GRAPHENE SYNTHESIS AND ASSEMBLY FOR GRAPHENE ACTUATORS

By
YICHEN CHEN

A THESIS PRESENTED TO THE GRADUATE SCHOOL

OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF SCIENCE
UNIVERSITY OF FLORIDA
2012
1

 2012 Yichen Chen

To my family and friends

ACKNOWLEDGMENTS
I would like to thank my advisor, Dr. Peng Jiang, for offering me the opportunity to
join this project and giving me numerous of precious advice for my research. I would
also like to thank my fellow lab-mates who have assisted me with my work. I want to
take this opportunity to acknowledge former graduate students Wei-han Huang and
Tzung-hua Lin, my research partner Ta-ching Wu and all the students in Dr. Peng
Jiangs group. I also want to express my appreciation to my committee member Dr. Kirk
J. Ziegler for his valuable inputs and guidance. Last but not least, I want to specially
thank my parents for teaching me the value of life and for always being there when I
need them.

TABLE OF CONTENTS
page
ACKNOWLEDGMENTS .................................................................................................. 4
LIST OF FIGURES .......................................................................................................... 6
LIST OF ABBREVIATIONS ............................................................................................. 8
ABSTRACT ..................................................................................................................... 9
CHAPTER
1

RESEARCH BACKGROUND ................................................................................. 11

1.1 Graphite ............................................................................................................ 11
1.2 Graphite Oxide .................................................................................................. 12
1.3 Graphene .......................................................................................................... 12
1.4 Graphene Oxide................................................................................................ 13
1.5 Methods to Produce Graphene ......................................................................... 14
1.5.1 Micro-mechanical cleavage ..................................................................... 14
1.5.2 Drawing method22 .................................................................................... 14
1.5.3 Epitaxial growth on SiC24 ......................................................................... 14
1.5.4 Graphene oxide reduction25..................................................................... 15

SYNTHESIS OF GRAPHENE ................................................................................ 18

2.1 Synthesis of Graphite oxide .............................................................................. 18
2.2 Exfoliate Graphite Oxide into Graphene Oxide ................................................. 20
2.3 Synthesis of Graphene from Graphene Oxide .................................................. 21
2.4 Results and Discussion..................................................................................... 22

ASSEMBLY OF GRAPHENE SHEET..................................................................... 27

3.1 Experimental ..................................................................................................... 27
3.2 Results and Discussions ................................................................................... 28

GRAPHENE ACTUATORS ..................................................................................... 33

4.1 Introduction ....................................................................................................... 33
4.2 Experiment ........................................................................................................ 34
4.3 Results and Discussions ................................................................................... 35

LIST OF REFERENCES ............................................................................................... 40

BIOGRAPHICAL SKETCH ............................................................................................ 44

LIST OF FIGURES
Figure

page

1-1

Structure of Graphite Oxide................................................................................. 15

1-2

Structure of Graphite Oxide................................................................................. 16

1-3

Structure of Graphene ......................................................................................... 16

1-4

Different structure formed by graphene ............................................................... 17

1-5

micro-mechanical cleavage produce graphene by break the Van der Waals

force between the monolayer carbon plane inside graphite................................ 17

2-1

Filtration system for rinsing graphite oxide products. .......................................... 24

2-2

Graphite Oxide after one night drying in the oven ............................................... 24

2-3

Graphite oxide solution after diluted .................................................................... 25

2-4

Graphite oxide aqueous colloids in a Petri Dish .................................................. 25

2-5

0.5 mg/mL Graphene oxide solution in a centrifuge tube ................................... 25

2-6

Graphene solution .............................................................................................. 26

2-7

Color difference of graphite oxide solution and graphene solution ..................... 26

2-8

Aggregation in the graphene solution................................................................. 26

3-1

Filtration system for graphene actuator .............................................................. 30

3-2

Ideal graphene paper ......................................................................................... 30

3-3

SEM picture of the surface of A) GO paper B) Graphene paper ........................ 31

3-4

SEM picture of cross-section of A) GO paper B) graphene paper...................... 31

3-5

Graphene paper with particle on the surface...................................................... 32

3-6

Cracked and wrinkled graphene paper .............................................................. 32

4-1

Graphene actuator with Au electrodes on both side of the graphene strips. A)

front view. B) side view. ...................................................................................... 37

