Professional Documents
Culture Documents
Energy Applications II. Batteries
Energy Applications II. Batteries
Battery types:
Primary Battery: Non reversible chemical reactions (no recharge)
Secondary Battery: Rechargeable
Common characteristics
Electrode
complex coposite of powders of active material and conductive
diluent, polymer matrix to bind the mix
typically 30% porosity, with complex surface throughout the material
allows current production to be uniform in the structure
Current distribution
primary cell geometry
secondary production sites within the porous electrode
parameters affecting the secondarycurrent distribution are
conductivity of diluent (matrix)
electrolyte conductivity,
exchange current
diffusion characteristics of reactants and products
total current flow
porosity, pore size, and tortuosisity
What are Batteries, Fuel Cells, and Supercapacitors, Chem Rev, 2004, 104, 4245, Martin Winter and
Ralph J. Brodd
What are Batteries, Fuel Cells, and Supercapacitors, Chem Rev, 2004, 104, 4245, Martin Winter and
Ralph J. Brodd
What are Batteries, Fuel Cells, and Supercapacitors, Chem Rev, 2004, 104, 4245, Martin Winter and
Ralph J. Brodd
What are Batteries, Fuel Cells, and Supercapacitors, Chem Rev, 2004, 104, 4245, Martin Winter and
Ralph J. Brodd
Capacitance of
electrode
Internal Discharge
Rate (e.t.)
Resistance of
electrolyte
ad Acid Battery
Support grids
PbO
2 ,s
2e H 2SO
aq
PbSO
4 ,s
2H
Beta PbO2 is formed under acid and can be compressed to shorten bonds
overlap induces semiconductor behavior which increases the performance
Of the battery
Add antiomony
To drive reaction
To beta phase
2 ,s
2H
aq
2H SO
aq
2 PbSO
4 ,s
2 H 2O
PbO
2 ,s
2 ,s
aq
4 ,s
2e
4H
aq
PbSO
PbO
4H
2e SO
2e SO
Pbs SO
Pbs PbO
V V
2 ,s
Pbs SO
2H
2
aq
aq
2
aq
PbSO
4 ,s
2 H 2O
Vo
1.69
2
aq
2
aq
PbSO
2H SO
-0.35
PbSO
4 ,s
4 ,s
2 H 2O
-(-0.35)
2e
aq
1.69
2.04
2 PbSO
4 ,s
2 H 2O
0 .0 5 9 2
0 .0 5 9 2
l o g Q 2 .0 4
lo g Q
n
2
2 ,s
2H
aq
2H SO
aq
2 PbSO
2 H 2O
4 ,s
P b S O 4 ,s H 2 O
0 .0 5 9 2
0 .0 5 9 2
V 2 .0 4
l o g Q 2 .0 4
lo g
2
2
2
Pb PbO H SO
H 3O
s
s
aq
0 .0 5 9 2
0 .0 5 9 2
V 2 .0 4
l o g Q 2 .0 4
lo g
2
2
H SO
0 .0 5 9 2
1
V 2 .0 4
lo g
2
2
2
4 .5 4 .5
V 2 . 0 4 0 . 0 2 9 6 2 . 6 2 .1 1
aq
H
2
c.
What is the free energy associated with the
lead acid battery?
