Electrochemical Power Sources E-Book

Vladimir S. Bagotsky

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Serie: Electrochemical Society Series
• Sprache: Englisch

Seitenzahl: 680

Veröffentlichungsjahr: 2015

Beschreibung

Electrochemical Power Sources (EPS) provides in a concise way the operational features, major types, and applications of batteries, fuel cells, and supercapacitors * Details the design, operational features, and applications of batteries, fuel cells, and supercapacitors * Covers improvements of existing EPSs and the development of new kinds of EPS as the results of intense R&D work * Provides outlook for future trends in fuel cells and batteries * Covers the most typical battery types, fuel cells and supercapacitors; such as zinc-carbon batteries, alkaline manganese dioxide batteries, mercury-zinc cells, lead-acid batteries, cadmium storage batteries, silver-zinc batteries and modern lithium batteries

Leseprobe

Table of Contents

Cover

Series

Title Page

Copyright

Dedication

Foreword

Acknowledgements

Preface

Symbols

Abbrevations

Introduction

Part I: Batteries With Aqueous Electrolytes

Chapter 1: General Aspects

1.1 Definition

1.2 Current-Producing Chemical Reaction

1.3 Classification

1.4 Thermodynamic Aspects

1.5 Historical Development

1.6 Nomenclature

Reviews and Monographs

Chapter 2: Main Battery Types

2.1 Electrochemical Systems

2.2 LeclanchÉ (Zinc–Carbon) Batteries

2.3 The Zinc Electrode in Alkaline Solutions

2.4 Alkaline Manganese–Zinc Batteries

2.5 Lead Acid Batteries

2.6 Alkaline Nickel Storage Batteries

2.7 Silver–Zinc Batteries

References

Monographs and Reviews

Chapter 3: Performance

3.1 Electrical Characteristics of Batteries

3.2 Electrical Characteristics of Storage Batteries

3.3 Comparative Characteristics

3.4 Operational Characteristics

References

Chapter 4: Miscellaneous Batteries

4.1 Mercury–Zinc Batteries

4.2 Compound Batteries

4.3 Batteries with Water as Reactant

4.4 Standard Cells

4.5 Reserve Batteries

Reference

Reviews and Monographs

Chapter 5: Design and Technology

5.1 Balance in Batteries

5.2 Scale Factors

5.3 Separators

5.4 Sealing

5.5 Ohmic Losses

5.6 Thermal Processes in Batteries

Chapter 6: Applications of Batteries

6.1 Automotive Equipment Starter and Auxiliary Batteries

6.2 Traction Batteries

6.3 Stationary Batteries

6.4 Domestic and Portable Systems

6.5 Special Applications

Chapter 7: Operational Problems

7.1 Discharge and Maintenance of Primary Batteries

7.2 Maintenance of Storage Batteries

7.3 General Aspects of Battery Maintenance

Chapter 8: Outlook for Batteries with Aqueous Electrolyte

References

Part II: Batteries with Nonaqueous Electrolytes

Chapter 9: Different Kinds of Electrolytes

9.1 Electrolytes Based on Aprotic Nonaqueous Solutions

9.2 Ionically Conducting Molten Salts

9.3 Ionically Conducting Solid Electrolytes

References

Chapter 10: Insertion Compounds

Monographs and Reviews

Chapter 11: Primary Lithium Batteries

11.1 General Information: Brief History

11.2 Current-Producing and Other Processes in Primary Power Sources

11.3 Design of Primary Lithium Cells

11.4 Fundamentals of the Technology of Manufacturing of Lithium Primary Cells

11.5 Electric Characteristics of Lithium Cells

11.6 Operational Characteristics of Lithium Cells

11.7 Features of Primary Lithium Cells of Different Electrochemical Systems

Monographs

Chapter 12: Lithium Ion Batteries

12.1 General Information: Brief History

12.2 Current-Producing and Other Processes in Lithium Ion Batteries

12.3 Design and Technology of Lithium Ion Batteries

12.4 Electric Characteristics, Performance, and Other Characteristics of Lithium Ion Batteries

12.5 Prospects of Development of Lithium Ion Batteries

Monographs

Chapter 13: Lithium Ion Batteries: What Next?

