Aung1

Making  Graphene-­‐Based  Supercapacitors  by  LightScribe    

 
Theint  Aung,  Advisor:  Dr.  Derin  Sherman  
 
Cornell  College,  Department  of  Physics,  Mount  Vernon,  IA    
 
 
I.  Introduction  
 
Supercapacitors,  also  known  as  electrochemical  capacitors,  fundamentally  differ  from  
conventional  capacitors  in  that  a  standard  capacitor  comprises  two  metal  plates  and  a  
dielectric  material  whereas  a  supercapacitor  makes  use  of  two  electrodes  separated  by  
an  ion  porous  medium  in  an  electrolyte  [1].  Given  the  added  advantages  of  short  
charging  period,  flexibility,  being  lightweight  and  environmentally  safe  compared  to  
batteries,  supercapacitors  are  considered  to  be  the  solutions  to  our  energy  storage  
issues  [2].  A  recent  study  done  by  researchers  at  UCLA  introduces  a  novel  way  of  making  
graphene,  which  then  can  be  used  to  build  high  performance  supercapacitors  [1].  For  
my  project,  I  aim  to  repeat  the  experiments  and  study  the  electrical  properties  of  
graphene-­‐based  supercapacitors.    
 
II.  Project  Overview  
 
Although  batteries  are  widely  used  for  their  high  energy  densities  (20-­‐150Wh/kg),  their  
low  power  density,  i.e.,  long  charging  time,  raises  practical  issues  when  used  in  certain  
devices  such  as  electric  vehicles.  Capacitors,  on  the  other  hand,  exhibit  high  power  
densities  despite  their  low  energy  densities  (4-­‐5Wh/kg)  [2].  Without  a  doubt,  an  
innovation  that  combines  the  best  attributes  of  batteries  and  capacitors  will  be  a  
revolutionary  advancement  in  energy  storage  technology.  Currently,  graphene-­‐based  
supercapacitors  have  fast  become  the  most  promising  options  since  in  theory  they  can  
provide  both  high  power  densities  and  ultrahigh  energy  densities  given  their  high  
capacitance.    
 
Similar  to  that  of  standard  capacitors,  the  capacitance  of  supercapacitors  depend  on  the  
surface  area  of  the  electrodes  accessible  to  the  electrolyte  since  the  capacitance  comes  
from  the  charge  accumulated  at  the  electrode/electrolyte  interface  [2].  Therefore,  to  
achieve  high  capacitance  levels  without  increasing  the  size  of  the  electrodes,  the  
electrode  material  should  have  exceptionally  high  surface  area  to  volume  ratio.  One  
such  candidate  that  has  long  been  considered  is  graphene.  
 
Graphene  is  a  single  atom-­‐layered  sheet  of  graphite  where  sp2  carbon  atoms  are  
covalently  bonded  to  form  a  2D  hexagonal  lattice.  Since,  in  a  graphene  sheet,  a  carbon  
atom  with  four  valence  electrons  is  only  bonded  to  three  other  carbon  atoms,  one  
electron  is  left  unbounded  per  atom.  Such  abundance  of  free  electrons  provides  
   Aung2  

graphene  with  excellent  electrical  conductivity  [2].  Additionally,  it  has  been  shown  that  
graphene  sheets  have  high  mechanical  flexibility  with  only  ~1%  change  in  the  electrical  
resistance  after  1000  bending  cycles.  Most  importantly,  the  specific  surface  area  of  
graphene  is  a  staggeringly  high  2675m2/g.  Given  the  fact  that  the  intrinsic  capacitance  of  
a  single-­‐layered  graphene  sheet  is  approximately  21μF/cm2,  if  we  can  make  full  use  of  
the  surface  area  available,  a  graphene-­‐based  supercapacitor  can  achieve  capacitance  as  
high  as  550F/g  [1-­‐2].    
 
