Batteries Slides

Energy Storage
Batteries I
Anis Allagui
University of Sharjah
Sustainable and Renewable Energy Engineering
aallagui@sharjah.ac.ae
Last Updated: February 15, 2016
Introduction
Sort History
Applications
How Does it Work?
Thermodynamics
Electrochemistry
Outline
1 Introduction
2 A Short History
3 Applications
4 How Does it Work?
5 Thermodynamics
Chemical Thermodynamics
Electric Properties
6 Electrochemistry
Cell Polarization
Electrode Processes and Reaction Rates
Electrical Double-Layer
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Thermodynamics
Electrochemistry
Introduction I
Electrochemical devices for energy storage and conversion:

1
2
3
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batteries,
fuel cells, and
electrochemical supercapacitors (ESs)
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Thermodynamics
Electrochemistry
Galvanis Frog Experiment

Short history electrochemical cells
hown here is an illustration of Luigi Galvani's famous frog experiments taken from his work, De
Figure 2.1: Luigi Galvanis famous frog experiments (De Viribus - Electricitatis in
ribus - Electricitatis in Motu Musculari. 1792. A chance observation led Luigi Galvani (1737-98)
A chance
observation
Luigi wife
Galvani
to discover animal
discoverMotu
animalMusculari.
electricity in 1792).
1871. When
the nerve
of a frog thatled
Galvani's
was preparing
r soup was
accidentally
a knife
a muscle
occurred
despitewife
the frog
electricity
intouched
1871, with
when
the nerve
ofcontraction
a frog that
Galvanis
wasnot
preparing for
eing connected
to anaccidentally
electrical machine.
soup was
touched with a knife; a muscle contraction occurred despite
the frog not being connected to an electrical machine.
28 February 2013
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Thermodynamics
Electrochemistry
Voltaic Pile
Figure 2.2: Voltaic pile (the first electrical battery): alternately stacked copper and zinc plates with a piece of paper soaked in salt solution between the
two plates. This "voltaic pile" (named
"artificial electrical organ" by Volta) provided electricity when the plates were
connected with a wire, GNU Free Documentation License.
Remark
The connection between chemical reactions and electrical energy was
quickly recognized. A battery is a device that converts the chemical energy
contained in its active materials directly into electric energy by means of
an electrochemical oxidation-reduction (redox) reaction
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Thermodynamics
Electrochemistry
Plant Cell
ochemical cells
Figure 2.3: The lead/sulfuric acid/lead

dioxide system was discovered by Gaston
Plant in 1859: the lead-acid rechargeable battery was born. This system was
used for storing electricity for telegraphy,
e.g. he used lead plates as electrodes.
These batteries were not yet suitable for
industrial production.
11
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Thermodynamics
First car with combustion engine 1885 (Karl Benz)
Electrochemistry
First electrical car 1881
Electrical Car is not New

Around 1900, competing options electric versus combustion.
Speed record 1899-1901 Camille Jenatzy

Figure 2.4: "La Jamais Contente", first automobile to reach 100 km/h in 1899.
First
car2013
with combustion engine 1885 (Karl Benz), but the first electrical car was
28
February
built in 1881. Around 1900, competing options electric versus combustion.
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Thermodynamics
Electrochemistry
electrochemical cells
Fuel Cells
d in
be
gen
ning
,
rse
ce
2e
Figure 2.5: The Fuel Cell was first demonstrated in 1839 by Sir William Grove.
At the time, it was already known that water could be decomposed into H2 and O2
by electrolysis; Grove tried recombining the two gases in a simple apparatus, and
=electrolysis":
0v
discovered what he called "reverse
recombination of H2 and O2 into
water causing a potential difference to be generated between the two electrodes
2e H2O(l)
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= +1.23 v
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Thermodynamics
Electrochemistry
Nickel-metal Hydride Cells

Figure 2.6: Nickel-metal hydride cells
(1960s): The discovery that certain
compounds such as LaNi5 can act as
"hydrogen sponges" (LaNi5 H6 ) made it
practical to employ metal hydrides as a
cathode material. These reversible (secondary) batteries are widely used in cell
phones, computers, and portable power
tools
Anode: MH + OH M + H2 O + e
Cathode: NiOOH + H2 O + e Ni(OH)2 + OH
Net (1.2 V): MH + NiOOH M + Ni(OH)2
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ectrochemical
Lithium-ioncells
Batteries
Thermodynamics
Electrochemistry
I
Figure 2.7: Lithium cells (1990s Sony
Corp.) Lithium is an ideal anode material owing to its low density and high reduction potential, making Li-based cells
the most compact for storing electrical energy. Lithium cells are used in
wristwatches, cardiac pacemakers, digital
cameras, laptops etc.
LixCoO2
LixCoO2
15
Anode: Lix C C + cLi+ + xe

Cathode: CoO2 + xLi+ + xe Lix CoO2
Net (2.6 V): Lix C + CoO2 C + Lix CoO2
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Thermodynamics
Electrochemistry
Moores law for Li-ion batteries?

