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2016 | Book

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Lithium Batteries

Science and Technology

Authors: Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Publisher: Springer International Publishing

Part of: Springer Professional "Wirtschaft+Technik" , Springer Professional "Technik"

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About this book

The book focuses on the solid-state physics, chemistry and electrochemistry that are needed to grasp the technology of and research on high-power Lithium batteries. After an exposition of fundamentals of lithium batteries, it includes experimental techniques used to characterize electrode materials, and a comprehensive analysis of the structural, physical, and chemical properties necessary to insure quality control in production. The different properties specific to each component of the batteries are discussed in order to offer manufacturers the capability to choose which kind of battery should be used: which compromise between power and energy density and which compromise between energy and safety should be made, and for which cycling life. Although attention is primarily on electrode materials since they are paramount in terms of battery performance and cost, different electrolytes are also reviewed in the context of safety concerns and in relation to the solid-electrolyte interface. Separators are also reviewed in light of safety issues. The book is intended not only for scientists and graduate students working on batteries but also for engineers and technologists who want to acquire a sound grounding in the fundamentals of battery science arising from the interaction of electrochemistry, solid state materials science, surfaces and interfaces.

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Table of Contents

Frontmatter

Chapter 1. Basic Elements for Energy Storage and Conversion

Abstract

Major challenges of the twenty-first century will concern the global climate change and dwindling fossil energy reserves that motivate to develop sustainable solutions based on renewable sources of energy. Because they are intermittent systems, accumulators of electric power are required. This chapter provides basic concept for the energy storage and conversion systems. Basic elements of technologies are also given, which make an introduction of the topics.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 2. Lithium Batteries

Abstract

First attempts to create batteries using an ion other than the proton were done in the 1970s with the fabrication of lithium primary cells. It was the fast development of the electronic devices that pouch electrochemists in the new world of lithium. After primary cells came secondary (rechargeable) lithium batteries in the 1980s. Innovations and advances in insertion electrode materials have improved the stored energy compared with other systems. For half-a-century, lithium batteries are increasingly used in a huge number of applications from watches, portable electronics to electric transportation and stationary grid storage. While older technologies such as Zn-MnO₂, lead-acid, and Ni-Cd are still used, the increasing battery market is now dominated by Li-ion batteries. The purpose of this chapter is to introduce the technologies of primary and secondary lithium electrochemical cells with a special focus on lithium-ion batteries and lithium-metal polymer batteries.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 3. Principles of Intercalation

Abstract

In this chapter, we describe the basic concept of intercalation applied to electrode materials for batteries. This phenomenon has attracted considerable attention in electrochemistry because of the use of intercalation compounds (ICs) as ion and electron exchangers in energy storage and conversion devices. The need for more efficient electrical energy storage devices has prompted research on new electrode materials. In lithium-ion batteries, positive and negative electrodes are ICs with electronic and ionic properties. The different classes of mechanism that controls the electrochemical reactions in galvanic cells are presented and the relationship structure-energy is examined.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 4. Reliability of the Rigid-Band Model in Lithium Intercalation Compounds

Abstract

Numerous layered structured compounds are interesting materials in which lithium intercalation occurs primarily without destruction of the host lattice. In many cases a rigid band model is a useful first approximation for describing the changes in electronic properties of the host material with intercalation. We observed, nevertheless, that the rigid-band model is not applicable to all of the layered compounds. One may argue that the applicability of the rigid-band model may be taken as a test for the properties most desirable in a good intercalation material. This needs yet to be more extensively documented for their promising applications as insertion electrode in rechargeable lithium batteries. This chapter presents the applicability of the rigid-band model on intercalation compounds with a layered structure namely the transition-metal chalcogenides MX ₂ (X = S, Se) and the transition-metal oxides LiMO₂ (M = Co, Ni) as well.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 5. Cathode Materials with Two-Dimensional Structure

Abstract

This chapter is devoted to the role of layered structured materials, since they have peculiar properties of mixed conduction for electrons and ions, so that redox reaction can be delocalized in their volume, so that they can be used as active materials of electrodes. We present the relationship between structure and electrochemical features with special attention for materials currently used as positive electrode in lithium batteries for their high capability to host foreign ions. Different crystal chemistries are examined from the basic lithiated metal dioxides structure to the very sophisticated solid solutions or composites.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 6. Cathode Materials with Monoatomic Ions in a Three-Dimensional Framework

