SUPERCAPACITOR ELECTRODES BASED ON GRAPHENE MATERIALS

A Term Paper Presented to Prof. Barbara Murphy-Wesley San Jos e State University

In Partial Fulllment 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 denitions 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.

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, Id like to thank Prof. Tim Hsu of the SJSU
A Math department for updating and providing the L TEX thesis style guide.

vi

TABLE OF CONTENTS

CHAPTER 1 INTRODUCTION 2 SUPERCAPACITORS 2.1 2.2 Capacitive charge storage . . . . . . . . . . . . . . . . . . . . . . . . 1 3 3 5 7 7 8 9 10 10 13 14 17

Double-layer and pseudocapacitance . . . . . . . . . . . . . . . . . . .

3 GRAPHENE 3.1 3.2 3.3 Graphene materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . Reduced graphene oxide . . . . . . . . . . . . . . . . . . . . . . . . . Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4 GRAPHENE-BASED ELECTRODES 4.1 4.2 4.3 Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Graphene and electrode synthesis . . . . . . . . . . . . . . . . . . . . State of the art . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

5 CONCLUSION

REFERENCES

18

vii

LIST OF FIGURES

Figure 1 2 3 4 Ragone comparison of energy storage devices [1] . . . . . . . . . . . 1 3 7

Double-layer charge storage mechanism . . . . . . . . . . . . . . . . . Dierence between graphite and graphene structures . . . . . . . . . Model of graphite oxide proposed by Szabo et al. [2], illustrated by Dreyer et al. [3] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Cyclic voltammetry of a graphene-based composite electrode at various scan rates [4] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 12 16

6 7

Nyquist plot of a graphene-based composite electrode [4] . . . . . . . Reduced ESR in a vertically-oriented graphene electrode [5] . . . . .

viii

electric eld in the electrochemical double layer is very high and assumes values of up to 106 V/cm easily. Compared to conventional capacitors where a total capacitance of pF and mF is typical, the capacitance of and the energy density stored in the electrochemical double layer is rather high per se and the idea to build a capacitor based on this effect is tempting. In order to achieve a higher capacitance the electrode surface area is additionally increased by using porous 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 electrochem2. 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. respective device. In addition, electrochemical capacitors are expected to have a much longer cycle life than batteries because no or negligibly small chemical charge transfer reactions are involved. A monograph volume on electrochemical capacitors was recently published by Conway [4]. In the following the basic principal of electrochemical capacitors, the different types of ECs, some theoretical considerations as to the performance of ECs, and some applications will be discussed.

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 dierent 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 dierent 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.

CHAPTER 2 SUPERCAPACITORS

activated carbon

+ + + + +

+ + + + + + + + + +

+ + + + + + + + + +

anode

+ + +

+ + + +

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 rst 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 eld. 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 ows 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 dened by the ratio of stored charge, Q, over the potential dierence 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 1012 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 dened as 1 coulomb per volt (C/V). Q A = V d

Equation 1

The potential energy stored in a capacitor can be calculated according to Equation 2. Q2 1 = C V 2 2C 2

U=

Equation 2

Often, the energy density, u, is a more useful term than just the potential energy, because it allows one to compare relative storage eciencies between devices of dierent 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 eld magnitude ([] = F/m, [E ] = V/m). 1 u = E 2 2 Equation 3

Charge storage in supercapacitors can occur via two dierent 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 signicant 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.

CHAPTER 3 GRAPHENE

(a) graphite structure (hcp)

(b) single-layer graphene

Figure 3: Dierence 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 attened 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 signicantly dierent from many-layer graphite. Furthermore, bilayer and trilayer graphene also have unique respective properties. Electrical and thermal conductivities, strength, and surface area are all dierent 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 specic surface area of 2675 m2 /g and the corresponding theoretical specic 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 ka ny and coworkers (adapted Structure of GO proposed by De

Another related material, known as reduced graphene oxide (RGO), is from ref. 27).
updated the Ruess and ScholzBoehm models, which 8 suggested a regular, corrugated quinoidal structure interrupted by trans-linked cyclohexyl regions, functionalized by tertiary alcohols and 1,3-ethers. Reevaluation of the FTIR features
38

D 13C/13C chemical-shift correlation eled GO with (C) slices selected from d positions (70, 101, 130, 169, and green, red, and blue areas in (B) and

sometimes called graphene. Although RGO is signicantly dierent 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 dierences. Firstly, RGO usually has a signicant 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.

