Masters Thesis in program of Masters degree in ENERGY AND POWER ELECTRONICS

State-of-the-Art in EDLC

Student: lez Ferna ndez de Bobadilla Ander Gonza

Director: a Jon Andoni Barrena Brun

Mondrag on Goi Eskola Politeknikoa July 16, 2013

Abstract

This document is focused on the study of electric double layer capacitors (EDLCs), oriented to the working principle, the materials used and under research, and the application of this technology, also including aspects to take into account when an application is being designed such as module building and sizing. This is a literature review with the objective of gathering enough information to build up the knowledge required to start working with supercapacitors.

Contents

1 Introduction 2 Working principle and materials 2.1 Electric double layer . . . . . . . . . . . . . . . . . . . . . . . . 2.1.1 2.1.2 2.1.3 2.1.4 2.2 2.3 Helmholtz model . . . . . . . . . . . . . . . . . . . . . . Gouy-Chapman or diuse model . . . . . . . . . . . . . .

1 3 8 9 9

Stern modication of the diuse double layer . . . . . . . 10 Electric double layer in supercapacitors . . . . . . . . . . 11

Pseudocapacitance . . . . . . . . . . . . . . . . . . . . . . . . . 12 Electrode materials . . . . . . . . . . . . . . . . . . . . . . . . . 13 2.3.1 2.3.2 2.3.3 Carbon materials . . . . . . . . . . . . . . . . . . . . . . 13 Metal Oxides . . . . . . . . . . . . . . . . . . . . . . . . 19 Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 Aqueous and organic electrolytes . . . . . . . . . . . . . 25 Ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . 25 Lithium-ion capacitors (LICs) . . . . . . . . . . . . . . . 27

2.4

Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.4.1 2.4.2

2.5 2.6

Supercapacitor cell construction . . . . . . . . . . . . . . . . . . 26 2.5.1 Manufacturers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 33

3 EDLC modeling 3.1

Electric models . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

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3.1.1 3.1.2 3.1.3 3.1.4 3.1.5 3.1.6 3.2 3.2.1 3.2.2 3.2.3 3.2.4 3.3 3.3.1

One branch RC model . . . . . . . . . . . . . . . . . . . 34 RC parallel branch models . . . . . . . . . . . . . . . . . 34 RC transmission line models . . . . . . . . . . . . . . . . 49 RC series-parallel branch models . . . . . . . . . . . . . 51 Other models . . . . . . . . . . . . . . . . . . . . . . . . 58 Relationship between RC network models . . . . . . . . 68 Heat generation within a cell . . . . . . . . . . . . . . . . 75 Thermal study for activated carbon and organic electrolyte cylindrical supercapacitors . . . . . . . . . . . . . 77 Thermal model of a prismatic cell . . . . . . . . . . . . . 90 Electrical analogy for thermal modeling of a cell . . . . . 93 Heuristic aging model . . . . . . . . . . . . . . . . . . . 108 111 115

Thermal models . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

Aging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106

4 Workgroups 5 Testing methods and characterization 5.1 5.1.1 5.1.2 5.1.3 5.1.4 5.1.5 5.1.6 5.2 5.3 5.4

IEC 62391 standard . . . . . . . . . . . . . . . . . . . . . . . . . 116 Capacitance . . . . . . . . . . . . . . . . . . . . . . . . . 116 Internal resistance . . . . . . . . . . . . . . . . . . . . . 118 Leakage current . . . . . . . . . . . . . . . . . . . . . . . 119 Self discharge . . . . . . . . . . . . . . . . . . . . . . . . 119 Power density . . . . . . . . . . . . . . . . . . . . . . . . 120 Standard conditions . . . . . . . . . . . . . . . . . . . . 120

Consistent measurements and normalization procedure . . . . . 121 Power and energy . . . . . . . . . . . . . . . . . . . . . . . . . . 123 Electrochemical techniques . . . . . . . . . . . . . . . . . . . . . 126 5.4.1 5.4.2 5.4.3 5.4.4 Cyclic voltammetry . . . . . . . . . . . . . . . . . . . . . 127 Chronoamperometry / Chronocoulometry . . . . . . . . 127 Galvanostatic cycling with potential limitation . . . . . . 130 Impedance spectroscopy . . . . . . . . . . . . . . . . . . 132

CONTENTS

5.5

Electrochemical impedance spectroscopy . . . . . . . . . . . . . 135 5.5.1 5.5.2 5.5.3 Analysis in frequency domain . . . . . . . . . . . . . . . 136 Local electrochemical impedance spectroscopy . . . . . . 138 Experimental design . . . . . . . . . . . . . . . . . . . . 138 Electrode construction . . . . . . . . . . . . . . . . . . . 141 Cell construction . . . . . . . . . . . . . . . . . . . . . . 141 143

5.6

Laboratory cell testing example . . . . . . . . . . . . . . . . . . 139 5.6.1 5.6.2