Abstract

The relationships between structural and electrochemical properties are examined for materials having three-dimensional (3D) structure for the diffusion paths for Li⁺ ions. Among the 3D lithium insertion compounds with M = manganese and vanadium cations, namely, binary M _xO_y and ternary LiM _xO_y phases are the most popular. A special emphasis to the different forms of spinel structures that are normal-spinel, defect-spinel, and doped-spinel frameworks are currently used as positive electrodes in high-power batteries for EVs.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 7. Polyanionic Compounds as Cathode Materials

Abstract

Polyanionic compounds have emerged as novel lithium insertion compounds and considered as the most advanced positive electrodes for the next generation of Li-ion batteries owing to their advantages with regard to low cost, non-toxicity, environmental friendliness, and high safety. From the safety view point, compared to metal-oxide cathodes, these materials rank number one, with a remarkable thermal stability and tolerance to overcharge and over-discharge. This chapter outlines the structural, physical, and electrochemical properties of lithium-phosphate compounds. Several aspects that are important for applications are discussed such as morphology upon synthesis, residual impurities and surface state of particles. These impurities are identified and a quantitative estimate of their concentrations is deduced from the combination of analytical methods. LiFePO₄ has won the challenge to be the active element for the positive electrode of Li-ion batteries for electro-mobility. An optimized preparation provides materials with carbon-coated particles free of any impurity phase, insuring structural stability and electrochemical performance that justify the use of this material as a cathode element in new generation of lithium secondary batteries operating for powering hybrid electric vehicles and full electric vehicles.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 8. Fluoro-polyanionic Compounds

Abstract

In this chapter, we present the progress that allows several lithium-intercalation compounds to become the active cathode element of a new generation of Li-ion batteries, namely the materials with a poly-anion-based structure M _x(XO₄)_y (M is a transition-metal cation and X = P, S), which are promising to improve the technology of energy storage and electric transportation, and address the replacement of gasoline engine by meeting the increasing demand for green energy power sources. The electrode materials considered here are fluorine-containing compounds including fluorophosphates LiMPO₄F (M = V, Fe, T), Li₂ M′PO₄F (M = Fe, Co, Ni), hybrid ion Li_xNa_1−xVPO₄F, and fluorosulfates LiMSO₄F; M = Fe, Co, Ni, Mn, Zn, Mg). The electrochemical performance of these materials as the active cathode element of Li-ion batteries is also discussed.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 9. Disordered Compounds

Abstract

Several investigations have shown that an ordered and well-crystallized framework is not necessary to fabricate good battery electrodes. The performance of such “disordered electrodes” displays facile lithium diffusion. This chapter is a brief overview of the intercalation compounds in their disordered state that identifies the limitation of materials used within the field of energy storage. We discuss the trends in materials design and document the role of the crystalline nature, e.g., amorphous vs. crystallized, of electrode materials for lithium batteries. The electrochemical properties are examined in relation with the physical chemistry of materials. Attention is also focused on the importance of local probes for a well-defined characterization of the structural features of disordered materials.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 10. Anodes for Li-Ion Batteries

Abstract

The active elements for negative (anode) electrodes are reviewed here according to the following sequence. First, the carbon anode is considered, since almost all the Li-ion batteries on the market are presently equipped with graphitic carbon. Then the next elements of the Mendeleev table (Si, Ge, …) are considered. Then the metal oxides have been divided according to the three different Li insertion processes that determines their advantages and disadvantages: intercalation, alloying/de-alloying, conversion reaction. Only the promising elements for the next generations of Li-ion batteries have been selected. Emphasis is made on the progress achieved the last 5 years, since the reader is guided to other reviews for elder works.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 11. Electrolytes and Separators for Lithium Batteries

