Prospects for Li-ion Batteries and Emerging Energy Electrochemical Systems

Laure Monconduit, Laurence Croguennec

• Publisher: WSPC
• Year: 2018
• eBook ISBN: 9789813228153
• Topic: Ciencias físicas
• Subtopic: Química

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The Li-ion battery market is growing fast due to its ever increasing number of applications, from electric vehicles to portable devices. These devices are in demand due to safety reasons, energy efficiency, high power density and long life duration, which drive the need for more efficient electrochemical energy storage systems. The aim of this book is to provide the challenges and perspectives for Li-ion batteries (chapters 1 and 2), at the negative electrode as well as at the positive electrode, and for technologies beyond the Li-ion with the emerging Na-ion batteries and multivalent (Mg, Al, Ca, etc) systems (chapters 4 and 5). The aim is also to alert on the necessity to develop the recycling methods of the millions of produced batteries which are going to further flood our societies (chapter 3), and also to continuously increase the safety of the energy storage systems. For the latter challenge, it is interesting to seriously consider polymer electrolytes and batteries as an alternative (chapter 6).

This book will take readers inside recent breakthroughs made in the electrochemical energy systems. It is a collaborative work of experts from the most known teams in the batteries field in Europe and beyond, from academics as well as from manufacturers.

--> Contents:

• Negative Electrodes for Li-Ion Batteries: Beyond Carbon (Phoebe K Allan, Nicolas Louvain and Laure Monconduit)
• Li-Rich Layered Oxides: Still a Challenge, but a Very Promising Positive Electrode Material for Li-Ion Batteries (Ségolène Pajot, Loïc Simonin and Laurence Croguennec)
• Recycling of Li-Ion Batteries and New Generation Batteries (Jean Scoyer)
• Na-Ion Batteries — State of the Art and Prospects (Patrik Johansson, Patrick Rozier and M Rosa Palacín)
• Battery Systems Based on Multivalent Metals and Metal Ions (Doron Aurbach, Romain Berthelot, Alexandre Ponrouch, Michael Salama and Ivgeni Shterenberg)
• Lithium Polymer Electrolytes and Batteries (Gebrekidan Gebresilassie Eshetu, Michel Armand and Stefano Passerini)

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--> Readership: Researchers and professionals in electrochemistry, materials chemistry/nanochemistry, inorganic chemistry, solid state chemistry and physical chemistry. -->
Keywords:Battery;Li-ion;Na-ion;Mg-ion;Li Polymer;Energy;Recycling;ElectrochemistryReview: Key Features:

• Prominent authors or contributors who for some of them belong to the European Research Institute, Alistore ERI (headed by Dr M R Palacin (ICMAB, CSIC, Barcelona, Spain) and by Dr P Simon (CIRIMAT, University Paul Sabatier, Toulouse, France)), and more generally to prestigious European Institutes and Universities developing high level research in the field of the electrochemical energy storage
• Selected topics which highlight the main trends in the battery field, focusing especially on the emerging research axes
• Original approach with fundamental aspects (understanding of the mechanisms and failure mechanisms in batteries through the use of advanced characterization tools, often operandi during the cycling of the battery), as well as industrial concerns such as the recycling

1	Negative Electrodes for Li-Ion Batteries: Beyond Carbon

Phoebe K. Allan*^,†, Nicolas Louvain^‡,§ and Laure Monconduit^‡,§,¶,||

*University of Cambridge, University Chemical Laboratory, Lensfield Road, Cambridge, CB2 1EW, UK

^†Gonville and Caius College, Trinity Street, Cambridge, CB2 1TA, UK

^‡Institut Charles Gerhardt de Montpellier (ICGM) — CNRS, France

^§Réseau Français sur le Stockage Electrochimique de l’Energie (RS2E), CNRS FR3459, 33 Rue Saint Leu, 80039 Amiens Cedex, France

^¶ALISTORE-ERI European Research Institute, FR CNRS 3104, F-80039 Amiens Cedex 1, France

^||[email protected]