6 Applications 6.1 6.2 6.3 6.4 6.5

Low power applications . . . . . . . . . . . . . . . . . . . . . . . 144 Elevators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144 Uninterruptible power supplies . . . . . . . . . . . . . . . . . . . 147 Utility voltage stabilizer . . . . . . . . . . . . . . . . . . . . . . 148 Wind Turbines . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 6.5.1 6.5.2 6.5.3 Blade pitch control . . . . . . . . . . . . . . . . . . . . . 150 Low voltage ride through operation . . . . . . . . . . . . 151 Power output smoothing . . . . . . . . . . . . . . . . . . 152 Connected to grid photovoltaic systems . . . . . . . . . . 152 Grid isolated photovoltaic systems . . . . . . . . . . . . 153

6.6

Photovoltaic systems . . . . . . . . . . . . . . . . . . . . . . . . 152 6.6.1 6.6.2

6.7 6.8 6.9

Material handling trucks . . . . . . . . . . . . . . . . . . . . . . 155 Cranes and hoists . . . . . . . . . . . . . . . . . . . . . . . . . . 156 Earth moving equipment . . . . . . . . . . . . . . . . . . . . . . 160 6.10.1 Types of EV . . . . . . . . . . . . . . . . . . . . . . . . . 164 6.10.2 FCV . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167 6.10.3 Electric buses . . . . . . . . . . . . . . . . . . . . . . . . 169

6.10 Transportation and automotive market . . . . . . . . . . . . . . 163

6.11 Railway applications . . . . . . . . . . . . . . . . . . . . . . . . 170 6.11.1 Starting of diesel engines . . . . . . . . . . . . . . . . . . 171 6.11.2 Series hybrid diesel engine powered trains . . . . . . . . 171 6.11.3 Tramway and subway regenerative braking . . . . . . . . 174

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6.11.4 Tramway and subway autonomous operation . . . . . . . 176 6.12 Hybrid ESSs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176 6.12.1 Passive hybrid ESSs . . . . . . . . . . . . . . . . . . . . 177 6.12.2 Semiactive hybrid ESSs . . . . . . . . . . . . . . . . . . 178 6.12.3 Active hybrid ESSs . . . . . . . . . . . . . . . . . . . . . 180 7 Series/parallel associations 7.1 7.1.1 7.1.2 183

Supercapacitor series connection . . . . . . . . . . . . . . . . . . 184 Dissipative equalization methods . . . . . . . . . . . . . 185 Non-dissipative equalization methods . . . . . . . . . . . 188 197

8 Conclusions 8.1 8.2 8.3 8.4

Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197 Testing methods and characterization . . . . . . . . . . . . . . . 198 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198 Series/parallel associations . . . . . . . . . . . . . . . . . . . . . 199

Chapter 1

Introduction

Recently there has been a growing interest in developing high power and high energy density energy storage system (ESS). Being less dependent on fossil fuels is a goal that can be achieved developing other energy sources and storage technologies. Among the prots of lowering the dependence on these kind of fuels are its increasing costs, geopolitical concerns, pollution and global warming. There are several ways to deal with this problem, increasing the penetration of the renewable sources and increasing the eciency of the transportation systems are two important ways to overcome this problem. ESSs are the key to deal with the intermittent nature of the renewable sources and increase the power transmitted into the grid of this kind of systems, such as wind power and solar power. Besides, in order to increase the eciency in a vehicle, the kinetic energy must be stored somewhere when vehicles slow down or stop. Although these operations were performed with batteries successfully for a low power scale, new eciency enhancement methods will require large amounts of power that will require other energy storage technologies such as supercapacitors. These have attracted signicant attention due to their high power capabilities and long cycle-life, giving a very good chance to build more advanced hybrid ESSs, either for on board or stationary applications. The objective of this Masters Thesis is to collect information from the literature about supercapacitors, also known as ultracapacitors or electrochemical capacitors. Starting from the materials used for the fabrication of these devices, going toward their application and nally discussing the design of a product or ESS. In chapter 2, the most important supercapacitor active materials both in

Introduction

production and research are gathered, giving brief explanations of their dierent properties and achieved capacitance and surface area values. In chapter 3 the way to model electric double layer capacitor (EDLC) behavior is discussed. This chapter is divided in dierent sections explaining the electrical behavior, the thermal evolution of the cells and modules, and the aging of supercapacitors. In chapter 4, dierent research groups focused on supercapacitor technology and knowledge development are gathered. In chapter 5, dierent testing procedures and characterization techniques are collected. This are standards and also dierent techniques used by researchers and the industry. In chapter 6 dierent applications in which would t a supercapacitor based ESS are explained, arguing the advantage of the technology for its of the mentioned applications. In chapter 7 some aspects concerning the series and parallel connection of supercapacitors are explained. Besides, solutions to deal with the series connection of both, supercapacitors and lithium-ion batteries, are also discussed. Finally in chapter 8 all the conclusions regarding this work are gathered.