VI.

Electrokinetics
Lecture 31: Electrokinetic Energy Conversion

1 Principles
1.1 General Theory
We have the following equation for the linear electrokinetic response of a nanochan
nel:
! " ! "! "
Q KP KEO P
=
I KEO KE V

The basic idea1 is to apply P and to try to harvest the streaming current I
or streaming voltage V.

1.1.1 Open-circuit Potential (Streaming Voltage)

I = KEO P + KE V
KEO
I = 0 VO = P
KE
Where KEO P is the streaming current and KE V is the Ohmic current.
1
J.F. Osterle, A unied treatment of the thermodynamics of steady state energy conversion, Appl.
Sci. Res. 12 (1964), pp. 425-434.
J.F. Osterle, Electro-kinetic energy conversion, J. Appl. Mech. 31 (1964), pp. 161-164.

The same idea was also discovered by Quincke in the 1800s.

Lecture 31: Electrokinetic energy conversion 10.626 (2011) Bazant

P = Pin Pout
VO = Vin Vout

Then

Q = KP P + KEO V
2
KEO
= KP 1 P
KP KE
= (1 )KP P

K2
Where = KPEO KE .
Pressure-driven ow is reduced by electro-osmotic back ow. Net ow is 0
when = 1, but this is not possible.

1.1.2 Second Law of Thermodynamics

Work done on system to drive motion per time (power input):

P = QP + IV >0
! "
P
= (PV)K >0
V

P must be positive since irreversible work produces heat in the system.

The conductance tensor K must be positive denite, since this inequality holds
for any P, V. So det(K) > 0 and thus < 1.
So, we cant apply pressure and get a ow in the reverse direction! (Q =
(1 )KP P).

2
Lecture 31: Electrokinetic energy conversion 10.626 (2011) Bazant

1.1.3 Streaming Current Harvesting

Consider harvesting the streaming current via two electrodes connected by a total
load resistance RL (= Rexternal + Rinternal from interfaces). Then V = IRL . Also:

I = KEO P + KE V

= KEO KE RL I

! "

KEO
= P
1 + KE RL
RL external load
Let = KE RL = RE = internal resistance . So:

KEO P
I=
1+
So, applied pressure leads to a current source via streaming current, which
ows through internal and external resistors in parallel. We have the equivalent
circuit:

Q = KP P + KEO V
K 2 RL V
= KP P EO
1+
) *
= KP P 1
! 1+ "
1 +
= KP P
1+

Lecture 31: Electrokinetic energy conversion 10.626 (2011) Bazant

Efficiency

Pout IV I 2 RL
EK = = =
Pin QP QP
+ K P ,2
EO
1+ RL
= 1+
= = EK
KP P2 1+ (1 + )(1 + )

Maximum at load resistance given by:

max = 4 for % 1
+ 2( 1 + 1 )

Also:
1
max =
1

Since < 1 and max > 1, RL > RE = K1E for optimal energy efficiency.
The same results apply to the efficiency of electro-osmotic pumping through
an external uidic resistance RP = K1P .

2 Porous Media
Porous or composite materials are useful to scale up microuidic phenomena to
macroscopic volumes and useful ow rates. We will discuss general theories of
transport in porous media later in the class. For now, we just need some basic con
cepts to facilitate our discussion of electrokinetic energy conversion, using porous
media or microchannels.
First, dene the porosity $ p as the ratio of the volume of pores to the total
volume of the system:
Pore Volume
$p =
Total Volume

4
Lecture 31: Electrokinetic energy conversion 10.626 (2011) Bazant

Figure 1: Sketch of an example pore.

Similarly we can dene a measure of the pore wall area density as:
Pore Surface Area
ap =
Total Volume
Now consider how to dene a mean pore size, h p . It is clear that
$p
hp =
hp
has the correct dimensions, lets consider the case of cylindrical pores to conrm
that it is a reasonable approximation. For cylindrical pores:

$ p = r2p L
a p = 2r p L
rp
hp =
2
so we conclude that h p is a good measure of the mean pore size. The last parameter
we will dene is the tortuosity , which measures how much longer is the mean
distance L p between two points traveling through the pores compared to the straight
line distance L between them:
Lp
=
L

3 Linear Electrokinetics: Scaling Analysis

First we will consider a simple scaling analysis of the electrokinetic behavior of a
pore as sketched in Figure 1. As discussed in the previous lecture we can relate the
ow rate Q, and current I, to the applied pressure and voltage differences P, V
through the conductance tensor K by:
! "
K p Keo
K= (1)
K sc Ke

Lecture 31: Electrokinetic energy conversion 10.626 (2011) Bazant

Additionally, from Onsagers symmetry principle we know that K must be a sym

metric matrix so K sc = Keo . In order to perform our scaling analysis we will
develop approximate expressions for each of the components of K.

