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journal homepage: www.elsevier.com/locate/apsusc

in aqueous electrolyte: Insights from standard models

Md. Shihab Uddin a , Himadri Tanaya Das a , Thandavarayan Maiyalagan b ,

Perumal Elumalai a,∗

a

Electrochemical Energy and Sensors Lab, Department of Green Energy Technology, Madanjeet School of Green Energy Technologies, Pondicherry

University, Puducherry 605014, India

b

SRM Research Institute & Department of Chemistry, SRM University, Kattankulathur, Chennai 603203, India

a r t i c l e i n f o a b s t r a c t

Article history: Standard models, Helmholtz, Gouy-Chapman, Stern and Grahame models have been validated on the

Received 26 October 2017 electrical double layers (EDLs) formed from three different electrode surfaces, i.e., plain, semi-sphere

Received in revised form and cylindrical pore in aqueous electrolyte. The double layer potential () and areal capacitance (Cdl )

24 November 2017

were estimated in the three models using MATLAB Simulink. It was found that the areal capacitance

Accepted 11 December 2017

Available online 13 December 2017

of the double layer strongly inﬂuenced by the nature/ type of the electrode surface in contact with the

electrolyte. The cylindrical-type pore surface exhibited the large areal capacitance. The charge-discharge

and impedance characteristics of the EDLs were also analyzed.

Keywords:

Supercapacitor © 2017 Elsevier B.V. All rights reserved.

Electrical double layer

Helmholtz

Gouy-Chapman

Stern

Grahame models

Electrochemical Impedance

charge separation at electrode/electrolyte interface. The electrodes

Batteries and supercapacitors are typical electrochemical for the EDLCs are typically made of high surface area carbon-based

energy storage devices. Among them, the batteries have the capa- materials because of their porous nature. Aqueous electrolytes are

bility to deliver energy over a long time at a relatively lower rate generally employed as an electrolyte in EDLC, where water dipole

of current (low power). The batteries fail to deliver high power acts as a dielectric material to provide high relative permittiv-

because, at high power discharge, the lifetime of the battery reduces ity. The presence of water dipole in the electrolyte signiﬁcantly

drastically due to degradation of electrode material and diffusion reduces the distance between the two electrodes, to the order of

limitation of ions involved in the electrochemical reactions. Thus, angstrom (Å). Because of aforesaid aspects, the EDLC having high

current trends in the electrochemical energy storage technology capacity is different from the conventional parallel plate capaci-

focus on the development of storage device that can deliver high tor whose capacity is directly proportional to relative permittivity

power as well as high energy. In this regard, supercapacitors seem () and surface area (A), but inversely proportional to the distance

attractive storage device that can deliver high power for the large between the two electrodes [1]. Modeling and simulations provide

cycle of as high as 105 cycles. In fact, the supercapacitors can bridge insights about designing novel materials for developing efﬁcient

the power gap between the batteries and conventional capacitors, device by reducing manufacturing cost as well as technical losses.

especially for hybrid electric vehicles and electrical tools. Unfortu- Recently, Bang et al., has studied optical pore development of car-

nately, the supercapacitors have severe issues such as low energy bon models [2]. Similarly, Lu et al., has reported the porous carbon

density, high cost and high self-discharge. By addressing these as high ion transport channel for electrode materials in superca-

issues, the market demand for the supercapacitors can be real- pacitor [3]. Thus, to develop highly performing EDLC electrode for

energy storage device, a proper understanding of electrical double

layer (EDL) formed by different electrode surface in an electrolyte

∗ Corresponding Author. is indispensable.

E-mail addresses: drperumalelumalai@gmail.com, Wang et al., presented scaling law for the estimation of the

elumalai.get@pondiuni.edu.in (P. Elumalai). integral capacitance of EDLC supported by rigorous analysis and

https://doi.org/10.1016/j.apsusc.2017.12.088

0169-4332/© 2017 Elsevier B.V. All rights reserved.

446 Md.S. Uddin et al. / Applied Surface Science 449 (2018) 445–453

ions of the solution [13,14]. A uniform dipole distribution is present

at the interface where potential varies linearly from the electrode

surface to the bulk solution as schematically shown in Fig. 2(a).

