Spinel Ferrite Nanostructures for Energy Storage Devices

Spinal Ferrite Nanostructures for Energy Storage Devices provide up-to-date coverage of ferrite properties and applications, with a particular focus on electrochemical and electrocatalytic energy storage applications. The book covers the basics of ferrites, including synthesis methods, structures and properties in the first few chapters, focusing on topics such as the properties of ferrites and the electrochemical and electro catalytic energy storage applications of unitary, binary and mixed ferrite nanostructures. Limitations for using ferrites in these devices are also covered. This book is an important reference source for materials scientists and engineers who want to gain a greater understanding of how ferrites are being used to enhance energy storage devices.

• Shows how ferrites are being used in a variety of energy storage systems, including electrochemical supercapacitor systems
• Discusses how ferrites are being used as an abundantly available, cheaper alternative to their materials for energy storage applications
• Evaluates the challenges and limitations of using ferrites for energy storage applications

• Language: English
• Publisher: Elsevier Science
• Release date: Jun 13, 2020
• ISBN: 9780128192382

Book preview

Spinel Ferrite Nanostructures for Energy Storage Devices

Edited by

Rajaram S. Mane

Center for Nanomaterials & Energy Devices, School of Physical Sciences, Swami Ramanand Teerth Marathwada University, Nanded, Maharashtra, India

Vijaykumar V. Jadhav

Department of Physics, Shivaji Mahavidyalaya, Udgir, Maharashtra, India

Department of Material Science and Engineering, Guangdong Technion-Israel Institute of Technology, Shantou, Guangdong Province, China

Department of Materials Science and Engineering, Technion-Israel Institute of Technology, Haifa, Israel

Table of Contents

Cover image

Title page

Copyright

Contributors

Chapter 1. Basics of ferrites

1.1. Introduction

1.2. Magnetic materials

1.3. Types of magnetic materials

1.4. Properties of magnetic materials

1.5. Spinel ferrites

1.6. Classification of spinel ferrites

1.7. Conclusions

Chapter 2. Ferrite nanostructures: synthesis methods

2.1. Introduction

2.2. Methods of synthesis

2.3. Conclusions

Chapter 3. Properties of ferrites

3.1. Introduction

3.2. Classification of ferrites

3.3. Properties of spinel ferrites

3.4. Conclusions

Chapter 4. Types, Synthesis methods and applications of ferrites

4.1. Introduction

4.2. Classification of ferrites

4.3. Structural classification of ferrites

4.4. General properties

4.5. Synthesis methods

4.6. Applications

4.7. Conclusions

Chapter 5. Ferrites for Electrochemical Supercapacitors

5.1. Introduction

5.2. Ferrites

5.3. Ferrites in electrochemical supercapacitors

5.4. Ferrite-based energy storage supercapacitor devices

5.5. Conclusions and future perspectives

Chapter 6. Ferrites for electrocatalytic water splitting applications

6.1. Introduction

6.2. Electrocatalytic water splitting

6.3. Ferrites in electrocatalysis

6.4. Conclusions

Chapter 7. Ferrites for Batteries

7.1. Introduction

7.2. Characteristics of ferrites

7.3. Ferrites and their nanocomposites for LIBs

7.4. Conclusions

Chapter 8. Ferrites in energy: limitations and perspectives

8.1. Introduction

8.2. Limitations

8.3. Perspectives

8.4. Conclusions

Index

Copyright

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Contributors

Abdullah M. Al-Enizi,     Department of Chemistry, College of Science, King Saud University, Riyadh, Saudi Arabia

Balaji Gautam Ghule,     Centre of Nanomaterials & Energy Devices, School of Physical Sciences, Swami Ramanand Teerth Marathwada University, Nanded, Maharashtra, India

Shyam K. Gore,     D. S. M's Arts, Commerce and Science College, Jintur, Maharashtra, India

Vijaykumar V. Jadhav

Department of Physics, Shivaji Mahavidyalaya, Udgir, Maharashtra, India

Department of Material Science and Engineering, Guangdong Technion-Israel Institute of Technology, Shantou, Guangdong Province, China

Department of Materials Science and Engineering, Technion Israel Institute of Technology, Haifa, Israel

Santosh S. Jadhav,     D. S. M's Arts, Commerce and Science College, Jintur, Maharashtra, India

