SUPERCAPACITOR ELECTRODES BASED ON GRAPHENE MATERIALS

A Term Paper

Presented to

Prof. Barbara Murphy-Wesley

San José State University

In Partial Fulfillment

of the Requirements for Completion of

E200W

by

Steven M. Selverston

November 2011
 c 2011
�

Steven M. Selverston

ALL RIGHTS RESERVED

 ABSTRACT

SUPERCAPACITOR ELECTRODES BASED ON GRAPHENE MATERIALS

by Steven M. Selverston

Graphene is a new type of carbon material with promising potential in

energy-storage applications such as supercapacitor electrodes. This paper introduces

engineering of graphene, as well as a related material called reduced graphene oxide,

as materials for use in supercapacitors. The introduction explains the basic

definitions of supercapacitors and graphene materials. Then, the fundamentals of

supercapacitors and graphene materials are described in more detail in Chapters 1

and 2, respectively. Chapter 3 covers the synthesis and characterization of

graphene-based electrodes.

iv
 DEDICATION

To my parents, without whose support this would not have been possible.

v
 ACKNOWLEDGEMENTS

I would like to thank Prof. Barbara Murphy-Wesley for a great E200W class.

Also, I would like to thank Richard Chung, Bin Chen, and Mike Oye for all the

thoughtful advice and help. Finally, I’d like to thank Prof. Tim Hsu of the SJSU

Math department for updating and providing the LATEX thesis style guide.

vi
 TABLE OF CONTENTS

CHAPTER

1 INTRODUCTION 1

2 SUPERCAPACITORS 3

2.1 Capacitive charge storage . . . . . . . . . . . . . . . . . . . . . . . . 3

2.2 Double-layer and pseudocapacitance . . . . . . . . . . . . . . . . . . . 5

3 GRAPHENE 7

3.1 Graphene materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.2 Reduced graphene oxide . . . . . . . . . . . . . . . . . . . . . . . . . 8

3.3 Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

4 GRAPHENE-BASED ELECTRODES 10

4.1 Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

4.2 Graphene and electrode synthesis . . . . . . . . . . . . . . . . . . . . 13

4.3 State of the art . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

5 CONCLUSION 17

REFERENCES 18

vii
 LIST OF FIGURES

Figure

1 Ragone comparison of energy storage devices [1] . . . . . . . . . . . 1

2 Double-layer charge storage mechanism . . . . . . . . . . . . . . . . . 3

3 Difference between graphite and graphene structures . . . . . . . . . 7

4 Model of graphite oxide proposed by Szabo et al. [2], illustrated by

Dreyer et al. [3] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

5 Cyclic voltammetry of a graphene-based composite electrode at various

scan rates [4] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

6 Nyquist plot of a graphene-based composite electrode [4] . . . . . . . 12

7 Reduced ESR in a vertically-oriented graphene electrode [5] . . . . . 16

viii
respective device. In addition, electrochemical capaci- electric field in the electrochemical double layer is very
tors are expected to have a much longer cycle life than high and assumes values of up to 106 V/cm easily.
batteries because no or negligibly small chemical charge Compared to conventional capacitors where a total
transfer reactions are involved. A monograph volume capacitance of pF and !F is typical, the capacitance of
on electrochemical capacitors was recently published by and the energy density stored in the electrochemical
Conway [4]. double layer is rather high per se and the idea to build
In the following the basic principal of electrochemical a capacitor based on this effect is tempting.
capacitors, the different types of ECs, some theoretical In order to achieve a higher capacitance the electrode
considerations as to the performance of ECs, and some surface area is additionally increased by using porous
applications will be discussed. electrodes with an extremely large internal effective
CHAPTER 1
surface. Combination of two such electrodes gives an
electrochemical capacitor of rather high capacitance.
Fig. 2 shows a schematic diagram of an electrochem-
2. Principle of energy storage ical double-layer capacitor consisting of a single cell
INTRODUCTION
with a high surface-area electrode material, which is
Electrochemical capacitors store the electric energy in loaded with electrolyte. The electrodes are separated by
an electrochemical double layer (Helmholtz Layer) a porous separator, containing the same electrolyte as
formed at a solid/electrolyte interface. Positive and the active material. The potential drop across the cell is
negative ionic charges within the electrolyte accumulate also shown in Fig. 2.

Fig. 1. Sketch of Ragone plot for various energy storage and conversion devices. The indicated areas are rough guide lines.

