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How to Differentiate Capacitances using Trasatti and Dunn Methods

Method · December 2018

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Differentiating
Capacitances
Tianyu Liu
Group Meeting
10/23/2015
Outline
Capacitances

Differentiation methods
Trasatti Method
Dunn Method

Examples

Conclusions
Capacitances
Capacitance vs. Capacity
Capacity (q)
The amount of charge stored C/g, mAh/g etc.
Capacitance (C)
The amount of charge stored per voltage F/g, mF/cm2 etc.

q
C
U
Potential window
Electrical Double Layer Capacitance (EDLC)
+ - -
e- + +
-
e- - -
+
-
EDL Electrode

+
e- + +
- +
e-
+
- - -
+
e-
+
- +
e- +
- -
- -
+
e- + + +

e-
+ - - -
- Bulk Electrolyte Ion Solvation
1st layer 2nd layer
Pseudo-capacitance Energy & Environmental Science 2014, 7, (5), 1597-1614

Rare ca. 12 nm Common

Pseudo-capacitance vs. Battery-like Capacity
“Pseudocapacitance arises when the extent of
reaction, Q, is some continuous function of potential, V, so that the
derivative, dQ/dV, arises that has the properties of a capacitance”
B. E. Conway, Electrochemical Capacitors: Scientific Fundamentals and Technology Applications

Battery-type Behavior

Pseudocapacitive Behaviour

Ideal Capacitive Behavior

Journal of The Electrochemical Society 2015, 162, (5), A5185-A5189
Example
α-MnO2
Pseudocapacitive Behavior

Capacitance

Journal of Power Sources 2014, 259, 219-226

Ni(OH)2 Ni(OH)2 and Co(OH)2

Battery-type Behavior

Co(OH)2
Ni(OH)2 Co(OH)2 Capacity

Journal of Power Sources 2013, 221, 128-133

Summary

Redox Insertion
EDLC
Pseudo-capacitance Pseudo-capacitance
Electrolyte Aqueous/Organic Aqueous/Organic Organic
Structure Amorphous Amorphous/Nanocrystalline Nanocrystalline
Charge Storage Electrode/Electrolyte
Electrode Surface/near-surface Bulk
Location Interface
Activated Carbon,
Typical Materials MnO2, TiN T-Nb2O5, h-WO3
Graphene

Nature Materials 2013, 12, (6), 518-522

Semi-infinite Linear Diffusion
O O
ne- Diffuse to interface
Electrode

O Charge transfer

R R
Diffuse to bulk electrolyte Electrolyte
0 +∞
Cottrell Equation (diffusion-controlled) - Current
5 3/ 2 1/ 2 * 1/ 2
i (v) (2.69 10 )n AD C v O O i (v ) 1/2
v
Semi-infinite Linear Diffusion
O O
ne- Diffuse to interface
Electrode

O Charge transfer

R R
Diffuse to bulk electrolyte Electrolyte
0 +∞
Cottrell Equation (diffusion-controlled) - Charge

i (v ) 1/2 1/2 1 1/2

v q (v) i (v)t q (v ) v v
v
Differentiation
Method
(Trasatti)
Trasatti Method - Concepts Electrochimica Acta 1990, 35, (1), 263-267

S. Trasatti, 1990 Charge stored @ “inner surface”

qT qi qo
Total voltammetric capacity Charge stored @ “outer surface”

CT Ci Co
“Outer Surface” v Just allow surface processes to happen

More accessible areas: electrode/electrolyte interfaces

“Inner Surface” v 0 Giving sufficient time to for ions to diffuse and react

Less accessible areas: near surface, loose grain boundaries, etc.

Procedures
Step #1: Collect cyclic voltammograms at various scan rates,
including very slow scan rates (e.g. 1 – 10 mV/s)
Procedures
Step #1: Collect cyclic voltammograms at various scan rates,
including very slow scan rates (e.g. 1 – 10 mV/s)
Step #2: Evaluate capacitance from each cyclic voltammogram.