Sandhya A. Jagadale,     Karmaveer Bhaurao Patil Mahavidyalaya, Pandharpur, M.S., India

A.S. Kadam,     Department of Botany, D. S. M.’s Arts, Commerce and Science College, Jintur, Maharashtra, India

Kwang Ho Kim,     Global Frontier R&D Center for Hybrid Interface Materials, Pusan National University, Busan, Republic of Korea

Rajaram S. Mane,     Center for Nanomaterials & Energy Devices, School of Physical Sciences, Swami Ramanand Teerth Marathwada University, Nanded, Maharashtra, India

Sarita P. Patil

Sanjay Ghodawat University, Kolhapur

Karmaveer Bhaurao Patil Mahavidyalaya, Pandharpur, M.S., India

S.D. Raut,     School of Physical Sciences, Swami Ramanand Teerth Marathwada University, Nanded, Maharashtra, India

Sushil Sangale,     School of Physical Sciences, Swami Ramanand Teerth Marathwada University, Nanded, Maharashtra, India

Shoyebmohamad F. Shaikh,     Department of Chemistry, College of Science, King Saud University, Riyadh, Saudi Arabia

Zeenat Parveen Shaikh,     Centre of Nanomaterials & Energy Devices, School of Physical Sciences, Swami Ramanand Teerth Marathwada University, Nanded, Maharashtra, India

Nanasaheb M. Shinde,     Global Frontier R&D Center for Hybrid Interface Materials, Pusan National University, Busan, Republic of Korea

Pritamkumar V. Shinde,     Global Frontier R&D Center for Hybrid Interface Materials, Pusan National University, Busan, Republic of Korea

Shubhangi D. Shirsat,     SRTMU`s New Model Degree College, Hingoli, Maharashtra, India

Umakant B. Tumberphale,     Center for Nanomaterials & Energy Devices, School of Physical Sciences, Swami Ramanand Teerth Marathwada University, Nanded, Maharashtra, India

Mohd Ubaidullah,     Department of Chemistry, College of Science, King Saud University, Riyadh, Saudi Arabia

M.K. Zate,     Department of Physics, G. M. D. Arts, B. W. Commerce and Science College, Sinnar, Maharashtra, India

Chapter 1

Basics of ferrites

Shyam K. Gore, and Santosh S. Jadhav     D. S. M's Arts, Commerce and Science College, Jintur, Maharashtra, India

Abstract

This chapter provides an overview on the basics of ferrites. It will start with an introduction to the classification of energy storage and ferrite with properties. Ferrites are very important materials having electrical and magnetic properties. These ferrites are used in various applications; mainly this book gives the detail use of spinel ferrites in energy storage application. This chapter gives the overview of the basics of ferrites.

Keywords

Bohr magneto; Cation distribution; Energy storage devices; Magnetization; Mixed spinel; Nanoferrites; Supercapacitors

1.1. Introduction

Energy plays a crucial role in human life and environment protection. The economy of the whole word depends on the generation, storage, harvesting, and transportation policies of energy. Today, energy production mainly depends on fossil fuels, which severely affects world's ecology. Therefore, use of high-performance and eco-friendly renewable energy devices is on high demand [1]. The market of energy storage devices increases and is expected to grow at 19.8% compound annual growth rate during the period of 2019–24. The Mackenzie power and renewable report energy storage requirement will be about 158   GWh at 2024. The above demand is equal to $71 billion investment into storage devices. Mostly, this growth is concern with the United States and China, which is about 54% of global deployment in year 2024. The most challenging issue is the energy scarcity and security, climate change, and rise in oil prices. Exhaustion of fossil fuel, climate change, increase of population, and pollution are serious issues in upcoming years for maintaining clean eco-system, thereby sustainable, efficient, and hygienic energy sources, in addition to new efficient technologies, for energy conservation and storage are of high essence. All the above issues can be fulfilled by fuel cells, batteries, and supercapacitors that basically are considered as energy storage systems [2,3]. These technologies obey different principles but are employed to store energy for different applications. Electrochemical supercapacitor (ES) is one of the energy storage technologies which has the capability of handling a high power and energy due to surface storing mechanism [4]. The basic aim of ES devices is to provide a high power density, longer cycle life than batteries, and high power density than dielectric capacitors, which have made them potential entity in digital cameras, hybrid electrical vehicles, industrial equipment and electronic items including toys, motors, and small-scale machineries [5]. According to storage criteria, ESs are classified as: electric double layer supercapacitors (EDLSs), pseudocapacitors and hybrid capacitors (combination of ELDCs & pseudo-capacitors). The operation of ESs is different than batteries but they are complementary for storage of energy and specific power. The ES devices with high specific energy, power, and suitable cell design can store a large amount of energy; therefore, they obtained a place between batteries and conventional capacitors. As electrodes are merged within electrolytic solution on avoiding electrolytic ions diffusion, ESs are free from the short circuiting or direct contacting. On the other hand, conventional capacitors consist of dielectric materials and metal plates for electrostatic charge storage kinetics. In the rechargeable batteries, power density or charging and discharging rate depends on intercalation and deintercalation of cations [6]. The hybrid supercapacitors have capability to store a large amount of charges in comparison to rechargeable batteries [7]. The hybrid supercapacitors are promising devices for fast operation with high power energy output. The developments of hybrid supercapacitor are shifting to achieve high energy density, extensive cycle life, and adequate speed kinetics with enhanced security.