List of Abbreviations

I.Introduction

II.Lithium Titanates

A.Introduction

B.The Li₄Ti₅O₁₂ Structure

C.Lithium Insertion Properties

D.Electrochemical Properties

E.Disadvantages of Lithium Titanium Oxide as Electrode

1.The Gassing Problem

F.Improving the Performance of LTO

1.SEI Management

2.Surface Coatings

3.Tailoring Ionic and Electronic Conductivities

G.Critical Perspectives

III.p-Block Element–Based Electrodes

A.Silicon

1.Mechanisms of (De)Lithiation in Silicon Anodes

a.Atomistic-Scale Lithiation Mechanisms

b.Electrode-Scale Lithiation Mechanisms

2.Failure mechanisms in silicon electrodes

a.Volume Expansion on Lithiation

b.Issues Relating to the SEI

3.Improving the Cyclability of Silicon Electrodes

a.Electrode Formulation

b.Nanosizing Electrode Particles

c.Electrode Coating and Electrolyte Additives

d.Association with Inactive Species

B.Other p-block Elements: Antimony, Tin, and Germanium

1.Tin

2.Antimony

3.Germanium

4.Improving the Performance of Tin, Antimony, and Germanium

a.Binary, Ternary Alloys, SnSb, TiSnSb

IV.Summary and Conclusions

V.References

List of Abbreviations

C/x	charge rate such that the full capacity is reached in x hours
CMC	carboxymethyl cellulose
CVD	chemical vapor deposition
DEC	dimethyl ethyl carbonate
DFT	density functional theory
DMC	dimethyl carbonate
EC	ethylene carbonate
FEC	fluroethylcarbonate
FIB	focused ion beam
GITT	galvanostatic intermittent titration technique
LCO	LiCoO2
LIB	lithium-ion battery
LMO	LiMn2O4
LTO	Li4Ti5O12
NMR	nuclear magnetic resonance
OCV	open-circuit voltage
PAA	polyacrylic acid
PC	propylene carbonate
PDF	pair function distribution
PTSI	p-toluenesulfonyl isocyanate
PVDF	polyvinylidene fluoride
SEI	solid-electrolyte interphase
SFG-VS	sum frequency generation vibrational spectroscopy
TEM	transmission electron microscopy
ToF-SIMS	time-of-flight secondary ion mass spectrometer
XPS	X-ray photoelectron spectroscopy
XRD	X-ray diffraction

I.Introduction

Conventional lithium-ion batteries (LIBs) are composed of a layered LiCoO_x material cathode and a carbon/graphite anode. Graphite has a layered structure and can be electrochemically reduced in an aprotic organic electrolyte containing lithium salts. Lithium is intercalated between the layers of graphite to form a Li–C alloy. The carbon/graphite anode possesses a theoretical specific capacity of 372 mAh·g⁻¹ according to the following lithium intercalation equation:

Li⁺ + e⁻ + C₆ ↔ LiC₆

In the LiCoO₂/graphite full-cell system, the overall cell reaction is as follows:

LiCoO₂ + Li_n-xC ↔ Li_1-xCoO₂ + Li_nC

This equation indicates that the cell reaction is a simple migration of lithium ions between positive and negative electrodes. Nevertheless, the lithium intercalation primarily occurs at a voltage below 0.1 V versus Li⁺/Li, close to the lithium electroplating potential.¹ For high discharge rates, and harsh operating conditions, graphite electrode can be polarized to such an extent that reactive lithium metal dendrites may grow on the electrode surface and sporadically cause “soft” short circuiting of the cell.²

New electrode materials that can improve the performance and cycle life of LIB have been extensively explored. As part of this, considerable effort has been directed toward developing alternative negative electrodes that are able to deliver higher capacities and higher energies than graphite electrodes, particularly when charged at high rates.³ The reader is pointed toward several reviews that extensively explore the range of materials proposed by researchers to replace graphite in future batteries.^4–6 This chapter describes some of the most promising alternative materials proposed to date: (1) titanates, a material undergoing typical intercalation reactions, and (2) metals and semimetals, which form alloys electrochemically, such as silicon, tin, or antimony.

This study describe how the utilization of advanced characterization tools and theoretical calculations have informed researchers about how these materials behave electrochemically and how improvements in understanding of failure mechanisms of cells are able to suggest directions for improving their electrochemical performance.

II.Lithium Titanates

A.Introduction

Titanium oxides, both those that contain lithium in their starting composition and those that do not, have been proposed as an alternative to carbon/graphite electrodes in LIBs in order to improve specific capacities, high-rate cyclability, and safety.^3,7–9 These materials store lithium through intercalation of lithium into the structure and reduction and oxidation of the titanium during lithiation and delithiation, respectively. This intercalation mechanism is analogous to that of metal oxide cathodes such as LiCoO₂, but takes place at lower voltages. In a full-cell configuration, lithium removed from the LiCoO₂ cathode is inserted into the titanate host; while the cobalt ions are oxidized, the titanium ions are simultaneously reduced. Among lithium titanium oxides, spinel Li₄Ti₅O₁₂ (LTO) is one of the most studied electrode materials as a potential carbon/graphite replacement in LIBs for power applications such as electric vehicles.^8,9 Lithium-free titanium oxides, TiO₂, are still considerably investigated as electrode materials,¹⁰ while their use in commercial lithium-ion systems might appear unfavorable because of high potential and unlithiated negative.¹¹

LTO is a lithium intercalation compound with an average lithium insertion/deinsertion voltage close to 1.55 V versus Li⁺/Li.⁹ This is a relatively high voltage for a negative electrode, and this suggests that lithium dendrites formation and the organic el...

Table of contents

• Cover Page
• Title
• Copyright
• Contents
• Preface
• 1 Negative Electrodes for Li-Ion Batteries: Beyond Carbon
• 2 Li-Rich Layered Oxides: Still a Challenge, but a Very Promising Positive Electrode Material for Li-Ion Batteries
• 3 Recycling of Li-Ion Batteries and New Generation Batteries
• 4 Na-Ion Batteries — State of the Art and Prospects
• 5 Battery Systems Based on Multivalent Metals and Metal Ions
• 6 Lithium Polymer Electrolytes and Batteries
• Index