U2
S
S IdU C
U1
2v U
Procedures
Step #1: Collect cyclic voltammograms at various scan rates,
including very slow scan rates (e.g. 1 – 10 mV/s)
Step #2: Evaluate capacitance from each cyclic voltammogram.

U2
S
S IdU C
U1
2v U

Step #3: Extrapolation

Determine Co
Assuming semi-infinite linear diffusion
C
Based on Cottrell Eqn.
q (v) v 1/2
When v→+∞, q→qo
const.
q (v ) qo
v Co
divide by ΔU
const.'
C (v ) Co v-1/2
v
Determine CT
Assuming semi-infinite linear diffusion 1/C
Based on Cottrell Eqn.
1/2
q (v ) v
When v→0, q→qT
1 1
const v
q (v ) qT1/CT
multiply by ΔU
1 1
const ' v v1/2
C (v ) CT
Deviation
Non-linear behavior when v is large
C C

Co 1/CT

Ohmic drop due to intrinsic resistance

v-1/2 v1/2
Example #1 Journal of Power Sources 2013, 227, 300-308

Differentiate EDLC and pseudo-capacitance

Pseudo-

CT Ci Co

EDL-
Example #1 Journal of Power Sources 2013, 227, 300-308

Differentiate EDLC and pseudo-capacitance

1/2 1
q vs. v q vs. v1/2

Pseudo-

q (C/g)

q-1 (g/C)
CT Ci Co

EDL-
EDL capacitance 1/(voltammetric capacity)
=1/(total capacitance)
Example #2
Differentiate shell capacitance with core capacitance

Core

qT , CT

Shell

qo , Co
Example #2 Nature Nanotechnology 2014, 9, (12), 1031-1039

Differentiate shell capacitance with core capacitance

Shell
Ru Core

V2O5 Shell

Total
Example #2
Differentiate shell capacitance with core capacitance

Ru Core

V2O5 Shell
Differentiation
Method
(Dunn)
Definitions Journal of Physical Chemistry C 2007, 111, (40), 14925-14931

Dunn, 2007 At a fixed potential

Capacitive current: i (v ) v i (v ) k1v

1/2
Diffusion-controlled current: i (v) v 1/2
i (v ) k2 v
(Cottrell Equation)

1/ 2
The current measured by CV: i (v ) k1v k2 v
divide by v1/2

i (v ) 1/2
1/2
k1v k2
v
Procedures
Step #1: Collect cyclic voltammograms at various scan rates,
including very slow scan rates (e.g. 1 – 10 mV/s)
Current (A)

v3
v2
v1
Ideal case 0

0 U
Potential (V vs. NHE)
Procedures
Step #1: Collect cyclic voltammograms at various scan rates,
including very slow scan rates (e.g. 1 – 10 mV/s)
Step #2: Fix a potential and read the current from different
cyclic voltammograms.
Procedures
Current (A)

v3
v2
v1
0

0 U
Potential (V vs. NHE)
Procedures
Step #1: Collect cyclic voltammograms at various scan rates,
including very slow scan rates (e.g. 1 – 10 mV/s)
Step #2: Fix a potential and read the current from different
1/2
cyclic voltammorgams. i/v
Step #3: Plot i/v1/2 vs. v1/2

i (v ) 1/ 2
1/ 2
k1v k2
v
v1/2
Procedures
Step #1: Collect cyclic voltammograms at various scan rates,
including very slow scan rates (e.g. 1 – 10 mV/s)
Step #2: Fix a potential and read the current from different
1/2
cyclic voltammorgams. i/v
Step #3: Plot i/v1/2 vs. v1/2
Step #4:
k1
i (v ) 1/ 2
1/ 2
k1v k2 k2
v
Slope y-intercept
v1/2
Procedures
Step #5: Differentiate current @ a certain scan rate
1/2
Current (A) i (v ) k1v k2 v icapacitive idiffusion
v2
idiffusion
icapacitive
0