CHAPTER 4 GRAPHENE-BASED ELECTRODES

4.1

Characterization Perhaps the most dicult 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 m 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 ngerprints of materials There are at least ve dierent 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 5: Cyclic voltammetry a each) graphene-based composite electrode at various graphene electrode (6.6 of mg at a constant current density of 1 scan rates [4] A/g, using EMIMBF ionic liquid electrolyte, and (b) cyclic voltam-

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

4

mograms for graphene electrode at different scan rates using EMIMBF4 ionic liquid electrolyte.
Most supercapacitor characterization is performed using comprehensive

electrochemical workstations perform data dozensbased of tests. One can alone, determine Compared with that the can literature on EDL

as shownof in Figure 4b, the room temperature energy density the capacitance an ideally-polarizable electrode according to Equation 4, wherein of our curved graphene-based supercapacitors is much 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/ current kg[9]. (135 F/g) and 21.5 Wh/kg (99 F/g) for a chemically modied graphene supercapacitor with aqueous and organic 17 t separately reported valelectrolytes, respectively and the C = i Equation 4 18 V ues of 7.1 Wh/kg (205 F/g) and 9.2 Wh/kg (264 F/g).19 In To determine the capacitance from of cyclic voltammetry (CV), one generally Figure 4d, the Nyquist plot the curved graphene based supercapacitor shows a straight line in the low-frequency uses the area of the either the anodic or cathodic portion. 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 between graphene sheets. The vertical shape at lower frequen11 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
the capacitance is calculated as the inverse of the slope of the linear portion of the

e of a curved nt density of 1 cyclic voltamn rates using

shown in Equation 5, where

n EDL alone, ergy density ors is much 60 C for a es of 4.7 Wh/ chemically and organic eported val64 F/g).19 In phene based w-frequency n. This high sistance bewer frequenesentative of more vertical behaves as valent series e x-intercept ermines the /discharged. han aqueous ture (mostly eets remain

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

idV is the total area of the CV curve, m is the mass

is the scan rate. idV V 2m V ( ) T

C=

Equation 5

In the case of thin-lm electrode materials, the mass term m can be very challenging to obtain experimentally, so it is sometimes estimated. This is because the deposited mass may be on the order of micrograms (g).

FIGURE 4. (a) Ragone plot of graphene supercapacitor, (b) relationFigure 6: Nyquist plot of a graphene-based composite electrode [4] ship between the energy density and current density of a curved graphene electrode in EMIMBF4 ionic liquid electrolyte, (c) discharge curve at 2, 4, and 8 A/g current density, and (d) Nyquist plot for Impedance is determined from electrochemical impedance spectroscopy (EIS). graphene electrode using a sinusoidal signal of 5 mV over the frequency range importance from 100 for kHz to 1 mHz. Z as is the real impedance. This is of fundamental supercapacitors, equivalent 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 DOI: 10.1021/nl102661q | Nano Lett. 2010, 10, 4863-4868 4866 shown in Figure 6. The ESR can also be determined from galvanostatic 12

charge/discharge, and the value can be used to estimate the specic power from Equation 6, where V is the cell voltage, m is the electrode mass, and R is the ESR. V2 4Rm

P =

Equation 6

In porous supercapacitors, the each pore has associated resistance, and if the pore network is extensive enough, the series resistance has undesirable eects. Recent graphene-based electrode materials have been designed specically 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 lms 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 specic capacitances of about 100 - 250 F/g. Pseudocapacitors (PC) typically have about double the specic capacitance of EDLCs, and there have been reports of specic 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 specic 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 polytetraouroethylene (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 specic 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 eorts 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 signicantly dierent from traditional porous carbon composites, if only for their relatively low thickness values (ex: < 1 m) and negligible weights. As such, these more advanced electrodes can be called thin-lm electrodes. In principle, thin-lm 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 m and an overall device length of 13.8 cm [11]. Table 1: Specic capacitances of RGO/graphene-based electrodes material RGO modied graphene graphene RGO RGO RGO graphene/polyaniline graphene/poly(pyrrole) graphene/MnO2 graphene/NiO graphene/MnO2 synthesis method PTFE composite PTFE composite PTFE composite ionic liquid composite electrolytic deposition LBL self-assembly drop casting EPD electrostatic LBL EPD/CBD solution LBL type edlc edlc edlc edlc edlc edlc pc pc pc pc pc Cs , F/g ref 205 [12] 135 [13] 250 [4] 187 [14] 128 [15] 247 [16] 480 [17] 1510 [10] 263 [18] 400 [19] 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-lm deposition method used frequently in the semiconductor industry [5]. The focus was on the ac