13.1 Lithium–Air Batteries

13.2 Lithium–Sulfur Batteries

13.3 Sodium Ion Batteries

Reviews

Chapter 14: Solid-State Batteries

14.1 Low-Temperature Miniature Batteries with Solid Electrolytes

14.2 Sulfur–Sodium Storage Batteries

Monographs and Reviews

Chapter 15: Batteries with Molten Salt Electrolytes

15.1 Storage Batteries

15.2 Reserve-Type Thermal Batteries

References

Part III: Fuel Cells

Chapter 16: General Aspects

16.1 Thermodynamic Aspects

16.2 Schematic Layout of Fuel-Cell Units

16.3 Types of Fuel Cells

16.4 Layout of a Real Fuel Cell: The Hydrogen–Oxygen Fuel Cell with Liquid Electrolyte

16.5 Basic Parameters of Fuel Cells

Reference

Monographs

Chapter 17: The Development of Fuel Cells

17.1 The Period Prior to 1894

17.2 The Period from 1894 to 1960

17.3 The Period from 1960 to the 1990

17.4 The Period After the 1990

References

Monographs and Reviews

Chapter 18: Proton-Exchange Membrane Fuel Cells (PEMFC)

18.1 The History of PEMFC

18.2 Standard PEMFC Version of the 1990

18.3 Operating Conditions of PEMFC

18.4 Special Features of PEMFC Operation

18.5 Platinum Catalyst Poisoning by Traces of CO in the Hydrogen

18.6 Commercial Activities in Relation to PEMFC

18.7 Future Development of PEMFC

18.8 Elevated-Temperature PEMFC (ET-PEMFC)

References

Reviews

Chapter 19: Direct Liquid Fuel Cells with Gaseous, Liquid, and/or Solid Reagents

19.1 Current-Producing Reactions and Thermodynamic Parameters

19.2 Anodic Oxidation of Methanol

19.3 Use of Platinum–Ruthenium Catalysts for Methanol Oxidation

19.4 Milestones in DMFC Development

19.5 Membrane Penetration by Methanol (Methanol Crossover)

19.6 Varieties of DMFC

19.7 Special Operating Features of DMFC

19.8 Practical Prototypes of DMFC and their Features

19.9 The Problems to be Solved in Future DMFC

19.10 Direct Liquid Fuel Cells (DLFC)

Reference

Reviews

Chapter 20: Molten Carbonate Fuel Cells (MCFC)

20.1 Special Features of High-Temperature Fuel Cells

20.2 The Structure of Hydrogen–Oxygen MCFC

20.3 MCFC with Internal Fuel Reforming

20.4 The Development of MCFC Work

20.5 The Lifetime of MCFC

References

Reviews and Monographs

Chapter 21: Solid Oxide Fuel Cells (SOFC)

21.1 Schematic Design of a Conventional SOFC

21.2 Tubular SOFC

21.3 Planar SOFC

21.4 Varieties of SOFC

21.5 The Utilization of Natural Fuels in SOFC

21.6 Interim-Temperature SOFC (ITSOFC)

21.7 Low-Temperature SOFC (LT-SOFC)

21.8 Factors Influencing the Lifetime of SOFC

References

Monographs and Reviews

Chapter 22: Other Types of Fuel Cells

22.1 Phosphoric Acid Fuel Cells (PAFC)

22.2 Redox Flow Fuel Cells

22.3 Biological Fuel Cells

22.4 Direct Carbon Fuel Cells (DCFC)

References

Monographs

Chapter 23: Alkaline Fuel Cells (AFC)