Figure 1: Ragone comparison of energy storage devices [1]

Capacitors are energy storage devices similar to batteries, but which use

different mechanisms. Namely, batteries store energy chemically, and capacitors

store it physically (through dielectric polarization or ionic double-layers). Using

chemical storage allows batteries to store relatively large amounts of energy, but

there are several disadvantages. In many cases, the lifetime of a galvanic battery is

relatively short. Typically, advanced batteries can be completely cycled no more

than a few thousand times. Another problem with batteries is the relatively low

power density, which means that the device cannot be charged or discharged quickly

without overheating and perhaps being destroyed. An general comparison of the

energy characteristics of capacitors, electrochemical capacitors (supercapacitors),

batteries, and fuel cells is shown in Figure 1. Generally, fuel cells and batteries can

store more energy by weight, but capacitors can charge and discharge faster (lower

RC time constants).

Supercapacitors, also known as electrochemical capacitors or ultracapacitors,

can overcome some of the limitations of batteries, but generally cannot replace

them. Rather, they can be used in certain applications where batteries fail (ex:

regenerative braking), and also they can be used as supplements to batteries (ex:

hybrid engine-starting modules). Supercapacitors are similar in principle to

capacitors, but they use a different mechanism for charge storage. Instead of storing

the charge directly in dielectric materials, supercapacitors use electrolyte ions,

which create charge storage in electrical double layers. A subclass of

supercapacitors, called pseudocapacitors, exploits yet another mechanism for charge

storage via faradaic chemical reactions at the anode. The other subclass of

supercapacitors is electrochemical double-layer capacitors (EDLC), which use

almost entirely double-layer charge storage. In general, supercapacitor performance

depends most strongly on the electrode materials engineering.

Ever since the 2009 Nobel Prize in physics was given to Andre Geim and

Konstantin Novoselov for their work on single-layer graphite [6], which is usually

called graphene, engineers worldwide have attempted to see if graphene can be used

for practical applications. A related graphene material is called reduced graphene

oxide (RGO), which is similar to graphene but with more structural disorder and

more oxygen functionalities. One of the many possible applications of graphene

materials is for electrodes, and in particular for supercapacitor electrodes.

2
 CHAPTER 2

SUPERCAPACITORS

+ -

activated carbon
✑❍❍
- ✑ ❍
-
- ✑ + ❍ +
+ ❍
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✑-
✑
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- + +
- - - +
- + +
+
- - +
- +
- -
+ + + +
- -
+
+
- - + +
- +
- +
+ +
- -
anode ✲ - -
+
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✛ cathode
- +
+
+ + +
-
- - +
+
+ +
-
✒
�
�
❅
■
❅ anions ✻ cations

porous separator

Figure 2: Double-layer charge storage mechanism

2.1 Capacitive charge storage

To understand supercapacitors, it is necessary to understand common

capacitors. Some of the first capacitors were built in the mid-1800s by Michael

Faraday (1791-1867), and were referred to as “condensers.” The devices had a

capacity to store electrical charge, and therefore eventually came to be known as

capacitors. The common capacitor is composed of only three parts: two metallic

electrodes (ex: aluminum) and one dielectric separator (ex: stretched-out

polyethylene).

3
 A dielectric is a material that becomes polarized in an electric field. That is,

the material does not (ideally) allow DC charges to pass through it, but rather the

material itself becomes electrically polarized. This polarization occurs when, for

example, a battery is connected to the capacitor electrodes. The electrode that is

connected to the positive terminal of the battery is known as the anode, and the

electrode connected to the negative terminal of the battery is known as the cathode.

When the battery is connected to the capacitor, electrical charge flows from the

battery into the capacitor, but not through it. Instead of passing through the

electrodes, the charges accumulate on the electrodes. That charge accumulation,

which is proportional to the amount of polarization of the dielectric, is the

mechanism for charge storage and therefore energy storage.

Capacitance is defined by the ratio of stored charge, Q, over the potential

difference between the electrodes, �V , as shown in Equation 1. The term �

represents the permittivity of the material between the plates. In a vacuum,

� � 8.85 ∗ 10−12 F/m.

Even after the power supply is disconnected from the plates, the charges

remain. The capacitor is then said to be “charged,” and it can be used to supply

power to other devices. The SI unit of capacitance is the farad, and one farad (F) is

defined as 1 coulomb per volt (C/V).

Q A
C≡ =� Equation 1
�V d
The potential energy stored in a capacitor can be calculated according to

Equation 2.

Q2 1
U= = C�V 2 Equation 2
2C 2

4
 Often, the energy density, u, is a more useful term than just the potential

energy, because it allows one to compare relative storage efficiencies between devices

of different geometric scales. The energy density of a capacitor is found by dividing

2 by the volume V , which for a parallel-plate capacitor is equal to the product of

area and distance, Ad. In that case, the energy density is given by 3, where � is the

permittivity and E is the electric field magnitude ([�] = F/m, [E] = �V/m).