4-2

Actuator partly immersed in the Nacl solution holding by the rectangular

glass tank. .......................................................................................................... 37

4-3

Actuations of a graphene actuator operated by potential step method. A)

cross-sectional images of a graphene actuator. B) Displacements of actuator
tip........................................................................................................................ 38

4-4

Actuations of a graphene actuator operated by cyclic volatmettry method. A)

Two-electrode cyclic valtammogram. B) Corresponding displacements of the
actuator .............................................................................................................. 39

LIST OF ABBREVIATIONS
CMG

Chemically modified graphene

CNT

Carbon Nano Tube

DI

Deionized

GO

Graphene Oxide

MWCNT

Multi-walled Carbon Nano Tube

Abstract of Thesis Presented to the Graduate School

of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Master of Science
GRAPHENE SYNTHESIS AND ASSEMBLY FOR GRAPHENE ACTUATORS
By
Yichen Chen
December 2012
Chair: Peng Jiang
Major: Chemical Engineering
In this thesis, we provide an improved method to synthesize graphene and also
introduce the assembly of a new kind of graphene actuators. Graphene is an allotrope
of carbon with a unique one-atom thick structure. It exhibits many exciting properties
such as excellent electrical/thermal conductivity, high surface area, great mechanical
strength and inherent flexibility. The synthesis of graphene contained two steps. First
graphite oxide was synthesized from nature graphite by a modified Hummer method.
Then we exfoliated the graphite oxide into GO using ultra-sonication and reduced GO to
graphene by chemical reduction. After using flow-filtration method, we were able to
assemble conductive graphene paper, which consisted of parallel graphene sheets.
After studying the properties of graphene paper, we developed electromechanical
actuators based on two strips of graphene paper with an intermediate dielectric layer.
The actuation mechanism of graphene actuators was most likely due to swelling of
electrodes originating from dopant intercalations. Graphene actuator strips in the size
of 1 mm by 15 mm were assembled. The displacement of actuators under the repeated
potential steps between -2 and 2 volts in 1 M NaCl solution was determined to be
around 1.2 mm when 10 mm of graphene actuator was immersed in electrolyte.

Actuations of a graphene actuator operated by cyclic voltammetry at a scan rate of 50

mV/s reached almost the same displacement. The actuation didnt die out until140
cycles.

10

CHAPTER 1
RESEARCH BACKGROUND
1.1 Graphite
Graphite is an allotrope of carbon. It is a low density, non-expensive material and
microcrystalline graphite has been commonly used in pencil manufacturing for years.
Graphite has high electrical and thermal conductivity.1 The conductivity of graphite
depends on its structure. A single crystal of graphite has an electrical resistivity from 4
to 6x10-5 Ohm-cm,2,3 which has the same order of the conductivity of a poor metal.
However, polycrystalline graphite has a much higher resistivity due to the crystal
boundaries. Graphite has a multi-layer structure and each layer contains hexagonal
lattice arrays. As shown in Figure 1-1, graphite is made of parallel layers of graphene
which has hexagonal rings.4 Each yellow sphere stands for a carbon atom and each
blue line stands for the covalent bond between carbon atoms. The dotted line
represents the weak Van der Waals forces between the parallel hexagonal rings that
allow sliding movement. The angle between the two covalent bonds is 120. The space
between the lattice planes of graphite is 3.37 and every hexagonal lattice in the same
plane has a distance of 1.42 between each other.5 Each layer of graphite is of sp2
carbon atoms.
There are three kinds of natural graphite: flake graphite, vein graphite and
microcrystalline graphite. Flake graphite is the most common source of graphite used in
chemical reactions. It is a natural mineral that is purified to remove heteroatomic
contamination.6 Vein graphite structure has high electrical conductivity because of its
high crystallinity. Microcrystalline graphite is also called amorphous. Besides natural
graphite, there are also synthetic graphite such as primary synthetic graphite and