3.1 Hydraulic Conductance

An estimate of the hydraulic conductance K p is given by:

h2p
Kp ! kp
Lp

where k p is given by:

h2p
kp !

plugging this in gives the scaling of K p as:

h4p
Kp ! (2)
L p

3.2 Electrical Conductance

In general a scaling estimate of Ke is given by:

h2p
Ke ! ke (3)
Lp

where ke is the electrical conductance of the material in the pore. We will consider
two limits of ke corresponding to the thin double layer, small surface charge regime
and the thick double layer, large surface charge regime.

d
3.2.1 Thin Double Layers ($ = hp << 1)

In this limit the conductance of the bulk electrolyte dominates the conductance of
the double layer giving:

De2 c0 D$
ke ! kebulk ! ! 2 (4)
kb T d

Lecture 31: Electrokinetic energy conversion 10.626 (2011) Bazant

3.2.2 Thick Double Layers

In the limit of thick double layers and large surface charge the pore is lled almost
entirely with counter ions and they dominate the electrical conductance. Since we
know that the counterions will balance out the surface charge on the pore wall we
have:
De |q s |
ke ! (5)
kb T h p
Now plugging in Equations 4 and 5 back in to Equation 3 we obtain the scaling
of the electrical conductance in each limit:
h2

D$ p
thin double layers or low charge
L p 2 ,

Ke !
De|q
d
|h
(6)

s p
, thick double layer, large charge
kb T L p

3.3 Electroosmotic Conductance

As for the electrical conductance we will estimate the electroosmotic conductance
in the limits of thin and thick double layers. First, the electroosmotic conductance
is given generally by: 1
$
Keo ! dxdy( ) (7)
L p Atyp

3.3.1 Thin Double Layers

In the limit of thin double layers = 0 over most of the area of the pore so the
integral reduces to h2p giving:
$
Keo ! h2
L p p

Since we are more interested in the case of constant surface charge than constant
zeta potential we use the relation
q s d
!
$
to obtain:
h2p
Keo ! q s d (8)
L p

Lecture 31: Electrokinetic energy conversion 10.626 (2011) Bazant

3.3.2 Thick Double Layers

For the case of thick double layers we estimate the order of magnitude of ( )
from the capacitance of the pore giving:
qs qsh p
( ) ! !
C pore $
plugging this in to Equation 7 yields:
q s h3p
Keo ! (9)
L p

3.4 Energy Conversion Efficiency

Now that we have scaling estimates for each component of K we will estimate the
maximum efficiency that can be obtained from an electrokinetic device using the
relation
K2
$max ! eo (10)
K p Ke
derived last lecture for the limit of low efficiencies. By substituting the values of
Keo , K p , and Ke from Equations 9, 8, 2, 6 we get the scaling estimate for $max in
the two limits of interest:
2 4

q s d

$Dh2p , thin double layers or low charge
$max !
(11)

|q | k T
D e h p , thick double layers, large charge
s b

It is important to note here that $max scales as 1/h2p for the thin double layer case,
and as h p in the thick double layer case. Since the thick double layer case corre
sponds to small mean pore sizes this means that the efficiency increases with pore
size in the small pore limit, but decreases with pore size for large pores. Therefore
there must be a maximum efficiency that occurs for intermediate pore sizes on the
order of d , this effect is depicted in Figure 2.
Two recent papers by van der Heyden et al have solved the full non-linear set
of equations to determine $max and performed experiments to test the theory [1, 2].
The theoretical and experimental efficiency curves are plotted in Figures 3(a), and
3(b) respectively.

References
[1] Frank H. J. van der Heyden, Douwe Jan Bonthuis, Derek Stein, Christine
Meyer, and Cees Dekker. Electrokinetic energy conversion efficiency in
nanouidic channels. Nano Letters, 6(10):22322237, October 2006.

8
Lecture 31: Electrokinetic energy conversion 10.626 (2011) Bazant

Figure 2: Scaling of the maximum efficiency with pore size

[2] Frank H. J. van der Heyden, Douwe Jan Bonthuis, Derek Stein, Christine
Meyer, and Cees Dekker. Power generation by Pressure-Driven transport of
ions in nanouidic channels. Nano Letters, 7(4):10221025, April 2007.

Lecture 31: Electrokinetic energy conversion 10.626 (2011) Bazant

h|| (nm x C/m2)

0 0.5 1 1.5
12
Li+
10

8 TAmA+ = m
20

max(%)
max(%)

K+ Na+
6 10 Li +
K+
0
4 0 0.5 1
/k+
H+
2

0
0 5 10 15 20
h/22

Image by MIT OpenCourseWare.

(a) Theoretical eciency

250

200 1.5

150 1.0
P (pW)

(%)

100 0.5

0.0
50 0 50 100

0
0 20 40 60 80 100
RL (G)

Image by MIT OpenCourseWare.

(b) Experimental eciency

Figure 3: Plots of the theoretical and experimentally observed efficiencies of elec

trokinetic energy conversion from the work of van der Heyden et al [1, 2]

10

MIT OpenCourseWare
http://ocw.mit.edu

10.626 / 10.462 Electrochemical Energy Systems

Spring 2011

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