However, Helmholtz model did not account for the inﬂuence of

thermal motion and ion absorption on the resultant double layer

capacitance (Cdl ). Gouy-Chapman described the EDL by considering

the thermal motion of ions near the charged surface and is driven

by diffusion and electrostatic forces, in particular at low concentra-

tion of electrolyte [15,16]. However, this model did not account for

the inﬂuence of ion absorption on the electrode/ electrolyte inter-

face. According to the Gouy-Chapman model, the double layer is

not rigid at the electrode/ electrolyte interface; rather there is ion

concentration gradient from electrode surface to the bulk solution

due to thermal motion of ions as schematically shown as in Fig. 2(b).

The Stern model recommends a combination of the concepts

of the Helmholtz and Gouy-Chapman models [17]. According to

the Stern model, the electrical potential varies linearly with the

distance from electrode surface up to Gouy-Chapman layer (rigid

layer) and after that decreases exponentially (i.e., diffused layer)

as schematically shown in Fig. 2(c). So, as per the Stern model, the

Fig. 1. Schematics of cross section of (a) Planar Surface, (b) Cylindrical pore surface, capacitance is regarded as two series connected capacitors as given

(c) Semi-sphere pore surface and (d) Front view of pore surfaces. in (Eq. 1):

1 1 1

experimental data on porous carbon-based electrodes [4]. Gav- = + (1)

C dl CH C GC

ish et al., examined the inﬂuence of relative permittivity on the

EDLC properties by changing electrolyte concentration [5]. It was where, Cdl , CH , and CGC are double layer, Helmholtz and Gouy-

reported that higher concentration having less number of dipoles Chapman capacitances, respectively [14].

in the solution resulted in low capacitance, whereas lower concen- The currently accepted Grahame model represents the real sit-

tration reduced the capacitance because ions extend to a longer uation of an EDL. Grahame introduced concepts of inner Helmholtz

distance from electrode surface due to thermal motion [6–9]. plane (IHP) where ion absorption occurs on the electrode surface

Ohshima et al., described a simple algorithm for the potential and outer Helmholtz plane (OHP). As shown in the Fig. 2(d), the

distribution in EDLC cylindrical pore surface [10]. He considered anions are tightly attached to the electrode surface and partially

Poisson-Boltzman equation to describe potential distribution in a desolated. This fact causes a reversal of electrostatic potential in

charged cylindrical pore ﬁlled with an aqueous electrolyte solu- the region between the IHP and OHP. The capacitance as per the

tion. Martin et al., estimated capacitance of EDLC based on carbon Grahame model is shown below [14]:

nanotube (CNT) using classical theory [11]. The curvature effect

on Gouy-Chapman limit has been established. Shuai Bana et al., 1 1 1 1 dqa

= +( + )(1 − ) (2)

worked on the electrochemical equivalent circuit (Randle circuit) Cdl CIHP COHP CGC dqM

to analyze the charging-discharging properties of the EDLC [12].

To the best of our knowledge, the inﬂuence of different types where qa and qM are absorption charge and metal surface charge,

of electrode surfaces on the capacitance of EDLC has not been well respectively.

examined. Thus, in this work, we re-visited the EDLC characteris-

tics of electrode surfaces having different types/ shapes of pores

(plain, semi-sphere and cylindrical) as shown in Fig. 1 by applying 3. Analysis

Helmholtz, Gouy-Chapman, Stern and Grahame models in aqueous

electrolyte. Alongside, we have also studied electrochemical charg- In this work, we have modeled EDLC for three different elec-

ing/discharging and impedance features of the aforesaid model trode surfaces namely plain layer, semi-sphere and cylindrical in

surfaces in aqueous electrolyte. the aqueous electrolyte. The schematic of three different surfaces

and the cross-section of the semi-sphere/ cylindrical surface are

shown in Fig. 1. The areal capacitances of the EDL resulted on

2. Various models for electrical double layer the three electrode surfaces were estimated based on Helmholtz,

Gouy-Chapman, Stern and Grahame models. We have assumed the

A metal in contact with an aqueous solution generates solvated surface potential of 0.5 V and uniform dipole distribution. To calcu-

charged ions on its surface, where positive and negative ions are late the potential change, in the parallel plane layer, linear Gauss

equally distributed throughout the surface. The free electrons will law equation has been applied and similarly in the bulk solution,

move away from or towards the interface depending on the direc- Poisson-Boltzmann equation has been applied. In addition, charg-

tion of the electric (E) ﬁeld. Thus, a net charge is induced on the ing/ discharging and impedance characteristics of the EDLC have

metal, which will be equal in magnitude and opposite in sign to that been also examined.