1
u = �E 2 Equation 3
2
Charge storage in supercapacitors can occur via two different possible

mechanisms (or some combination of the two). Commonly, both fall under the

broader nomenclature of electrochemical double-layer capacitors (EDLC). Such

capacitors are typically composed of:

• Two electrodes (ex: activated carbon)

• Porous membrane separator (ex: polyethylene)

• Electrolyte solution (ex: 6 M H2 SO4 or KOH)

It should be noted that supercapacitor electrodes based on activated carbon

require metallic connectors that can be used for making electrical connections to

other devices such as batteries. Such components are known as current-collectors,

and their contribution to charge storage is negligible. Therefore, the focus is on the

active carbon material, which is where virtually all of the charge is stored.

2.2 Double-layer and pseudocapacitance

The simpler of the two charge-storage mechanisms uses only the formation of

an electrical double layer (EDL) at the interfacial area where the electrolyte ions

5
meet the electrode, as in Figure 2. An electrolyte solution such as potassium

hydroxide provides charged ions that form double layers when the electrodes are

connected to a power supply such as a battery. Electrolyte choice and optimization

is not necessarily trivial, and there is significant research focusing on both aqueous

electrolytes and ionic liquids.

Pseudocapacitance, the more complex mechanism of charge-storage, uses

chemical (faradaic) reactions on the anode. The anodic chemical charge storage of

pseudocapacitors is distinct from that which occurs in batteries, and typically is

based on metal oxides (ex: RuO2 , MnO2 ) or specialized polymers. In both cases of

“pure” double layer capacitors (EDLC) and pseudocapacitors, the electrode

material properties are of fundamental importance.

6
 CHAPTER 3

GRAPHENE

(a) graphite structure (hcp) (b) single-layer graphene

Figure 3: Difference between graphite and graphene structures

3.1 Graphene materials

By far, the most common element used for supercapacitors is carbon. When

graphitic carbon is treated for improved properties such as high porosity, it is

usually called activated carbon. High porosity is desirable because it implies high

surface area for EDL formation (more contact area between electrolyte ions and the

plates). Nearly all commercial supercapacitors use electrodes based on activated

carbon materials because of its relatively low cost. In the last decade, many

attempts have been made to use other, more advanced forms of carbon to build

supercapacitor electrodes. In particular, carbon nanotubes have been of primary

interest. Carbon nanotubes are very similar to graphene materials; if a single-wall

carbon nanotube (SWCNT), taking the shape of a straw, were to be cut down one

7
 edge and flattened out, its wound then be called a graphene sheet or carbon

nanosheet. Conversely, if a sheet of graphene were to be rolled up into the shape of

a straw, it would then be called a carbon nanotube.

Graphene is simply a single layer of graphite. A single sheet of graphite,

however, has properties significantly different from many-layer graphite.

Furthermore, bilayer and trilayer graphene also have unique respective properties.

Electrical and thermal conductivities, strength, and surface area are all different

between graphene and graphite. In many cases, the properties of graphene are more

desirable. In practice, conductivity of a single-layer graphene sheet has been

measured up to 649 S/cm [7]. This value is similar to that of graphite, but well

below the conductivity of copper, which is in the order of 105 S/cm. The most

important property of graphene with respect to supercapacitors is, naturally, its

high theoretical specific surface area of 2675 m2 /g and the corresponding theoretical

specific capacitance of 550 F/g [4].

3.2 Reduced graphene oxide

Figure 4: Model of graphite oxide proposed by Szabo et al. [2], illustrated by Dreyer
et al. [3]

Fig. 5 Structure of GO proposed by Dékány and coworkers (adapted

Anotherfrom
related material, known as reduced graphene oxide (RGO), is
ref. 27).

updated the Ruess and Scholz–Boehm

8 models, which
D 13C/13C chemical-shift correlation suggested a regular, corrugated quinoidal structure interrupted
eled GO with (C) slices selected from by trans-linked cyclohexyl regions, functionalized by tertiary
d positions (70, 101, 130, 169, and alcohols and 1,3-ethers. Reevaluation of the FTIR features
green, red, and blue areas in (B) and 38
sometimes called graphene. Although RGO is significantly different from graphene,

it retains some of the desirable properties such as high surface area. Reduced

graphene oxide is made by reducing graphene oxide, which is made by exfoliating

graphite oxide. Graphite oxide is made via a Hummers’ reaction in solution [8]. The

reduction can be accomplished chemically with sodium borohydride (NaBH4 ) or

hydrazine (N2 H4 ). Alternatively, the graphene oxide can also be reduced thermally

or electrochemically. The resulting RGO is sometimes called graphene, although

there are some important differences. Firstly, RGO usually has a significant amount

of residual oxygen (ex: several percent). Secondly, RGO is highly disordered and

distorted compared to pristine graphene. Finally, RGO is rarely single-layer (also

called monolayer), but rather it is usually “few-layer,” which usually means about 2

- 10 graphene layers.

