NASA URETI: Bio-Inspired Materials

Functionalized Graphene and Graphene

Oxide: Materials Synthesis and Electronic
Applications
Zhi An, Sourangsu Sarkar, Owen C. Compton, SonBinh T. Nguyen
Northwestern University
NASA URETI: Bio-Inspired Materials
Funding
Owen Compton
Zhi An
Sourangsu Sarkar
The Ruoff group (Mech. E, Northwestern University UT Austin)
Mohammad Naraghi, Tobin Filleter, and Horacio Espinosa (Mech. E, Northwestern University)
Stephen Cranford and Markus Buehler (Civil and Environmental Engineering, MIT)
Ali Abouimrane and Khalil Amine (Battery Group, Argonne National Laboratory)
Karl Putz and L. Catherine Brinson (Mech. E, Northwestern University)
Collaborators
NASA URETI: Bio-Inspired Materials
Synthesis and functionalization of graphene
oxide and graphene
Nanocomposites with graphene oxide and
graphene
Vacuum-assisted self-assembly (VASA)
fabrication of graphene oxide paper and
nanocomposites
Graphene-based structures for energy
storage and electronic applications
VASA-prepared
graphene oxide/PVA thin film
Graphene oxide paper
Outline
aqueous
graphene oxide
dispersion
Hot-pressed
graphene/PS thin film
NASA URETI: Bio-Inspired Materials
Synthesis and functionalization of graphene
oxide and graphene
Nanocomposites with graphene oxide and
graphene
Vacuum-assisted self-assembly (VASA)
fabrication of graphene oxide paper and
nanocomposites
Graphene-based structures for energy
storage and electronic applications
VASA-prepared
graphene oxide/PVA thin film
Graphene oxide paper
Outline
aqueous
graphene oxide
dispersion
Hot-pressed
graphene/PS thin film
NASA URETI: Bio-Inspired Materials
H
2
SO
4
KMnO
4
graphite
sonication
Hummers, W.S.; Offeman, R.E., J. Am. Chem. Soc. 1958, 80, 1339-1339.
aqueous
graphene oxide
dispersion
Bulk quantities
attainable only via
chemical route
Oxygenation expands
interlayer gallery
Sonication exfoliates
structure into individual
nm-thick sheets
C/O ratio from 1-2
graphite
oxide
graphite oxide
suspension
Synthesis and characterization of graphene oxide
with Ruoff group
NASA URETI: Bio-Inspired Materials
Thermogravimetric analysis (TGA)
reveals pyrolysis of oxygen-containing
functional groups
Fourier transform-infrared (FT-IR) and X-
ray photoelectron spectroscopy (XPS)
identify functional groups
TGA FT-IR XPS
Characterization of graphene oxide
with Ruoff group
NASA URETI: Bio-Inspired Materials
CO
2
Thermal reduction can tune C/O ratio in the 2-10 range
Nanosheets can be coated with surfactants to maximize interaction
between nanofiller and polymer
Isocyanates and amines can react to cover the basal plane and
sheet edge with nearly limitless number of functional groups
Stankovich, S.; Piner, R.D.; Nguyen, S.T.; Ruoff, R.S., Carbon 2006, 44, 3342-3347.
TEM image of phenyl isocyanate-
functionalized graphene
Compton, O.C.; Dikin, D.A.; Putz, K.W.; Brinson, L.C.; Nguyen, S.T., Adv. Mater. 2010, 22, 892-896.
Surface functionalization
with Ruoff group
NASA URETI: Bio-Inspired Materials
TEM image of phenyl isocyanate-
functionalized graphene
Thermal reduction can tune C/O ratio in the 2-10 range
Nanosheets can be coated with surfactants to maximize interaction
between nanofiller and polymer
Isocyanates and amines can react to cover the basal plane and
sheet edge with nearly limitless number of functional groups
Stankovich, S.; Piner, R.D.; Nguyen, S.T.; Ruoff, R.S., Carbon 2006, 44, 3342-3347.