on the solution side of the phase boundary. Therefore, charge sepa-

ration occurs in the electrode surface/ solution interface known as

an interfacial potential difference (). The properties of such elec- 3.1. Helmholtz capacitance of model surfaces

triﬁed interface have been explained by Helmholtz (compact layer),

Gouy-Chapman (diffuse layer), Stern and Grahame models. According to Helmholtz, the electric double layer is the align-

As per Helmholtz model, two compact layers of charges are ment of charge on the electrode and electrolyte interface similar to

formed at the electrode/ electrolyte interface as a result of elec- parallel plate capacitor. Gauss law states that the surface integral of

Md.S. Uddin et al. / Applied Surface Science 449 (2018) 445–453 447

Fig. 2. Schematics of (a) Helmholtz, (b) Gouy-Chapman, (c) Stern and (d) Grahame model for the EDL.

the electric ﬁeld in any closed surface is equal to the enclosed charge where is ionic charge density and (x) is the electric potential

with the multiplication of inverse permittivity as shown below: at distance x [19]. The Boltzmann distribution gives the position of

a particle in a system over the various possible states. In the bulk

Qenclose

E · dA = = Q · 0 −1 solution, the Boltzmann equation for ions can be written as Eq. (7):

0 zi qϕ(x) zi qϕ(x)

ni = n∞

i

e(− kB T

)

= C∞ NA e(− kB T

)

(∵ n∞

i

= C ∞ NA ) (7)

where E is the electric ﬁeld, Qenclose is total enclose charge and

0 is free space permittivity, respectively [18]. So, the potential where zi , q, T, kB , C∞ and NA are the valence of ionic species i, unit

difference () between the two rigid layers at distance x is charge (q = 1.6 × 10−19 C), temperature (T = 20 ◦ C) and Boltzmann

constant (kB = 1.63 × 10-23 m2 kg K-1 s-2 ), molar concentration of

Q

ϕ (x) = ϕ0 − xH (4) solution and Avogadro number, respectively [18]. So, the resultant

Aεr ε0 Poisson – Boltzmann equation is,

where 0 is the electric potential at xH = 0, A is area, xH is the z i qn∞

d 2 ϕ(x) z qϕ(x)

− i

thickness of Helmholtz layer and r is the relative permittivity of =− i

e kB T (8)

dx 2 ε0 εr

the electrolyte. The ﬁrst derivative of the potential with respect i

∂ϕ

to charge ( ) will give inverse capacitance (1/CH ). Therefore, the

∂Q For binary solute of unit charge (z1 = z2 = z) and same con-

Helmholtz model capacitance per unit area for the EDLC formed

centration of positive and negative ions (C∞- = C∞+ = C∞ ), the

from three different electrode surfaces derived from Eq. (4) are:

Poisson-Boltzmann Eq. (8) can be rewritten as

⎧εε

⎪

⎪

r 0

for plain surface (5a) d 2 ϕ(x)

zqϕ(x)

⎪

⎪ xH =−

zqC ∞ N A −

zqϕ(x)

−e

⎪

⎨ εr ε0 dx2 ε0 εr

(e kB T kB T ) (9)

r2

CH = 1+ for semi-spherical pore surface (5b)

xH A Or

⎪

⎪

⎪

⎪

zqϕ(x)

⎪

⎩ εr ε0 1 + 2Lr for cylindrical pore surface (5c) d 2 ϕ(x) 2zqC ∞ N A

xH A =− sinh (10)

dx2 ε0 εr kB T

where r is pore radius and L is the length of the cylindrical pore. Multiplying 2

dϕ(x)

on the both sides of Eq. (10) yields Eq. (11).

dx

zqϕ

(x)

2 =− 2 sinh (11)

dx dx2 ε0 εr dx kB T

The electric potential due to charge distribution in any medium

is given by the Poisson equation shown below: The Eq. (11) can be rearranged as

dϕ(x) 2

d 2 ϕ(x) d( dx

) 2qzC ∞ N A zqϕ(x)

=− (6) dx = − sinh( )dϕ(x) (12)

dx2 ε0 εr dx ε0 εr kB T

448 Md.S. Uddin et al. / Applied Surface Science 449 (2018) 445–453

Fig. 3. (a) Charging equivalent circuit of EDLC, (b) Discharging equivalent circuit of EDLC, (c) Electrochemical equivalent (Randle) circuit, (d) Impedance diagram of Randle

circuit excluding Warburg coefﬁcient and (e) Impedance diagram of Randle circuit including Warburg Coefﬁcient.

