5AT01 Secondary batteries and Hydrogen Storage 2012-2013

Iron-phosphate cell: main storage reaction

ch

Positive (iron-phosphate) electrode (de-intercalation at charge)

Graphite
electrode

charge

Li1 x FePO 4 + xLi + + xe , (0 x 1)

LiFePO 4

Iron-phosphate
electrode

discharge

Negative (graphite) electrode

Li z C6 . (0 z 1)
C6 + zLi + ze

storage
discharge
+

charge

LiC
LiC6

FePO 4

charge

ch
Li+

capacity

Net effect of the reaction is the transport

of Li+ ions between electrodes

Lie++2
CoO
Li

CC6
Li+
e--

charge

Li1 x FePO 4 + Li x C6 .
LiFePO 4 + C6

discharge

d
LiFePO
LiCoO24

discharge

Separator impregnated
with LiPF6 /solvent

Negative

Positive
1

5AT01 Secondary batteries and Hydrogen Storage 2012-2013

LiFePO4: discharge voltages,

room temperature
3.6
3.4
3.2

Voltage [V]

3
EMF
0.05 C
0.10 C
0.15 C
0.20 C
0.30 C
0.50 C
0.75 C
1.00 C
1.50 C
2.00 C

2.8
2.6
2.4
2.2
2
0

0.5

1.5

2.5

Qout[Ah]

5AT01 Secondary batteries and Hydrogen Storage 2012-2013

Thermodynamics: basics

dU
= dq + dw

Compression work, first law:

Pexternal

dw =
F dz =
Pexternal Adz =
Pexternal dV
Vend

Vend

dz
V0

w=

Pexternal dV

V0

Reversible process: process

performed infinitely slowly

Pexternal = P

Vend

wrev =

PdV

V0

Ideal gas equation: PV = nRT, where n is number of moles

3

5AT01 Secondary batteries and Hydrogen Storage 2012-2013

NiMH Batteries concept: main storage reaction

Positive electrode (oxidation of nickel hydroxide to oxyhydroxide)

Ni(OH) 2 + OH
NiOOH
H
O
e
+
+

2
discharge
charge

ch

Negative electrode (water reduction)

Nickel
electrode

charge

MH + OH
M + H 2 O + e

discharge

Hydride
electrode
O2
xOH MHx

eH2O
NiOOH
ch
OHd

capacity

Net effect of the reaction is transport of

hydroxyl ions (OH-) between electrodes

H2

Ni(OH)2
OH-

M
xH2O
xeH2

dissociation

K + + OH
KOH
recombination

Negative

Positive
Separator impregnated
with KOH solution

5AT01 Secondary batteries and Hydrogen Storage 2012-2013

Electrode kinetics: parameters

charge, reduction

M + H 2 O + e
MH
OH
+

discharge,oxidation

) F
F

(1RT

RT
I I 0 e
=
e

I0

Exchange current is a measure of the equilibrium reaction rate

Charge transfer coefficient is an indicator of the symmetry of the barrier to reaction

J0 = I0 / A

Exchange current (density)

Bard and Faulkner, Electrochemical methods, Wiley (2001)

5AT01 Secondary batteries and Hydrogen Storage 2012-2013

Geometrical interpretation of
Z
tan( ) =
X

Y F Z
tan( ) = =
X
X
Define as:

Z
=
F

then

Z = F
tan( )
=
tan( ) + tan( )
6

5AT01 Secondary batteries and Hydrogen Storage 2012-2013

Power and energy efficiency

Eff
=
P

Power efficiency:

Energy
(real battery):

Ereal =

Preal Ebat I Ebat

= =
Pideal Eeq I
Eeq

Qmax

Ebat dQ

Energy efficiency:
Energy
(ideal battery):

Eideal =

Qmax

Ereal
Eff E =
Eideal

Eeq dQ

Analytical integration:

dx
=
,
log( x )
e dx e=
x
x