11

graphite fiber. Based on graphites unique properties, graphite can be used as carbon
brushes, refractory materials, lubricants, friction materials and cathode material in zinccarbon and lithium-ion batteries.
1.2 Graphite Oxide
Graphite Oxide is a compound of carbon, oxygen and hydrogen. It is nearly
amorphous and has the structure of graphene oxide, which is very hydrophilic.7 As
shown in the Figure 1-2, the structure of graphite oxide contains two kinds of regions,
the aromatic region with unoxidized benzene rings and the aliphatic six-membered
rings.8 The sizes of both regions depend on the degree of oxidation of graphite oxide.
The inter-layer distance between the graphene oxide sheets of graphite increases
reversibly with increasing humidity in the environment and it varies from 6 to 12 .
Graphite oxide is also the middle product in the process of graphene synthesis since
graphite oxide can be fully exfoliated into graphene oxide sheet when it is in the form of
aqueous colloidal suspensions. It can be seen that graphite oxide sheets carry a
negative charge when they are dispersed in water. Due to the electrostatic repulsion
between graphite oxide sheets, graphite oxide can form a stable aqueous suspension.7
1.3 Graphene
Similar to graphite, graphene is an allotropy of carbon. Graphene has a twodimensional structure packed in a honeycomb crystal lattice.9,10 As shown in Figure 1-3,
graphene is a one-atom-thick carbon layer of sp2-bonded carbon atoms containing
hexagonal lattice arrays. The yellow dots represent the carbon atoms and the blue lines
represent the bonds between two carbon atoms. The length of the carbon-carbon bond
in graphene is about 0.142 nm. On 2010, Andre Geim and Konstantin Novoselov at the
University of Manchester were awarded the Nobel Prize of Physics for groundbreaking
12

experiments regarding the two-dimensional material graphene. Graphene has a high

value of Youngs modulus (~1,100 Gpa),2,11 great fracture strength (125GPa),2 good
thermal conductivity (~5.000 Wm-1K-1),3 excellent mobility of charge carriers (200,000
cm2V-1S-1)4,12 and high specific surface area (calculated value, 2,630 m2g-1).5 In
addition, graphene also has several transport phenomena (the electron transport is
described by the relativistic-like Dirac equation) such as quantum Hall effect. All those
significant properties of graphene and chemically modified graphene (CMG) hold great
promise for potential application in the area of energy-storage materials,13 paper-like
materials, polymer composites, liquid crystal devices and mechanical resonators7.
Figure 1-4 is an image of 2-D graphene forming different dimensional carbon materials.
As shown in the Figure, graphene can be wrapped up into 0-D buckyballrolled into 1D nanotube or stacked into 3-D graphite.9 Although the monolayer of nanostructure
provides graphene with both chemical and chemical stability, the properties of graphene
still depend on the way it is aligned.14 For example, electrons move faster in the 2-D
graphene structure with a mobility exceeding 15,000 m2V-1s-1, while graphene
nanoribbon shows semi-conductivity when it has narrow width and smooth edges.15 The
most common method for producing graphene sheets in large quantities is by using a
chemical process that involves graphite oxidation, exfoliation and reduction.
1.4 Graphene Oxide
Graphene oxide (GO) is an oxygen-rich monolayer nanomaterial. It is provided by
the controlled oxidation of graphite.16 GO can be prepared by exfoliating or heat
expanding of graphite oxide. GO are hydrophilic since the hydroxyl (OH) groups are
bonded to the surface of the GO nanosheets,17 therefore GO is the precursor material

13

for synthesis of hydrophobic graphene.18 GO is considered as a new type of

macromolecular form of carbon. In most cases graphene nanosheets are hydrophilic
and this property can be enhanced by reacting it with allylamine, graphene nanosheets
can also be changed into hydrophobic via functionalizing its surface with
phenylisocynate (C6 H5HCO) through the solvothermal synthesis process.19

The reaction is
1.5 Methods to Produce Graphene
1.5.1 Micro-mechanical cleavage
Micro-mechanical cleavage is a physical way to produce graphene.20 It can
produce one- atom-thick graphene structures by repeated exfoliation of small mass of
high oriented pyrolytic graphite.21 Figure 1-5 shows that micro-mechanical cleavage
produces graphene by breaking the Van der Waals force between the monolayer
carbon planes inside the graphite.
1.5.2 Drawing method22
On 2004, a research group in Manchester University provided graphene by
rubbing the pencil against an oxidized silicon wafer, turning the thick graphite flakes of
the pencil into monolayer carbon structure graphene.23
The reason that oxidized silicon wafers were used instead of paper was that
oxidized silicon wafers reflected a rainbow of colors, which enhanced the interface
contrast between the thin layer of graphene and the wafer.22
1.5.3 Epitaxial growth on SiC24
Graphitization of silicon carbide (SiC) by Si sublimation during high temperature
(>1100C) vacuum annealing reduces it to graphene. Silicon carbide is a material with
14