Lithium-ion Batteries II
Lead-Acid
1850
1900
NiMH
1960
1965
108
Nano-Li-ion
107
106
105
102
104
Improved
Li-ion
Li-ion
103
1970
1975
1980
1985
1990
1995
2000
101
Energy density [Wh/kg]
NiCd
Number of transistors per integrated ciruit
109
100
Figure 2.8: Moores law for Li-ion batteries?

28 February 2013
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Thermodynamics
Electrochemistry
mWh to kWh Storage Applications I

mWh-kWh Storage applications
EV
PHEV
Efficient use of Energy
EV
Mobile Energy Storage

HEV
1 mWh
1 Wh
100 Wh
50 kWh
21
Figure 3.1: mWh to kWh storage applications; HEV: hybrid electric vehicle
PHEV: plug-in hybrid electric vehicle
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mWh to kWh Storage Applications II
Range: 175 km
Capacity: 24 kWh
Power: 90 kW
Weight: 300 kg
Full charge time: 8 hours
Lifetime: 160000 km
Battery: Li-ion, (+) LiMn2 O4 based,
(-) Carbon?
Figure 3.2: Nissan Leaf
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Thermodynamics
Electrochemistry
MWh to GWh Storage Applications

MWh GWh StorageApplications
Efficient use of Energy
Energy: Enable Solar and Wind, store energy on a scale of hours/days
Not for batteries

Strategic reserves
Power: Backup, Grid stabilisation, Efficiency, timescale minutes/seconds
100 kWh
10 MWh
10000 MWh
22
Figure 3.3: MWh to GWh storage applications

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Thermodynamics
Electrochemistry
Common Battery Types: Energy = f (size) I
Table 1: Classification of batteries vs. size [1]

Type
Miniature batteries
Energy
100 mWh 2 Wh
Batteries
for
portable
equipment
Starting, lighting and ignition (SLI) batteries
Vehicles traction batteries
2 Wh 100 Wh
100 600 Wh
Stationary batteries
20 630 kWh
3 MWh
250 Wh 5 MWh
Load leveling batteries
5 100 MWh
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Applications
Watches, calculators, implanted
medical devices
Flashlights, toys, portable radio and
TV, phones, laptops
Cars, trucks, buses, lawn mower
traction
Fork-lift trucks, locomotives
Submarines
Emergency power, local energy storage, remote relay stations
Spinning reserve, peak shaving, load
leveling
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Ragone Plot
Ragone Plot Energy vs Power density

Figure 3.4: Energy vs. Power
density.
0.28 kWh = 1 MJ: energy to accelerate a car of 1 ton to 161
km/h (no air resistance);
10 kWh = 36 MJ: energy content
of 1 L of gasoline
1 W: power to burn 1 Watt light
(bike);
3 MW: large wind turbine;
1 GW: large power plant
27
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move (diffuse) through it, to come into contact with the other reactant on the oth
Thermodynamics
Electrochemistry
side. If, for example, A moves through the AB phase to the B side, additional AB w
form at the AB/B interface. Since some B is consumed, the AB/B interface will mo
to the right. As the amount of A on the A side has decreased, the A/AB interface w
likewise move to the left. AB will grow in width in the middle. The action will
the same when species B, rather than species A, moves through the AB phase in t
process. There are experimental methods to determine the identity of the movi
species, but that is not relevant here.
How Does it Work?
Simple Chemical and Electrochemical Reactions I

A
Chemical reaction: A + B = AB;

The driving force for this reaction is
the difference in the values of the standard Gibbs free energy of the products
(AB), and the standard Gibbs free energies of the reactants, A and B [2]:
X
Gr0 =
Gf0 (Products)
X
Gf0 (Reactants) (1)
AB
AB
AB
Fig. 1.1 Simple schematic model of chemical reaction of A and B to form AB, indicating how
microstructure of the system varies with time
Figure 4.1: Schematic model of chemical reaction of A and B to form AB
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be an electronic insulator.
Thermodynamics
Electrochemistry
The reaction between A and B involves not just ions but electrically neutral
atoms. Hence for the reaction to proceed there must be another path whereby electrons can also move through the system. This is typically an external electrical
circuit connecting A and B. If A is transported in the system, and the electrolyte
contains A+ ions, negatively charged electrons, e , must pass through the external
circuit in equal numbers, or at an equal rate, to match the charge flux due to the
passage of A+ ions through the electrolyte to the other side.
For an electrochemical discharge reaction of the type illustrated in Fig. 1.2 the
reaction at the interface between the phase A and the electrolyte can be written as
Simple Chemical and Electrochemical Reactions II

Electronic Path
Electrochemical mechanism: like the

chemical reaction case, AB must form
as the result of a reaction between A
and B, but with an additional element:
an electrolyte (passage of ionic, but
not electronic species).
A and B are connected to an external
electrical circuit.
Remark
Driving force is the same as for the
chemical mechanism (Eq. 1)
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Electrolyte
Electrolyte
Electrolyte
Electrolyte
Electrolyte
AB
AB
AB
AB
Fig. 1.2 Simple schematic model of time evolution of the microstructure during the electrochemical reaction of A and B to form AB, a mixed conductor. In this case it is assumed that A+ ions are
the predominant ionic species in the electrolyte. To simplify the figure, the external electronic path
is shown only at the start of the reaction
Figure 4.2: Schematic model of electrochemical reaction of A and B to form AB;

