See discussions, stats, and author profiles for this publication at: [Link]
net/publication/330238104
Coulombic Efficiency, Energy Efficiency and Effective Capacitance
Method · January 2019
CITATIONS READS
0 845
1 author:
Tianyu Liu
John Wiley And Sons - Shanghai China
212 PUBLICATIONS 5,417 CITATIONS
SEE PROFILE
Some of the authors of this publication are also working on these related projects:
energy storage View project
Methods, Concepts and Technical Notes View project
All content following this page was uploaded by Tianyu Liu on 09 January 2019.
The user has requested enhancement of the downloaded file.
Tianyu Liu, 2019
Coulombic Efficiency, Energy Efficiency and Effective Capacitance
❑ Tianyu Liu
◼ Two Typical Constant-Current Charge-Discharge Profiles
Below are two typical galvanostatic (constant-current) charge-discharge profiles observed for
electrochemical capacitors:
Figure 1
Ideally capacitive (e.g., pure electrical double layer capacitive) electrodes and devices usually
exhibit profile (a), while non-optimal potential windows involving electrolyte decomposition or
some pseudocapacitive electrodes and devices display profile (b). Coulombic efficiency and energy
efficiency are identical for profile (a) but are different for profile (b). See below for more details.
◼ Coulombic Efficiency (CE)
The definition of CE of a supercapacitor is “the ratio between the charge removed from a
supercapacitor compared with the charge used to restore the original capacity”. The word
“supercapacitor” in this definition can be replaced by “battery” when defining the CE of batteries. A
mathematical expression of CE is:
Qoutput
CE = (1)
Qinput
where Q represents the amount of charge, or capacity. For constant-current charge and discharge
operations, Q=It in equation 1 and Equation (1) is converted to Equation (2):
Qoutput I dischargetdischarge
CE = = (2)
Qinput I chargetcharge
where I and t represent current and time, respectively. In this case, Idischarge=Icharge due to
“constant-current”, thus
Qoutput I dischargetdischarge tdischarge
CE = = = (3)
Qinput I chargetcharge tcharge
-1-
Tianyu Liu, 2019
Equation (3) is derived directly from the definition of CE and involves no assumptions on what a
charge-discharge profile looks like, it should be a general conclusion [i.e., applicable to both
situation (a) and (b)]. It means that if the charge time and discharge time in both situations are the
same (Figure 2), the CE of both profiles should equal to 100%. However, it seems counter-intuitive
that the “efficiency” of profile (b) is lower than that of profile (a). To address this issue, we need to
introduce a new parameter called “energy efficiency”.
Figure 2
◼ Energy Efficiency (EE)
EE is analogous to CE. It is defined as “the ratio between the energy generated from a
supercapacitor compared with the energy used to restore the original energy”, or mathematically:
Eoutput
EE = (4)
Einput
For constant-current charge and discharge, the energy is expressed as:
Q2 ( It )2 t2
E = UdQ = Ud ( It ) =I Udt =IA (5)
Q1 ( It )1 t1
where I is the charge or discharge current, which is a constant. A is the area enclosed by charge or
discharge profile and the time-axis (x-axis) or, integral area. Substitute equation (5) into equation
(4):
I discharge Adischarge Adischarge
EE = = (6)
I charge Acharge Acharge
Let’s revisit Figure 2. Based on Equation (6), since area A equals to area B, and area D is smaller
than area C, the EEs of profiles (a) and (b) are 100% and <100%, respectively. The EE of an ideal
supercapacitor should be 100%.
◼ Effective capacitance
-2-
Tianyu Liu, 2019
Following the previous discussion, “effective capacitance” can be defined. One way to calculate
capacitance based on the area of the discharge profile is:
1
E = Ceff ( U ) (7)
2
2
where ∆U is potential window. Combine Equation (5) and (7), the effective capacitance (Ceff) is:
t2
2I
( U ) t
Ceff = 2
Udt (8)
1
When a supercapacitor behaves ideally, i.e., U changes linearly with time
t2
1
Udt = 2 t
t1
discharge U (9)
Substitute Equation (9) in Equation (8):
2I 1 I tdischarge
Ceff = tdischarge U = (10)
( U ) U
2
2
Equation (10) is the conventional equation used to calculate capacitance for both EDLC and
pseudo-capacitance. We demonstrate that Equation (10) only applies to when U is linear with time
for capacitance calculations. In other words, Equation (10) is a specific case of Equation (9), and
Equation (9) is general.
The relationship between Ceff and C [capacitances evaluated using Equation (10)] depends on the
shape of the discharge profile.
Curve 1 (convex shape): Ceff > C
Curve 2 (straight line): Ceff = C
Curve 3 (concave shape): Ceff < C
Figure 3
Reference
Yang, P.; Mai, W., Flexible solid-state electrochemical supercapacitors. Nano Energy 2014, 8,
274-290.
-3-
View publication stats
