15.

Energy Applications I: 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
 We will briefly look at: Lead and Lithium insertion

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
 Require very good conductivity
Throughout the system
Which tends to lower the energy
Content of the system
In the lead acid system a significant amount
Of the weight Is in the grids required
To hold the paste

What are Batteries, Fuel Cells, and Supercapacitors, Chem Rev, 2004, 104, 4245, Martin Winter and
Ralph J. Brodd
Equivalent Circuit for a Battery

External Resistance, Rext

Terminals, Resistance
To current flow of, RM

Capacitance of
electrode

Internal Discharge
Rate (e.t.)

Resistance of
electrolyte
 Basic requirements for a battery
1. chemical energy stored near the electrode ( if too far away current will
be controlled by time to get to electrode)
2. The chemical form coating the electrode must allow ion transport, or
better yet, electronic conduction
3. The chemical form of the energy must be mechanically robust
4. The chemical form of the energy should generate a large voltage

ad Acid Battery
 The capacity of the battery depends on
The type of material present.

Fitch lead book Support grids

 
PbO 2 ,s  2e  H 2SO 
aq  PbSO 4 ,s  2H
One possible mechanism:. simultaneous dissolution of PbO2 and introduction of 2e
Requires electronic conductivity of PbO2 and pore space for motion of wat

1. Add e, H+ and OH- to PbO2

2. Add 2nd e to reduce valence of Pb
3. Add 3rd e to reduce valence while r
4. PbO is more soluble than PbO2 so
5. Initiate formation of PbSO4, nuclea
6. PbSO4 structure is rhombic which
7. Therefore need to control the alletr
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

Alpha forms when Pb metal

Corrodes – reduces lifetime of
Battery, is more compressible.
Lead Acid battery
a.What is the potential associated with a lead
acid battery with the overall reaction:
  
Pbs  PbO 2 ,s  2H aq  2H SO aq  2 PbSO 4 ,s  2 H 2O 

at the following concentration:

[H2SO4] = 4.5 M
  2 
Vo
PbO 2 ,s  4H aq  2e  SO aq  PbSO 4 ,s  2 H 2O  1.69
2
PbSO 4 ,s  2e 
 Pbs  SO aq -0.35
 2 
PbO 2 ,s  4H aq  2e  SO aq  PbSO 4 ,s  2 H 2O  1.69
Pbs  SO 2 
aq  PbSO 4 ,s  2e -(-0.35)
2.04
  
Pbs  PbO 2 ,s  2H aq  2H SO aq  2 PbSO 4 ,s  2 H 2O 

0 .0 5 9 2 0 .0 5 9 2
V  V o
 l o g Q  2 .0 4  lo g Q
n 2
Lead Acid battery energy
  
Pbs  PbO 2 ,s  2H aq  2H SO aq  2 PbSO 4 ,s  2 H 2O 


  
2
0 .0 5 9 2 0 .0 5 9 2  P b S O 4 ,s H 2 O
V  2 .0 4  l o g Q  2 .0 4  lo g 
    
2
2 2  Pb PbO H SO  H 3O  2
 s s aq

 
0 .0 5 9 2 0 .0 5 9 2  1 
V  2 .0 4  l o g Q  2 .0 4  lo g 
  H 

2
2 2  H SO 
O  2
 aq 3 
0 .0 5 9 2  1 
V  2 .0 4  lo g  2 
2   4 .5   4 .5  
2

V  2 . 0 4  0 . 0 2 9 6   2 . 6    2 .1 1
c. What is the free energy associated with the
lead acid battery?

 nFV o
  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

No e

 2 
PbO 2 , s o lid  4H aqueous  SO 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)
One way to “image” the various processes described above is by an
Equivalent Circuit
 In a simplified system

V D is c h a rg e  I D  R  ext
R ext I D is c h a rg e

V t0  Id R  ext  R app 

R I
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
V r e m a in in g  I D  R  app

As the battery is discharged the discharge voltage is the

Difference between what we started with and the remaining
Voltage in the battery
V D is c h a rg e  V t0  IDR 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 pressurized

Under pressure
Insulating layer which can conduct only protons and lead

Solubility

Diffusion

Et at conducting PbO2
Solubility

Diffusion

Et at conducting PbO2

Modeled effect of diffusion

Solubility

Diffusion

Et at conducting PbO2

Modeled effect of proton conc

 Solubility

Diffusion

Et at conducting PbO2

Different magnitude of discharge

Changes the solubility and proton conc
As well as the conductivity of the film
 P  VDI V t0
 Id
R 
D

ext  R app

P  I D R I  I  2
R
V 
ext D D ext 2
0 R ext
P 
R 
2
app  R ext

R ext I V D is c h a rg e  I D  R 
ext
D is c h a rg e

V t0  Id R  ext  R app 

R a p p a r e n t in t e r n a l r e s is ta n c e I D is c h a rg e V r e m a in in g  I D  R 
app