high resistivity and it is already available in the form of large-diameter wafers. Epitaxial
growth on SiC is the most common way to produce graphene-based electronics.
However, epitaxial growth on SiC can lead to problems of graphene growth disorder.24
1.5.4 Graphene oxide reduction25
There are four steps to make graphene nanosheets from graphite flakes: 1.
Prepare graphite oxide by using Hummer method for starting graphite.26 2. Exfoliate
graphite oxide into hydrophilic graphene oxide by ultrasonic vibration. 27 3. Reduce
hydrophobic graphene oxide into hydrophilic graphene by reacting with hydrazine.28

Figure 1-1. Structure of Graphite Oxide

15

Figure 1-2. Structure of Graphite Oxide.

Figure 1-3. Structure of Graphene

16

Figure 1-4. Different structure formed by graphene

Figure 1-5. Micro-mechanical cleavage produce graphene by break the Van der Waals
force between the monolayer carbon plane inside graphite.

17

CHAPTER 2
SYNTHESIS OF GRAPHENE
2.1 Synthesis of Graphite oxide
The aim of this process is to transform graphite flakes into graphite oxide. We
measured 1 g of powdered graphite (Grade 3243, Asbury Graphite Mills Inc, Khtanning,
Pa) and left it in a Petri dish. When we took the graphite from its container, we checked
and made sure the graphite wasnt decayed and that it was in powder form. Using a
graduated cylinder, we measured 3 mL of H2SO4 (95% - 98%, Sigma-Aldrich Inc, St.
Louis, MO) and put it in a 50 mL beaker, adding 1 g of K2S2O8 (99+%. Sigma-Aldrich
Inc, St. Louis, MO) and 1 g of P2O5 (>=98%, Sigma -Aldrich Inc, St. Louis, MO) into the
beaker. At the same time we set up a water bath system and heated the water. When
the water temperature reached 80 C, we placed the beaker with all the chemicals into
the water bath and stirred all the reactants with a glass stick for 15 minutes. Afterwards,
we took the beaker out of the water bath and let it cool down in room temperature for 6
hours. After the beakers temperature equilibrated to room temperature, we took out the
black mud-like products from the beaker. This reaction is part of the modified Hummers
method, which involves an additional oxidation step prior to the real Hummers method.
In order to remove the acid residue from the product, we built a vacuum filter and put
the product we got on top of the filter paper. Figure 2-1 shows the equipment setup for
this step, the pipe on the left opening side of the Erlenmeyer flask was connected to an
air vacuum pump.
By adding water into the product and letting the vacuum to drain the water away
through the filter, we ensure that the product gets rinsed thoroughly. When the PH strips
we put on the outlet of the filter shows that the PH of the liquid is between 6 and 7, it

18

indicates that the product doesnt contain acid residue anymore and therefore we can
stop adding more water. The next step is to dry out the water from the product. We put
the black mud-like product into a 200 mL beaker and then we left it in a lab drying oven
(Isotemp vacuum oven, model 281 A) with a medium-high temperature (Level 6, about
85C) over night. Figure 2-2 shows the graphite inside the beaker was partially oxidized
and it formed a uniform fine powder with a dark metallic grey color.
The next morning we picked up the product from the oven and started to run the
Hummers method to make graphite oxide. The first thing we did was to build a 0C ice
bath by adding ice cubes into a water bath to offset the heat released from the
Hummers reaction. Afterwards we added 26 mL 98% H2SO4 with a stir-bar followed by 3
g of KMnO4 into the beaker really slowly, leaving it stirring under 35C for 2 hours. Two
hours later we added 46 mL of water into the graphite oxide and this gave the product a
bright brown color.
Soon another 140 mL of water and 4 mL (the range is 2-5 mL according to the
recipe) of H2O2 were added into the solution to stop the reaction. By now we finished
the Hummers method and the next step is to purify the products. Instead of using DI
water, we used 250 mL 1/ 10 HCl solution ( using 25 mL HCl (32% - 38% solution.
Fisher Scientific, Fair lawn, NJ) and 225 mL DI water under 50 60 C) to wash the
extra ion residue from the graphite oxide. After adding the 1/10 HCl solution, we put the
solution in a centrifuge (IEC centra cl2, Thermo Electron Corporation) and kept the
bottom aqueous colloids while pouring away the clear solution on the top of the
centrifuge tube after every centrifuging. After finishing the first round of centrifuging, we
added 15 mL of DI water to each tube and ran the same centrifuge steps another 2

