Previously on Electrochemistry

φ
Ox ( aq )

ne − ( M )

Red ( aq )
M
φ φ(x )

aq
φ

M RT  ared 
M o
∆ φ=∆ φ −
aq ln 
aq  1
nF  aox 
The Electrochemical Double
Layer
The metal|electrolyte junction

The Helmholtz layer model

The Gouy-Chapman model

The Stern Model

2
6.1 The metal|electrolyte junction

IHP OHP
Solvated Anion

-
Inner Helmholtz plane (IHP) – solvent

- molecules and “specifically adsorbed” ions
+
Charged surface
σsurf > 0

- + -
Outer Helmholtz plane (OHP) – plane of

closest approach of solvated ions.
- -
-
Helmholtz layer – demarcated by OHP
+
-
-
Diffuse layer – excess charge ≠ 0
DL

diffuse layer

3
Fig. 6.1 Molecular dynamics illustration of the double layer in the presence of 3 M NaCl
solution. The charge on the electrode is –1mC cm–2 [Girault 2005].
4
5.2 The Helmholtz layer model

Surface charge compensated by a “fixed” sheet of ions at the outer Helmholtz plane.

Helmholtz layer: parallel plate capacitor
εε r
dH
+ -
+ -

dH

Potential drop across the Helmholtz layer (∆φH)

σ dH
∆φH = eqn. 6.1
εε r

Helmholtz capacitance (CH)

Fig. 6.2 Schematic representation εε r

of the Helmholtz layer model [Atkins CH = eqn. 6.2
dH
2002].
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5.3 The Gouy-Chapman Model

Surface charge counterbalanced by a dynamic ionic atmosphere – diffuse layer

Ions: non-interacting punctual charges
φ
IHP σdiff = - σM
potential
distribution
-
-
+ -
σsurf > 0

- x
- +
+ -  zF 
-
 RT
( )
ci ( x ) = ci ( aq ) exp  − i φ ( x ) − φ aq 

-
eqn. 6.3
- + +
Bulk concentration

6

Potential drop across the diffuse layer: determined by the Debye Length (1/κ)

2000F 2 1
2
κ =
εε r RT
Ic eqn. 2.15 Ic – Ionic strength Ic = ∑ ii
2 i
c z 2
eqn. 2.16

Potential drop across the diffuse layer

φ ( x ) = ∆ Maqφ exp ( −κ x ) eqn. 6.6

∆ Maqφ = 100mV 1:1 electrolyte

φ (x) / mV

7
x / nm
Concentration profile of ions across the diffuse layer:

∆ Maqφ = 100mV Fig. 6.7 Ionic concentration

profile as derived from the
Boltzmann distribution
[Girault 2005].

ci (aq ) = 0.1moldm-3

Capacitance of the diffuse (Gouy-Chapman) layer (CGC):

dσ M 2000ci ( aq ) εε r F 2  F ∆ Maqφ 
CGC = = cosh   eqn. 6.7
( M
d ∆ aqφ ) kBT  2RT 
8

CGC: parabola shape - minimum is the potential of zero charge (pzc).

Epzc: metal and diffuse layer charge is zero.

Fig. 6.8 Differential capacitance of

a mercury electrode in a KF
solution (pzc = –0.433V) and the
corresponding Gouy-Chapman
capacitance (eqn. 6.7) [Girault
2005].

Potential of zero charge (Epzc).

σdiff = σsurf = 0
9
6.4 The Stern model

Series combination of the Helmontz and diffuse layers

Fig. 6.9 Schematic representation of the Stern model of

the double layer [Atkins 2002].

1 1 1
= + eqn. 6.8
Ctot CH CGC

Smallest capacitance dominates the total

capacitance (Ctot).

CH CGC
10
Stern model: as the concentration of the electrolyte increases:
The thickness of the diffuse layer decreases
The Gouy-Chapman capacitance increases
The total capacitance is determined by CH

Helmholtz
layer
150

Diffuse layer
100 Fig. 6.10 Potential distribution across
the double layer as predicted by the
φ / mV

1:1 electrolyte the Stern model.

0.010
0.025
50 0.100 mol dm-3

0
0 OHP
4 8 12 11
x / nm

Large σsurf and ci: Ctot ≈ CH

Low ci and E ~ Epzc : Ctot ≈ Cd

Fig. 6.11 Comparison of the experimental and calculated capacitance using eqn. 6.8
for a mercury electrode in a 0.001M KF solution. CH is obtained from the experimental
12
curves in 1M solution of KF (Fig. 6.8) [Girault 2005].
6.5 Supercapacitors

Energy storage systems

Large surface area (porous) carbon electrodes
1 1 1
= + eqn. 14
Ctot Ca Cc

1
Energy = QV 2 eqn. 15
- - - - - - Cc 2
-
+ + + + + + +

- - - - - - -
Carbon and metals: CH ~ 10 to 40 µF cm-2

+ + +
+ ++ + Ca
High surface area C electrodes: 4 F g-1

Research oriented towards new materials and
electrolytes

Block-copolymers and colloids as templates for
highly corrugated carbon electrodes

13

Supercapacitors and fuel cells: key for automobile industry

Ragone plot
Aligned carbon nanotubes

specific power / W kg-1

Riccardo Signorelli/MIT
specific energy / Wh kg-1

Winter and Brod, Chem. Rev., 104 (2004) 4245

14
 Summary
Charged surfaces generates an interfacial excess of ionic species – double layer

Helmholtz layer: “fixed” solvated ions at the outer Helmholtz plane

Diffuse layer: distributed excess charge in a dynamic ionic atmosphere

Diffuse layer thickness: affected by surface charge and electrolyte concentration

Colloidal systems: stabilisation linked to overlapping diffuse layers

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 Giants of the day

Hermann Ludwig Ferdinand von Helmholtz Ludwig Eduard Boltzmann

German Physicist/Chemist/Philosopher Austrian Physicist
1821 - 1894 1844 - 1906

16
 Giants of the day

Louis Georges Gouy David Leonard Chapman Otto Stern

French Physicist English Physicist German Physicist
1854 - 1926 1869 - 1958 1888 - 1969

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