However,  up  until  recently,  one  major  problem  with  using  graphene  in  supercapacitors  
persisted.  Due  to  strong  Van  Der  Waals  attractive  forces  between  individual  graphene  
sheets,  the  sheets  in  close  proximity  tend  to  restack  during  processing.  Such  restacking  
not  only  causes  a  lowering  of  accessible  surface  area  to  electrolytes  but  also  decreases  
the  charge/discharge  rates  of  the  supercapacitors.  With  restacking  posing  as  a  problem,  
the  supercapacitors  built  only  attained  capacitance  values  only  on  the  order  of  100F/g,  
which  is  only  ~20%  of  the  theoretical  upper  limit  [1].    
 
The  major  breakthrough  for  graphene-­‐based  supercapacitors  came  when  the  
researchers  at  UCLA  discovered  an  all-­‐solid  approach  of  making  graphene  that  avoided  
the  restacking  issue  [1].  As  shown  in  the  schematic  diagram  below  (Figure  1),  a  thin  film  
of  graphite  oxide,  an  oxidized  form  of  graphite,  dispersion  in  water  was  drop-­‐casted  
onto  a  flexible  substrate  supported  on  a  disc.  The  graphite  oxide  film  was  then  burned  
with  infrared  laser  irradiation  using  a  commercially  available  LightScribe  drive  to  
produce  graphene.    
 

 
 
Figure  1:  Schematic  Diagram  of  Making  Graphene-­‐Based  Supercapacitors  
 
 
 
   Aung3  

III.  Experimental  Procedure  

 
Equipment  
 
I  used  Fisher  Scientific  Ultrasonic  Cleaner  (100W,  42kHz)  for  ultrasonication  and  Thermal  
Spa  UV  Gel  Nail  Polish  Dryer  (45W,  375nm)  as  a  UV  lamp  device.  The  LightScribe  drive  
was  LG  Super  Multi  Drive  GE24  complete  with  CyberLink  Media  Suite  Labeling  Software.  
Verbatim  DVD-­‐R  16x  LightScribe  discs  were  used.    
 
III.  A  Preparation  of  Graphite  Oxide  from  Graphite  
 
The  following  two-­‐step  synthesis  is  referenced  from  the  modified  Hummer’s  method  
reported  previously  [3].    
 
Procedure:  Pre-­‐oxidation  step:  Pour  7.5mL  of  concentrated  sulfuric  acid  into  a  100mL  
beaker  with  a  thermometer  in  place.  With  stirring,  add  potassium  persulfate  (2.5g)  and  
phosphorus  pentoxide  (2.5g)  to  the  acid  solution  and  gently  heat  the  mixture.  Care  
should  be  taken  during  this  step  since  the  reaction  is  highly  exothermic  and  the  
temperature  will  go  as  high  as  130oC.  Once  the  solution  turns  clear  and  colorless,  
remove  the  solution  from  heat.  When  the  temperature  of  the  solution  drops  to  80oC,  
add  graphite  crystals  (5g)  slowly  to  the  beaker.  Frothing  and  volume  expansion  will  be  
observed  upon  graphite  addition.  Stir  the  mixture  until  the  mixture  has  turned  into  a  
thick,  silvery  dark  blue  paste.  Wrap  the  beaker  in  aluminum  foil  and  allow  the  paste  to  
cool  to  room  temperature  over  3  hours.  After  the  cooling  period,  add  enough  distilled  
water  to  the  beaker  (~70mL)  to  thin  the  paste.  Afterwards,  filter  the  solution  and  wash  
the  solids  with  additional  distilled  water  until  the  pH  of  the  washes  tests  neutral.  Dry  the  
solids  overnight  at  room  temperature.  The  dried  graphite  obtained  should  be  silvery,  
grey  flakes.    
 