19

times. At this stage we have successfully synthesized the graphite oxide solution from
graphite. Figure 2-5 shows a sample of graphite oxide solution with dark brown color.
We also obtained the weight percentage data by leaving a graphite oxide colloid
sample in a Petri dish and letting it dry out overnight in the lab oven.
The formula used to calculate the wt % is

We needed to dilute graphite oxide colloids into 30 mL of graphite oxide solution with a
concentration of 1 mg/mL with the aim of making graphite oxide paper and graphene
paper later. So we prepared the amount of graphite oxide aqueous colloids and the DI
water we needed based on the wt% calculated for the aqueous colloid graphite oxide.
Shortly afterwards, we mixed them together in a large glass vial and used ultrasonic
vibration to make the graphite oxide homogenously dispersed in water.
2.2 Exfoliate Graphite Oxide into Graphene Oxide
We used ultrasonic vibration to exfoliate the multi-layered structure of graphene
oxide. The parameters we set for the ultrasonic vibration in the lab was level 9 and we
let it run for one hour while protecting the glass vial in a room-temperature water bath.
Once the vibration was done, we took out the graphen oxide solution and separated it
into two centrifuge tubes. The solution then got centrifuged under 3900 rpm for 30
minutes.29 By that time we had already obtained the uniform graphite oxide solution with
a concentration of 1 mg/ mL, the last step involved the extraction of the extra ions
generated from the reaction. Therefore we cut a adequate length of ion exchange
membrane ( Dialysis tubng,#21-152-4, Fisher Scientific) for 30 mL graphite oxide
solution and withdrew up the clean solution from the centrifuged solution into the

20

membrane. After sealing both ends of the membrane with clips, we placed it in a big
bowl of water with a stir-bar and let it dialysis in DI water overnight. As shown in Figure
2-5, graphene oxide solution had a similar carbon black color as the graphite oxide
colloids. The graphene oxide was well dispersed and there were no graphene oxide
flakes that could be seen in the solution.
Before we used the graphene oxide solution, we let the solution go through the
ultrasonic vibration again for 5 minutes to make sure there was no aggregated
graphene oxide turned into graphite oxide in the solution. To prevent aggregation of
graphene oxide from occurring during the following filtration process, we took out 10 mL
of the 1mg/mL graphite oxide solution and diluted it with another 10 mL of DI water.
After dilution, the GO solution showed a light yellow color as shown in Figure 2-3. Later
on, the same 0.5 mL/ mg graphene oxide solution was used to prepare both graphene
actuator and graphene paper.
2.3 Synthesis of Graphene from Graphene Oxide
During this process we reduced the 0.5 mg/mL graphene oxide solution into 0.25
mg/mL graphene solution. 20 mL 0.5 mg/mL graphene oxide solution was used in this
process. Before we used it in this process, we let the solution go through the ultrasonic
vibration to eliminate the possible aggregation of graphene oxide. Then we took 5 mL
from the same solution and put it in a small glass vial. Later we mixed it with another 5
mL of DI water and we got 10 mL of graphene oxide solution with a concentration of
0.25 mg/mL. Since 10 mL solution was only enough for one piece of graphene paper
and we wanted two pieces every time, we diluted another 5 mL of 0.5 mg/mL graphene
oxide solution in another small glass vial. After the dilution, we brought another clean
glass vial and injected 2 mL of NH4OH into it. Using a 1-200 L syringe, we added 35
21

