadium fluorophosphate (Na3V2O2x(PO4)2F3-2x) as
a high voltage cathode material for SIB.100 They prepared Na3V2O2x(PO4)2F3-2x electrode by simple
hydrothermal process. The Na3V2O2x(PO4)2F3-2x cathode showed two distinct plateaus at 4.1 V and
3.6 V vs. Na+/Na, first one corresponds to V5+/V4+ redox couple whereas 2nd plateau is due to
V4+/V3+ redox couple. The carbon free Na3V2O2x(PO4)2F3-2x electrode showed high specific
capacity of ~ 118 mAh g-1 at 0.1 C but at a higher rate at 1 C delivered a discharge capacity of 102
mAh g-1 with poor cycling stability. However, after carbon encapsulations, the cycling stability
was enhanced (after 30 cycles without capacity fading) due to good electronic conductivity,
although it has less initial specific capacity (86 mAh g-1 at 0.1 C).100 After one year, Rojo’s group
further enhance the electrochemical performance of Na3V2O2x(PO4)2F3-2x cathode materials by
incorporating mesoporous carbon into the material which helps better access of liquid electrolyte
and electron to the active material.106 It showed a specific capacity of 95 mAh g-1 at 1 C rate with
95% capacity retention after 200 cycles.106 So, from the above discussion, we observed that all of
this polyanion based vanadium cathode materials have a limited specific capacity and carbon or

27
graphene was incorporated to enhance the cycling performance which further enhances the dead
mass of the battery and hence deduce the overall energy density.
Pyrophosphate: Pyrophosphate is generally mixed polyanionic compound has a 3D framework
structure which provides well-defined channels for sodium-ion diffusion. Besides, during the
charge-discharge process, the structure did not change and it provides a high operating potential
which makes it a promising cathode candidate for SIBs. Different configurations vanadium-based
pyrophosphates were tried as a cathode material for SIBs. Deng et al. reported a high purity 1D
nanostructured Na7V4(P2O7)4(PO4) as a high performance cathode for SIB.107 They prepared this
sodium vanadium pyrophosphate by sol-gel method followed by a calcination process. It showed
two distinct plateaus at 3.87 V and 3.88 V during the charging process corresponds to (V3+/V3.5+)
and (V3.5+/V4+) redox couple respectively. It delivered a specific discharge capacity of 92.5 mAh
g-1 at 0.05 C with good cycling stability (80% of the capacity retention after 200 cycles). Yamada
group also investigated a high voltage t-Na2(VO)P2O7 Pyrophosphate cathode for SIB.108
Tetragonal Na2(VO)P2O7 material with an open framework was synthesized by a simple solid state
reaction. It exhibited a prominent plateau at a high potential of 3.8 V ascribed to V5+/V4+ redox
activity. It delivered a reversible capacity approaching 80 mAh g-1 with excellent cycling stability
and moderate rate kinetics. Deng et al. also studied another vanadium based pyrophosphate
(Na7V3(P2O7)4) structured as a high-potential cathode material for sodium-ion battery.109 A
molten-salt mechanism was developed to synthesize high-purity single-phase ultrafine carbon
decorated Na7V3(P2O7)4. The quasi-2D framework with well-defined ion-conducting planes helps
for better electrochemical activities. It provided a high average potential of 4.0 V on the basis of
one electron reaction. The quasi-2D Na7V3(P2O7)4 electrode showed a specific capacity of 79.6
mAh g-1 at 1 C current density with good cycling stability. However, most of the vanadium-based
pyrophosphates are limited by its specific capacity and poor electronic conductivity.109

Ammonium Vanadium Oxide (Vanadium Bronze):

Another kind of vanadium-based cathode material was used in the sodium-ion battery system is
vanadium bronzes which have attracted great attention due to cheap, easy to synthesize, huge
abundance in the earth and high-energy density. Vanadium oxide bronzes are a wide range of
crystalline structures with mixed valence networks [VxOy] containing the V5+/V4+ or V4+/V3+
couples whose electrical balance of the ionic covalent network is directly linked to the amount of
inserted or intercalated elements alkalis, alkaline earth or metals.110
28
Figure 1.13 Crystal structure of ammonium vanadium oxide (NVO) with possible sodium
insertion cites.