23.1 Hydrogen–Oxygen AFC

23.2 Problems in the AFC Field

23.2.2 The Present State and Future Prospects of AFC Work

23.3 Anion-Exchange (Hydroxyl Ion Conducting) Membranes

23.3.1 Methanol Fuel Cell with an Invariant Alkaline Electrolyte

References

Monograph

Chapter 24: Applications of Fuel Cells

24.1 Large Stationary Power Plants

24.2 Small Stationary Power Units

24.3 Fuel Cells for Transport Applications

24.4 Portables

24.5 Military Applications

References

Chapter 25: Outlook for Fuel Cells

25.1 Alternating Periods of Hope and Disappointment—Forever?

25.2 Development of Electrocatalysis

25.3 “Ideal Fuel Cells” Do Exist

25.4 Expected Future Situation with Fuel Cells

Reference

Monographs

Part IV: Supercapacitors

Chapter 26: General Aspects

26.1 Electrolytic Capacitors

References

Chapter 27: Electrochemical Supercapacitors with Carbon Electrodes

27.1 Introduction

27.2 Main Properties of Electric Double-Layer Capacitors (EDLC)

27.3 EDLC Energy Density and Power Density

27.4 Fundamentals of EDLC Macrokinetics

27.5 Porous Structure and Hydrophilic–Hydrophobic Properties of Highly Dispersed Carbon Electrodes

27.6 Effect of Ratio of Ion and Molecule Sizes and Pore Sizes

27.7 Effect of Functional Groups on EDLC Characteristics

27.8 Electrolytes Used in EDLC

27.9 Impedance of Highly Dispersed Carbon Electrodes

27.10 Nanoporous Carbons Obtained Using Various Techniques

27.12 SELF-DISCHARGE OF CARBON ELECTRODES AND SUPERCAPACITORS

27.13 Processes of EDLC Degradation (Aging)

References

Monograph and Reviews

Chapter 28: Pseudocapacitor Electrodes and Supercapacitors

28.1 Electrodes Based on Inorganic Salts of Transition Metals

28.2 Electrodes Based on Electron-Conducting Polymers (ECP)

28.3 Redox Capacitors Based On Organic Monomers

28.4 Lithium-Cation-Exchange Capacitors

References

Monograph and Reviews

Chapter 29: Hybrid (Asymmetric) Supercapacitors (HSC)

29.1 HSC of MO/C TYPES

29.2 HSC of ECP/C Type

References

Review

Chapter 30: Comparison of Characteristics of Supercapacitors and Other Electrochemical Devices. Characteristics of Commercial Supercapacitors