L of NH4OH(Fisher Scientific, Fair lawn, NJ) into each graphene oxide solution vial
and shook both vials by hand to ensure good mixing. Then we switched to a 1-200 L
syringe to add 5 L of Hydrazine (35 wt%, solution in water. Sigma-Aldrich Inc, St.
Louis, MO ). For this step we mixed the hydrazine with the solution by shaking both
vials for 5 minutes. We then prepared a 98 C water bath and let both vials get heated
up in the water bath for 1 hour. As shown in Figure 2-6 and 2-7, compared to the
graphite oxide solution, graphene solution seemed to be darker. The graphene solution
was homogenous and had almost the same density as pure water.
2.4 Results and Discussion
The concentration of graphite oxide colloids was 6.773 g/cm3. Figure 2-4 was a
picture of a GO colloid sample in a Petri dish. We could tell that GO colloids has a large
surface tension. During the graphene oxide reduction process, we found serious
aggregation of graphene in the solution after reacting in 98 C water bath for one hour.
We made two assumptions based on that fact: the first was that the 0.5 mg/mL
graphene oxide solution we used to manufacture graphene had aggregated or small
graphene oxide flakes inside it; the second assumption was that there were extra ions in
the graphene oxide solution when we ran the reduction. Figure 2-8 shows the poor
dispersion of graphene in aggregated graphene solution.
In order to avoid the aggregation, we sonicated the graphene oxide solution for 20
minutes before we reduction step. In addition, we sonicated the graphite oxide solution
every time we used it after a while. However those measures didnt have any effect on
the aggregations.
Therefore we started to think about the possibility that the graphene solution was
contaminated by some extra ions before or after the reduction step. The first
22

contaminant source we thought about was water; therefore we ran the whole process
again using all DI water. But the aggregation didnt reduce because of that. The second
possibility was that the ions were introduced into the solution after reduction, which
could be caused by having excess hydrazine or NH4 OH in graphene solution. This
reminded us about the fact that there might not be enough graphene oxide to reduce
during the reaction. After the centrifuging step for the dialysis of the 1mg/mL graphite
solution, we removed all the flakes present that might contain aggregated graphite from
the bottom of the centrifuge tube. Although the amount of hydrazine and NH4 OH was
designed to reduce the exactly 10 mL of 0.25 mg/mL graphene oxide solution, the
concentration was calculated based on data we got from the graphite oxide collides and
we hadnt updated the concentration of graphite oxide or graphene oxide solution after
that. There were chances that the solute in the solution might decrease; for example,
the graphite oxide flakes left in the bottom of the centrifuge tube before we ran dialysis,
the solution we lost while transfering it from one container to another.

23

Figure 2-1. Filtration system for rinsing graphite oxide products.

.

Figure 2-2. Graphite Oxide after one night drying in the oven

24

Figure 2-3. Graphite oxide solution after diluted

Figure 2-4. Graphite oxide aqueous colloids in a Petri Dish

Figure 2-5. 0.5 mg/mL Graphene oxide solution in a centrifuge tube

25

Figure 2-6. Graphene solution

Figure 2-7. Color difference of graphite oxide solution and graphene solution

Figure 2-8. Aggregation in the graphene solution

26

CHAPTER 3
ASSEMBLY OF GRAPHENE SHEET
3.1 Experimental
During this process we manufactured conductive graphene paper from the
homogenous graphene solution we made from the last step. We built a filtration system
with a water circulation pump that provided a low pressure difference.30 The same
system was also used to manufacture graphene actuators.
Figure 3-1 is the equipment setup for the filtration. The right opening on the
Erlenmeyer flask can help attract water down from the solution by providing a pressure
difference between the inside of the flask and the solution on top. The pipe connects the
open end of the flask with the water-circulation pump installed in the air cabinet. For the
filter, we used a anodisc membrane filter (25 mm diameter, 0.2 micrometer porosity.
Whatman Inc, Maidstone,England) instead of regular filter paper to gain a more smooth
graphene paper surface31. After setting up the filtration system, we used a pipette to
take 8 mL 0.25mL/ mg graphene solution and dropped it carefully onto the filtration
membrane. We observed the status of the filter system and made sure that it was
stable. After six hours the graphene solution became a cake slightly attached to the
membrane. In order to remove the graphene cake from the filtration system, we took off
the clip and used slight air flow to dry the graphene inside the pipe. After that we used a
razor to lift up the membrane slightly, and the graphene oxide cake slid from the pipe
with the membrane. We used another old membrane to cover the naked side of the
graphene cake and put a weight on top of it to reduce the moistness inside the cake.
After one night we came back and removed the weight and the graphene cake became
a thin, conductive graphite paper with a smooth surface.