Hummer’s  method:  Pour  23mL  of  concentrated  sulfuric  acid  in  a  250mL  beaker  with  a  
thermometer  in  place.  Refrigerate  the  beaker  in  an  ice  bath  for  about  20  minutes  to  
cool  the  acid  solution  down  to  about  0-­‐4oC.  Add  1g  of  graphite  crystals  obtained  
previously  to  the  beaker  with  stirring.  Slowly  add  potassium  permanganate  (3g)  to  the  
mixture  over  5-­‐10  minutes  while  carefully  maintaining  the  temperature  below  20oC  at  
all  times.  By  the  end  of  the  addition,  the  mixture  should  have  thickened  slightly  and  is  
very  dark  green.  Stir  the  mixture  for  2  hours  at  45-­‐50oC.  You  will  notice  that  the  reaction  
itself  produces  heat  and  you  will  only  need  to  heat  intermittently.  During  this  time,  the  
mixture  should  completely  lose  its  green  color  and  thicken  into  a  deep  purplish  grey  
paste.  At  the  end  of  stirring,  slowly  add  46mL  of  distilled  water  into  the  paste.  The  
solution  is  now  a  slight  reddish  brown  color.  Stir  the  solution  for  15  more  minutes  
before  adding  140mL  of  distilled  water  and  2.5mL  of  30%  hydrogen  peroxide  solution.  
Upon  the  addition  of  hydrogen  peroxide,  the  solution  should  immediately  turn  into  a  
bright  shade  of  yellow.  Since  the  filtration  process  takes  a  long  time  (on  the  order  of  2-­‐3  
hours),  I  suggest  centrifuging  the  solution  and  decanting  the  supernatant  in  order  to  
   Aung4  

speed  up  the  process  if  such  equipment  is  available.  After  the  filtration,  disperse  the  
solids  in  250mL  of  hydrochloric  acid  solution  (220  mL  of  distilled  water  and  30mL  of  
hydrochloric  acid)  to  get  rid  of  the  metal  ions  (Figure  2).  Filter  the  solution  in  small  
portions  to  obtain  brownish  yellow  cake  of  graphite  oxide.  Dry  graphite  oxide  in  a  
desiccate  chamber  overnight.    
 

 
 
Figure  2:  Graphite  Oxide  Solids    
 
III.  B  Preparation  of  Graphite  Oxide  Sample  for  LightScribe    
 
Procedure:  Cut  a  polyethylene  terephthalate  (PET)  film  into  the  shape  of  a  disc.  Care  
should  be  taken  so  that  the  cut  film  is  perfectly  flat  and  does  not  cover  up  the  silver  ring  
of  barcode  on  the  LightScribe  disc.  Also  since  the  LightScribe  drive  is  very  sensitive,  
make  sure  that  the  film  has  no  stray  ends  that  can  potentially  interfere  with  the  disc  
rotation.  Dissolve  100mg  of  graphite  oxide  in  27mL  of  distilled  water  (3.7gmg/ml)  and  
ultrasonicate  for  1  hour  until  the  solution  is  a  homogenous,  light  brown  viscous  mixture  
[4].  Draw  approximately  15mL  of  the  dispersion  in  a  syringe  and  drop-­‐cast  onto  the  pre-­‐
cut  PET  film.  Let  the  film  dry  at  room  temperature  for  24  hours  (Figure  3)  [1].    
 
Prior  to  burning  the  graphite  oxide  film  in  LightScribe  drive,  expose  the  film  to  
ultraviolet  radiation  for  4  hours  in  a  UV  lamp  device,  which,  in  this  experiment,  is  a  UV  
nail  polish  dryer.  After  the  treatment  with  UV,  the  film  should  be  darkened  (Figure  4)  
with  the  resistance  markedly  decreased  from  >20MΩ  to  <0.5MΩ.  
 
   Aung5  

 
 
Figure  3:  Dried  Graphite  Oxide  Film  on  PET  Substrate  
 

 
 
Figure  4:  Graphite  Oxide  Film  After  4Hrs  UV  Exposure  
 
III.  C  Preparation  of  Laser  Scribed  Graphene  (LSG)    
 
Procedure:  Load  the  graphite  oxide  film  onto  the  Light  Scribe  disc  using  Scotch  Spray  
Mount.  The  film  should  be  adhered  to  the  label  side  of  the  disc,  i.e.,  the  textured  side  of  
the  disc.  Place  the  disc  in  the  LightScribe  drive  with  the  film  side  down.  With  the  
contrast  set  to  the  best,  burn  the  disc  for  at  least  6  cycles  to  get  consistently  reduced  
areas  of  graphene  on  the  film  (Figure  5)  [1].  To  burn  the  entire  surface  of  the  film,  each  
cycle  of  LightScribe  may  take  up  to  2  hours  depending  on  the  contrast  settings.    
 