A = A+ + e (left) and A+ + e = A
(right)
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Review of Thermodynamic Concepts
How Does it Work?
Thermodynamics
Reversible Fuel Cell Potential
Electrochemistry
Fuel Cell Efficiency
Introduction
III
Simple
Chemical
and Electrochemical Reactions III
Figure4.3:
1.1: Thermodynamic
Thermodynamic relations
Figure
relations
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Thermodynamics
Electrochemistry
Simple Chemical and Electrochemical Reactions IV
The balance between the chemical and electrical forces upon the ions under
open circuit conditions can be simply expressed as an energy balance:
Gr0 = zFE
(2)
where z is the charge number of the mobile ionic species, E the voltage
between the electrodes, and F is the Faraday constant (96500 C/mol).
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Thermodynamics
Electrochemistry
Electrochemical
cells,cells,
Definitions
Electrochemical
Definitions
Electrolytic
cell (Charge)
cell (Charge)
Direction of Redox Reaction
I Electrolytic
Galvanic cell
(Discharge)
Galvanic
cell (Discharge)
Chemical ->Chemical
Electrical->energy
Electrical energy
Electrical ->Electrical
Chemical
->Energy
Chemical Energy
redox
reaction
G>0
G<0 Forced
Forced
redox
reaction
G>0
Electrolytic
cell
(Charge)
+ Cathode +
(red)
/ - Anode
+ Anode (ox)
/ - Cathode
Cathode
(red)(ox)
/ - Anode (ox)
+ Anode
(ox) / (red)
- Cathode (red)
redox reaction
Spontaneous
redoxG<0
reaction
GalvanicSpontaneous
cell (Discharge)
Zn2+
NO3-
Zn2+
Cu2+
2e-
NO3-
Cu(NO
Zn(NO
3)32)2
Cu(NO3)2
2e-
2e-
Zn2+
porous
barrier
2eCu2+
2eNO
NO33 Zn2+
Zn(NO3)2
Cu(NO
Zn(NO
3)32)2
anode
porous
barrier
Cu2+
I
e-+
+
DC supply
DC supply
anode
cathode
2e-
Zn(NO3)2
Note:
e-
cathode
anode
2e-
porous +
barrier
cathode
- porous
barrier
anode
e-
cathode
I
e-
Cu2+
2e-
Cu(NO3)2
oxidation
always
occurs
at the
anode,
reduction
the cathode
(not
related(not
to related to
Note:
oxidation
always
occurs
at the
anode,atreduction
at the
cathode
Figure 4.4: Chemical

electrical
the sign
of the
the
electrode!)
sign
of the electrode!)Figure 4.5: Electrical chemical
Spontaneous
redox reaction G < 0
Forced redox reaction G >38 0
28 February 201328 February 2013
38
+ Cathode (red) / - Anode (ox)
+ Anode (ox) / - Cathode (red)
Remark
Oxidation always occurs at the anode, reduction at the cathode.
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Electrochemicalcells,
cells,Introduction
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Thermodynamics
Direction of Redox Reaction II

Anodic
Anodic(Oxidation)
(Oxidation)Reaction:
Reaction:
Anodic (Oxidation) Reaction:
- Reductant
Reductant->->Oxidant
Oxidant++zeze
Reductant
Oxidant + ze
Zn(s) -> Zn2+2++ 2e- Zn(s) -> Zn
+ 2e
Zn(s) Zn2+ + 2e
ZnZnisisoxidized
oxidizedunder
underthe
the
loss
ofofelectrons
loss
electrons
Zn is oxidized
under
the loss of elec-
trons; by definition
I >0
Definition
DefinitionI>0
I>0
Electrochemistry
Cathodic
Cathodic(Reduction)
(Reduction)Reaction:
Reaction:
Cathodic (Reduction)- Reaction:
- ->
Oxidant
Reductant
Oxidant++zeze->
Reductant
Oxidant
+ ze
Reductant
Cu2+2++ 2e- ->
Cu(s)
Cu
+ 2e -> Cu(s)
Cu2+ + 2e Cu(s)
2+
2+2+
Cu
isisreduced
Cu
reducedbybythe
the
gain
gainofofelectrons
electrons
Cu is reduced by the gain of electrons; by definition

II<0
<0
Definition
DefinitionI<0
II
2+2+
ZnZn
e-e-
2828
February
2013
February
2013
Figure 4.6:
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cathode
cathode
anode
anode
II
2+2+
Cu
Cu
e-e-
Figure 4.7:
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Thermodynamics
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Voltage Generated by a Redox Reaction I
Laws of Thermodynamics introduce three state variables:

0th law: introduces the absolute temperature T
1st law: introduces the internal energy U by conservation of energy:
dU = Q + W
2nd law: introduces the entropy S:
dS >
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Q
T
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Voltage Generated by a Redox Reaction II
State variable introduced by different forms of work W in the form:

X
W =
Yi dXi
i
where Yi intensive "forces" and Xi are extensive "displacements", such as:
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Mechanical pressure work: W = pdV
Electrical work: W = EdQ (E electric field, and Q electric charge)
Adding mass work: W = dn ( chemical potential, and n number

of moles added)
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Thermodynamics
Electrochemistry
Voltage Generated by a Redox Reaction III

Fundamental equation of reversible thermodynamics :
X
Yi dXi
dU = Q + W = TdS +
(3)
With the new variable G = U TS + pV (Gibbs free energy), we write:

dG = dU TdS SdT + pdV + Vdp
X
= TdS pdV +
i dni TdS SdT + pdV + Vdp
i
which simplifies to:

Definition
dG = Vdp SdT +
Yi dXi
(4)
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Thermodynamics
Electrochemistry
Voltage Generated by a Redox Reaction IV
Remark
As the battery electrochemically converts chemical energy into electric
energy, it is not subject, as are combustion or heat engines, to the
limitations of the Carnot cycle dictated by the second law of
thermodynamics.
Batteries are capable of having higher energy conversion efficiencies!
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G = H TS
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Thermodynamics
Electrochemistry
In a Battery . . .
We have
mass flow in the battery
(ions) that cause the charge flow. The
Equilibrium
electrochemistry
mass flow is represents chemical work (moving ions) which is converted to
Think of Battery: we have mass flow in the battery (ions) that cause the charge flow. The mass
electrical work outside the battery.
flow is represents chemical work (moving ions) which is converted to electrical work outside the
battery.
During discharge
e-
Cathions (+)
Anions (-)
In the Resistance outside the battery:
WElec
cathode
anode
Resistance
Ecell dQ
In the battery:
Wchem
dn j
The battery does chemical work which is converted to useable electrical work outside:
Figure 5.1:
The battery does chemical work which is converted to useable
electrical work outside: Wchem = Welec
WChem
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On the Cell Voltage I
j dnj = Ecell dQ
(5)
Note
In general chemical reactions can be written as:
1 A1 + 2 A2 + . . . + n An = 0
where Aj is the chemical species and j the coefficient (negative if
reactant and positive if product).
Example: in H2 + Cl2 2HCl, we have A1 = H2 , A2 Cl2 , A3 = HCl,
1 = 1, 2 = 1 and 3 = 2
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On the Cell Voltage II
So we can write:
!
X
j
j dnj =
dn = Ecell dQ
j j
(6)
With dQ = zFdn (Faradays law):

P
Ecell =
j j
zF
(7)
where F is Faradays constant (96500 C or 26.8 Ah) and z the number of

electron involved in stoichiometric reaction.
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Electrochemistry
On the Cell Voltage III

Example
At the anode (-) oxidation of Zn:

Zn(s) Zn2+ + 2e
Calculate the theoretical cell

potential of the Daniel battery shown
in figure 5.2.
At the cathode (+) reduction of Cu2+ :

Cu2+ + 2e Cu(s)
hemistry
Thermodynamics
Electric Properties
Zn2+
Zn(NO3)2
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Zn
NO3-
cathode
porous
barrier
anode
2e-
Cu 2
Overall reaction:
Cu2+ + Zn(s) Cu(s) + Zn2+
Cu2+
Cu(NO3)2
Figure 5.2:
2e-
P
Ecell = c a =
j j
zF
Cu + Zn2+ Cu2+ Zn
=
2F
Zn2+ Zn
Cu2+ Cu
=
2F
2F
0
0
= ECu/Cu
2+ EZn/Zn2+
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Electric Properties
On the Cell Voltage IV

Remark
The potential of an electrochemical cell is equal to the difference of the
potential of the half cells, which is determined by the chemical potential
difference of the redox couple.
ical cells, driving force
F, the
tant
r the
More noble
More likely to run to the right
.
293
ns)
es
ually
oxidant
(electron acceptor)
Na+ + e- ->
Zn2+ + 2e- ->
Fe2+ + 2e- ->
Cd2+ + 2e- ->
Pb2+ + 2e- ->
2 H+ + 2e- ->
AgCl(s) + e- ->
Hg2Cl2(s) + 2e- ->
Cu2+ + 2e- ->
I2(s) + 2e- ->
Fe3+ + e- ->
Ag+ + e- ->
O2(g) + 4H+ + 4e- ->
Cl2(g) + 2e- ->
reductant
(electron donor)
Na(s)
Zn(s)
Fe(s)
Cd(s)
Pb(s)
H2(g)
Ag(s) + Cl(aq)
2Cl(aq) + 2Hg(l)
Cu(s)
2 I(s)
Fe2+(aq)
Ag(s)
2 H2O(l)
2 Cl(g)
Discharge
E, volts
2.71
.76
.44
.40
.126
0.000
+.222
+.268
+.337
+.535
+.771
+.799
+1.23
+1.36
For the Daniel cell, we would have a

cell potential:
0
0
Ecell = ECu/Cu
2+ EZn/Zn2+
= 0.337 (0.76)
= 1.097 V
(Volt, V=J/C) build up?