Reference

Reviews

Chapter 31: Prospects of Electrochemical Supercapacitors

Chapter 32: Electrochemical Aspects of Solar Energy Conversion

32.1 Photoelectrochemical Phenomena

32.2 Photoelectrochemical Devices

32.3 Photoexcitation of Metals (Electron Photoemission into Solutions)

32.4 Behavior of Illuminated Semiconductors

32.5 Semiconductor Solar Batteries (SC-SB)

*

32.6 Dye-Sensitized Solar Cells (DSSC)

References

Reviews and Monographs

Author Index

Subject Index

Series

End User License Agreement

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Guide

Cover

Table of Contents

Preface

Introduction

Part II: Batteries With Aqueous Electrolytes

Chapter 1: General Aspects

List of Illustrations

Figure 1.1

Figure 2.1

Figure 2.2

Figure 2.3

Figure 3.1

Figure 3.2

Figure 3.3

Figure 4.1

Figure 4.2

Figure 4.3

Figure 4.4

Figure 9.1

Figure 10.1

Figure 10.2

Figure 11.1

Figure 11.2

Figure 11.3

Figure 11.4

Figure 12.1

Figure 12.2

Figure 13.1

Figure 16.1

Figure 16.2

Figure 16.3

Figure 16.4

Figure 17.1

Figure 18.1

Figure 20.1

Figure 21.1

Figure 27.1

Figure 27.2

Figure 27.3

Figure 27.4

Figure 27.5

Figure 27.6

Figure 27.7

Figure 27.8

Figure 27.9

Figure 27.10

Figure 27.11

Figure 27.12

Figure 27.13

Figure 27.14

Figure 27.15

Figure 27.16

Figure 27.17

Figure 27.18

Figure 27.19

Figure 27.20

Figure 27.21

Figure 27.22

Figure 27.23

Figure 27.24

Figure 27.25

Figure 27.26

Figure 27.27

Figure 27.28

Figure 27.29

Figure 27.30

Figure 28.1

Figure 28.2

Figure 28.3

Figure 28.4

Figure 28.5

Figure 28.6

Figure 28.7

Figure 28.8

Figure 29.1

Figure 29.2

Figure 30.1

List of Tables

Table 1.1

Table 9.1

Table 11.1

Table 12.1

Table 24.1

Table 24.2

Table 24.3

Table 27.1

Table 27.2

Table 27.3

Table 27.4

Table 27.5

Table 27.6

Table 27.7

Table 27.8

Table 27.9

Table 27.10

Table 28.1

Table 28.2

Table 28.3

Table 28.4

Table 28.5

Table 28.6

Table 29.1

Table 30.1

Table 30.2

Table 30.3

Electrochemical Power Sources

Batteries, Fuel Cells, and Supercapacitors

Vladimir S. Bagotsky

Alexander M Skundin

Yurij M Volfkovich

Copyright © 2015 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

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Library of Congress Cataloging-in-Publication Data:

Bagotskii, V. S. (Vladimir Sergeevich)

Electrochemical power sources : batteries, fuel cells, and supercapacitors / Vladimir S. Bagotsky, Alexander M. Skundin, Yurij VM. Volfkovich.

1 online resource.

Includes bibliographical references and index.

Description based on print version record and CIP data provided by publisher; resource not viewed.

ISBN 978-1-118-94253-6 (epub) – ISBN 978-1-118-94251-2 (pdf) – ISBN 978-1-118-46023-8 (cloth) 1. Electric batteries. 2. Fuel cells. 3. Supercapacitors. I. Skundin, A. M. II. Volfkovich, Yurij V., 1940- III. Title.

TK2896

621.31′242–dc23

2014023307

Dedicated to Professor V. S. Bagotsky.

Foreword

When the major part of this book was written, Vladimir Bagotsky, its initiator and the first author passed away in his home in Boulder, Colorado, at the age of 92. It was a shock for us as all our scientific life was connected with Bagotsky who was our teacher and friend. We hope this book will be some kind of a memorial to this outstanding scientist, recognized authority in electrochemistry and battery science.

A. Skundin

Yu. M. Volfkovich

Acknowledgements

We are very much obliged to V. Bagotsky's daughter Natalia Bagotskaya and to his granddaughter Katya Lysova for their invaluable assistance at the manuscript preparing.

We are grateful also to Dr. Marie Ehrenburg, who translated several chapters from Russian.

A. Skundin

Yu. M. Volfkovich

Preface

In 1980 Academic Press London & New York published the book Chemical Power Sources written by two of the authors of this book (V.S. Bagotsky and A.M. Skundin). Now, almost 35 years later, this book is outdated and has become an obsolete rarity.

During this period in the field of batteries two entirely new directions emerged, which are now mass-produced (i) nickel–metal hydride batteries that practically replaced same-sized nickel–cadmium batteries (not a word about these batteries can be found in our 1980 book) and (ii) lithium ion batteries that are the only possible power source for cell phones and other small-size electronic equipment, and thus, they substantially helped to change our everyday life. In the chapter about lithium batteries of the 1980 book containing 10 of the 370 pages, the not yet developed lithium ion batteries could not be mentioned. The same is true for supercapacitors and photogalvanic devices.

The aim of the authors of the present book is to update in a concise manner the information contained in the 1980 book and to add all new relevant information published up to 2012.

With the kind permission of Elsevier (which is the legal successor of Academic Press), in this book, excerpts of the 1980 book that do not need renewal are extensively used.

Chapters 1–9, 14–25, and 32 have been written by V.S. Bagotsky, Chapters 10–13 have been written by A.M. Skundin, and Chapters 26–31 have been written by Yu. M. Volfkovich.

Symbols

Symbol

Meaning (values)

Dimensions

Roman symbols

c

j

Concentration

mol/dm

3

D

j

Diffusion coefficient

cm

2

/s

E

Electrode potential

V

E

Equilibrium electrode potential

V

ε

Electromotive force

V

F

Faraday constant

9485 C/mol

G

Gibbs energy

kJ/mol

H

Enthalpy

kJ/mol

i

Current density

mA/cm

2

i

0

Exchange current density

mA/cm

2

I

Current

A, mA

M

(1) Mass

kg

(2) Molar concentration

mol/dm

3

n

Number of electrons in the reaction's elementary act

none

p

Power density

W/kg, W/L

Power

W, kW

Q, q

Heat

kJ, eV

R

(1) Resistance

Ω

(2) Molar gas constant

8.314 J/mol K

S

(1) Entropy

kJ/K

(2) Surface area

cm

2

T

Absolute temperature

K

U

Cell voltage

V

w

Energy density

kWh/kg, kWh/L

W

Work, useful energy

Wh, kWh

Symbol

Meaning (values)