   Aung6  

 
 
Figure  5:  Graphene  Produced  After  6  Cycles  of  LightScribe  
 
III.  D  Preparation  of  All  Solid  Gel-­‐Electrolyte  Supercapacitor  
 
Procedure:  Mix  1g  of  polyvinyl  alcohol  powder  (PVA)  with  10mL  of  distilled  water  in  a  
beaker  equipped  with  a  stir  bar  and  a  thermometer.  Stir  and  heat  the  mixture  at  ~90oC  
until  the  mixture  thickens  and  turns  clear.  Take  the  mixture  off  the  heat  and  allow  it  to  
cool  down  under  ambient  conditions.  Add  0.8g  of  concentrated  phosphoric  acid  (85.3%)  
to  the  mixture  and  stir  thoroughly  [4].    
 
Cut  out  two  identical  pieces  of  LightScribed  graphene  to  serve  as  electrodes.  Put  on  a  
piece  of  copper  tape  on  the  handle  of  each  electrode  to  ensure  firm  contact  with  the  
alligator  clips.  Coat  the  surface  of  the  electrodes  with  PVA/phosphoric  acid  electrolyte  
(~100μL/cm2)  and  let  the  electrodes  sit  for  5  hours  before  assembling  the  two  
electrodes  (Figure  6).  Allow  the  electrolyte  to  solidify  overnight  [1].    
 

 
 
Figure  6:  Solid  Electrolyte  Graphene  Supercapacitor  (Area:  4cm2)  
 
III.  E  Preparation  of  Aqueous  Electrolyte  Supercapacitor  
 
Procedure:  Cut  out  two  identical  pieces  of  LightScribed  graphene  to  serve  as  electrodes.  
Put  on  a  piece  of  copper  tape  on  the  handle  of  each  electrode  to  ensure  firm  contact  
   Aung7  

with  the  alligator  clips.  Soak  a  piece  of  lens  cleaning  tissue  in  1M  phosphoric  acid  and  
wedge  the  tissue  in  between  the  two  electrodes  to  serve  as  the  separator.  Place  the  
entire  ensemble  between  two  microscope  slides  held  together  by  paper  clips.  
 
III.  F  Measuring  the  Capacitance  of  Supercapacitors  
 
Procedure:  Construct  a  simple  RC  circuit  by  placing  a  known  resistor  in  series  with  the  
supercapacitor  of  which  the  capacitance  is  unknown.  With  a  function  generator  
outputting  square  waves  with  amplitudes  of  3V  for  gel-­‐electrolyte  supercapacitors  and  
5V  for  aqueous  electrolyte  supercapacitors  at  a  frequency  of  1kHz,  record  the  change  in  
voltage  across  the  capacitor  with  an  oscilloscope.  Determine  the  time  taken  by  the  
capacitor  to  drop  to  half  of  its  initial  voltage  (t).  Using  the  following  equation  that  
relates  resistance  (R),  capacitance  (C)  and  half  life  (t),    
 
𝑡
𝑅𝐶 =    
ln 2
 
the  capacitance  of  the  supercapacitor  can  be  determined.  
 
IV.  Results  &  Discussion  
 
IV.  A  Preparation  of  Graphite  Oxide  from  Graphite    
 
The  first  part  of  this  project  is  synthesizing  graphite  oxide,  the  starting  material,  from  
graphite.  Although  there  are  multiple  variations  of  Hummer’s  method  used  for  graphite  
oxide  synthesis,  a  pre-­‐oxidation  step  is  shown  to  be  necessary  before  graphite  is  
subjected  to  Hummer’s  method.  Since  the  primary  goal  of  Hummer’s  method  is  to  
oxidize  graphite,  the  pre-­‐oxidation  step  minimizes  the  occurrence  of  incompletely  
oxidized  graphite-­‐core  in  the  final  product  [3].  If  unoxidized  graphite  is  mixed  with  
graphite  oxide,  it  will  be  apparent  in  the  color  of  the  mixture,  which,  instead  of  bright  
yellow,  will  take  after  a  shade  of  brownish  orange  after  the  addition  of  hydrogen  
peroxide  at  the  end  of  the  synthesis.    
 