The surface charge density ( ) is the change of potential with

∂x

13b) respect to distance in any arbitrary medium as shown below:

At x = 0, ϕ (x) = ϕ (0) (13a) dϕ(x)

(x) = εo εr (17)

dϕ(x) dx

At x = ∞, ϕ (x) → 0, =0 (13b)

dx Thus, the capacitance is given by:

the solution for Eq. (12) is, d

zqϕ(x)

CGC =

dϕ

(18)

dϕ(x) 8C ∞ N A kB T

= sinh (14)

dx ε0 εr 2kB T So, the Gouy-Chapman capacitance for the electric double layer

is,

dϕ 8C ∞ N A kB T

= dx (15) 2z 2 q2 C ∞ N A ε0 εr zqϕ(x)

zqϕ ε0 εr C GC = cosh( ) (19)

sinh 2kB T kB T 2kB T

The solution for Eq. (15) is It is noted that the Gouy-Chapman capacitance is independent

⎧ of the surface area of the electrode; the change in capacitance for

⎪

⎪ 2C ∞ NA

⎪

⎪ (qzx ) three surfaces are almost negligible.

⎪

⎨ ϕ(0)e ε0 εr kB T

; where

zqϕ(x) zqϕ(0)

, ( →= )0 (16a)

ϕ(x) = 4kB T 4kB T 3.3. Stern model capacitance for model surfaces

⎪

⎪ 2C ∞ NA

⎪

⎪ 4kB T (qzx )

⎪

⎩ −1

tanh (e

ε0 εr kB T

tanh(

zqϕ(0)

)); Otherwise (16b) The Stern model is a combination of both Helmholtz and Gouy-

zq 4kB T Chapman models. So, the Stern model capacitances for the EDLC

formed in the three different surfaces are:

⎧

⎪

⎪

⎪

⎪ 1 1

⎪

⎪ εr ε0 + 2 2 for planar surface (20a)

⎪

⎪

⎪

⎪ 2z q C∞ A 0 εr

N ε zqϕ(x)

⎪

⎪

xH cosh( )

⎪

⎨

kB T 2kB T

1 1 1

= + for Semi-spherical pore surface (20b)

Cdl ⎪ εr ε0 r 2 2z 2 q2 C∞ NA ε0 εr

⎪

⎪ (1 + ) zqϕ(x)

⎪

⎪ xH A cosh( )

⎪

⎪

kB T 2kB T

⎪

⎪ 1 1

⎪

⎪ + for cylindrical pore surface (20c)

⎪

⎪ εr ε0 2Lr

2z 2 q2 C∞ NA ε0 εr

⎩ x (1 + A ) cosh(

zqϕ(x)

)

H kB T 2kB T

the electrode surface. He divided the electric double layer into

three-parts; the ﬁrst layer is electrode surface to IHP, second layer

Md.S. Uddin et al. / Applied Surface Science 449 (2018) 445–453 449

is IHP to outer Helmholtz OHP and third layer is OHP to bulk multiplying 1/Cdl Rs in both sides gives Eq. 26,

solution (Fig. 2(d)). The electric ﬁeld (E) due to Coloumbic attrac-

dV c Rp + Rs Vs

tion/repulsion of unit charge on the dipole separated by a distance +( )V c = (26)

dt C dl R p R s C dl R s

x [20] is given below:

q The Eq. (26) is the ﬁrst order partial differential equation and

E= (21) boundary conditions are:

4ε0 εr x2

The potential at three different layers, i.e., surface to inner att = 0, Vc = 0 (27a)

Helmholtz plane is:

att = ∞, Vc = Vs (27b)

q

ϕ (x) = ϕ0 − (22) So, the solution for the ﬁrst order differential Eq. (26) is

4ε0 εr xIHP

R p +R s

where 4ε εqr x deﬁne the potential drop due to ion adsorption. V c (t) = V s [1 − e− C dl R p R s

t

] (28)

0 IHP

On the other hand, the potential at the inner Helmholtz plane Thus, the Eq. (28) gives the charging voltage for the EDLC.

to the outer Helmholtz plane is same as Helmholtz potential (Eq.

4). The potential variation from Outer Helmholtz plane to the bulk

3.5.2. Discharging

solution is similar to Gouy-Chapman potential (Eq. 6).