3.3 Composites

Both graphene and RGO are frequently made into composites for

experimental electrode devices [4]. Composite materials can be simple to make

when various materials (ex: conductivity boosters, adhesive binders, etc.) are mixed

together. The electrical conductivity of most graphene materials is not exceptional,

so conductive additives are often used. Binders are required in order to glue the

materials together. There are disadvantages to these types of composites, however,

because the high porosity causes pore resistance (impedance), which increases the

capacitor time constant. Additives also reduce active surface area for double-layer

charge storage. Graphene-based composites can also be made other methods that

avoid binders (ex: electrophoretic impregnation). For pseudocapacitive electrodes,

metal oxides or polymers can be made into composites with the carbon materials.

9
 CHAPTER 4

GRAPHENE-BASED ELECTRODES

4.1 Characterization

Perhaps the most difficult aspect involved in building new materials is

characterization, and graphene is no exception. The characterization of graphene

and graphene-based electrode materials is an intensive process, requiring

state-of-the-art instruments. Some of the most frequently used characterization

tools include:

• Scanning electron microscopy (SEM): a visualization tool for imaging on the

order of 30 nm to 1 µm

• Cyclic voltammetry (CV): an electrochemical method used to quickly check

capacitance and chemical reactivity of potential electrode materials

• Atomic-force microscopy (AFM) : a visualization and

thickness-measurement tool for very small length scales on the order of 5 -

50 nm

• Electrochemical impedance spectroscopy (EIS): a method used to determine

information regarding porosity and equivalent-series-resistance (ESR)

• Raman spectroscopy (RS): a laser-based method that returns structural

“fingerprints” of materials

There are at least five different experiments that can be used to estimate the

capacitance of an electrode, including galvanostatic charge/discharge, voltage and

10
current sweeping techniques, self-discharge through known resistance, and ac

impedance spectroscopy [9].

FIGURE 3. (a) Galvanostatic charge-discharge curve of a curved

Figure 5: Cyclicelectrode
graphene voltammetry
(6.6 of
mga each)
graphene-based composite
at a constant electrode
current densityatofvarious
1
scan rates [4]
A/g, using EMIMBF ionic liquid electrolyte, and (b) cyclic voltam-
4
mograms for graphene electrode at different scan rates using
EMIMBF4 ionic liquid electrolyte.
Most supercapacitor characterization is performed using comprehensive

Compared
electrochemical with that
workstations the can
literature
perform data
dozensbased
of [Link] EDL
One can alone,
determine
as shownofinanFigure
the capacitance 4b, the room
ideally-polarizable temperature
electrode energy
according to density
Equation 4, wherein
of our curved graphene-based supercapacitors is much
the capacitance is calculated as the inverse of the slope of the linear portion of the
higher than the value of 31.9 Wh/kg (75 F/g) at 60 °C for a
plot of potential as a function of time while the electrode is charged at constant
graphene-ionic liquid supercapacitor,16 the values of 4.7 Wh/
kg[9].(135 F/g) and 21.5 Wh/kg (99 F/g) for a chemically
current
modified graphene supercapacitor with aqueous and organic
17 �
electrolytes, respectively and the
C = i·
�t separately reported val-
Equation 4
18 �V9.2 Wh/kg (264 F/g).19 In
ues of 7.1 Wh/kg (205 F/g) and
Figure 4d, the
To determine Nyquist plot
the capacitance from of thevoltammetry
cyclic curved graphene based
(CV), one generally
supercapacitor
uses the area of the eithershows a straight
the anodic or cathodicline in the
portion. low-frequency
A typical CV plot is
region and an arc in the high frequency region. This high
shown in Figure 5. In some cases, an average is taken between the two. That case is
frequency loop is related to the electronic resistance be-
tween graphene sheets. The vertical 11 shape at lower frequen-
cies indicates a pure capacitive behavior, representative of
the ion diffusion in the electrode structure. The more vertical
the curve, the more closely the supercapacitor behaves as
e of a curved
nt density of 1
cyclic voltam-
n rates using �
shown in Equation 5, where idV is the total area of the CV curve, m is the mass

of the active electrode material (ex: graphene-based composite), �V is the range of

n EDL alone, voltage, and �V

�T
is the scan rate.
ergy density
�
ors is much C=
idV
Equation 5
60 °C for a 2m�V ( �V
�T
)

es of 4.7 Wh/ In the case of thin-film electrode materials, the mass term m can be very

chemically challenging to obtain experimentally, so it is sometimes estimated. This is because

