Hydrogen, Batteries and Fuel Cells

Hydrogen, Batteries and Fuel Cells

Bengt Sundén

Table of Contents

Cover image

Title page

Copyright

Preface

Nomenclature

Chapter 1. Introduction and background

1.1. Primary energy sources - fossil fuels

1.2. Renewable energy resources

1.3. Conclusion energy sources

1.4. Hydrogen

1.5. Electrochemical devices

1.6. Batteries

1.7. Fuel cells

1.8. Electrolyzers

1.9. Summary

1.10. Intention

Chapter 2. Electrochemistry and thermodynamics

2.1. Introduction

2.2. The electrochemical cell

2.3. Thermodynamics

2.4. The electrical double layer and electrode kinetics

2.5. Polarization curve and overpotential

2.6. Heat generation

2.7. Mass transport

2.8. Porous media

Chapter 3. Hydrogen

3.1. Introduction

3.2. Properties of hydrogen

3.3. Production of hydrogen

3.4. Storage of hydrogen

3.5. Transportation of hydrogen

3.6. Pros and cons for hydrogen

3.7. Competitive fuels

Chapter 4. Battery technologies

4.1. Introduction

4.2. Lead-acid batteries

4.3. Nickel-metal hydride batteries

4.4. Lithium batteries

4.5. Nickel-zinc batteries

4.6. Zinc-carbon batteries

4.7. Zinc-air batteries

4.8. Other battery types

4.9. Voltage characteristics

4.10. Standards and nomenclature

4.11. Ragone plot

4.12. Summary

Chapter 5. Transport phenomena in batteries

5.1. Introduction

5.2. Electrolyte charge conservation

5.3. Electrolyte species conservation

5.4. Electrode charge conservation

5.4. Electrode species conservation

5.6. Chemical kinetics

5.7. Thermal analysis

5.8. Memory effect

5.9. Self-discharge

Chapter 6. Thermal management of batteries

6.1. Introduction

6.2. Thermal runaway

6.3. Importance of temperature

6.4. Examples of thermal management systems

6.5. Mathematical modeling and experimental approaches

6.6. Available softwares

6.7. Summary

Chapter 7. Applications of batteries

7.1. Introduction

7.2. Electrical vehicles

7.3. Battery types for electric vehicles

7.4. Batteries for aviation

7.5. Batteries for aerospace

7.6. Batteries in shipping and marine applications

7.7. Stationary batteries

7.8. Grid storage batteries

7.9. Bottlenecks of batteries

7.10. Critical metals

Chapter 8. Fuel cell types - overview

8.1. Introduction

8.2. Complementary electrochemistry and thermodynamics for fuel cells

8.3. Solid oxide fuel cells – SOFC

8.4. Intermediate solid oxide fuel cells – ITSOFC

8.5. Proton exchange membrane fuel cells – PEMFC

8.6. Aerospace applications

Chapter 9. Transport phenomena in fuel cells

9.1. Introduction

9.2. Heat transfer

9.3. Mass transfer

9.4. Charge transport

9.5. Water transport

9.6. Diffusion coefficients

Chapter 10. Modeling approaches for fuel cells

10.1. Introduction

10.2. Zero-order models of analysis

10.3. One-dimensional models of analysis

10.4. Multi-dimensional models of analysis

10.5. Example proton exchange membrane fuel cells – PEMFC

10.6. Example solid oxide fuel cells – SOFC

10.7. Softwares

10.8. Summary

Chapter 11. Fuel cell systems and applications

11.1. Introduction

11.2. Portable power

11.3. Transportation

11.4. Stationary power

11.5. Maritime applications

11.6. Aerospace applications

11.7. Aircraft applications

11.8. Bottlenecks for fuel cells

11.9. Current status FCEVs versus BEVs

11.10. System aspects

Appendices-tables

Index

Copyright

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Preface

Strong demands prevail worldwide to reduce consumption and dependence of fossil fuels and to develop a sustainable future energy system. In the short time period, work on improving energy efficiency and gradual introduction of renewable energy sources seem most reasonable while in the long term renewable energy sources are supposed to be the dominating energy resources. This also requires a transition to use hydrogen as a fuel or energy carrier as well as introduction and increased application of electrochemical devices like batteries, fuel cells and electrolyzers.

