Modelarea A A Bateriilor

Manuel Landstorfer
Institute of Numerical Mathematics

15.09.2009
Mathematical Modeling All Solid State
Batteries
Toskana
Page 1/23
Mathematical Modeling All Solid State Batteries
Introduction
Transport Equtions
Boundary Condtions for
(Flux) boundary conditions for c
Summary: Equation System and Conclusion
Page 2/23
Mathematical Modeling All Solid State Batteries Introduction
Introduction
Project LISA: Lithium Insertationsverbindungen f ur Solare Anwendungen
Part of the BMBF network: fundamental research on renewable energies
Compound Project: Uni Kiel, TU Darmstadt, ZSW Ulm, Uni Ulm
Uni Ulm: Mathematical Modeling of all solid state thin lm lithium ion
batteries
Page 2/23
Introduction
Project LISA: Lithium Insertationsverbindungen f ur Solare Anwendungen
Part of the BMBF network: fundamental research on renewable energies
Compound Project: Uni Kiel, TU Darmstadt, ZSW Ulm, Uni Ulm
Uni Ulm: Mathematical Modeling of all solid state thin lm lithium ion
batteries
Tasks
Developing a rigorous Mathematical Model
Account for various eects on various time/length scales
Numerics and Simulation
Validation with Experimental Data
Page 3/23
What is a Lithium Ion Battery?
Li Li
+
+e
Li
+
+e
Li
E
ux of electrons
Anode Cathode
Electrolyte
ux of Lithium Ions
d
e
e
c
t
o
r
d
e
e
c
t
o
r
Discharge of a Lithium Ion Cell
Crystal
Li
x
Ti
1x
O
2
Li
x
Co
1x
O
2
C
Page 3/23
What is a Lithium Ion Battery?
Li Li
+
+e
Li
+
+e
Li
E
ux of electrons
Anode Cathode
Electrolyte
ux of Lithium Ions
d
e
e
c
t
o
r
d
e
e
c
t
o
r
Discharge of a Lithium Ion Cell
Crystal
Li
x
Ti
1x
O
2
Li
x
Co
1x
O
2
C
Solid state diusion
Page 4/23
Mathematical Modeling All Solid State Batteries Transport Equtions
Outline
Introduction
Transport Equtions
Page 5/23
Transport Equations
L
1
L
2
Solid
Electrolyte
Lithium
Foil
Discharge
Intercalation
Electrode
Page 5/23
Transport Equations
L
1
L
2
Solid
Electrolyte
Lithium
Foil
Discharge
Intercalation
Electrode
Solid Electrolyte
Nernst Planck Flux:

Li
+ = D
Li
+c
Li
+ c
Li
+
Continuity Equation:

t
c
Li
+ =
Li
+
Poisson Equation:
Electrolyte
=
Electrolyte
Page 5/23
Transport Equations
Solid Electrolyte
Nernst Planck Flux:

Li
+ = D
Li
+c
Li
+ c
Li
+

t
c
Li
+ =
Li
+
Poisson Equation:
Electrolyte
=
Electrolyte
Page 5/23
Transport Equations
E
Solid Electrolyte
Nernst Planck Flux:

Li
+ = D
Li
+c
Li
+ c
Li
+

t
c
Li
+ =
Li
+
Poisson Equation:
Electrolyte
=
Electrolyte
Page 5/23
Transport Equations
E = 0
Solid Electrolyte
Nernst Planck Flux:

Li
+ = D
Li
+c
Li
+ c
Li
+

t
c
Li
+ =
Li
+
Poisson Equation:
Electrolyte
=
Electrolyte
Page 5/23
Transport Equations
E = 0
Solid Electrolyte
Nernst Planck Flux:

Li
+ = D
Li
+c
Li
+ c
Li
+

t
c
Li
+ =
Li
+
Poisson Equation:
Electrolyte
=
Electrolyte
Page 5/23
Transport Equations
L
1
L
2
Solid
Electrolyte
Lithium
Foil
Discharge
Intercalation
Electrode
Solid Electrolyte
Nernst Planck Flux:

Li
+ = D
Li
+c
Li
+ c
Li
+

t
c
Li
+ =
Li
+
Poisson Equation:
Electrolyte
= F(c
Li
+ c
Anions
. .
=const
)
Nernst Einstein Relation: =
D
Li
+F
RT
Page 5/23
Transport Equations
L
1
L
2
Solid
Electrolyte
Lithium
Foil
Discharge
Intercalation
Electrode
Solid Electrolyte
Nernst Planck Flux:

Li
+ = D
Li
+c
Li
+
D
Li
+F
RT
c
Li
+

t
c
Li
+ =
Li
+
Poisson Equation:
Electrolyte
= F(c
Li
+ c
Anions
)
Intercalation Electrode
Fickian Flux:

s
= D
s
c
Li
+

t
c
s
=
s
Page 6/23
Non-dimensional Transport Equations
Non-dimensional Variables
x
1
=
X
1
L
1
x
1
[0, 1] x
2
=
X
2
L
2
x
2
[0, 1]
c(x
1
, ) =
c
Li
+
c
Max
Li
+
(x
2
, ) =
c
s
c
Max
s
(x
1
) =
F
RT
= t
Page 6/23
Non-dimensional Variables
x
1
=
X
1
L
1
x
1
[0, 1] x
2
=
X
2
L
2
x
2
[0, 1]
c(x
1
, ) =
c
Li
+
c
Max
Li
+
(x
2
, ) =
c
s
c
Max
s
(x
1
) =
F
RT
= t
Solid Electrolyte
Nernst Planck Equation: L
1
c = (D
1
c +D
1
c) in
1
Poisson Equation:
2
e
=
1
2
(c c
Anion
) in
1
Diusion Equation: L
2
= (D
2
) in
2
Page 6/23
x
1
1
x
2
2
Solid
Electrolyte
Intercalation
Electrode
Solid Electrolyte
1
c = (D
1
c +D
1
c) in
1
Poisson Equation:
2
e
=
1
2
(c c
Anion
) in
1
Diusion Equation: L
2
= (D
2
) in
2
Page 7/23
Mathematical Modeling All Solid State Batteries Boundary Condtions for
Outline
Introduction
Transport Equtions
Page 8/23
Derivation of Robin boundary conditions for
E = 0
(x
1
) =
0

S
treat the Stern layer as (plate)
capacitor
C
S
=
Q
S
=
1
S
A
0
r
E

S
=
A
C
S
r
d
dx
=
1
C
S
r
d
dx
x=x
1
Robin boundary condition for :

n
+
C
S
x=x
1
=
C
S
r

0
Page 8/23
E = 0
(x
1
) =
0

S
capacitor
C
S
=
Q
S
=
1
S
A
0
r
E

S
=
A
C
S
r
d
dx
=
1
C
S
r
d
dx
x=x
1

n
+
C
S
x=x
1
=
C
S
r

0
Page 8/23
solid!
bulk!
material
E
(x
1
) =
0

S
capacitor
C
S
=
Q
S
=
1
S
A
0
r
E

S
=
A
C
S
r
d
dx
=
1
C
S
r
d
dx
x=x
1

n
+
C
S
x=x
1
=
C
S
r

0
Page 8/23
S
x
1
= 0
(x
1
)
solid!
bulk!
material
E
Stern Layer
(x
1
) =
0

S
capacitor
C
S
=
Q
S
=
1
S
A
0
r
E

S
=
A
C
S
r
d
dx
=
1
C
S
r
d
dx
x=x
1

n
+
C
S
x=x
1
=
C
S
r

0
Page 8/23
S
x
1
= 0
(x
1
)
solid!
bulk!
material
E
Stern Layer
(x
1
) =
0

S
capacitor
C
S
=
Q
S
=
1
S
A
0
r
E

S
=
A
C
S
r
d
dx
=
1
C
S
r
d
dx
x=x
1

n
+
C
S
x=x
1
=
C
S
r

0
Page 8/23
S
x
1
= 0
(x
1
)
solid!
bulk!
material
E
Stern Layer
(x
1
) =
0

S
capacitor
C
S
=
Q
S
=
1
S
A
0
r
E

S
=
A
C
S
r
d
dx
=
1
C
S
r
d
dx
x=x
1

n
+
C
S
x=x
1
=
C
S
r

0
Page 8/23
S
x
1
= 0
(x
1
)
solid!
bulk!
material
E
Stern Layer
(x
1
) =
0

S
capacitor
C
S
=
Q
S
=
1
S
A
0
r
E

S
=
A
C
S
r
d
dx
=
1
C
S
r
d
dx
x=x
1

n
+
C
S
x=x
1
=
C
S
r

0
Page 9/23 Mathematical Modeling All Solid State Batteries (Flux) boundary conditions for c
Outline
Introduction
Transport Equtions
Mathematical description of chemical reactions
Basics:
A redox reaction A B, as a reaction of 1. order is described via
d[A]
dt
= k
f
[A] +k
b
[B],
where [A] and [B] are the concentrations of A, B, respectively and k
1,2
are
reaction rate coecients. (standard notation in chemistry).
Basics:
d[A]
dt
= k
f
[A]
. .
AB
+k
b
[B]
. .
BA
1,2
are
Basics:
dc
A
dt
= k
f
c
A
. .
AB
+k
b
c
B
. .
BA
1,2
are
Basics:
1,2
are
Transiton State Theory:
k
i
=
k
B
T
h
exp
_
G
i
RT
_
with G
is the Gibbs free energy of activation.