and organic the deposited mass may be on the order of micrograms (µg).
eported val-
64 F/g).19 In
phene based
w-frequency
n. This high
sistance be-
wer frequen-
esentative of
more vertical
behaves as
valent series
e x-intercept
ermines the FIGURE 4. (a) Ragone plot of graphene supercapacitor, (b) relation-
Figure 6: Nyquist plot of a graphene-based composite electrode [4]
/discharged. ship between the energy density and current density of a curved
han aqueous graphene electrode in EMIMBF4 ionic liquid electrolyte, (c) discharge
curve at 2, 4, and 8 A/g current density, and (d) Nyquist plot for
ture (mostly Impedance is determined from electrochemical impedance spectroscopy (EIS).
graphene electrode using a sinusoidal signal of 5 mV over the
eets remain Thisfrequency range importance
is of fundamental from 100 for kHz to 1 mHz. Z′ as
supercapacitors, is the
realequivalent
impedance.
series Z′′ is
imaginary impedance.
resistance (ESR) can be calculated if the impedance data are known. The

impedance data area usually interpreted via Nyquist plot, an example of which is
4866 DOI: 10.1021/nl102661q | Nano Lett. 2010, 10, 4863-–4868
shown in Figure 6. The ESR can also be determined from galvanostatic

12
charge/discharge, and the value can be used to estimate the specific power from

Equation 6, where V is the cell voltage, m is the electrode mass, and R is the ESR.

V2
P = Equation 6
4Rm
In porous supercapacitors, the each pore has associated resistance, and if the

pore network is extensive enough, the series resistance has undesirable effects.

Recent graphene-based electrode materials have been designed specifically to

address the ESR problem [5].

4.2 Graphene and electrode synthesis

Graphene-based materials may be obtained many ways. The most common

are:

• Exfoliation of graphite (ex: mechanical, thermal, or electrochemical)

• Vapor deposition

• Chemically via graphene oxide

Mechanical exfoliation was the method used by Novoselov et al. [6], who

famously used Scotch tape to separate the graphite layers. However, mechanical

exfoliation appears better suited for fundamental research rather than scalability.

Vapor deposition, particularly chemical vapor deposition, is an active area of

graphene research [5]. Decomposition of a carbon source such as methane can be

used to grow thin films of graphene onto various substrates. Plasma processing is

often used for improved properties.

The simplest and most common way to make graphene-based electrodes, after

the graphene material has been made, is to simply mix the graphene with additives

13
that improve conductivity and binding [4].

4.3 State of the art

Pure electrochemical double-layer capacitors (EDLC) have been found to

support specific capacitances of about 100 - 250 F/g. Pseudocapacitors (PC)

typically have about double the specific capacitance of EDLCs, and there have been

reports of specific capacitances of over 1000 F/g [10]. A summary of some recent

research papers is shown in Table 1. In the table, edlc and pc refer to

electrochemical double-layer capacitors and pseudocapacitors, respectively. It

should be noted that the specific capacitance Cs , of a supercapacitor is only one of

several important performance metrics. Other performance parameters of electrode

materials include cycling stability, volumetric density, voltage range, frequency

response (impedance), among others. Practical considerations for manufacture

include cost, toxicity, and material availability.

Typically, the carbon material to be used in a supercapacitor electrode needs

to be mixed with other additives such as binders and conductivity boosters. For

most researchers working on graphene-based supercapacitor electrodes, this is the

case. The Jang group, for instance, has made promising graphene-based

supercapacitor electrodes by mixing many sheets of graphene with 5 %w Super-P

(conductivity booster) and 10 %w polytetraflouroethylene (PTFE) [4]. The

graphene-based composite is then typically applied to a metallic substrate, which is

known as the current collector. Two such electrodes can then be separated by a

porous membrane such as the Celguard-3501, which is what was used by the Jang

group [4]. Their fabricated cell was estimated to have a specific energy density of

over 80 Wh/kg at room temperature, which is about twice that of an average

14
lead-acid battery and approaching that of a lithium ion battery.

Many laboratory-scale efforts have been made to grow graphene and carbon

nanotubes vertically (perpendicular to the current-collector) in order to achieve high

surface area and low porosity. The active carbon materials grown in this fashion are

significantly different from traditional porous carbon composites, if only for their

relatively low thickness values (ex: < 1 µm) and negligible weights. As such, these

more advanced electrodes can be called thin-film electrodes. In principle, thin-film

supercapacitors using the spiral geometry could outperform commercial devices. A

calculation based on the spiral architecture predicted a capacitance C > 14, 000 F

for a graphene electrode with thickness of 0.6 µm and an overall device length of

13.8 cm [11].