This book covers hydrogen as an energy carrier and how to produce, store and transport it. The role of hydrogen in future energy systems and the relation to renewable energy sources like solar and wind power are discussed. Fundamental concepts of thermodynamics and electrochemical conversion in batteries and fuel cells are described and analyzed. All major transport processes (of momentum, heat, mass, ion and electrons (charge)) and thermal management issues are presented. Properties and characteristics of energy relevant materials and their role in electrochemical devices are treated. Relevance for energy systems and the transportation sector is discussed. Various engineering applications of batteries and fuel cells are presented.

The idea to write this book was created as the author initiated and started a course on Hydrogen, Batteries and Fuel Cells for the M.Sc. Mechanical Engineering program at Lund University, Lund Sweden from the academic year 2016/2017. As the topic is multidisciplinary, many students from Electrical Engineering, Environmental Engineering as well as International Exchange students have found the topic of great interest. The author also gave a lecture series on this topic in a summer school on Renewable Energy at Northwestern Polytechnical University, Xi'an, China in 2018. During the preparation stages it was found that no textbook treated these integrated topics sufficiently well.

The writing of the book has also been possible as the author has been researching in the topic areas of the book since 1998 and several PhD students, post docs and senior co-workers have contributed in building up the knowledge basis. Excellent assistance in preparation and finalizing many of the Figures, has been provided by my co-worker and colleague Dr, University lecturer Zan Wu. In bringing this book to completion, Ali Afzal-Khan and Glyn Jones at Elsevier were quite helpful.

Lund in February 2019

Bengt Sundén

Nomenclature

A    Area or surface area [m²]

A    Constant

A    Pre-exponential constant

a

aox    Chemical activity of oxidized species

ared    Chemical activity of reduced species

as    Active surface area per electrode unit volume [cm²/cm³]

Cf    Convection flux

Cμ, C1, C2    Constants in turbulence model

c    Concentration

cp    Specific heat constant pressure [J/(kg K)]

cv    Specific heat constant volume [J/(kg K)]

c    Specific heat [J/(kg K)]

D    Diffusion coefficient [m²/s]

Df    Diffusion flux

E    Voltage or electric potential [V]

E    Activation energy

E    Internal energy

EB    Blackbody emissive power [W/m²]

e    Electron charge

F    Faraday constant

Fik    View factor between surfaces i and k

f ∓    Electrolyte activity coefficient

G    Gibb's free energy

g    Specific Gibb's free energy

Gr    Grashof number

h    Specific enthalpy [J/kgK]

h    Heat transfer coefficient [W/(m²K)]

h f ⁰    Enthalpy of formation [J/kgK]

H    Enthalpy [J]

HHV    Higher heating value

H2    Hydrogen molecule

H2O    Water molecule

I    Total current [A]

Iλ    Monochromatic radiation intensity

i    Current density (A/m²)

iL    Limiting current density [A/m²]

i0    Exchange current density [A/m²]

J    Radiosity [W/m²]

Ji    Mass flux or molar flux of species i

j    Volumetric current density [A/m³]

K    Permeability

Kn    Knudsen number

k    Thermal conductivity [W/(mK)]

k    Boltzmann constant

k    Turbulent kinetic energy

km    Mass transfer coefficient [m/s]

krk    Relative permeability of phase k

k0    Rate constant of a reaction

L    Length [m]

Le    Lewis number

LHV    Lower heating value

LH    Latent heat [J/kg]

M    Molecular or molar weight

M+    Arbitrary ion

mi    Mass of species i [g or kg]

   Mass flow rate [kg/s]

N    Number pf moles

NA    Avogadro number

Nc    Number of cells

Nu    Nusselt number

n, ne    Number of moles, number of moles of electrons

nf    Fuel supply rate

O2    Oxygen molecule

O²−    Oxide ion

OH −    Hydroxyl ion

p, P    Pressure [Pa]

p    Bruggeman exponent

P1, P2    Products 1 and 2, respectively

p1, p2    Numbers of moles of products 1 and 2, respectively

Pr    Prandtl number

Pt    Platinum

Pt/C    Ratio of platinum to carbon by weight in platinum supported on carbon

Ptotal    Power [W]

   Heat transfer rate [W]

Q    Heat amount [J]

Q    Electric charge [As]

Q’    Heat source (W/m³)

QL    Latent heat [J/kg]

Qr    Reaction quotient

Qth    Theoretical specific capacity [Ah/kg]

q    Heat flux [W/m²]