∂ϕ The Kirchhoff current law at node ‘a’ of Fig. 3(b) [22] is,

The ﬁrst derivative ( ) of Eq. (22) give the inverse capacitance

∂Q

which is similar to that of Helmholtz model. As a result, the capac- dV c Vc Vc

C dl + + =0 (29)

itance variation as per the Grahame model is almost similar that dt Rp Rs + RL

of the Stern model, when the ion absorption at electrode surface is

Re-arranging the Eq. (29)

negligible. In the case of high ion absorption, the electrode would

lose the EDLC property and behave as an ideal Pseudocapacitor. dV c Rp + Rs + RL

So, the areal capacitance for the three electrode surfaces accord- + Vc = 0 ((30))

dt C dl R p (R s + R L )

ing to Eq. (5) is written as:

⎧ ⎛ ⎞

⎪

⎪

⎪

⎪ ⎜ 1 ⎟

⎪

⎪ 1 1 ⎟ 1 − dqa

⎪

⎪ +⎜ ε ε + (23a)

⎪ ε ε ⎝

⎠ dqM

⎪

⎪

r 0 r 0

2z 2 q2 C∞ NA ε0 εr zqϕ(x)

⎪

⎪ xIHP xOHP cosh

⎪

⎪ ⎛ kB T 2kB T ⎞

⎪

⎪

⎪

⎪

⎨ 1 ⎜ 1 1 ⎟

1

= +⎜ + ⎟ 1 − dqa (23b)

Cdl ⎪ r 2 ⎝ εr ε0 r 2 zqϕ

⎠ dqM

⎪

⎪

εr ε0

1+ 1+ 2z 2 q2 C∞ NA ε0 εr (x)

⎪

⎪ x A x A cosh

⎪

⎪

IHP

⎛ OHP kB T 2kB T ⎞

⎪

⎪

⎪

⎪

⎪

⎪ ⎜ ⎟

⎪

⎪

1

+ ⎜

1

+

1 ⎟ 1 − dqa

⎪

⎪ εr ε0 2Lr ⎝ εr ε0 2Lr zqϕ(x)

⎠ dqM

(23c)

⎪

⎪ 2z 2 q2 C∞ NA ε0 εr

⎩ xIHP 1 + A xOHP

1+

A cosh

kB T 2kB T

semi-spherical pore surface and cylindrical pore surface, respec-

tively.

Initial conditions:

att = ∞, Vc = 0 (31b)

3.5.1. Charging

For electrostatic capacitors, the current and voltage are related So, the solution

as given below:

for the Eq.

(30) is:

R p +R s +R L

V dc (t) = V s e− C dl (R s +R L )R p

t

(32)

dV c

iC = C dl (24)

dt Thus, Eq. (32) gives the discharging voltage of EDLC.

where Cdl is the double layer capacitance, Vc is the potential across

the capacitor and iC is the capacitor current [21]. 3.6. Electrochemical impedance characteristics of EDLC

The Kirchhoff Voltage law for the closed loop as shown in

Fig. 3(a) can be written as Eq. (25a) [22,23]. The Randle circuit for the EDLC can be best described as shown in

Fig. 3(c–e), where Rs is solution resistance, Cdl is double layer capac-

Vc dV c itance and W is Warburg element. The Randles circuit consists of

Vc + + C dl Rs = V s (25a)

Rp dt an active electrolyte resistance (RS ) in series with the parallel com-

bination of the double-layer capacitance (Cdl ) and an impedance of

where Vs is the supply voltage. Re-arranging this Eq. (25a), we get Faradic reaction in series with Warburg element [24–26]. Solution

Eq. (25b) resistance is often a signiﬁcant factor in the impedance of an elec-

trochemical cell. The resistance of an ionic solution is a function of

Vc Rs dVc

Vc + + Cdl Rs = Vs (25b) ionic concentration, type of ions, temperature, and the geometry of

Rp dt

the area of the electrochemical cell.