Table 1: Specific capacitances of RGO/graphene-based electrodes

material synthesis method type Cs , F/g ref

RGO PTFE composite edlc 205 [12]
modified graphene PTFE composite edlc 135 [13]
graphene PTFE composite edlc 250 [4]
RGO ionic liquid composite edlc 187 [14]
RGO electrolytic deposition edlc 128 [15]
RGO LBL self-assembly edlc 247 [16]
graphene/polyaniline drop casting pc 480 [17]
graphene/poly(pyrrole) EPD pc 1510 [10]
graphene/MnO2 electrostatic LBL pc 263 [18]
graphene/NiO EPD/CBD pc 400 [19]
graphene/MnO2 solution LBL pc 380 [20]

A leader in supercapacitor applications is John R. Miller, who recently

succeeded in growing and characterizing vertically-oriented graphene sheets using

plasma-enhanced chemical vapor deposition (PECVD), a thin-film deposition

method used frequently in the semiconductor industry [5]. The focus was on the ac

15
 with ac Line-Filtering Performance
particulate electrodes, thus contributing a capacitor.
additional proximately 10 to 15 nm thick. After 20
lesswas
electronic resistance. Capacitors constructed with growth, the resulting coating inherent
Thus,
minhigh-surface-area
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composed of have
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materials at
of inductive behavior
examined.
transition
with
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DLCsthese two limits occurs
between
John R. Miller,1* R. [Link]
Outlaw,[Link]
C. Holloway3graphene electrode as vertically oriented graphitic nanosheets approxi- over a single decade in frequency for the graphene
fabricated from felt-like electrodes comprising entan-
reported were not capable of 120-Hz filtering. mately 600 nm high with a gled, crossmultiwall
section <1 carbon
nm nanotubes
nanosheet (CNTs) did estab-
capacitor, whereas it occurs over ap-
Electric double-layer capacitors (DLCs) can
Electrodes withhave high storage
vertically capacity,
oriented graphenebut their porous
thick, butelectrodes
often terminatinglish witha frequency
an edge ofresponse record in 1997:
a proximately seven 6decades
Hz in frequency for the
cause them to perform like resistors coating
nanosheets in filter circuits
carbon thatfibersremove ripplebeen
have also from rectified
graphene direct current.
sheet (one atomic for an impedance phase angle
layer). of –45°
activated (8). (Resist-
carbon capacitor. This disparity is due
We have demonstrated efficient filtering of 120-hertz current
examined (15). Capacitor designs were devel- with DLCs with electrodes made from ance and reactance have equal magnitudes
A plan view of vertically oriented graphene almost entirely to electrode porosity [Link] a
vertically oriented graphene opednanosheets
for a 14,900 grown directlybut
F device, onno metal current collectors.
two-terminal This design
nanosheet electrode (Fig. 1A)phase shows angle
the of –45°, making
irregular Thethis frequency phase
impedance conve- angle of the graphene
minimized electronic andelectrical
ionic resistances
responsesand wereproduced
[Link] with RC time
Such vertical- constants of
morphology of less than (exposed
the surface nient for edge
comparison
planes purposes.)
nanosheet These DLCs reached
capacitor had –45° at ~15,000 Hz
200 microseconds, in contrast with ~1 second for typical DLCs. Graphene nanosheets have a thin electrodes and used a high-conductivity
ly oriented graphene nanosheets are believed to and the random expansive open areas) created by in comparison with 0.15 Hz for the activated car- aqueous
preponderance of exposed edge planes that greatly increases charge storage as compared with that of electrolyte but were still
offer a near-ideal structure for DLC electrodes defects that arise from stress and hydrogen in- bon capacitor and ~30,000 Hz for the electrolyticincapable of filtering at
designs that rely on basal plane surfaces.
capable Capacitors operation.
of high-frequency constructedFirst,
with these
they electrodes could
corporation. bestructures
The smaller grow 120vertically
Hz for two fromreasons. First, the At
the capacitor. felt-like
120 Hz, struc-
the impedance phase angle
than the low-voltage aluminum electrolyte capacitors
of edgethat are that
typically used inmetal
electronic devices. ture createdconnected
porosity with of athe
pore length nanosheet
equal to capacitor was approx-

Downloaded from [Link] on July 25, 2011

have a preponderance planes provide substrate and are electronically graphene
2 the electrode thickness,
2
capacitance of 50 to 70 mF/cm in comparison to it. The measured surface area was ~1100 m /g. imately –82° as compared with ~0° for the activatedthus creating distributed

E
lectric double-layerwithcapacitors (DLCs), al- whichmid-1990s
providetocapaci-
“load-level” the graphene
power profile chargeinstorage
of is shown Fig. 1B,with
but associated ionic resistance.
impedance behavior, which appeared, via EIS, to have been optimized (low pore
so called supercapacitors
that of basal
tance of only or~3
planes,
ultracapaci- battery-powered
mF/cm2 (16). Second, charge-storage
Similar
electricon
vehicles thatfiber
a circular
growth
weresothen Second,both
as to display the plan
structure
and relied
carbon capacitor
on manifold
aluminum
and approximately –83° for the
electrical
electrolytic capacitor. The phase angle