1.1.1. Classification of energy storage devices

Basically, the types of energy storage devices include batteries, fuel cells and supercapacitors. The difference between them resides in a fact that a fuel cell converts available fuel to energy, while battery and supercapacitor store energy within themselves. Fuel cell can use battery or supercapacitor for storing energy generated by it. Batteries and super-capacitors are basically composed of two electrodes, with separator in between them, which are surrounded by an electrolyte solution.

1.1.2. Fuel cells

A fuel cell is an energy device that converts chemical energy into electric energy [8]. The fuel cell uses hydrogen H2 and oxygen O2 as fuel. It consists of cathode and anode with electrolyte membrane. The reaction between electrodes is to transfer charges from cathode to anode and produces electricity. Hydrogen and oxygen act as fuels in a fuel cell. The reaction between hydrogen and oxygen from air produces water as by-product with generation of heat and electricity [9]. The fuel cells are classified on the basis of electrolyte used. In the fuel cell, hydrogen reacts with the anode and causes oxidation reaction to generate positively charged ions and electrons. Fuel cell requires continuous fuel as well as oxygen from air for its operation, which is quite different than conventional battery operation. The potential produced by fuel cell is very less, i.e., close to 0.7   V. The requirement of more voltage can be fulfilled by connecting few fuel cells in series for desired applications. Fuel cells are commercially used in buses, motorcycles, boats, and various vehicles which are classified according to type of electrolyte used, such as solid state fuel cell, proton exchange membrane fuel cell, alkaline fuel cell, phosphoric acid fuel cell and high-temperature fuel cell, etc.

1.1.3. Batteries

Battery is a device which provides constant voltage with two terminals known as anode of positive polarity and cathode of negative polarity as the external terminals for devices to be connected. The current flows from positive terminal to negative terminal on connecting to the load. The electrical energy is produced in the battery by a chemical reaction taking place between the cathode and anode in presence of electrolytic solution. Batteries are classified into two categories: primary and secondary. The batteries which do not recharge are known as primary and the batteries which can be charged several times are the secondary batteries [10]. In primary battery, continuous reaction takes place, which cannot be reversed where active carbonaceous materials are generally used, which once reacted do not go back to their original form. Primary batteries are compact and portable. Zinc-carbon alkaline primary batteries are used for several applications. In secondary batteries, original form of materials can be maintained by reversing the reactions. The most popular batteries are lead acid which are used in vehicles and other applications. Another type, i.e., dry batteries, is used in mobile devices such as cell phones, laptops, and cameras. These are lithium ion (Li-ion), nickel cadmium (Ni-Cd), and nickel metal hydroxide (NiMH) batteries where the charging and discharging processes are very slow; therefore, continuous reaction, inside the battery, degrades the electrode material. As a result, both life and power density are mitigating with time.