nFV
G R T ln K
G 2 9 6 , 4 8 5 2 .0 4
G 3 9 3 .6 k J
Dendrites are
Good: porous (makes more
Of possible energy available)
Bad: fragile, break and fall
from underlying
electrode
= NO CURRENT
e
No e
PbO
2 ,s o lid
4H
aqueous
SO
2
4 ,a q u e o u s
2e
PbSO
4 ,s o lid
2 H 2O
The type of structure that forms depends upon the rate of crystallization which
Depends upon rate of reaction which depends upon:
Loss/production of products (current)
Which depends also upon the rate constant (potential dependent)
In a simplified system
ext
R
ext
D is c h a rg e
V
R
D is c h a rg e
a p p a r e n t in t e r n a l r e s is ta n c e
D is c h a rg e
t0
Id R
ext
r e m a in in g
R
I
D is c h a rg e
t0
IDR
App
app
R
app
Lead acid batteries can be valve regulated to control the pressure associated
With
No pressure
1.29 V
1.38 V
Suggests higher
Degree of interparticle
Contact under pressure
Lower CT resistance
Under pressure
pressurized
Solubility
Diffusion
Et at conducting PbO2
Solubility
Diffusion
Et at conducting PbO2
Solubility
Diffusion
Et at conducting PbO2
Solubility
Diffusion
Et at conducting PbO2
P VDI
P I D R
ext
ext
ext
ext
t0
a p p a r e n t in t e r n a l r e s is ta n c e
app
D is c h a rg e
V
R
app
Id
t0
D is c h a rg e
ext
ext
D is c h a rg e
Id R
V
r e m a in in g
ext
app
R
app
R
ext
D is c h a rg e
t0
IDR
App
2.5
V
0
app
1.2
0.8
0.6
1
0.4
0.5
0.2
0
0
0.5
1.5
Current Density
2.5
1.5
ext
ext
Increasing
Charge transfer
Resistance due
To layer of PbSO4
Small diameter
Of impedance
Circle here indic
The fast et kine
O2 reaction.
Reaction
Li++e
K+ + e
Na+ + e
NCl3_4H+ + 6e
2H2O + 2e
Fe2+ + 2e
Pb2+ + 2e
2H+ + 2e
N2(g) + 8H+ + 6e
Cu2+ + 2e
O2 + 2H2O + 4e
O2 + 2H+ + 2e
Ag+ + e
NO3- + 4H+ + 3e
Br2 + 2e
2NO3- + 12H+ + 10e
Cl2 + 2e
Au+ + e
Li
K
Na
3Cl- + NH4+
H2 + 2OHFe
Pb
H2(gas)
2NH4+
Cu
4OHH2O2
Ag
NO(g) +2H2O
2BrN2(g) +6H2O
2ClAu
Vo
-3.0
-2.95
-2.71
-1.37
-0.828
-0.44
-0.13
0
0.275
0.34
0.40
0.68
0.799
0.957
1.09
1.246
1.36
1.83
7g/mol
207g/mol
1 e L i L iC
Anode
M
M
m
x
m
x
m
x
X
X
X
x
z
x
z
x
z
M
Li
Li
m 1
x
fas t
fa s t
m
x
e
m
x
X
x
z
x
z
Li
Li e
M. Stanley Whittingham, Lithium Batteries and Cathode Materials, Chem. Rev. 2004, 104, 4271-4301
Group II
V 2O
Group I
L iT iS 2
L iN iO
L iV S e 2
2
L iC o O
M oO
Group III
Spinels
M n2O
M. Stanley Whittingham, Lithium Batteries and Cathode Materials, Chem. Rev. 2004, 104, 4271-4301
L iT iS
Single phase
Went to market
Allotropes would alter the structure,
Light weight
In the late 1970s
Porosity, and the ease of intercalation,
Conducting, but not
Potential, and conductivity
Reactive (oxidised or reduced)
Li ion intercalates in response to double layer charging
M. Stanley Whittingham, Lithium Batteries and Cathode Materials, Chem. Rev. 2004, 104, 4271-4301
IV
L iV S e 2
L i xV
IV x
IV x
S e 2 1 x L i 1 x e L i V
octahedral
Lithium ion inserts in response
To reduction of vanadium
S e 2 x L i x e L i xV
L iV
III
S e 2 L i e L i2V
II
Se2
III
Se2
Se2
2nd is tetrahedral
Different phases of VSe2 have similar structures
So the distortion is not great
M. Stanley Whittingham, Lithium Batteries and Cathode Materials, Chem. Rev. 2004, 104, 4271-4301
Group II
V 2O
M oO
M. Stanley Whittingham, Lithium Batteries and Cathode Materials, Chem. Rev. 2004, 104, 4271-4301
Group III
Spinels
M n2O
M. Stanley Whittingham, Lithium Batteries and Cathode Materials, Chem. Rev. 2004, 104, 4271-4301