Compton, O.C.; Dikin, D.A.; Putz, K.W.; Brinson, L.C.; Nguyen, S.T., Adv. Mater. 2010, 22, 892-896.
Surface functionalization
with Ruoff group
NASA URETI: Bio-Inspired Materials
Synthesis and functionalization of graphene
oxide and graphene
Nanocomposites with graphene oxide and
graphene
Vacuum-assisted self-assembly (VASA)
fabrication of graphene oxide paper and
nanocomposites
Graphene-based structures for energy
storage and electronic applications
VASA-prepared
graphene oxide/PVA thin film
Graphene oxide paper
Outline
aqueous
graphene oxide
dispersion
Hot-pressed
graphene/PS thin film
NASA URETI: Bio-Inspired Materials
Graphene
in DMF with PS
GraphenePS
nanocomposite powder
GraphenePS
thin film
PS
thin film
SEM image of graphene
dispersed in PS matrix
Isocyanate-treated
graphene oxide
in DMF with PS
hydrazine
90 C
precipitate
MeOH
Powder is amenable to
melt-processing
Fabricating thin film of nanocomposites
NASA URETI: Bio-Inspired Materials
PS/Graphene Composite (1 wt%)
Stankovich, S. et al., Graphene-based Composite Materials. Nature 2006, 442, 282-286.
The reduced sheets have a crumpled morphology
Even at 1 wt% loading the polymer matrix appears to be
completely filled with sheets
NASA URETI: Bio-Inspired Materials
Graphene transforms insulating poly-
styrene matrix into electrically
conductive composite
Percolation threshold of only 0.1 vol%
due to excellent dispersion of
functionalized graphene in PS matrix
Stankovich, S. et al., Nature 2006, 442, 282-286.
Ramanathan, T. et al., Nat. Nanotechnol. 2008, 3, 327-331.
Mechanical and thermal properties of
parent matrix enhanced by addition of
1 wt% graphene
CNTs afford similar improvement,
but can cost $250 per gram
Enhanced conductivity, mechanical, and thermal
properties in PS-graphene nanocomposites
NASA URETI: Bio-Inspired Materials
Synthesis and functionalization of graphene
oxide and graphene
Nanocomposites with graphene oxide and
graphene
Vacuum-assisted self-assembly (VASA)
fabrication of graphene oxide paper and
nanocomposites
Graphene-based structures for energy
storage and electronic applications
VASA-prepared
graphene oxide/PVA thin film
Graphene oxide paper
Outline
aqueous
graphene oxide
dispersion
Hot-pressed
graphene/PS thin film
NASA URETI: Bio-Inspired Materials
Graphene oxide paper via vacuum-assisted self-
assembly (VASA)
Vacuum
Membrane
filter
Graphene oxide
paper
Filtration
Graphene
oxide
sheets
5 10 15 20 25
I
n
t
e
n
s
i
t
y
2q (deg)
Stankovich, S. et al. Nature 2006, 448, 457-460.
with Ruoff group
NASA URETI: Bio-Inspired Materials
VASA in the presence of metal ions
Rinsing
if necessary
graphene oxide paper
Mg-modified
graphene oxide paper
with Ruoff group
NASA URETI: Bio-Inspired Materials
Lateral crosslinking of graphene oxide sheet by MCl
2
Edge-linked M-carboxylate works against
tensile force to enhance mechanical
properties
Weakly bound, can
be rinsed away
Tightly bound, still
remain after rinsing
Park et al., ACS Nano 2008, 2(3), 572-578
with Ruoff group
NASA URETI: Bio-Inspired Materials
Hydrogen bonding is weak
link in cross-linking network
Annealing drives condensation
reactions between borate and
surface-bound hydroxyls
Covalent linkage increases
mechanical stiffness up to
120 GPa
Practical tests demonstrate
films can accommodate
~50 MPa of strain
An, Z.; Compton, O.C.; Putz, K.W.; Brinson, L.C.; Nguyen, S.T., submitted for publication.