Electrochemistry:
Chemical reactions are accelerated due to electric potential dierences between
reacting phases.
Electrochemistry:
reacting phases.
Reaction coordinate
E
n
e
r
g
y
G
0
f
k
f
=
k
B
T
h
exp
_
G
0
f
RT
_
k
b
=
k
B
T
h
exp
_
G
0
b
RT
_
Electrochemistry:
reacting phases.
Reaction coordinate
E
n
e
r
g
y
G
0
f
k
f
=
k
B
T
h
exp
_
G
0
f
RT
_
k
b
=
k
B
T
h
exp
_
G
0
b
RT
_
Electrochemistry:
reacting phases.
G
b
Reaction coordinate
E
n
e
r
g
y
f
G
0
f
k
f
=
k
B
T
h
exp
_
G
f
RT
_
k
b
=
k
B
T
h
exp
_
G
b
RT
_
Electrochemistry:
reacting phases.
G
b
Reaction coordinate
E
n
e
r
g
y
f
G
0
f
k
f
=
k
B
T
h
exp
_
(G
0
f
)
RT
_
k
b
=
k
B
T
h
exp
_
G
b
RT
_
Electrochemistry:
reacting phases.
G
b
Reaction coordinate
E
n
e
r
g
y
f
G
0
f
k
f
=

k
f
exp
_
+
RT
_
k
b
=
k
B
T
h
exp
_
(G
0
b
+)
RT
_
Electrochemistry:
reacting phases.
G
b
Reaction coordinate
E
n
e
r
g
y
f
G
0
f
k
f
=

k
f
exp
_
+
RT
_
k
b
=

k
b
exp
_
RT
_
Electrochemistry:
reacting phases.
dc
A
dt
=
k
f
c
A
exp () +

k
b
c
B
exp ()
Electrochemistry:
reacting phases.
dc
A
dt
=
k
f
c
A
exp () +

k
b
c
B
exp ()
Main Question:
How to relate chemical reactions to ux boundary conditions?
Relate (surface) concentration to concentration ux
Everything yet said about chemical reactions was for particles per Volume
_
mol
m
3
.
Denition: Surface concentration (in a continuum mechanical sense)
c = c(x)
x
d
V
_
mol
m
2
_
Surface reaction:
d c
A
dt
= k
f
c
A
+k
b
c
B
Interpretation: Surface reaction as outward ux of c
A
.
n
A
=
Neumann boundary condition for c
A
_
mol
m
3
.
c = c(x)
x
d
V
_
mol
m
2
_
Surface reaction:
d c
A
dt
= k
f
c
A
+k
b
c
B
A
.
n
A
=
A
_
mol
m
3
.
c = c(x)
x
d
V
_
mol
m
2
_
Surface reaction:
d c
A
dt
= k
f
c
A
+k
b
c
B
A
.
n
A
=
A
_
mol
m
3
.
c = c(x)
x
d
V
_
mol
m
2
_
Surface reaction:
d c
A
dt
= k
f
c
A
+k
b
c
B
A
n
A
.
n
A
=
A
_
mol
m
3
.
c = c(x)
x
d
V
_
mol
m
2
_
Surface reaction:
d c
A
dt
= k
f
c
A
+k
b
c
B
surface reaction
A
n
A
n
A
.
n
A
=
A
_
mol
m
3
.
c = c(x)
x
d
V
_
mol
m
2
_
Surface reaction:
d c
A
dt
= k
f
c
A
+k
b
c
B
surface reaction
A
n
A
n
A
.
n
A
=
A
_
mol
m
3
.
c = c(x)
x
d
V
_
mol
m
2
_
Surface reaction:
d c
A
dt
= k
f
c
A
+k
b
c
B
A
.
n
A
=
d c
A
dt
x
A
_
mol
m
3
.
c = c(x)
x
d
V
_
mol
m
2
_
Surface reaction:
d c
A
dt
= k
f
c
A
+k
b
c
B
A
.
n
A
=
d c
A
dt
x
= k
f
c
A
k
b
c
B
A
_
mol
m
3
.
c = c(x)
x
d
V
_
mol
m
2
_
Surface reaction:
d c
A
dt
= k
f
c
A
+k
b
c
B
A
.
n
A
=
d c
A
dt
x
= k
f
c
A
k
b
c
B
= k
f
d
V
c
A
x
k
b
d
V
c
B
x
A
_
mol
m
3
.
c = c(x)
x
d
V
_
mol
m
2
_
Surface reaction:
d c
A
dt
= k
f
c
A
+k
b
c
B
A
.
n
A
=