0 U
Potential (V vs. NHE)
Procedures
Step #6: Repeat step #3 - #5 for other potentials
Current (A)

v2
idiffusion
icapacitive
0

0 U
Potential (V vs. NHE)
Procedures
I know it is tedious….

Nature Nanotechnology 2014, 9, (12), 1031-1039

Procedures
Step #6: Repeat step #3 - #5 for other potentials
Current (A)

∝v1/2 idiffusion
icapacitive
0
∝v
∝v1/2

0 U
Potential (V vs. NHE)
Procedures
Step #7: Evaluate Ccapacitive and Cdiffusion
Current (A)

∝v1/2 S
C
2v U
0
∝v
U2

∝v1/2 S i (v)dU
U1

0 U
Potential (V vs. NHE)
Example
Reality
Carbon foams with multiscale pores

2
Current Density (A/g)

-2

-4

-6
10 mV/s
-0.8 -0.6 -0.4 -0.2 0.0
Potential (V vs. Hg/HgO)
Tedious!
∝
Challenge

Current Density (A/g)

0

The boundaries! -2

-4

-6
10 mV/s
-0.8 -0.6 -0.4 -0.2 0.0
Potential (V vs. Hg/HgO)
Challenge
10 mV/s
20 mV/s
40 mV/s
40 60 mV/s
80 mV/s
100 mV/s
20

Current Density (A/g)

The boundaries! 0

-20

-40

-60
-0.8 -0.6 -0.4 -0.2 0.0
Potential (V vs. Hg/HgO)
Crux #1
Deal with boundaries

2
Current Density (A/g)

-2

-4

-6
10 mV/s
-0.8 -0.6 -0.4 -0.2 0.0
Potential (V vs. Hg/HgO)
Crux #1
Crux #1

Current Density (A/g)

0 89%

-2

-4

-6
10 mV/s
-0.8 -0.6 -0.4 -0.2 0.0
Potential (V vs. Hg/HgO)
Crux #2
Point connection
Crux #2
Crux #2

Spline
Crux #2

Fill Area Under Curve

Crux #2
“Plot + Line” “Line”
4 4

2 2
Current Density (A/g)

Current Density (A/g)

0 0

-2 -2

-4 -4

-6 -6
10 mV/s 10 mV/s
-0.8 -0.6 -0.4 -0.2 0.0 -0.8 -0.6 -0.4 -0.2 0.0
Potential (V vs. Hg/HgO) Potential (V vs. Hg/HgO)
 Crux #2

2
Current Density (A/g)

0 89%
Not diffusion controlled
-2
𝑁𝑜𝑡 𝐷𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝐶𝑜𝑡𝑟𝑜𝑙𝑙𝑒𝑑%
-4

-6
336.09
10 mV/s = × 100% = 88%
336.09 + 44.13
-0.8 -0.6 -0.4 -0.2 0.0
Potential (V vs. Hg/HgO)
Limitation of Dunn’s method
Peak shift
Conclusions
Conclusions
To differentiate capacitances:
const '
q (v ) qo Outer-surface Charge
Trasatti v
1 1
const ' v Total Voltammetric Charge
Charge q (v ) qT
q (v ) C (v )

1/ 2 Diffusion-controlled Current
Dunn i (v ) k1v k2 v
Capacitive Current
U2
Current 1
C i (v)dU
2v U U1
References
[1] Ardizzone, S. et al., “Inner” and “outer” active surface of RuO2
electrodes. Electrochimica Acta 1990, 35, (1), 263-267.
[2] Wang, J. et al., Pseudocapacitive Contributions to Electrochemical Energy
Storage in TiO2 (Anatase) Nanoparticles. Journal of Physical Chemistry C 2007,
111, (40), 14925-14931.

[3] Duay, J. et al., Self-Limiting Electrodeposition of Hierarchical MnO2 and

M(OH)2/MnO2 Nanofibril/Nanowires: Mechanism and Supercapacitor Properties.
ACS Nano 2013, 7, (2), 1200-1214.

[4] Augustyn, V. et al., High-rate electrochemical energy storage through Li+

intercalation pseudocapacitance. Nature Materials 2013, 12, (6), 518-522.
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