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Electric Properties
On the Cell Voltage

V field and chemical potential
Balancing
2e-
porous
barrier
Zn2+
NO3-
Zn(NO3)2
Cu2+
Cu(NO3)2
Zn/Zn2+)
-2F( A- E)=-2F
Zn/Zn2+
2e-
cathode
Anode
Cu/Cu2+)
(Zn2+)- Zn)
(Cu2+)- (Cu)
2F( C- E)=2F
Cu/Cu2+
x
x)
ocv
E
A
=(
Cu/Cu2+
Zn/Zn2+
Cu2+
Cu/Cu2+
Cu)/2F
-(
Zn2+
Zn)/2F
Zn/Zn2+
x
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55
Figure 5.3: Balancing field and chemical potential; EOCV = ECu/Cu2+ EZn/Zn2+
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Thermodynamics
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Electric Properties
Cell Voltage Variation with Concentration: the

Nernst Equation I
We have already found that:
P
Ecell =
j j
zF
By introducing equation = 0 + RT ln C (derived for ideal gases, diluted

solutions), we obtain the Nernst equation:
"
#
Y
RT
i
0
Ecell = E
ln
Ci
(8)
zF
i
where Ci is the concentration of species i, i is the stoichiometric coefficient
of species
and E 0 is the reversible voltage at standard conditions.
Q i,
i
K = i Ci is the equilibrium constant of the redox reaction.
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Nernst Equation II
How do the electrode potentials

of
the
reactions
and
Cu2+ + 2e Cu(s)
Zn2+ + 2e Zn(s) depend on
the concentration.
10. Does
open
voltagegogo
Does
the the
open
cellcell
voltage
a)
up
or
up, down or remains unchanged
down?
ifb)we
add Cu(NO3 )2 and less
c)
no
Zn(NOclue
3 )2 ?
ee- Zn2+
e- Zn2+
eA
porous
barrier
EA
NO3NO3NO3NO3E
+
+
+
+
EC
When does
the Daniel
reaction
= OCu/Cu2+
- RT/2F [ln
(cCu(s)/cCu2+)]= 0.337 - 0.013 Figure
[ln (cCu(s)5.4:
/cCu2+)] > 0.337
stop?
=
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Add less Zn(NO3)2 and more Cu(NO3)2
cathode
Question Electrochemistry 2
Anode
Example
O
Zn/Zn2+
- RT/2F [ln (cZn(s)/cZn2+)]= -0.76 - 0.013 [ln (cZn(s)/cZn2+)]< -0.76
cell
Cu/Cu2+
Zn/Zn2+
Energy Storage
Batteries
I 34/61
= (0.337+x) (-0.76-y) = 1.097+x+y
V | =>
a) up
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Electric Properties

Nernst Equation III
1
1
For Cu2+ + 2e Cu(s), K = CCu(s)
CCu
2+ , hence:
0
E = ECu/Cu
2+
RT
ln
2F
CCu(s)
CCu 2+

= 0.337 0.013 ln
CCu(s)
CCu 2+
Similarly for Zn2+ + 2e Zn(s)

E = 0.760 0.013 ln
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CZn(s)
CZn 2+
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Nernst Equation IV
2
When we add more Cu(NO3 )2 , we have

CCu(s)
0.337 0.013 ln
= 0.337 + x > 0.337 V
CCu 2+
and with less Zn(NO3 )2 we have:

CZn(s)
= 0.760 y < 0.760 V
0.760 0.013 ln
CZn 2+
The Ecell is:
Ecell = ECu/Cu2+ EZn/Zn2+
= (0.337 + x) (0.760 y) = 1.097 + x + y > 1.097 V
Voltage goes up.
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Nernst Equation V
The condition for the Daniel reaction to stop is if:

ECu/Cu2+ = EZn/Zn2+

CCu(s)
CZn(s)
0.337 0.013 ln
= 0.760 0.013 ln
CCu 2+
CZn 2+
which would give CZn 2+ /CCu 2+ = 4.4 1036
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Electrochemistry
Electric Properties

Nernst Equation VI
Example
Does the cell voltage of the Daniel battery remain constant during
discharge?
The battery reaction is Cu2+ + Zn(s) Cu(s) + Zn2+ .
When it proceeds, Cu2+ is consumed and Zn2+ in produced. Therefore,
from Nernst equation, the voltage cannot remain unchanged:
0
Ecell = ECu/Cu
2+
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RT
ln
2F
CCu(s)
CCu 2+
0
EZn/Zn
2+ +
RT
ln
2F
CZn(s)
CZn 2+
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Thermodynamics
Electrochemistry
Electric Properties
Cell Voltage and Gibbs Free Energy I

From equation 4, we have
dG = Vdp SdT +
i dni
(9)
At constant pressure and temperature, it reduces to:

X
dG =
i dni
(10)
but
j dnj = Ecell dQ (from Wchem = Welec ), thus:
G = EQ
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and G 0 = zFE 0 (@ standard conditions)
(11)
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Thermodynamics
Electrochemistry
Electric Properties
Cell Voltage and Gibbs Free Energy II