k
f
d
V

_
c
A
(x) e
((
0
(x)))
_
k
b
d
V

_
c
B
e
((
0
(x)))
_
x
A
Page 13/23
Mathematical Modeling All Solid State Batteries Summary: Equation System and Conclusion
Outline
Introduction
Transport Equtions
Page 14/23
Equation System
Transport and Potential Equations
1
c = (D
1
c +D
1
c) in
1
Poisson Equation:
2
e
=
1
2
(c c
Anion
) in
1
Diusion Equation: L
2
= (D
2
) in
2
n (D
1
c +D
1
c) =R(c, c
Li
,
0
, 1) for x
1
= 0
n (D
1
c +D
1
c) =R(c, |
x
2
=0
, 0, 2) for x
1
= 1
n +
C
S
r
=
C
S
r

0
for x
1
= 0
n +
C
S
r
= 0 for x
1
= 1
n D
2
= R(, c|
x
1
=1
, 0, 2)
x
2
=0
n D
2
= 0
x
2
=1
R(c
A
, c
B
, , i ) = k
f ,i

_
c
A
e
(())
_
k
b,i

_
c
B
e
(())
_
Page 14/23
Equation System
Transport and Potential Equations
1
c = (D
1
c +D
1
c) in
1
Poisson Equation:
2
e
=
1
2
(c c
Anion
) in
1
Diusion Equation: L
2
= (D
2
) in
2
n (D
1
c +D
1
c) =R(c, c
Li
,
0
, 1) for x
1
= 0
n (D
1
c +D
1
c) =R(c, |
x
2
=0
, 0, 2) for x
1
= 1
n +
C
S
r
=
C
S
r

0
for x
1
= 0
n +
C
S
r
= 0 for x
1
= 1
n D
2
= R(, c|
x
1
=1
, 0, 2)
x
2
=0
n D
2
= 0
x
2
=1
R(c
A
, c
B
, , i ) = k
f ,i

_
c
A
e
(())
_
k
b,i

_
c
B
e
(())
_
Page 15/23
Numerical implementation
Comsol Multiphysics: Some useful facts
FEM for space discretization
Various methods for time discretization
Possibility to solve coupled PDE systems (Multiphysics)
Include own code (C,C++)
Write Matlab scripts using Comsol functions
Easy to use
Example: Time dependent 2D diusion
equation
Page 15/23
Easy to use
equation
Page 15/23
Easy to use
equation
Page 15/23
Easy to use
equation
Page 16/23
Solution: Full coupled PDE system
Example computation
Battery thickness: 100nm
Distance electrode/electrolyte: 0.1nm
Page 17/23
Solution: Full coupled PDE system c
Li
Example computation
Page 17/23
Li
Example computation
Page 17/23
Li
Example computation
Page 18/23
Solution: full coupled PDE system c
S
Example computation
Page 19/23
Still (a lot of) problems...
Page 20/23
Page 21/23
Page 22/23
Conclusion
Next topics: Short term
Finish Comsol implementation
Produce examples for the Vienna ECS Meeting
Literature work on some constants
Next topics: Mid term
Switch from constant D
2
to D
2
()
Material expansion due to intercalation
Anisotropic eects
Next topics: Long term
Heterogenous Multi Scale Method on coupling boundaries
Ab inito computation of model parameters
Yet unknown ideas, suggestions ...
Page 23/23
Mathematical Modeling All Solid State Batteries Further Questions?
Questions and Discussion
i

t
(r, t) =

2
2m
2
(r, t) + V(r)(r, t)
Ab initio - The Schrodinger Equation

Modelarea A A Bateriilor

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Manuel Landstorfer

Institute of Numerical Mathematics

is the Gibbs free energy of activation.

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