Downloaded from [Link] on July 25, 2011

tors, store charge edge
in the planes
double are formed andunder
layerexposed development (4) and, more recently, to cap- contacts among
directly accessible, shallow-angle views of the surface. Raman inten- for a blank (bare the individual CNTs andNi against
electrode prototype) was –85°.
at an electrolyte-electrode interface when voltage ture and store energy derived from kinetic
minimizing the distributed nature of the charge sity measurements of the coating had a D/G band energy the current collector, contributing to the electron-
A complex plane plot of the impedance data
resistance). The target application for such supercapacitors is for ac line filtering.
is applied. The electrodes are generally
storage. composed
Third, porosity effectsharvesting—for
are minimal because instance,intensity
the braking (ID/IG)ofofa0.67icbecause
ratioenergy [Link] Although
defects. these capacitors
obtained fromwere unable oriented graphene nano-
the vertically
of high-surface-area conductive
of the open material, usually
structure, reducing hybrid vehicle
ionic (5).
resistances. Capacitors were fabricatedtotofilter, they showed
measure the elec-that sheet
DLC capacitor
frequencyisresponse
shown in Fig. 3, with an expanded
activated carbon (1). DLCs typically store more The delayed introduction of DLCs was caused could be improved by using electrode
And fourth, graphene nanosheets themselves have trical performance of the vertically oriented graphene view in the inset. There is no evidence of porous materials
than an order of magnitude more high energy per unit and bycan
a limited market
fromfor capacitors that could Two with 2.5-cm-diameter,
onlyidentical external rather thanelectrode
internal surface area.
An SEM image of the vertical graphene sheets is shown in Figure 4.7(a), and the
volume than conventional
extremely
a conductive
conductivity
capacitorssurface, like storeelectronic
(2) but,minimizing
be grown
charge but
nanosheet electrodes.
performed
resist- poorly atNi
75-mm-thick their other
disks with graphene
behavior,
Further improvements in frequency response
which would manifest itself by
nanosheet a line that intersects the real axis at a near-45° angle.
batteries, are low-voltage devices, so they often main task: filtering voltage ripple (6). The typical were reported from electrodes of multiwall CNTs
ances. These factors, we expect, should provide coatings grown over their 1.6-cm-diameter cen- There are also no features associated with a series-
must be connected in series to meet system volt- resistor-capacitor (RC) time constant for2a DLC that were deposited onto a metal current collector,
high levels of charge storage that is accessible through tral region (2.0 cm area) were separated by a 25-mm- passive layer (high-frequency semicircle), which would
corresponding Nyquist plot is shown in Figure 4.7(b). The nearly-vertical
age requirements. Electric double-layer charge stor- is ~1 s—far too long to be useful for the common cleared of oxygen surface groups, and bonded to
minimum series resistance and thus allow crea- thick microporous separator. The coatings and the add series resistance. Data fit a near-vertical line as
age was first observed more than 100 years ago, but application of 120-Hz filtering (8.3 ms period), the collector with a hydrogen furnace treatment
tion of a DLC capable of high-frequency operation. separator were wetted with the aqueous electro- produced by a series-RC circuit. Raistrick modeled
DLC products did not reach the market until 1978 which entails smoothing the leftover ac ripple on (9–11). These capacitors reached a –45° phase
We synthesized vertically oriented graphene lyte [25% potassium hydroxide (KOH)] before the impedance of rough, saw-tooth-surface elec-
(3). The introduction of volatile computer memory dc voltage busses found in most line-powered elec- angle at 636 Hz, which is more than 100 times
orientation is indicative of low pore resistance. For comparison, the curved shape of
nanosheets directly on heated nickel (Ni) substrates sealing the perimeter of the disks with a thermo- trodes having various height-to-separation ratios
created the need for a power source that could be tronics. Sixty-Hz ac power is full-wave rectified the 1997 record. The phase angle at 120 Hz was
using radio frequency (RF) plasma–enhanced plastic by use of an impulse-heat-seal apparatus. (19). Fig. 3 follows such rough-surface behavior
charged repeatedly and then reliably deliver low and then filtered to create pure dc voltage. Filtering –65°, and thus they could not efficiently filter at
chemical vapor deposition (17, 18). After pump- These packaged prototypes, 2.5 cm diameter by with an aspect ratio of <2, which is consistent with
levels of dc power over a long time. Kilofarad- today is performed primarily by means of alumi- this frequency. Multi-wall, vertically aligned CNTs
down, the substrates were plasma-etched for 10 ~175 mm thick, had a mass of ~0.8 g. The active the observed scanning electron microscopy (SEM)
the Nyquist plot of the composite electrode, shown in Figure 6, is indicative of high
sized capacitors became available starting in the num electrolytic capacitors, which usually are grown directly on a metal current collector were
min in 40% argon (Ar) + 60% H2 (total pressure material-coating thickness on each electrode was micrograph structure.
among the largest components found in any elec- also investigated as DLC electrodes. One such
of 50 mT). After the Ar was shut off, the Ni sub- approximately 0.6 mm, which is negligible compared We used a series-RC circuit model in which
1
JME, Inc., 17210 Parkland Drive, Shaker Heights, OH 44120, tronic circuit: Smaller-sized filtering capacitors may study showed impedance data with a –45° phase
USA, and Case Western Reserve University, Great Lakes Energy with device dimensions and mass. Electrical con- resistance is the real part of the impedance and
allow system size reductions, which is particularly angle at 443 Hz (12). Yet another study bonded
pore resistance, and is a more typical of conventional porous electrode materials.
Institute, Cleveland, OH 44106, USA.
-90
2
Department
Science, College of William and Mary, Williamsburg, VA
of Applied nection was made to the back surface of each Ni capacitance is calculated as C = –1/(2pfZ″),
valuable in some portable electronics applications. vertically aligned CNT electrodes to an aluminum
disk. where f is frequency in Hz and Z″ is the imag-
23185, USA. 3Defense Advanced Research Projects Agency, Present DLCs have an impedance phase-angle current collector, but this also was unable to ef-
3701 North Fairfax Drive, Arlington, VA 22203, USA. at 120 Hz that is near 0°, which is far from the –90° ficiently filter 120-Hz ripple (13).
-60
*To whom correspondence should be addressed. E-mail: value needed for filtering. This -1000 drawback is a di- Agglomerated, chemically modifiedFig. graphene
3. Complex plane plot of the
-0.4
jmecapacitor@[Link] rect result of using porous electrodes, which store material was evaluated as a DLC electrode impedanceand of the graphene nano-
Phase angle (degrees)