Based on V. S. Bagotsky text, Fundamentals of Electrochemistry

 V  V  IDR
V  0
2
R ext
P 
R 
D is c h a rg e t0 App 2
app  R ext

2.5 1.2

1
2

0.8
1.5

0.6
V

P
1
0.4

0.5
0.2

0 0
0 0.5 1 1.5 2 2.5
Current Density

For the simplified model

Monitor structural changes at electrode as a function of the discharge power
 Charge transfer resistance
Decreases due formation of more porous PbO2
Small diameter
Of impedance
Circle here indic
High charge transfer The fast et kine
Resistance due to insulating O2 reaction.
PbSO4 layer

Increasing
Charge transfer
Resistance due
To layer of PbSO4
Reaction Vo
Li++e Li -3.0 7g/mol
K+ + e K -2.95
Na+ + e Na -2.71
NCl3_4H+ + 6e 3Cl- + NH4+ -1.37
2H2O + 2e H2 + 2OH- -0.828
Fe2+ + 2e Fe -0.44
Pb2+ + 2e Pb -0.13 207g/mol
2H+ + 2e H2(gas) 0
N2(g) + 8H+ + 6e 2NH4+ 0.275
Cu2+ + 2e Cu 0.34
O2 + 2H2O + 4e 4OH- 0.40
O2 + 2H+ + 2e H2O2 0.68
Ag+ + e Ag 0.799
NO3- + 4H+ + 3e NO(g) +2H2O 0.957
Br2 + 2e 2Br- 1.09
2NO3- + 12H+ + 10e N2(g) +6H2O 1.246
Cl2 + 2e 2Cl- 1.36
Au+ + e Au 1.83
 Lithium oxidation proceeds a little too
uncontrollably

Lithium reduction does not not result

in good attachment back to the lithium
metal

Forms dendrites which can grow to

Short circuit

C 6  1 e  L i   L iC 6

Lithium intercalated in graphite is close

to metallic, formal potential differs by
only 0.1 to .3 V = -2.7 to -2.9V
Anode –
Solid electroactive metal salt
(Can change overall charge so that it can electrostatically stabilize & localize Li+
Potential should be very positive (far from -2.5 V for Li/C reaction
Solid should conduct charge throughout
Solid should allow ion motion
Should have fast kinetics (open and porous)
Should be stable (does not convert to alleotropes)
Low cost
Environmentally benign

M x
m 
X z
x
 M

 x
m 1
X z
x
 e

M x
m 
X z
x
  Li
   f a s t 
  M x
m 
X z
x
 
Li 
 M x
m 
X z
x
 
Li 
 fa s t

 M x
m 
X z
x
 Li  e

M. Stanley Whittingham, Lithium Batteries and Cathode Materials, Chem. Rev. 2004, 104, 4271-4301
 Group II
V 2O 5 M oO 3

Group I Group III

Spinels
L iT iS 2 L iV S e 2 L iC o O 2

L iN iO 2 M n2O 4

M. Stanley Whittingham, Lithium Batteries and Cathode Materials, Chem. Rev. 2004, 104, 4271-4301
 Smooth galvanostatic curve indicates
That there are no sites nucleating
L iT iS 2 Alleotropes of the compound.
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
 Indicates various crystal forms

V IV
S e 2  x L i   x e  L i xV IV  x
Se2

L iV S e 2 L i xV IV  x
S e 2  1  x  L i   1  x  e  L i V III
Se2
octahedral
Lithium ion inserts in response L iV III
S e 2  L i   e  L i 2V II
Se2
To reduction of vanadium
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 5 M oO 3

M. Stanley Whittingham, Lithium Batteries and Cathode Materials, Chem. Rev. 2004, 104, 4271-4301
Major phase changes in LixV2O5
 (x<0.01) is well ordered
Є ( 0.35<x<0.7)is more puckered
 (x=1) shifting of layers
 (x>1) results in permanent structural change
ω (x>>1) is a rock salt form
Sol gel processes of the V2O5 materials
 Group III
Spinels

M n2O 4

These materials have a major change in

Unit cell dimensions when Mn changes
Oxidation state (see B). Need to keep the
Lattice parameter less than 8.23 A for good
Cycling, which

1. Keeps Mn in higher oxidation state,

therefore
less soluble
2. Prevents distortion in the coordination of
oxygen (Jahn-Teller)
around the manganese. These distortions
will alter the oxidation and
reduction potential as seen in the next slide
M. Stanley Whittingham, Lithium Batteries and Cathode Materials, Chem. Rev. 2004, 104, 4271-4301
M. Stanley Whittingham, Lithium Batteries and Cathode Materials, Chem. Rev. 2004, 104, 4271-4301