Example
Calculate the Gibbs free energy of the Daniel battery shown in figure 5.2.
Overall reaction: Cu2+ + Zn(s) Cu(s) + Zn2+
G 0 = nFE 0 = 2 96500 1.097 = 211731 J/mol
G 0 is negative reaction occurs spontaneously (battery discharge, exothermic reaction)
Remark
In general we have:
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G < 0 : E > 0 discharge exothermic
G > 0 : E > 0 charge endothermic
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Electric Properties
Energy Density I
The energy density of the battery Cu2+ + Zn(s) Cu(s) + Zn2+ is calculated from Gibbs free energy:
G 0 = nFE 0 = 211731 J/mol
With just considering the metals with the molar mass of Cu (63.5 g/mol)
and the molar mass of Zn (65.4 g/mol), the energy density is:
Energy density =
211731
= 1643 kJ/kg
(63.5 + 65.4) 103
Remark
For proper calculation of the energy density (and other electrical
properties), we need to account for the masses of the electrolyte, the
current collectors, and the packing of the cell, not just the active materials!
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the types
of active Applications
materials that
(this determines
amount
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Doesused
it Work?
Thermodynamicsthe voltage) and on the
Electrochemistry
of the active materials that are used (this determines ampere-hour capacity). In practice, only
a fraction of the theoretical energy of the battery is realized. This is due to the need for
electrolyte and nonreactive components (containers, separators, electrodes) that add to the
weight and volume of the battery, as illustrated in Fig. 1.3. Another contributing factor is
that the battery does not discharge at the theoretical voltage (thus lowering the average
Introduction
Electric Properties
Energy Density II
FIGURE 1.3 Components of a cell.
Figure 5.5: Component of a cell

* The energy output of a cell or battery is often expressed as a ratio of its weight or size.
The preferred terminology for this ratio on a weight basis, e.g. Watthours / kilogram
(Wh / kg), is specific energy; on a volume basis, e.g. Watthours / liter (Wh / L), it is energy
density. Quite commonly, however, the term energy density is used to refer to either
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ratio.
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Introduction
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Electric Properties
the materials
construction reduces
the theoretical energy density or
That the weight ofHow
Applications
Does it of
Work?
Thermodynamics
of the battery by almost 50 percent, and
Electrochemistry
That the actual energy delivered by a practical battery, even when discharged under conditions close to optimum, may only be 50 to 75 percent of that lowered value
Thus, the actual energy that is available from a battery under practical, but close to optimum,
discharge conditions is only about 25 to 35 percent of the theoretical energy of the active
materials. Chapter 3 covers the performance of batteries when used under more stringent
conditions.
Energy Density III
FIGURE 1.4 Theoretical and actual specific energy of battery systems.
Figure 5.6: Theoretical (based on the active anode and cathode materials only)
and actual specific energy of battery systems when discharged at 20 at optimal
conditions. The theoretical specific energy of a practical battery accounts for the
electrolyte and non-reactive components
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Thermodynamics
Electrochemistry
Electric Properties
Energy Density IV
Example
1
Write and plot the voltage of the Daniel element as a function of

CZn2+ concentration, assuming starting concentration CZn2+ (t = 0) =
0.1 mol/l and CCu2+ (t = 0) = 1.0 mol/l, CZn(s) = CCu(s) = 1, and
the cell volume = 10 ml.
Calculate the energy delivered by the battery.
We have CCu2+ = 1.1 CZn2+ (0.1 6 CZn2+ 6 1.1), therefore:

!
CZn2+
Ecell = 1.097 0.013 ln
1.1 CZn2+
Note that at t = 0, Ecell is:
Ecell (t = 0) = 1.097 0.013 ln
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CZn2+ (t = 0)
CCu2+ (t = 0)
!
= 1.127 V
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Thermodynamics
Electrochemistry
Electric Properties
Energy Density V
1.15
Ecell / V
1.1
1.05
1
0.95
0.9
0
0.2
0.4
0.6
0.8
CZn2+ / mol/l
1.2
Figure 5.7:
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Thermodynamics
Electrochemistry
Electric Properties
Energy Density VI
On the other hand, we have from equation 11 (with
x + ab ln(ax + b) x, a 6= 0):
dG = EdQ = E zF V dCZn2+
Z1.1"
G = 2 96500 0.01
1.097 0.013 ln
0.1
Z1.1
Z1.1
= 2117 dCZn2+ + 27.5 ln
0.1
0.1
ln(ax + b)dx =
CZn2+
1.1 CZn2+
CZn2+
1.1 CZn2+
!#
dCZn2+
!
dCZn2+

1.1

1.1
= 2117 CZn2+ 0.1 + 27.5 CZn2+ ln CZn2+ CZn2+ 0.1

1.1
27.5 CZn2+ 1.1/1 ln 1.1 CZn2+ CZn2+ 0.1
= 2113.3 J
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Thermodynamics
Electrochemistry
Cell Polarization
Cell Polarization I
We know that the maximum electric energy that can be delivered by the
chemicals that are stored within the electrodes in the battery depends
on G of the electrochemical couple.
Within any cell undergoing charge or discharge, at least three forms of
charge transmission can be considered:
Electron flow in the electronic conductors such as electrode materials
Ion flow in the electrolyte (aqueous, solid or molten salt)
Charge transfer at the electrode/electrolyte interfaces (e.g. in the
reaction: Zn(s) Zn2+ (aq))
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Cell Polarization
transport,
CellCharge
Polarization
II
Thermodynamics
kinetics
(4)
(2)
(1)
Electrochemistry
(3)
Figure 6.1: (1) Ionic conduction A+ (2) Charge transport over the electrolyteelectrode interface (3) Ionic conduction
A or B (4) electronic conduction
+
(1) ionic conduction A