Dimensions

Greek symbols

γ

Roughness factor

None

δ

Thickness

cm

λ

e

Amount of coulombs

None

η

Efficiency

None, %

σ

Conductivity

S/cm

Subscripts

ads

Adsorbed

app

Apparent

e

Electrical

exh

Exhaust

ext

External

h.e.

Hydrogen electrode

i

Under current

loss

Energy loss

o.e.

Oxygen electrode

ox

Oxidizer

S

Per unit area

red

Reducer

V

Per unit volume

j

Any ion, substance

0

Without current

+

Cation

−

Anion

Introduction

Electrochemical Power Sources (EPS) are autonomous devices based on electrochemical phenomena that produce electrical current and power and can be used in conditions when the connection to electrical grid power is not possible (e.g., for mobile and portable devices or in case of a grid failure). The most representative and widely used EPS type are batteries.

A battery is a device destined for the electrochemical conversion of the energy of a chemical reaction between two solid reactants to electrical energy. It is impossible to imagine human activity without batteries. Hundreds of millions of batteries are used worldwide for personal and domestic needs (wrist watches, cell phones, cameras, personal computers, audio and video players, hearing aids and other different electronic and medical devices), and also in different means of transport (ICE and hybrid cars, passenger carriages, planes, ferries, liners). They are also used in different municipal buildings (telephone stations, power backup in hospitals). A huge number of batteries are used for military purposes (soldiers' personal equipment, guided missiles, drones, rockets).

The definition of fuel cells is similar to the definition of batteries, but an important distinction is that in fuel cells the chemical reaction takes place between gaseous liquid and/or liquid reactants. The definition of compound batteries is also similar to that of batteries, the only difference being that in compound batteries the chemical reaction takes place between a solid reactant on one of the electrodes and a gaseous and/or liquid reactant on the other electrodes.

Two varieties of EPSs are now in the state of wide development and are beginning to be used in different fields: viz. (i) fuel cells for electric cars, small power plants for individual cottages, and for large grid power plants and (ii) supercapacitors (high-capacitance electrochemical capacitors) as rechargeable power sources with higher energy values and power capabilities, and with much better cycleability properties than those in existing storage batteries that are used in parallel with batteries for starting purposes of ICE cars, delivering the necessary initial peak power (especially at low temperatures) and thus increasing the battery lifetime.

Improvements of existing EPSs and the development of new kinds of EPS are the results of intense R&D work performed in industrial and academic institutions of many countries. The limited size of this book prevents the possibility to single out the contributions of the numerous researchers in these institutions. Therefore, in the book the number of references in most chapters is limited only to some important work in the corresponding field, particularly to achievements of historical significance. The main emphasis in the references is given to monographs and review papers, containing more detailed information about the contributions of different authors.

Part I

Batteries With Aqueous Electrolytes

Chapter 1General Aspects

1.1 Definition

Batteries are a variety of galvanic cells, that is, devices containing two (identical or different) electron-conducting electrodes, which contact an ion-conducting electrolyte. Batteries are destined to convert the energy of a chemical reaction between solid electrode components into electrical energy providing an electric current (when the circuit is closed) between two not-identical electrodes having different values of the (positive and negative terminals). A battery comprises one or several single galvanic cells. In each such cell a comparatively low voltage is generated, typically 0.5–4 V for different classes of cells. Where higher voltages are required, the necessary number of cells is connected in series to form a galvanic battery. Colloquially, the term “battery” is often used to denote single galvanic cells acting as electrochemical power sources as well as groups of single cells. This is retained in this book. Some battery types retain the term “cell” even for groups of single cells (e.g., fuel cell, not fuel battery). The term “cell” is also used when it is necessary to compare different aspects of single-cell and multicell batteries.