Compared with vanadium oxides, the advantages of vanadium bronzes as SIB electrode materials
are as follows. Metal ions would stabilize the crystal lattice, increase the diffusion rate of sodium-
ion and increase electric conductivity. In the vanadium bronze structure, the NH4+ ions lie into a
gallery space of VO layers and probably interacting with these VO layers via N—H---O hydrogen
bond. There are four sites available for the NH4+ in a gallery space with only two non-equivalent
pair of sites, due to the partial occupancy of N sites (crystal structure shown in Figure 1.10).77 Fei
et al. first time used ammonium vanadium bronze ((NH4)2V6O16) as a cathode material in the
SIB.111 Platelet-like (NH4)2V6O16 material was prepared by the hydrothermal process at 200 oC for
20 h. They also intercalated sodium-ion into the vanadium bronze matrix by the same process. The
(NH4)2V6O16) electrode showed high specific capacity of 200 mAh g-1, whereas
[(NH4)0.71Na0.72V6O16] materials delivered 164 mAh g-1 specific discharge capacity at 20 mA g-1
current density. However, both these cathode materials exhibited poor cyclic performance in
NaClO4 electrolyte.111 After that, the same group used different vanadium bronze (NVO) for
SIB.112 Same hydrothermal technique was used to prepared different morphology (nanoflower,
nanorods and platelet) NVO. Nanorods showed better specific capacity than other morphological
NVO electrodes, whereas platelet-like material showed better cycling stability. The nanorods NVO
exhibited a specific discharge capacity of 150.1 mAh g-1 at 100 mA g-1 current rate whereas platelet

29
like electrode delivered 108.8 mAh g-1 discharge capacity at the same rate. Later on, they prepared
nitrate-like vanadium bronze [(NH4)0.19V2O5.00.44H2O] and their graphene composite by a
hydrothermal technique.113 It showed a higher discharge capacity of 208.9 mAh g-1 at 20 mA g-1
current density, but after 40 cycles, it exhibited only 141.5 mAh g-1 (67.7% capacity retention).
So, most of the vanadium bronzes were suffered from poor cycling performances.

Figure 1.14 Electrochemical performances of vanadium-based cathode materials used in the

sodium-ion battery system.

Recent developments of vanadium-based cathode materials were shown in in Figure 2.1. It

showed that among all the vanadium-based cathode materials, VO2 and ammonium vanadium
bronze showed the highest specific capacity. Here, we chose NVO as our cathode material for the
development of sodium-ion battery technology. However, NVO shows lower cell potential and it
has a long-term cyclic stability issue. So, Fruitful research is required to improve the energy
density and cycling stability for future commercial applications.

30
1.7 Aim and Scope of the Present Work

Sodium-ion battery technology, the existing electrodes and electrolytes are in an early stage of
development and more intense research is necessary before going to mass production and
applications. The high capacity and rate capable electrodes are a mandate and very few
combinations of the cathode, anode and electrolyte are available with an excellent full-cell
performance with long cycle life. For simplicity, our work is mainly focused on cathode materials
for SIB development. Naturally, the sodium-ion has a larger ionic size and has lower energy
density compared to lithium, need more open void or interstitial site to accommodate or diffuse.
So, the present study is focused on to prepare a new intercalation-based electrode material which
has a wider framework to accumulate larger size sodium-ions so that it can deliver a high specific
capacity. Vanadium based oxides are well known for its larger inter-layer spacing and huge gallery
space with superior redox-couples which provided higher specific capacity and better rate
capability than any other transitions metal oxides. However, most of the vanadium-based oxides
cathode materials either limited by its poor cycling stability or have limited specific capacity and
here our aim to solve these problems by adopting a smart strategy or modifying the electrode
materials. The charge-discharge mechanism of sodium intercalation-deintercalation process has to
be studied in details to understand and overcomes these basic problems.