(2) Charge transport over the electrolyte-electrode interfac
Remark
(3) ionic conduction A or B
At the steady state, the condition of electroneutrality should be verified:
(4)ofelectronic
rate
electron flow conduction
in the external circuit should be equal to the rate of
charge transfer at each electrode/electrolyte process.
20 March 2013
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Cell Polarization
Cell Polarization III
It would be desirable if during the discharge all of this energy could be

converted to useful electric energy, but there are losses:
Anis Allagui
activation losses, needed to drive the electrochemical reaction at the

electrode surface,
concentration losses, which arises from the concentration differences of

the reactants and products at the electrode surface and in the bulk
(mass transfer), and
ohmic losses (IR drop)
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As shownSort
inHistory
Eq. (2.1),
the useful
voltage delivered
by the cell is reduced Electrochemistry
by polarization
Introduction
Applications
How Does it Work?
Thermodynamics
and the internal IR drop. It is only at very low operating currents, where polarization and
Polarization
theCellIR
drop are small, that the cell may operate close to the open-circuit voltage and deliver
most of the theoretically available energy. Figure 2.1 shows the relation between cell polarization
discharge current. IV
CellandPolarization
FIGURE 2.1 Cell polarization as a function of operating current.
Figure 6.2: Cell polarization as a function of operating current.
Although the available energy of a battery or fuel cell depends on the basic electrochemical reactions at both electrodes, there are many factors which affect the magnitude of the
charge-transfer
reaction, diffusion rates, and magnitude of the energyEnergy
loss.
These
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| Batteriesfactors
I 50/61
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Cell Polarization
Cell Polarization V
To achieve a high operating efficiency with minimal loss of energy:
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high conductivity of the electrolyte to minimize the IR polarization,
chemically stable electrolyte to avoid direct chemical reaction with

the electrodes materials,
fast rate of electrode reaction at both electrodes to minimize the

charge-transfer polarization (porous electrodes),
adequate electrolyte transport to facilitate the mass transfer and

avoiding building up excessive concentration polarization (porosity, thickness, structure of separator, concentration of reactants),
compatible current collector material with the electrode material and

the electrolyte without causing corrosion problems.
51/61
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Thermodynamics
Electrochemistry
Relationship between Current and Reaction Rate I

For the general electrode process:
Ox + ne Red
the forward and backward reactions can be described by heterogeneous rate
constants kf and kb , respectively:
The rates of the forward (kf CO ) and backward (kb CR ) reactions cab be
given by:
if = n FAkf CO
(12)
ib = n FAkb CR
(13)
where A is the area of the electrode.
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Relationship between Current and Reaction Rate II

The role of electrons in the process is established by assuming that the rate
constants depend on the electrode potential, E: a fraction E is involved
in driving the reduction process, while the fraction (1 E) is effective in
making the reoxidation process more difficult.
The potential-dependent forward and backward reaction rate coefficients can
be written:

n FE
kf = k0,f exp
(14)
RT

(1 )n FE
kb = k0,b exp
(15)
RT
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Electrochemistry
Relationship between Current and Reaction Rate III

With the equilibrium condition if = ib = i0 , where no net current flows,
we obtain from equations 12 to 15:

n FEeq
(1 )n FEeq
CO k0,f exp
= CR k0,b exp
(16)
RT
RT
or

RT
k0,f
RT
CO
ln
+
ln
nF
k0,b
nF
CR

RT
CO
= E0 +
ln
nF
CR
Eeq =
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(17)
(18)
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Relationship between Current and Reaction Rate IV

Remark
Equation 18 is consistent with the Nernst equation, expect that it is written
in terms of concentrations rather than activities.
From equations 12 and 14, at equilibrium conditions, we have:
i0 = if = nFAC0 k0,f exp
nFEeq
RT
(19)
The exchange current i0 is a parameter of interest in the battery field that

measures the rate of exchange of charge between oxidized and reduced species
at any equilibrium potential without net overall change, and can be expressed
using equations 12, 14, 17, and 19 as:
i0 = nFAkC01 CR
(20)
The rate constant k = k0,f exp nFE

is defined for a particular potential,
RT
the standard potential of the system E 0 .
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Electrochemistry
Relationship between Current and Reaction Rate V