1.1.4. Electrochemical supercapacitors

ESs are charge storage devices like batteries. They also called as ultracapacitors or hybrid capacitors and consist of cathode, anode, electrolyte, and separator. The electrolytes are of different types like liquid, solid, and gel which play an important role for redox reaction in supercapacitor. Two types of ESs exist, namely EDLS and faradaic supercapacitor (FS). EDLSs have inactive electrochemical material such as carbon particles. During charging/discharging process, chemical reaction takes place at the electrode material [11]. FSs are consisting of electrochemically active materials which store charges directly during charging/discharging process [12]. The ESs endow several advantages over batteries and fuel cells that include a long charging/discharging cycle, high power density, long shelf life, high efficiency, a wide range of operating temperatures, and economic and eco-friendly character [2]. Due to increasing demand of energy, ESs got a niche place in market where high power density, long cycling life, and high energy are essential criteria where, the use of abundant, cost-effective, and novel electrode materials rather than routinely used expensive and limited rare earth electrode materials is inevitable.

1.1.5. Ferrites

The development of magnetism begins with Greek philosopher Thales in sixth century recognized magnet as an attracting (magic) object. The naturally found ferrous oxide (Fe3O4) rock named magnetite is an attracting iron. The rocks showing mutual attracting properties were named magnesia in Asia Minor. The first metallic magnet was introduced by William Gilbert in CE 1600 for compass as iron needle [13]. The actual use of ferrites began from 1930 and its structural, electrical, and magnetic properties are extensively studied by many researchers including Snoek [14]. The ferrites being insulating materials of a very high electrical resistivity, low eddy current, high magnetic permeability, moderate permittivity, and low dielectric losses [15,16]. Ferrites are the only materials that are showing these wide range of properties and therefore are suitable to use in many fields for various applications. Ferrites are very sensitive to preparative methods, amount of constitute metal oxides, type and amount of dopants and sintering temperatures, etc. [17,18].

where A is the divalent transition element like Fe, Co, Ni, Zn, etc., and B is the trivalent iron [19]. The hexagonal ferrites avail general formula A²+Fe12O19 where, A²+   =   Ba, Ca, and Sr are transition elements. Garnet has formula R³+Fe5O12 where R   =   Sm, Y, Eu, Gd, and Tb are rare earth elements. Spinel ferrites demonstrate the MFe2O4 chemical formula where, M   =   Ni, Co, Mn, Zn, and Mg are divalent transition elements. The spinel ferrites exhibit a close-packed cubic crystal structure with oxygen and metal ions. The crystal of the spinel is divided into two lattice sites namely tetrahedral (A) and octahedral (B) where, cations of different valencies can be incorporated.

1.1.6. Magnetism in ferrites

The magnetism in ferrite materials is a result of spin of an electron about its own axis. Electromagnet can be produced by conductor wound on the base, and magnetic field is produced in the coil during flow of electricity through coil. Electricity is due to movement of electrons, so each electron works as nanoelectromagnet. The circulating electron thus produces its own orbital magnetic moment and spin magnetic moment (Fig. 1.1) measured as Bohr magneton (μB).

The magnetic moment is produced by electron because it has electric charge, and the spinning of electron creates movement of charge or electric current. The magnetic moment of atoms is the vector sum of orbital and spin moments of the electron in its outer shell. The fundamental unit of magnetic moment is Bohr magneton. One Bohr magneton (1   μB) is equal to the sum of orbital and spin movements of the electron. The spinning of electron is of two ways: clockwise and counterclockwise, which decides the direction of magnetic moment. The clockwise spinning of electron produces magnetic moment in downward direction. The counterclockwise rotation results in upward magnetic moment. If a pair of electrons in an atom shows clockwise and counterclockwise spins, the net magnetic moment is zero. The net magnetic moment in an atom is due to unpaired electrons only. The ferrous ion Fe²+ has four unpaired electrons as two electrons are removed from 4s, and ferric ion Fe³+ has five unpaired electrons as two electrons are removed from 4s and one electron from 3d. These unpaired electrons contribute to the net magnetic moment.

Figure 1.1 Orbital and spinning moments of electron around the nucleus.

1.2. Magnetic materials

When a material responds to applied magnetic field by producing magnetization in it, it is called magnetic material. The magnetization (M) produced in the material is a measure of magnetic moment per unit volume. The applied field (H) produces magnetic induction (B), which is the total number of magnetic field lines passing through unit area of the material. The magnetization M, applied field H, and magnetic induction B are related to one another through

(1.1)

(1.2)

where, μ0 is the permeability of free space.