450 Md.S. Uddin et al. / Applied Surface Science 449 (2018) 445–453

3.6.1. Randle circuit excluding Warburg element The R and F are gas constant (R = 8.13 J K−1 mole−1 ) and Faradic

If re-drawn the Randle circuit with respect to impedance where, constant (F = 96500 C), respectively, whereas Do , and Dr are oxidant

1

Z1 = Rs , Z2 = jωC , Z3 = Rp and is the angular velocity, the equiv- and reductant diffusion coefﬁcients.

dl

alent impedance of the circuit shown in Fig. 3(d) is

Z 2 *Z 3 4. Results and discussions

Z eq = Z 1 + = Z re + jZ im (33)

Z2 + Z3

The variation of double layer potential and areal capacitance for

where real impedance three different electrode surfaces were estimated using MATLAB

Rp R2009a software on aforementioned models. The surface of double

Zre = Rs +
2 layer depends on the concentration of medium in which the double

1 + ωCdl Rp layer forms. Higher the concentration longer the length of the dou-

ble layer formed and vice-versa. For the bulk solution, the extent

and imaginary impedance,

of diffusion length can be calculated by using Debye length (xD ),

ωCdl Rp2 shown in Eq. (37).

Zim =
2

1 + ωCdl Rp r 0 kB T

xD = (37)

2q2 NA C∞

3.6.2. Randle circuit including Warburg element where r, 0 B, T, q, NA , C∞ are relative permitivity, Boltzmann con-

If re-drawn the Randle circuit with respect to impedance where, stant, temperature, charge, avogadro number and concentration,

1

Z1 = Rs , Z2 = jωC , Z3 = Rp , Z4 = √

Aw

= √ Aw ; so the equivalent respectively. So, in all the cases the distance from the electrode

dl jω ej90 ω

impedance of the circuit (Fig. 3(e)) is given by: to the solution was kept constant at 20 nm. The capacitance was

estimated using 1 M aqueous electrolyte of relative permittivity r

Z 2 *Z 5 = 78.5, temperature T = 20 ◦ C, valence z = 1 and electrode surface

Z eq = Z 1 + = Z re + jZ im (34)

Z2 + Z5 potential (0) = 0.5 V. In case of concentrated electrolyte, more

1 Aw number of ions will be present in the solution. These ions require

Z re = R s + (R p + √ ) (35) high potential to accumulate/ integrate on the electrode-electrolyte

K ω2 C 2dl 2ω

interface. Thus, for all models, standard potential difference of 0.5 V

2 1

1 Aw Aw Aw was assumed for comparison.

Z im = Rp + √ +√ +√ (36)

K ωC dl 2ω 2ω ωC dl 2ω

4.1. Variation of potential on the model surfaces

where Aw is the Warburg coefﬁcient.

2

2

√Aw 1 √Aw

Fig. 4(a) shows the variation of double layer potential with the

and, K = Rp + + ωCdl

+

2ω 2ω distance from the electrode surface to the bulk solution estimated

RT 1 1 as per the Helmholtz model using Eq. (4). The potential varies lin-

Aw = √ ( +√ ) early with the distance. It approaches to zero with the distance (x∼

AZ 2 F 2 2 Do Co Dr Cr

20 nm). As per the Gouy-Chapman model estimated from Eq. (16b),

Fig. 4. (a) Variation of potential as per the Helmholtz (a), Gouy-Chapman (b), Stern (c) and Grahame models (d).

Md.S. Uddin et al. / Applied Surface Science 449 (2018) 445–453 451

Fig. 5. Areal capacitance as per the Helmholtz (a), Gouy-Chapman (b), Stern (c) and Grahame models (d).

the potential variation is exponential with the distance as shown in pores) with the distance, ‘x’ (from the electrode surface to the bulk

Fig. 4(b). It is seen that the signiﬁcant potential is extended even at of the solution) estimated based on aforementioned models (Eqs.

the distance of 20 nm. As is seen in Fig. 4(c), the double layer poten- 5(a–c), 20(a–c), 23(a–c)). It is seen that in all cases the Cdl decreases

tial as per the Stern model decreases sharply when we move from exponentially with the distance x’. As per the Eq. (19), the Gouy-

electrode surface to within 1–2 nm distance as predicted by Eqs. Chapmann capacitance is independent of nature of surface area as

(4 and 16b). Beyond 2 nm distance, the potential decays gradually all the three surfaces showed similar Cdl . In all other models, it can

and attain nearly zero at a sufﬁciently bulk solution (∼20 nm). The be clearly seen that the type of pore is strongly inﬂuencing the areal

sharp decrease in double layer potential () at the vicinity of the capacitance. High capacitance is seen in the vicinity of the dou-

electrode is due to the accumulation of charges due to the formation ble layer and low in the bulk solution. Interestingly, the cylindrical

of IHP. On the other hand, the gradual decrease of beyond 2 nm pore electrode exhibits high capacitance compared to the plain and

distance is due to diffused layer (OHP) formed by thermal motion. semi-spherical surfaces. Such a high capacitance is due to the large