When the net current is not zero, i.e when the potential is sufficiently different from the equilibrium potential, the net current approaches the net
forward current (or, for anodic overvoltages, the backward current):
i = nFAkC0 exp
nF (E Eeq )
RT
(21)
If E Eeq = 0, then i = i0 , and:

i = i0 exp
nF (E Eeq )
RT
(22)
A transformation into a net current would give (using equation 12, 15, 17
18):

nFE 0
(1 )nFE 0
i = if ib = nFAk C0 exp
CR exp
(23)
RT
RT
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Electrochemistry
Relationship between Current and Reaction Rate VI
Remark
Remember that in equation 23, CO and CR are concentrations at the
surface of the electrode, or are the effective concentrations. These are not
necessarily the same as the bulk concentrations.
Concentrations at the interface are often (almost always) modified by
differences in electric potential between the surface and the bulk solution.
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is called also the transfer coefficient

Exchange current
57/61
positive
and thus
is against the
adsorption.6 Figure 2.12 gives an
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Howmechanism
Does it Work?of contact
Thermodynamics
Electrochemistry
example of the ion Cs! contact-adsorbed on the surface of an electrode.
It would be expected that because anions have a negative charge, contact adsorption of
anions would not occur. In analyzing the free-energy balance of the anion system, it is found
that anion-electrode contact is favored because the net free-energy balance is negative. Both
from these calculations and from experimental measurements, anion contact adsorption is
found to be relatively common. Figure 2.13 shows the generalized case of anion adsorption
Introduction
Electrical Double-Layer and Ionic Adsorption I
FIGURE 2.10 Orientation of water molecules in

electrical double layer at a negatively charged electrode.
FIGURE 2.11 Typical cation situated in electrical

double layer.
Figure 6.3: Orientation of water molecules in ECDL at a negatively charged electrode (left) and cation situation close to the ECDL (right). This would influence
the real (actual) concentration of electroactive species at an electrode surface
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Electrochemistry
and IonicPRINCIPLES
Adsorption
II
ELECTROCHEMICAL
AND REACTIONS
2.15
FIGURE 2.14 Potential distribution of posi-
tively charged
electrode.
Figure 6.4: Schematic
of potential
distribution of positively charge electrode.
The potential at the Outer Helmholtz plane 0 is referred to the potential of the
bulk electrode.
As mentioned previously, the bulk concentration of an electroactive species is often not

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Energy Storage double
| Batteries I layer
59/61
the
value to be used in kinetic equations. Species which are in the electrical
Introduction
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Electrochemistry
Electrical Double-Layer and Ionic Adsorption III

As mentioned in Remark 11, it is the actual concentration at the interface
and not the bulk solution that we have to use in equation 23.
At equilibrium, the concentration C e of an ion or species that is about to
take part in the charge-transfer process at the electrode is related to the
bulk concentration by:
C e = C B exp
zF e
RT
(24)
where e is the potential of the closest species to the electrode (at the outer
Helmholtz plane) and z the charge on the ion.
Equations 23 and 24 would give:
i
zO Fe
nF(E e )
zR Fe
(1 )nF(E e )
= C0 exp
exp
CR exp
exp
nFAk
RT
RT
RT
RT
(25)
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Thermodynamics
Electrochemistry
References
[1] C. A. Vincent and B. Scrosati.

Modern Batteries.
Butterworth-Heinemann, Oxford, UK, 1997.
[2] Robert Huggins.
Advanced Batteries.
Springer US, Boston, MA, USA, 2009.
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Energy Storage

Last Updated: February 15, 2016

How Does it Work?

Energy Storage | Batteries I

How Does it Work?

Electrochemical devices for energy storage and conversion:

Energy Storage | Batteries I

How Does it Work?

Galvanis Frog Experiment

the frog not being connected to an electrical machine.

Energy Storage | Batteries I

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Energy Storage | Batteries I

How Does it Work?

Figure 2.3: The lead/sulfuric acid/lead

Energy Storage | Batteries I

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First car with combustion engine 1885 (Karl Benz)

First electrical car 1881

Electrical Car is not New

Speed record 1899-1901 Camille Jenatzy

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Nickel-metal Hydride Cells

Energy Storage | Batteries I

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Anode: Lix C C + cLi+ + xe

Energy Storage | Batteries I

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Moores law for Li-ion batteries?

Energy density [Wh/kg]

Number of transistors per integrated ciruit

Figure 2.8: Moores law for Li-ion batteries?

Energy Storage | Batteries I

How Does it Work?

mWh to kWh Storage Applications I

Efficient use of Energy

Mobile Energy Storage

Energy Storage | Batteries I

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mWh to kWh Storage Applications II

Energy Storage | Batteries I

How Does it Work?

MWh to GWh Storage Applications

Energy: Enable Solar and Wind, store energy on a scale of hours/days

Not for batteries

Power: Backup, Grid stabilisation, Efficiency, timescale minutes/seconds

Figure 3.3: MWh to GWh storage applications

Energy Storage | Batteries I

How Does it Work?

Common Battery Types: Energy = f (size) I

Table 1: Classification of batteries vs. size [1]

Load leveling batteries

Energy Storage | Batteries I

How Does it Work?

Ragone Plot Energy vs Power density

Energy Storage | Batteries I

How Does it Work?

Simple Chemical and Electrochemical Reactions I

Chemical reaction: A + B = AB;

Gf0 (Reactants) (1)

Figure 4.1: Schematic model of chemical reaction of A and B to form AB