15

resistance). The target application for such supercapacitors is for ac line ltering. An SEM image of the vertical graphene sheets is shown in Figure 4.7(a), and the corresponding Nyquist plot is shown in Figure 4.7(b). The nearly-vertical

orientation is indicative of low pore resistance. For comparison, the curved shape of the Nyquist plot of the composite electrode, shown in Figure 6, is indicative of high pore resistance, and is a more typical of conventional porous electrode materials.
Phase angle (degrees)
-30 Z imaginary (Ohms)

-800
0

-0.3

Z imaginary (Ohms)

-0.2

sheet capacitor showing vertical intersection with the real axis and not the usual porous electrode behavior shown by DLCs.

30

-600

-0.1

60

Graphene DLC Al electrolytic Activated carbon DLC

10-2 10-1 100 101 102 103 104 105

-400

90 10-3

0.1

0.1

Frequency (Hz)

-200

0.2 0.3 Z real (Ohms)

0.4

0.5

Fig. 2. Impedance phase angle versus frequency for the graphene nanosheet DLC. Measurements from a commercial DLC having an activated carbon electrode and an aluminum electrolytic capacitor are shown for comparison.

200

400

600

800

1000

Z real (Ohms)

24 SEPTEMBER 2010 VOL 329 SCIENCE www.sciencemag.org 1638 Fig. 1. (A) Plan SEM micrograph of coated Ni electrode. (B) SEM micrograph of a coated fiber, showing plan and shallow-angle views.
www.sciencemag.org SCIENCE VOL 329 24 SEPTEMBER 2010

(a) SEM of graphene sheets

(b) Nyquist plot showing very low ESR

1637

Figure 7: Reduced ESR in a vertically-oriented graphene electrode [5]