R    Gas constant [J/kgK]

R    Electric resistance [Ω]

R1, R2    Reactants 1 and 2, respectively

Ra    Rayleigh number

Re    Reynolds number

Rf    Electrode surface film resistance [Ωcm²]

RSEI    Solid-electrolyte interfacial film resistance [Ωcm²]

r    Radial coordinate [m]

rint    Internal equivalent resistance per unit volume

r1, r2    Number of moles of reactants 1 and 2, respectively

S    Total entropy [J/K]

s    Specific entropy [J/kgK] or [J/mole,K]

s    Path length [m]

s    Radiation direction vector

s    Saturation

Sc    Schmidt number

Sh    Sherwood number

T    Temperature [°C], [K]

T∗    Reference temperature [°C], [K]

t    Temperature [°C]

t − +    Transference number

U    Internal energy [J]

U    Velocity [m/s]

u    Velocity [m/s]

ui    Velocity vector [m/s]

V    Volume [m³] or voltage [V]

V    Velocity [m/s]

v    Specific volume [m³/kg]

Vc    Cell voltage

W,    Work rate [W]

Welectric    Electric work [J]

X    Thickness [m]

x, y, z    Coordinates [m]

xi    Mass fraction of species i

Yi    Mass fraction of species i

yi    Mole fraction of species i

zi    Charge number of charge carrier

Greek

α    Charge transfer coefficient

α    Thermal diffusivity [m²/s]

α    Bruggeman exponent

β    Transfer coefficient

β    Coefficient of thermal expansion [1/K]

β    Extinction coefficient

ε    Emissivity

ε    Porosity

ε    Dissipation of turbulent kinetic energy

ϕ    Electric potential or arbitrary variable

ϕf    Fraction of fuel taking part in the electrochemical reaction

Фλ    Scattering phase function

ζ    Dimensionless parameter

γ    cp/cv

κ    Electrokinetic permeability

κ    Ionic conductivity

κλ    Monochromatic emissivity

η    Overpotential

θ    Dimensionless temperature

θ    Contact angle

θ    Temperature difference

ϑ    Dimensionless temperature

λ    Dimensionless parameter

λ    Water content

λ    Thermal conductivity

μ    Chemical potential [J/mole]

μ    Dynamic viscosity [kg/(ms)]

μturb    Turbulent viscosity

ν    Kinematic viscosity [m²/s]

ξ    Stoichiometric factor

ρ    Density [kg/m³]

σ    Surface tension [N/m]

σ    Conductivity of protons, electrons and ions

σ    Stefan-Boltzmann constant [W/m²K⁴]