Covalent cross-linking with borate
NASA URETI: Bio-Inspired Materials
F
l
o
w

d
i
r
e
c
t
i
o
n
Composite solution loaded into vacuum filtration reservoir
Vacuum applied to initiate flow over a membrane
Filtered solution can be aqueous or organic solvent
Process is amenable to hydrophilic and hydrophobic polymers
Fabrication speed peaks near 0.1 min layer
-1
VASA in the presence of polymer additives
with Brinson group
NASA URETI: Bio-Inspired Materials
100 wt% graphene oxide
0 wt% PVA
spacing = 8.7 spacing = 16.4
51 wt% graphene oxide
49 wt% PVA
Putz, K.W.; Compton, O.C.; Palmeri, M.J.; Nguyen, S.T.; Brinson, L.C., Adv. Funct. Mater. 2010, 20, 3322-3329.
Tuning interlayer gallery
NASA URETI: Bio-Inspired Materials
PVA-based composites improve stiffness by 1000% in comparison to
pure polymer, well above the rule of mixtures (ROM)
Stiffness of PMMA-based composites is in line with the ROM, while
tensile strength increases over 1100% above the pristine polymer
Putz, K.W.; Compton, O.C.; Palmeri, M.J.; Nguyen, S.T.; Brinson, L.C., Adv. Funct. Mater. 2010, 20, 3322-3329.
graphene oxide/PVA graphene oxide/PMMA
Mechanical enhancement
NASA URETI: Bio-Inspired Materials
Composition of interlayer gallery
affects mechanical properties
Hydrogen bonding readily
occurs between nanosheet and
polymer within interlayer gallery
Carbon backbone introduces
covalent aspect to cross-linking
network
Resulting hybrid network of
covalent and hydrogen bonds
stiffens the composite thin film
Putz, K.W.; Compton, O.C.; Palmeri, M.J.; Nguyen, S.T.; Brinson, L.C., Adv. Funct. Mater. 2010, 20, 3322-3329.
graphene oxide film prepared from water
graphene oxide/PVA composite film
prepared from water
Relating structure and property
NASA URETI: Bio-Inspired Materials
graphene oxide film prepared from water
graphene oxide/PVA composite film
prepared from water
Putz, K.W.; Compton, O.C.; Palmeri, M.J.; Nguyen, S.T.; Brinson, L.C., Adv. Funct. Mater. 2010, 20, 3322-3329.
graphene oxide film prepared from DMF
graphene oxide/PMMA composite film
prepared from DMF
Relating structure and property
NASA URETI: Bio-Inspired Materials
Concentration of polymer in graphene oxide-polymer
nanocomposites can be tuned from near trace quantities
(<0.1 wt%) to primary component (>70 wt%)
Filler-matrix compatibilization affords unprecedented property
enhancements in properties
Modifying intersheet gallery composition drastically improves
mechanical and storage properties of thin films
Partial summary
NASA URETI: Bio-Inspired Materials
Synthesis and functionalization of graphene
oxide and graphene
Nanocomposites with graphene oxide and
graphene
Vacuum-assisted self-assembly (VASA)
fabrication of graphene oxide paper and
nanocomposites
Graphene-based structures for energy
storage and electronic applications
VASA-prepared
graphene oxide/PVA thin film
Graphene oxide paper
Outline
aqueous
graphene oxide
dispersion
Hot-pressed
graphene/PS thin film
NASA URETI: Bio-Inspired Materials
vacuum
filtration
graphene oxide
dispersion
graphene oxide
paper
vacuum
filtration
graphene paper reduction
hydrazine
Abouimrane, A.; Compton, O.C.; Amine, K.; Nguyen, S.T., J. Phys. Chem. C 2010, 114, 12800-12804.