-30
sheet capacitor showing vertical
-0.3
-800 intersection with the real axis and

Z imaginary (Ohms)
0
not the usual porous electrode be-
-0.2 havior shown by DLCs.

Z imaginary (Ohms)
-600
30
-0.1

60 Graphene DLC
-400 0
Al electrolytic
Activated carbon DLC
90 0.1
10-3 10-2 10-1 100 101 102 103 104 105 0 0.1 0.2 0.3 0.4 0.5
Frequency (Hz) -200 Z real (Ohms)

Fig. 2. Impedance phase angle versus frequency

for the graphene nanosheet DLC. Measurements
from a commercial DLC having an activated carbon 0
electrode and an aluminum electrolytic capacitor 0 200 400 600 800 1000

are shown for comparison. Z real (Ohms)

(a) SEM of graphene sheets

1638 24 SEPTEMBER 2010 VOL 329 SCIENCE [Link] (b) Nyquist plot showing very
Fig. 1. (A) Plan SEM micrograph of coated Ni electrode. (B) SEM micrograph of a coated fiber, showing plan and shallow-angle views.
low ESR
[Link] SCIENCE VOL 329 24 SEPTEMBER 2010 1637
Figure 7: Reduced ESR in a vertically-oriented graphene electrode [5]

16
 CHAPTER 5

CONCLUSION

Graphene-based materials are attractive candidates for supercapacitor

electrodes. Graphene may eventually replace or compliment other carbon materials

as sources of high surface area and therefore high capacitance. More

laboratory-scale capacitor cells need to be assembled and replicated to verify the

technological improvements over cheaper carbon materials, but some laboratory

data have looked promising. Cost effective mass production of single-layer graphene

has not yet been realized, although it may be possible. Nevertheless, few layer

graphene still shows improved performance over other carbon materials, and it is

much easier to obtain. In particular, reduced graphene oxide (RGO) materials are

very easy to make and could be competitive commercially.

Pristine single-layer graphene is usually made with vapor deposition methods,

whereas few-layer RGO is usually made chemically. Once the graphene or composite

material is made, there are many methods to synthesize electrodes, including

pressing, drop-casting, layer-by-layer (LBL) assembly, and electrophoretic deposition

(EPD). Pure electrochemical double layer capacitors made of graphene materials

have specific capacitances up to about 250 F/g. Graphene based pseudocapacitors,

which are composites with polymers or metal oxides, have specific capacitances of

over 400 F/g. Although pseudocapacitors hold more energy than pure EDLCs, they

are unstable in some circumstances. Thin-film electrodes, particularly those with

vertically-oriented sheets, hold promise for future developments. Ionic liquid

electrolytes can be used to extend voltage ranges, and therefore capacitance values.

17
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19