16

Downloaded from www.sciencemag.org on July 25, 2011

impedance behavior, which appeared, via EIS, to have been optimized (low pore

from felt-like electrodes comprising entanover a single decade in frequency for the graphene graphene electrode as vertically oriented graphitic fabricated nanosheets approxiJohn R. Miller,1* R. A.electrodes Outlaw,2of B.agglomerated C. Holloway3 carbon (CNTs) did estabnanosheet capacitor, whereas it occurs over apreported were not capable of 120-Hz filtering. mately 600 nm high with a gled, crossmultiwall section <1 nm nanotubes a frequency response record in 1997: Hz Electric double-layer capacitors (DLCs) can have high storage capacity, but their porous electrodes seven 6 decades in frequency for the Electrodes with vertically oriented graphene thick, but often terminatinglish with an edge of a proximately an impedance phase angle of 45 (8). (Resistcause them to perform like resistors coating in filter circuits remove ripple from rectified direct current. activated carbon capacitor. This disparity is due nanosheets carbon that fibers have also been graphene sheet (one atomic for layer). ance and reactance have equal magnitudes at a We have demonstrated efficient filtering of 120-hertz current with DLCs with electrodes made from examined (15). Capacitor designs were develA plan view of vertically oriented graphene almost entirely to electrode porosity differences. phase angle 45, making frequency phase conve- angle of the graphene vertically oriented graphene grown directly onno metal current collectors. This design Thethis impedance opednanosheets for a 14,900 F device, but two-terminal nanosheet electrode (Fig. 1A) shows the of irregular nient for edge comparison These DLCs reached had minimized electronic and ionic resistances and produced capacitors with RC time constants of than (exposed nanosheet capacitor 45 at ~15,000 Hz electrical responses were reported. Such verticalmorphology of less the surface planes purposes.) thin electrodes and used a high-conductivity aqueous 200 microseconds, in contrast with ~1 second for typical DLCs. Graphene nanosheets have a ly oriented graphene nanosheets are believed to and the random expansive open areas) created by in comparison with 0.15 Hz for the activated carelectrolyte but were still incapable of filtering at preponderance of exposed edge planes that greatly increases charge storage as compared with that of offer a near-ideal structure for DLC electrodes defects that arise from stress and hydrogen in- bon capacitor and ~30,000 Hz for the electrolytic 120 Hz for two reasons. First, the At felt-like strucdesigns that rely on basal plane surfaces. Capacitors operation. constructedFirst, with these could bestructures smaller grow 120 Hz, the impedance phase angle capable of high-frequency they electrodes corporation. The vertically from the capacitor. ture created porosity with pore length nanosheet equal to capacitor was approxthan the low-voltage aluminum electrolyte capacitors that are that typically used inmetal electronic devices. of a the graphene have a preponderance of edge planes provide substrate and are electronically connected 2 2 the electrode thickness, thus creating distributed 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 activated chargein storage with ionic resistance. mid-1990s tocapaciload-level the graphene power profile of is shown lectric double-layer capacitors (DLCs), al- which carbon capacitor and approximately 83 for the with that of basal planes, provide Similar growth Fig. 1B, but associated Second, the plan structure on manifold electrical battery-powered electricon vehicles that were so called supercapacitors or~3 ultracapacialuminum electrolytic capacitor. The phase angle tance of only mF/cm2 (16). Second, a circular fiber sothen as to display both and relied charge-storage contacts among the individual CNTs andNi against under development ( 4 ) and, more recently, to captors, store charge edge in the planes double are layer formed electrode prototype) was 85. exposed and directly accessible, shallow-angle views of the surface. Raman inten- for a blank (bare the current collector, contributing to the electronture and store energy derived from kinetic energy at an electrolyte-electrode interface when voltage A complex plane plot of the impedance data minimizing the distributed nature of the charge sity measurements of the coating had a D/G band icbecause resistance. capacitors unable oriented graphene nanofor instance, the braking is applied. The electrodes are generally composed obtained fromwere the vertically intensity ratioenergy (ID/IG)of storage. Third, porosity effectsharvesting are minimal because ofa0.67 of Although defects. these toto filter, they showed DLC capacitor frequency hybrid vehicle (5). of high-surface-area conductive material, usually isresponse shown in Fig. 3, with an expanded of the open structure, reducing ionic resistances. Capacitors were fabricated measure the elec-that sheet could be improved by using electrode materials The delayed introduction of DLCs was caused activated carbon (1). DLCs typically store more And fourth, graphene nanosheets themselves have trical performance of the vertically oriented graphene view in the inset. There is no evidence of porous with 2.5-cm-diameter, external rather thanelectrode internal surface area. bycan a limited market for capacitors that could Two onlyidentical than an order of magnitude more high energy per unit and behavior, which would manifest itself by extremely conductivity be grown from nanosheet electrodes. Further improvements in frequency response charge but performed atNi their other volume than conventional capacitorssurface, (2) but,minimizing like storeelectronic a conductive resist75-mpoorly m-thick disks with graphene 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 seriesmust 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 age requirements. Electric double-layer charge stor- is ~1 sfar 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 (911). 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 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) plasmaenhanced 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) 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 We used a series-RC circuit model in which of 50 mT). After the Ar was shut off, the Ni sub- approximately 0.6 mm, which is negligible compared 1 tronic circuit: Smaller-sized filtering capacitors may study showed impedance data with a 45 phase JME, Inc., 17210 Parkland Drive, Shaker Heights, OH 44120, with device dimensions and mass. Electrical con- resistance is the real part of the impedance and USA, and Case Western Reserve University, Great Lakes Energy allow system size reductions, which is particularly angle at 443 Hz (12). Yet another study bonded 2 nection was made to the back surface of each Ni capacitance is calculated as C = 1/(2pfZ), Institute, Cleveland, OH 44106, USA. Department of Applied -90 valuable in some portable electronics applications. vertically aligned CNT electrodes to an aluminum Science, College of William and Mary, Williamsburg, VA where f is frequency in Hz and Z is the imagdisk. Present DLCs have an impedance phase-angle current collector, but this also was unable to ef23185, USA. 3Defense Advanced Research Projects Agency, at 120 Hz that is near 0, which is far from the 90 ficiently filter 120-Hz ripple (13). 3701 North Fairfax Drive, Arlington, VA 22203, USA. -60 Agglomerated, chemically modifiedFig. graphene value needed for filtering. This drawback is a di-1000 *To whom correspondence should be addressed. E-mail: 3. Complex plane plot of the -0.4 and of the graphene nanorect result of using porous electrodes, which store material was evaluated as a DLC electrode jmecapacitor@att.net impedance

a capacitor. Thus, materials at with high frequency. However, particulate electrodes, thus contributing additional proximately 10 to 15 nm thick. After 20 minhigh-surface-area of inductive behavior with ac Line-Filtering Performance less inherent porosity been examined. DLCsthese two limits occurs the transition between electronic resistance. Capacitors constructed with growth, the resulting coating was composed of have

Downloaded from www.sciencemag.org on July 25, 2011

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 eective 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 specic capacitances up to about 250 F/g. Graphene based pseudocapacitors, which are composites with polymers or metal oxides, have specic capacitances of over 400 F/g. Although pseudocapacitors hold more energy than pure EDLCs, they are unstable in some circumstances. Thin-lm 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