27

3.2 Results and Discussions

The ideal product of graphene paper should be a metallic black thin membrane
with mirror smooth surface as shown in Figure 3-2. Compared to GO paper, graphene
paper should not have any aggregated carbon structure on the surface. From Figure 3-3
(a), we could see that there were lots of aggregations on the surface of GO paper thus
the surface was not smooth. Figure 3-3 (b) is a SEM image of graphene paper we
made showed that there was almost no aggregation on the surface(. From the crosssection SEM image Figure 3-4 (a), we could observe that GO paper had multiple layers
of carbon structure and they were connected with each other. Figure 3-4(b) shows that
the graphene paper we made consisted of a monolayer of carbon structure that is
parallel to each other. However we mainly found two kinds of defects in our graphene
paper products. The first kind of defect is non-smooth surface. Figure 3-5 was a SEM
picture of our graphene paper sample with some tiny particles scattered on the surface.
There were two possibilities for the presence of the particles: first possibility was that
the particles had dust on them that got into the solution during the previous step, the
second possibility was that the black particle was graphene aggregated into graphite
during the overnight filtration step. In both cases, it resulted in a reduction of the
conductivity of the graphene paper because both dust and graphite particles are
nonconductive. The other kind of defect present was cracks or wrinkled surfaces that
could be easily seen in Figure 3-6. The crack was usually due to there being less than
enough graphene solution added into the filtration system. The cracks on the surface
also reduce the conductivity of the graphene paper. The wrinkled surface was because
we dried the graphene cake too soon thus resulting in the shrinkage of the graphene
paper surface. Based on our measurement, most of the ideal graphene papers
28

synthesized had a resistance close to 200 , some even reached a excellent

conductivity with a resistance close to 100 ; while the non-ideal graphene paper
usually had a higher resistance ranged from 210 to 480 . Therefore it was very
important to ensure smooth surface for the graphene paper because most of the defects
will influence its performance with the graphene actuator.

29

Figure 3-1. Filtration system for graphene actuator

Figure 3-2. Ideal graphene paper

30

Figure 3-3. SEM picture of the surface of A) GO paper B) Graphene paper

Figure 3-4. SEM picture of cross-section of A) GO paper B) graphene paper.

31

Figure 3-5. Graphene paper with particle on the surface

Figure 3-6. Cracked and wrinkled graphene paper

32

CHAPTER 4
GRAPHENE ACTUATORS
4.1 Introduction
Actuator is the equipment that could mechanically respond to external change in
temperature, light, humidity and current.32 Reversible actuators have various
applications in sensors, artificial muscle, switches and memory chips.33 Graphene
actuators focused on developing the electromechanical feature of the material.
Graphene has a unique two-dimensional structure with a thickness of one atom. It is
zero band gap semi metallic conductor material,34 which exhibits excellent
electrical/thermal conductivity,35 high surface area, great mechanical strength and
inherent flexibility.36 Compared to carbon nano tube( CNT) material, graphene provides
a larger surface area (theoretically 2630 m2 g-1).37 Besides that, single-layer graphene
has a steady strength of 130 GPa, Youngs modulus of 1TPa, and high electricity
conductivity of 6000 S cm-1.38
Because of its natural inversion symmetry, graphene is not intrinsically
piezoelectric. In order to induce piezoelectricity for graphene, the inversion symmetry
needs to be broken by limiting the adsorption of atoms on the surface of graphene only
on one side.39 Research has already been done on graphene-based and CNT-based
actuators. A multi-walled CNTs( MWCNT) /GO bilayer actuator was built using solution
filtration method. Since the OH and COOH groups on the GO side were sensitive to
humidity while the other side( MWCNT) wasnt, the actuator curled in different directions
depending on the environment humidity.40 However, the high cost of CNTs synthesis as
well as the non-linear control of the actuators with humidity, limited the potential
application of this process. There was also research done on single-walled CNT

33

actuator that showed electromechanical material features.41,42 The actuation came from
chemical-based expansion via the non-faradaic charging/discharging.43
In order to improve the actuation performance and also lower the cost, we
assembled the electromechanical graphene actuators. The actuators were made with
two paper-thin graphene strips adhered on both side of a dielectric layer. We applied
cyclic voltammetry on the actuators and also we treated the actuators with repeated
potential steps. Cyclic stability of the graphene-based actuators was also explored.
4.2 Experiment
The actuators were made in sandwich structure with a strip of Scotch Double
Stick Tape as intervening dielectric between two graphene strips. After getting graphene