Magnetic susceptibility is the parameter that tells how a material responds to applied magnetic field. The relation between magnetization M and the intensity of applied field H is as follows.

(1.3)

The permeability is another parameter that discovers the ability of a material to allow magnetic field to develop in it. It is also defined as the depth of magnetization in response to an applied field intensity.

(1.4)

The units of magnetization are given in Table 1.1.

1.3. Types of magnetic materials

The magnetic materials are classified, according to their magnetic behavior, into five types by measuring their magnetic susceptibility. The most common forms of magnetic materials include diamagnetic, paramagnetic, ferromagnetic, antiferromagnetic, and ferrimagnetic.

Table 1.1

1.3.1. Diamagnetic

The diamagnetic materials do not have magnetic moment in absence of applied field. When magnetic field is applied, electron spinning produces a magnetization (M) in a direction opposite to applied field. Materials showing diamagnetic effect are a very small number. Magnetic susceptibility is small and negative. The susceptibility value is independent of temperature.

1.3.2. Paramagnetic

The magnetic moments of atoms are randomly orientated due to thermal agitation. When magnetic field is applied, a few aligned magnetic moments produce a low magnetization in the direction of the field applied. Susceptibility of paramagnetic material is small and positive.

1.3.3. Ferromagnetic

The magnetic moments of all atoms in the lattice are in parallel to each other and such material are known as ferromagnetic. The theory of ferromagnetism is proposed by Weiss with the help of magnetic domains. The magnetic domain in the material is the area where magnetic moments are aligned in a single direction. The domains in the material determine the magnetization of material with application of magnetic field. The alignments of magnetic moments in ferromagnetic material decrease with temperature. The temperature at which thermal agitation increases leads to decrease of alignment of magnetic moments and then material becomes paramagnetic, is called Curie temperature (Tc). Few elements such as Fe, Co, and Ni confirm ferromagnetic behavior. The susceptibility is large in ferromagnetic materials.

1.3.4. Antiferromagnetic

In the antiferromagnetic materials, magnetic exchange interaction occurs between neighboring atoms, which results in antiparallel alignment of magnetic moments. The magnetic fields of spins in the antiparallel alignment cancel out to each other and the net magnetic moment is very low like paramagnetic material. The susceptibility is low and positive for antiferromagnetic materials.

1.3.5. Ferrimagnetic

Ferrimagnetism is not observed in pure elements. It is observed in the compound which has a complex crystal structure. Such crystal structure can have parallel alignment of magnetic moments in one side and antiparallel alignment on the other side. The magnetic domains break the material into parts like ferromagnetic material. Saturation magnetization in ferrimagnetic material is less than ferromagnetic.

1.4. Properties of magnetic materials

The magnetic materials have intrinsic properties which depend on the material characteristics. These are saturation magnetization and magnetocrystalline anisotropy.

1.4.1. Saturation magnetization

The highest amount of magnetic field energy developed by the material is called saturation magnetization (Ms). The magnetic materials have a number of domains. When external field is applied to material domain, walls rotate and reframe as a single domain material. At the saturation magnetization, direction of applied field and easy magnetization axis match. It depends on the magnetic moments in atoms which can be affected by electronic structure in compound and nature of atoms. The crystal structure and the presence of nonmagnetic elements determine the density of the magnetic moments of atoms within the crystal. The saturation magnetization depends on the alignment of magnetic moments and surrounding temperature. As thermal vibration increases the misalignment reduces Ms.

1.5. Spinel ferrites

The spinel phase and cubic crystal structure of ferrite is noted in magnesium aluminum oxide (MgAl2O4). The spinel structure has many commercial applications, which is one of the the most important oldest magnetic materials. Magnetite, Fe3O4, a natural spinel oxide, is abundant, chemically stable, and environmentally robust. Spinels have close-packed crystal structure where transition element cations occupy sites influenced by several factors such as crystal field energy and covalent bonding effect of metal cations [20]. The ideal structure of spinel is close-packed cubic array of oxygen atoms with one-eighth of a tetrahedral sites and one-half of octahedral sites occupied by the cations [21]. The tetrahedral sites are called as A-sites and octahedral sites are B-sites. The smallest unit of