σλ    Scattering coefficient

τ    Tortuosity

Ω    Solid angle

Indices

a    Adiabatic

aw    Adiabatic wall

b    Bulk

c    Continuum

eff    Effective

fm    Free molecule

l    Liquid

lv    Liquid-vapor

tj    Temperature jump

v    Vapor

vol    Volume

w    Wall

∞    Free stream

Abbreviation

ACC    Advanced carbon carbon

AFC    Alkaline fuel cell

AFL    Anode functional layer

AGM    Absorbed glass mat

AGV    Automated guided vehicle

ANSI    American National Standards Institute

APU    Auxiliary power unit

BEM    Boundary element method

BEV    Battery electric vehicle

BMS    Battery management system

BOL    Beginning of life

BTMS    Battery thermal management system

CAD    Computer aided design

Cd    Cadmium

CFD    Computational fluid dynamics

CFL    Cathode functional layer

CFRP    Carbon fiber reinforced polymer

CHP    Combined heat and power

CH4    Methane

CL    Catalytic layer

CMC    Ceramic matrix composites

CMG    Compression mass gauge

CVFEM    Control volume finite element method

Co    Cobalt

CO2    Carbon dioxide

CxHy    Arbitrary hydrocarbon

DNS    Direct numerical simulation

DMFC    Direct methanol fuel cell

DOD    Depth of discharge

DSMC    Direct simulation Monte Carlo

ECS    Environmental control system

EOL    End of life

EV    Electric vehicle

FCEV    Fuel cell electric vehicle

FEM    Finite element method

FVM    Finite volume method

GDL    Gas diffusion layer

HEV    Hybrid electric vehicle

HGV    Heavy goods vehicle

HHV    Higher heating value

H2    Hydrogen

H2O2    Hydrogen peroxide

H2SO4    Sulfuric acid

HVO    Hydrogenated vegetable oil

IEC    International Electrotechnical Commission

Ir    Iridium

ITSOFC    Intermediate temperature solid oxide fuel cell

LBG    Liquid biogas

LDV    Light duty vehicle

LH2    Liquid hydrogen

LHV    Lower heating value

Li    Lithium

LNG    Liquefied natural gas

LO2    Liquid oxygen

LOHC    Liquid organic hydrogen carrier

MCFC    Molten carbonate fuel cell

MH    Metal hydride

Mn    Manganese

NaBH4    Sodium bor hydride

NB    Neighbor

NH3    Ammonia

Ni    Nickel

NiCd    Nickel cadmium

NiMH    Nickel metal hydride

O2    Oxygen

PAFC    Phosforic acid fuel cell

Pb    Lead

PbO2    Lead oxide

PCM    Phase change material

PEFC    Polymer electrolyte fuel cell

PEMFC    Proton exchange membrane fuel cell

PHEV    Plug-in hybrid electric vehicle

PISO    Pressure implicit splitting operators

QUICK    Quadratic upstream interpolation convective kinetics

RANS    Reynolds average Navier Stokes

RSM    Reynolds stress method

SEI    Solid-electrolyte-interface

SiC    Silicon carbide

SIMPLE    Semi implicit method pressure linked equations

SIMPLEX    Simple extended

SIMPLER    Simple revised

SiO    Silicon oxide

SOC    State of charge

SOF    State of function

SOFC    Solid oxide fuel cell

SOH    State of health

SST    Shear stress transport

TDMA    Tri diagonal matrix algorithm

TPB    Triple phase boundary

TPS    Thermal protection system

V    Vanadin

VOF    Volume of fluid

VRLA    Valve regulated lead acid

YSZ    Yttria stabilized zirconia

Zn    Zinc

Zr    Zirconium

Chapter 1

Introduction and background

Abstract

This chapter gives a brief background on various energy sources, hydrogen and electrochemical devices. Concepts of batteries, fuel cells and electrolyzers are presented. Finally a principle outline of how renewable energy sources and hydrogen can be integrated in the energy system.

Keywords

Renewable energy resources; Hydrogen; Electrochemical devices; Integrated energy systems

Electricity is an energy carrier which makes life easier by providing light, heat, hot water, cold food, computers and TVs etc. Energy sources are converted to electricity as it is easier to use and move. Currently, a great portion of the production of electric power is coming from so-called fossil fuels and only a smaller portion from renewable energy sources. For transportation also huge amounts of fossil fuels are used. The increased global concern for the high greenhouse gas emissions by fossil fuels and its effect on the global warming and the environment have demanded search for alternative systems for electricity production and alternative powertrains for transportation.

1.1. Primary energy sources - fossil fuels

The global primary energy sources for stationary power generation and for transportation are fossil fuels. Currently fossil-based fuels like oil, coal and natural gas, provide approximately 85 % of all energy being used worldwide. The current exploration of shale oil and shale gas also concerns fossil fuels. These resources are being depleted and cannot be replaced in any reasonable time period, i.e., they are non-renewable. Besides being finite, the energy production from fossil fuels results in by-products from combustion like particles and harmful gases like CO2 and NOx. It is well known that these emissions affect the environment, our health and cause changes of the climate. Fossil fuels also contribute to sulfur emission to the atmosphere leading to acid rains. Acid rains may cause damage to buildings. The global consumption of energy for, e.g., transportation, lighting and heating, production and delivery of goods, is expected to increase substantially not the least due to population growth and associated demands. Then to meet these demands and protect the environment as well as creating a sustainable future energy system, is a great challenge.

Fossil fuels have been formed from plants and animals that lived hundreds of millions years ago and became buried deep underneath the Earth's surface. Fossil fuels are primarily portable energy and can be stored and transported conveniently. This means that the fuel can be excavated where it is found, processed at a separate location and transported to wherever the energy is needed. Petroleum is a challenging resource as not only oil is consumed as a fuel but also is used as raw material for plastics, solvents, fertilizers, pesticides as well as other petrochemicals.