Fig. 4(d) shows the potential variation from electrode surface to the surface area associated with the cylindrical surface. It should be

bulk solution according to Grahame model (Eqs. 4, 16(b) and 22). noted that the larger surface area will lead to better interaction

The potential increases within a short distance of 1 nm and reach with the electrolyte leading effective charge separation and hence,

the maximum at 0.5 nm, then linearly decreases to ∼3 nm distance. resulted in high speciﬁc capacitance. The areal capacitance reduces

Beyond 3 nm, the potential gradually decreases with x. It is inter- sharply around 2–3 nm and beyond 3 nm the capacitance trends

esting to note that a signiﬁcant difference in the potential as per to zero. This shows that all the charge storage occurs in between

the Stern and Grahame models within a short distance of 1 nm. It is the 2–3 nm forming a surface of charge layer on the electrode sur-

noted that as per the Grahame model, the at very near the elec- face within this range. The pore size should be good enough for ions

trode surface increases (within the distance) due to IHP formation penetration; otherwise, the electrode behaves like as plane surface.

as well as ion absorption. Such an increase of potential has not been Alongside, the dipole size would be as small as possible to ensure

observed in the Stern model (Fig. 4(c)). Thus, the Grahame model r1 → r2 . As a result, the capacitance increases due to the small dis-

accounts for the ion adsorption at the vicinity of electrode surface tance between charge planes according to Helmholtz model. It is

which signiﬁcantly inﬂuences on the potential. Thus, larger sur- noteworthy that in this work, simple analytical models have been

face area leads to better electrode/ electrolyte interaction which developed for three difference electrode surfaces which accom-

has resulted in larger potential at the electrode surface. Interest- modated the standard EDL models. Unlike the works reported by

ingly, in all models, extent to the bulk in the cylindrical pore others which involved assumption and rigorous treatments, the

electrode compared to the plain and semi-spherical surfaces. Such analytical expressions derived for both potential and areal capaci-

a high potential is due to the large surface area associated with tance in all three different surfaces are simple which did not involve

the cylindrical surface. The larger surface area will lead to better assumption. This shows that cylindrical pore electrode can be the

interaction with the electrolyte leading reduction of resistance and best option to choose for developing high-performance practical

hence, resulted in high potential. EDLC material.

4.2. Variation of areal capacitance on the model surfaces 4.3. Charge/ discharge characteristics

Fig. 5 shows the variation of areal capacitances for three dif- Fig. 6(a) shows the obtained charge-discharge proﬁles for the

ferent electrode surfaces, (i.e. plain, semi-sphere and cylindrical EDLC formed by each of three different surfaces in the 1 M aqueous

452 Md.S. Uddin et al. / Applied Surface Science 449 (2018) 445–453

Fig. 6(b) shows the Nyquist plot of the EDLC simulated using

Eqs. (33 and 34). The Nyquist plot was simulated in 1 M aqueous

electrolyte of relative permittivity r = 78.5, temperature 20 ◦ C, ion

diffusion coefﬁcient Do = Dr = 1 × 10−9 m2 S-1 , whereas Faradic resis-

tance RP = 5 , solution resistance RS = 0.15 , and frequency f = 1 to

105 Hz. It can be seen that the Nyquist plot consists of the semicir-

cle in the high-frequency region and a spike at the low-frequency

region. The appearance of spike (Warburg element) conﬁrms the

presence of ion diffusion inﬂuencing the EDLC property.

5. Conclusions

the EDLC have been examined on three different surfaces on the

basis of standard models. The potential and the Cdl depend on the

type of surface, cylindrical pore surface exhibiting larger poten-

tial as well as areal capacitance. The Grahame model accounted for

the total capacitance which involves Cdl and ion adsorption. The

charging/ discharging and impedance characteristics conﬁrmed the

presence of ion diffusion contributing to Cdl . This study revealed

that a large surface area electrode can be utilized for developing

high-performance EDLC practically.

Acknowledgements

puter and laboratory facilities. PE thanks SERB, New Delhi, Govt.

of India for the research scheme (EMR/2016/001305). MSU thanks

South Asian Foundation for Fellowship.

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