Abstract

The current commercial Li-ion batteries are based on organic liquids, i.e., ethyl carbonates that have a high dielectric constant and thus are good solvents for salts. They also show a fairly large electrochemical window of stability. However, these organic solvents have high vapor pressures and in case of accidental battery shorts or thermal runaway, can lead to fires and explosions. The objective of the present chapter is to summarize the state of the art of nonaqueous electrolytes with development on control the SEI formation, safety concerns with Li salts, protection against overcharge and fire retardants.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 12. Nanotechnology for Energy Storage

Abstract

While lithium-ion batteries are currently the workhorses of portable electronics and power tools, the technology is just beginning to move up for power density applications such as electric drive vehicles and future energy storage options such as smart grids and back-up power systems. The later requires much higher charge rates that can be achieved to some extend by the use of nanomaterials. Two main reasons for electrochemical improvement are commonly evoked by designing electrode materials into the nanoscale domain: (1) the shorter diffusion lengths for the lithium ion across the active particle and (2) the increasing contact area between electrode and electrolyte. The purpose of this chapter is to draw attention to the technologies involved in the synthesis, layout and optimization of nano materials used as active components in Li-ion batteries. We present several nanostructured compounds such as lamellar compounds, manganese oxides and iron phosphates. Functional nanomaterials are also examined such are nanofibers, nanorods, nanocomposites, and nanocrystals.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 13. Experimental Techniques

Abstract

The development of various lithium insertion compounds used as electrode materials (positive and negative as well) requires knowledge of their transport properties, i.e., electrical and electrochemical properties. This chapter provides an overview of the various techniques used for the characterizations of thermodynamics and kinetics of the solid-state phases. DC and AC techniques are presented and discussed. Techniques for evaluating the semiconducting or metallic character of electrodes are also examined and some examples are provided.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 14. Safety Aspects of Li-Ion Batteries

Abstract

The carbon-coated LiFePO₄ Li-ion oxide cathode was studied for its electrochemical, thermal, and safety performance. This electrode exhibited a reversible capacity corresponding to more than 89 % of the theoretical capacity when cycled between 2.5 and 4.0 V. Cylindrical 18650 cells with carbon-coated LiFePO₄ also showed good capacity retention at higher discharge rates up to 5C rate with 99.3 % coulombic efficiency, implying that the carbon coating improves the electronic conductivity. Hybrid pulse power characterization (HPPC) test performed on LiFePO₄ 18650 cell indicated the suitability of this carbon-coated LiFePO₄ for high power HEV applications. The heat generation during charge and discharge at 0.5C rate, studied using an isothermal microcalorimeter (IMC), indicated cell temperature is maintained in near ambient conditions in the absence of external cooling. Thermal studies were also investigated by Differential Scanning Calorimeter (DSC) and Accelerating Rate Calorimeter (ARC), which showed that LiFePO₄ is safer, upon thermal and electrochemical abuse, than the commonly used lithium metal oxide cathodes with layered and spinel structures. Safety tests, such as nail penetration and crush test, were performed on LiFePO₄ and LiCoO₂ cathode based cells, to investigate on the safety hazards of the cells upon severe physical abuse and damage.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Chapter 15. Technology of the Li-Ion Batteries

Abstract

As we have seen in different chapters of this book, the electrodes are usually tested from half-cells consisting of lithium metal as the counter-electrode. This is a convenient tool to determine the irreversible capacity loss during the first and eventually the second cycle, the reversible capacity at available at different rates, the operating voltage. The properties of the full cell can then be anticipated from these data. The design of the batteries is dictated by different parameters that are reviewed in this chapter. The first one is the compatibility between the materials that are chosen for the two electrodes, according to the rules concerning the relative positions of their chemical potentials. We have detailed and explained these rules in Chap. 2, so we start here with electrodes which satisfy these compatibility rules allowing for the formation of a protective solid-electrolyte interface (SEI) layer at the surface of the negative electrode. The second most important parameter concerns the capacity of the electrodes.

Christian Julien, Alain Mauger, Ashok Vijh, Karim Zaghib

Backmatter

Title: Lithium Batteries
Authors: Christian Julien
Alain Mauger
Ashok Vijh
Karim Zaghib
Copyright Year: 2016
Publisher: Springer International Publishing
Electronic ISBN: 978-3-319-19108-9
Print ISBN: 978-3-319-19107-2
DOI: https://doi.org/10.1007/978-3-319-19108-9