REFERENCES

[1] R. Kotz and M. Carlen, Principles and applications of electrochemical capacitors, Electrochimica Acta, 45, 24832498 (2000). [2] T. Szabo, O. Berkesi, P. Forgo, K. Josepovits, Y. Sanakis, D. Petridis and I. Dekany, Evolution of Surface Functional Groups in a Series of Progressively Oxidized Graphite Oxides, Chemistry of Materials, 18, 27402749 (2006). [3] D.R. Dreyer, S. Park, W. Bielawski and R.S. Ruo, The chemistry of graphene oxide, Chemical Society Reviews (2010). [4] C. Liu, Z. Yu, D. Ne, A. Zhamu and B.Z. Jang, Graphene-Based Supercapacitor with an Ultrahigh Energy Density, Nano Letters, 10, 48634868 (2010). [5] J.R. Miller, Graphene Double-Layer Capacitor with ac Line-Filtering Performance, Science, 329, 16371639 (2010). [6] K. Novoselov, A.K. Geim, S. Morzov, D. Jiang, Y. Zhang, S. Dubonos, I. Grigorieva and A.A. Firsov, Electric Field Eect in Atomically Thin Carbon Films, Science, 306, 666669 (2004). [7] S.J. Wang, Y. Geng, Q. Zheng and J.k. Kim, Fabrication of highly conducting and transparent graphene lms, Carbon, 48, 18151823 (2010). [8] W.S. Hummers, Preparation of Graphitic Oxide, Journal of the American Chemical Society, 208, 1339 (1958). [9] B. Conway, Electrochemical Supercapacitors: scientic fundamentals and technological applications, 1st ed. (Kluwer Academic / Plenum Publishers, 1999). [10] P.A. Mini, A. Balakrishnan, S.V. Nair and K.R.V. Subramanian, Highly super capacitive electrodes made of graphene / poly ( pyrrole ), Chemical Communications, 1, 57535755 (2011). [11] X. Zhao, H. Tian, M. Zhu, K. Tian, J.J. Wang, F. Kang and R.A. Outlaw, Carbon nanosheets as the electrode material in supercapacitors, Journal of Power Sources, 194, 12081212 (2009).

18

[12] Y. Wang, Z. Shi, Y. Huang, Y. Ma, C. Wang, M. Chen and Y. Chen, Supercapacitor Devices Based on Graphene Materials, Journal of Physical Chemistry C, 113, 1310313107 (2009). [13] M.D. Stoller, S. Park, Y. Zhu, J. An and R.S. Ruo, Graphene-Based Ultracapacitors, Nano Letters, 8, 34983502 (2008). [14] T.Y. Kim, H.W. Lee, M. Stoller, D.R. Dreyer, C.W. Bielawski, R.S. Ruo and K.S. Suh, High-Performance Supercapacitors, ACS Nano, XXX (2010). [15] X.Y. Peng, D. Diamond and K.T. Lau, Synthesis of electrochemically-reduced graphene oxide lm with controllable size and thickness and its use in supercapacitor, Carbon, 49, 34883496 (2011). [16] J.J. Yoo, K. Balakrishnan, J. Huang, V. Meunier, B.G. Sumpter, A. Srivastava, M. Conway, A. Leela, M. Reddy, J. Yu, R. Vajtai and P.M. Ajayan, Ultrathin Planar Graphene Supercapacitors, Nano Letters, 11, 14231427 (2011). [17] K. Zhang, L.L. Zhang, X.S. Zhao and J. Wu, Graphene / Polyaniline Nanober Composites as Supercapacitor Electrodes, Chemistry of Materials, 22, 13921401 (2010). [18] Z. Li, J. Wang, X. Liu, S. Liu, J. Ou and S. Yang, Electrostatic layer-by-layer self-assembly multilayer lms based on graphene and manganese dioxide sheets as novel electrode materials for supercapacitors, Journal of Materials Chemistry, 21, 33973403 (2011). [19] X. Xia, J. Tu, Y. Mai, R. Chen, X. Wang and C. Gu, Graphene Sheet / Porous NiO Hybrid Film for Supercapacitor Applications, Chemistry: A European Journal, 00, 19 (2011). [20] G. Yu, L. Hu, N. Liu, H. Wang, M. Vosgueritchian, Y. Yang and Y. Cui, Enhancing the Supercapacitor Performance of Graphene/MnO2 Nanostructured Electrodes by Conductive Wrapping, Nano Letters, 00, 15 (2011).

19