Fossil fuels exist and they provide and have provided valuable services. The dilemma of these fuels are all the side effects occurring as they are used. It is well known as fossil fuels are burned, the number one greenhouse gas contributing to global warming, CO2, is created. It is also known that the average temperature of Earth has increased about 1   degree Fahrenheit in the 20th century. The impact of the global warming on the environment is extensive and its effect in various areas are known and often discussed publicly. Besides, there are effects on the natural ecosystems due to the collection of particularly oil and coal. For instance, oil spills have devastated ecosystems and coal mining has stripped lands of their vitality.

Nuclear energy is somewhat controversial in terms of classification. The supply of energy by nuclear technology only provides a few percent of the whole world's energy but locally the percentage might be much higher. Most likely nuclear energy will not be a major source of world energy consumption because of the public pressure and the relatively high danger associated with unleashing the power of atoms. Commonly nuclear energy is not regarded as a renewable energy source. Conventionally the nuclear energy is made by splitting up large unstable atoms of uranium. However, uranium needs to be digged out from the ground where it is available and used in nuclear fission reactors. However, some scientists hope to develop nuclear fusion reactors (making energy by joining small atoms) which will be cleaner, safer and renewable.

1.2. Renewable energy resources

Renewable energy is derived from various natural processes, such as the Sun's electromagnetic radiation, wind, tidal water, heat generation within the Earth. Solar and wind power are considered eco-friendly as they emit zero toxic gases to the environment. The main types of alternative and renewable energy sources are given below.

• Wind: the air motion can be harvested in wind turbines that spin the shaft of electric generators in windmills. Wind energy is formed from the heating and cooling of the atmosphere which causes air and air layers to rise and fall and move over each other.

• Biomass: various organic materials can be used for cooking and heating as well as for production of electricity and liquid fuels.

• Sunlight: the flux of solar photons can be converted to heat in solar collectors, to electricity in photovoltaic cells or to chemical energy.

• Water, Hydro power, Ocean: potential and kinetic energy of flowing water in a river can be recovered to produce electricity or mechanical work. In a tidal energy system, water is stored during high tide and released during low tide. The power is generated in a water turbine.

• Earth's internal heat: This heat is referred to as geothermal energy. This heat can be used for heating purposes using heat pumps and for production of electricity in geothermal plants including a steam generator, turbine, condenser and electric generator.

Renewable energy sources are inexhaustible and environmentally friendly. They are also suitable for distributed power technologies. However, renewable resources are not always available where the energy is needed. So for instance, hydro power resources are limited by geography and often they are located at remote areas. This calls for installation of expensive electric lines to cities. Wind and solar power sources are intermittent by nature. Then storage of energy between production and consumption becomes a concern. Wind mills and solar panels take large areas of space to collect energy.

The raw forms of energy are basically free and practically infinite but equipment and materials needed to collect, process and transport the energy to the end users are expensive. Currently also the plants based on renewable energy require higher investments than traditional ones based on fossil fuels and nuclear energy.

1.3. Conclusion energy sources

Strong demands prevail worldwide to reduce consumption and dependence of fossil fuels and to develop a sustainable future energy system. In the short term work on improving energy efficiency and gradual introduction of renewable energy sources seem most reasonable while in the long term renewable energy sources are supposed to be the dominating energy resources. This also requires a transition to use hydrogen as a fuel or energy carrier as well as introduction of electrochemical devices like batteries, fuel cells and electrolyzers to a large extent.

The World Energy Outlook 2017 makes a prognosis that in 2040 about 40 % of the global power production will be from renewable energy sources.

For further reading, Refs. [1–3] are recommended.

1.4. Hydrogen

Hydrogen is regarded as a proper fuel for future energy systems. Hydrogen is an energy carrier. It is clean, has a high energy content on mass and can be used for transportation, heating and electricity generation. However, as it does not exist as a gas on Earth, it has to be made. It can be produced in several ways like electrolysis, reforming of fossil and biomass fuels, cracking of hydrocarbons and iron-water reactions. Thermochemical conversion processes, like pyrolysis, gasification and steam gasification are available for converting biomass to a more useful energy. Hydrogen can also be generated from carbon-neutral biomasses or carbon-free energy sources like electric, solar and wind energy. Electrolysis is an electrochemical process where water molecules are split into hydrogen and oxygen by applying electricity. The hydrogen and oxygen can be stored and transported as appropriate. In so-called fuel cells these gases can be fed as fuel and oxidant, respectively, to convert chemical energy to electricity and water is ideally the only by-product.

Table 1.1