1.7.1 Selection of Cathode Material

Among all vanadium-based oxides cathode materials; here, we chose ammonium vanadium oxide
(NVO) as our cathode material for the development of SIB technology because of the following
reason

• Easy to synthesis
• Multiple redox couples offer higher specific capacity
• Large inter-layer d spacing and huge gallery space accumulate a larger number of large
size sodium-ions and offer better rate capability
• One dimensional growth (c axis) helps to enhance the sodium-ions insertions (b axis).

However, most of the NVO reported in the literature are limited by lower specific capacity,
provided lower cell potential and it has a long-term stability issue. So, need fruitful research to
improve energy density and cycling stability for future commercial applications.

31
1.7.2 Objective
The main goal of this project is to develop a low-cost new cathode material for SIB which can
provide better electrochemical performances (higher energy density, prolong cycling stability and
better rate capability). The main objectives of this project are as follows

1. Prepare ammonium vanadium oxide (NVO) nanostructured by simple, scalable and cost-
effective synthesis process
2. Understand the 1D nanobelts growth mechanism of NVO cathode material
3. Understand the sodium storage mechanism of this cathode material
4. Reason behind the capacity fading and overcome the problem to enhance the cycling
stability
5. Increase the specific capacity as well as cell potential to enhance the overall energy density
6. Pre-sodiation of the NH4V4O10 via a chemical process
7. Na2Ti3O7 anode material preparation and optimization of electrochemical performances
8. Reducing the 1st cycle irreversible loss of the anode material
9. Construct a sodium-ion full-cell with this cathode material vs. any intercalation-based
anode material
10. To overcome the first cycle irreversible loss and enhance the initial Coulombic efficiency
to enhance the overall energy density of the sodium-ion full-cell (as most of the anode
suffer from the huge first cycle irreversible loss).
11. Final objective of my project is to demonstrate a sodium-ion full cell prototype which can
provide similar electrochemical performances (similar energy and power density and
cycling stability) with existing commercial lithium-ion battery technology.

1.8 Outline of the Thesis

The present thesis discusses the new cathode material for SIB application in different chapters.
The thesis has ten chapters with one appendix, where Chapter 1 includes the introduction, and
literature survey of the cathode materials, experimental section is described in Chapter 2, Chapter
3-5 talks about the development of NVO cathode material, anode material development is shown
in Chapter 6,7, full-cell performance is displayed in Chapter 8 and finally Chapter 9 projects
summary and future scope.

32
In Chapter 1, we discussed the introduction of sodium-ion battery and the scope of the future
materials for the sodium-ion battery for next generation storage applications. Also, discussed the
literature of vanadium-based oxide cathode materials used in SIB system in details. Here, we also
talk about their limitations and strategies to overcome this problem. Chapter 2 shows the details
about the materials synthesis process, materials and electrode characterizations techniques and
electrochemical procedure.

In Chapter 3, we illustrate NVO 1D nanobelts as a cathode material for SIBs. The growth
mechanism of NVO 1D nanobelts is explored. The sodiation-desodiation mechanism of this
cathode materials is analyzed from DFT calculation. Further, the capacity fading mechanism is
understood and potential cut-off strategy is taken to improve cycling stability. In Chapter 4, we
enhance the specific capacity, rate capability, and cycling stability by zirconium doping into NVO
matrix. In Chapter 5, we incorporated sodium source into NVO cathode by a simple chemical
process, as this cathode does not contain sodium source.

Chapter 6 talks about sodium titanium oxide (Na2Ti3O7) as an intercalation-based anode material
for SIBs. We further discuss the enhancement of the electrochemical performance by zirconium
doping followed by hydrogenation technique. Although hydrogenated doped showed a high
specific capacity and super cycling stability, suffer from huge 1st cycle irreversible loss. So, we
introduced a new smart strategy to overcome this 1st cycle irreversible loss and enhance the initial
Coulombic efficiency.

In Chapter 7, we discuss the construction of a sodium-ion full-cell prototype based on the above
advance NVO cathode and Na2Ti3O7. In Chapter 8, we summarized the thesis and talked about
the opportunity in near future applications. Finally, Appendix I showed the strategies to synthesis
different morphology nanostructured vanadium tri-oxides and its electrochemical performances in
SIBs. We further explored the sodiation mechanism of this anode material.

33