sheet from pervious steps, we cut paper-like graphene discs into 1mm by 15 mm strips.
The graphene sheets were cut by a razor blade and usually one piece of graphene
sheet can be divided into four graphene strips with the required size. The double-sided
tape strips were prepared by cutting the Scotch Double Stick Tape into 1mm wide strips
with a length a little over 15 mm. For each actuator we attached two pieces of
Au/Cr/glass electrodes pointing opposite direction on the edge of both graphene strips.
The electrodes were made by sputter deposition of 20 nm of Cr and 200 nm of Au and
each were connected with a clip for applying voltage. Both of the electrodes play an
important role in its actuation performance. Figure 4-1 (A) and (B) show detailed
imagies of the experiment setting. Figure 4-2 shows that during the experiment there
was about 10 mm of the actuators immersed in the rectangular glass tank, which was
full of 1 M NaCl solution. First we used potential steps (-2/ 2 V) on actuators and
recorded the actuation. Then we used cyclic voltammetry, applying voltage between -2
and 2 volts with a scan rate of 50 mV/s through the electrode. By videotaping the
34

actuators, we could observe the bending of the actuators in the solution corresponding
to the voltage change.
A Kurt J. Lesker CMS-18 Multitarget Sputter was used for the sputtering
deposition of Cr and Au. Scanning electron microscopy (SEM) was carried out on a
JEOL 6335F FEG-SEM. A thin layer of carbon was sputtered onto the samples prior to
imaging. An EG&G Model 273A potentiostat/galvanostat (Princeton Applied Research)
was used for potential step and cyclic voltammetry operations.
4.3 Results and Discussions
We immersed 10 mm of graphene actuators in 1 M NaCl solution and then applied
repeatedly potential steps between -2 and 2 volts. Before we recorded the actuation
performance, we operated several steps to make sure the actuator reaches maximum
wetting. We also recorded the whole process and calculated the displacements of
actuators tip based on its position on the grid paper on the back of the water tank. The
initial position of the actuators tip was considered as origin. Figure 4-3(A) showed that
the actuator moved to the right when a positive charge was applied and to the left when
a negative charge was applied during the eight successive potential steps with a total of
four cycles( -2/ 2 V repeatedly). Based on the fact that the actuator always bended to
the cathode during the experiment, we believed what happened was anions (Cl -) and
cations ( Na+) in the electrolyte (NaCl) were moved to the anode and cathode. Since
chloride ions were larger than sodium ions in size, the dopant intercalations resulted in
the bending of [Link] 4-3 (B) showed that under the same operation as (A),
the displacement of the actuators tip was around 1.2 mm.
Then we operated actuators by using the cyclic voltammetry method between -2
and 2 volts in 1 M NaCl solution with a scan rate of 50 mV/s. This time we started
35

recording the data without waiting for the wetting of the actuator. Figure 4-4 (A) showed
the first several cycles of cyclic voltammograms of the graphene actuator and the
current in this stage increased with time, which demonstrated that the wetting of the
actuator occurred with dopant intercalations at the beginning. After several cycles , the
change of the current started to maintain a steady state. From Figure 4-4(B), we could
see that the actuation performance was also influenced by the wetting time. We could
barely observe displacement of the actuators tip at the beginning of the experiment. As
the cycle number increased, the extent of displacement also increased until it reached a
steady value around 1.2 mm, which almost matched the actuation performance under
potential steps. After maintaining steady actuation performance for a while, actuators
die out after about 140 cycles.

36

Figure 4-1. Graphene actuator with Au electrodes on both side of the graphene strips.
A) front view. B) side view.

Figure 4-2. Actuator partly immersed in the Nacl solution holding by the rectangular
glass tank.

37

Figure 4-3. Actuations of a graphene actuator operated by potential step method. A)

cross-sectional images of a graphene actuator. B) Displacements of actuator
tip.

38

(A)

(B)
Figure 4-4. Actuations of a graphene actuator operated by cyclic volatmettry method. A)
Two-electrode cyclic valtammogram. B) Corresponding displacements of the
actuator

39

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BIOGRAPHICAL SKETCH
Yichen Chen was born in 1988 in Shanghai, China. On 2006 she started her
undergraduate in East China University of Science and Technology (ECUST),
Shanghai. Three years later, she left the city that she had been living for twenty-one
years and went to the United States as an exchange student at Lamar University,
Beaumont, Texas. She completed her exchange study one year later then received her
Bachelor of Science in chemical engineering from ECUST. On that same year, she was
accepted by University of Florida as a graduate student and received a Master with
thesis degree in the fall of 2012.

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