IV.  B  Preparation  of  Graphene  from  Graphite  Oxide  
 
Although  the  published  procedure  does  not  call  for  irradiation  of  graphite  oxide  film  
with  UV  prior  to  the  LightScribe  process,  such  intermediate  step  was  included  to  
maximize  the  yield  of  graphene  on  film.  When  this  step  was  omitted,  only  sparse  and  
segmented  rings  of  graphene  were  observed.  Varying  the  reaction  parameters  such  as  
the  concentration  of  graphite  oxide  dispersion  and  the  amount  used  to  coat  the  
substrate  also  proved  to  have  very  little  to  no  effect  on  improving  the  results.  Although  
UV  radiation  has  been  shown  to  induce  reduction  of  graphite  oxide  to  graphene  in  
solution  [5],  there  is  no  previous  data  on  solid-­‐state  reduction.  However,  since  UV  
exposure  darkened  the  graphite  oxide  film  and  significantly  increased  its  conductivity,  
   Aung8  

the  reduction  of  graphite  oxide  to  graphene  must  have  occurred  to  a  considerable  
extent.  Such  darkening  of  the  film  increases  the  absorbance  of  the  irradiation  during  
LightScribe,  which  may  be  one  of  the  reasons  UV  exposure  helps  with  the  subsequent  
LightScribe  process.      
 
IV.  C  Graphene-­‐Based  Supercapacitors  
 
As  for  the  supercapacitors,  regardless  of  the  electrolyte  (PVA  gel  vs  phosphoric  acid),  
their  capacitance  values  were  measured  to  be  approximately  2.5nF/cm2.  Although  the  
capacitance  values  were  a  fraction  of  previously  reported  value  (~1.84mF/cm2),  it  is  
worth  noting  that  at  2.5nF/cm2,  the  graphene  capacitors  exhibited  capacitances  much  
higher  than  what  a  standard  parallel-­‐plate  capacitor  can  offer  (~9pF/cm2).  The  results  
may  be  improved  by  ensuring  a  complete  reduction  of  graphite  oxide  to  graphene  
through  more  cycles  of  LightScribe.  It  is  possible  that  partially  reduced  graphite  oxide  
present  in  the  electrodes  lowers  the  effective  capacitance  by  acting  as  a  small  capacitor  
in  series  with  a  large  one.    
 
V.  Conclusion  
 
Although  the  capacitors  produced  were  at  a  much  lower  capacitance  than  is  
experimentally  feasible,  I  was  able  to  make  graphene-­‐based  supercapacitors  using  
LightScribe  technique  and  address  problems  as  they  rose  throughout  the  process.  
Future  work  includes,  but  is  not  limited  to,  optimizing  the  performance  of  
supercapacitors,  determining  the  mechanism  behind  UV  irradiation  on  graphite  oxide  
and  characterizing  the  graphene  produced  after  UV  treatment  and  LightScribe.    
 
VI.  References  
 
 [1]  M.  F.  El-­‐Kady  et  al.,  Laser  Scribing  of  High-­‐Performance  and  Flexible  Graphene-­‐Based  
Electrochemical  Capacitors.  Science.  335,  1326  (2012).  doi:10.1126/science.1216744  
 
[2]  C.  Liu  et  al.,  Graphene-­‐Based  Supercapacitor  with  an  Utrahigh  Energy  Density.  Nano  
Letters.  10,  4863-­‐4868  (2010).  doi:10.1021/nl102661q  
 
[3]  N.  I.  Kovtyukhova  et  al.,  Layer-­‐by-­‐Layer  assembly  of  ultrathin  composite  films  from  
micronsized  graphite  oxide  sheets  and  polycations.  Chem.  Mater.  11,  771  (1999).  
doi:10.1021/cm981085u  

[4]  V.  Strong  et  al.,  Patterning  and  Electronic  Tuning  of  Laser  Scribed  Graphene  for  
Flexible  All-­‐Carbon  Devices.  ACS  Nano.  6,  2  (2012).  doi:10.1021/nn204200w  
 
[5]  P.  Kumar,  K.S.  Subrahmanyam,  C.N.  Rao,  Graphene  Produced  by  Radiation-­‐Induced  
Reduction  of  Graphene  Oxide.