Anode assembly
NASA URETI: Bio-Inspired Materials
Anode current
collector (Cu foil)
Polymer separator
Cathode current
collector (Al foil)
Graphene
paper
Coin cell scheme
Li metal
Graphene paper is loaded into coin
cell without any polymer binder or
additive
Graphene powder cells require
PVDF binder and acetylene black
Electrolyte solution containing
LiPF
6
in NMP is added between
separator and electrodes
Cells are prepared and sealed in a
He-filled glove box
Electrochemical measurements
made using a Maccor battery
cycler
LIB Cell assembly
NASA URETI: Bio-Inspired Materials
graphene paper graphene powder
Performance of graphene-based anode
Abouimrane, A.; Compton, O. C.; Nguyen, S. T.; Amine, K. J. Phys. Chem. C, 2010, 114(29), 1280012804
NASA URETI: Bio-Inspired Materials
CO
2
Functional groups can be covalently bound to the nanosheet surface
Isocyanates yield carbamate moieties on the basal plane, similar to
the carbonate ions that can facilitate SEI layer formation
Stankovich, S.; Piner, R.D.; Nguyen, S.T.; Ruoff, R.S., Carbon 2006, 44, 3342-3347.
TEM image of phenyl isocyanate-
functionalized graphene
Anode modification
NASA URETI: Bio-Inspired Materials
Compton, O.C.; Jain, B; Abouimrane, A; Dikin, D.A.; Amine, K.; Nguyen, S.T., ACS Nano 2011, 5(6), 4380-4391
Anode modification
NASA URETI: Bio-Inspired Materials
vacuum
filtration
graphene oxide
dispersion
graphene oxide
paper
Add polymer
vacuum
filtration
Graphene-
polymer paper
reduction
hydrazine
Abouimrane, A.; Compton, O.C.; Amine, K.; Nguyen, S.T., J. Phys. Chem. C 2010, 114, 12800-12804.
Anode assembly
NASA URETI: Bio-Inspired Materials
Lithium ion batteries poses some explosion hazards due to high
potential in proximity to flammable organic electrolytes
Polymers with high ionic conductivity for Li
+
ions (i.e., PEO) are
candidates to replace these electrolytes
Abouimrane, A.; Compton, O.C.; Amine, K.; Nguyen, S.T., J. Phys. Chem. C 2010, 114, 12800-12804.
charge-discharge profiles cell cyclability
Composite electrodes
NASA URETI: Bio-Inspired Materials
Specific energy values ~ theoretical prediction for lithium
insertion/extraction.
Material remains electrochemically stable over the course of 100
charge/discharge cycles
Donghai Wang; Rong Kou; Daiwon Choi; Zhenguo Yang; Zimin Nie; Juan Li; Laxmikant V. Saraf; Dehong Hu; Jiguang Zhang;
Gordon L. Graff; Jun Liu; Michael A. Pope; Ilhan A. Aksay; ACS Nano 2010, 4, 1587-1595.
Ternary metal oxide-graphene composites for LIBs
NASA URETI: Bio-Inspired Materials
Li-air battery based on porous 3-D graphene structures
Discharge capacity ~ 15000 mAh/g
carbon
Specific energy is ~40000 Wh/kg
carbon, with an average voltage of
2.65 (highest capacity reported to
date for nonaqueous LiO
2
batteries
Xiao, Liu, Zhang, and coworkers Nano Lett., 2011, 11 (11), 50715078
NASA URETI: Bio-Inspired Materials
Substrates for flexible LEDs
Hong and coworkers, Adv. Mater. 2011, 23, 4614-4619 DOI: 10.1002/adma.201102407
NASA URETI: Bio-Inspired Materials
Electrically conductive graphene-based ink for printed-
circuit labels
Vorbeck Materials (J essup, MD)
Roll-to-roll
production of
30-inch
graphene film
for transparent
electrodes
Sukang Bae, Hyeongkeun Kim,
Youngbin Lee, Xiangfan Xu, Jae-
Sung Park, Yi Zheng, Jayakumar
Balakrishnan, Tian Lei, Hye Ri Kim,
Young Il Song, Young-Jin Kim,
Kwang S. Kim, Barbaros Ozyilmaz5,
Jong-Hyun Ahn, Byung Hee Hong,
and Sumio Iijima, Nat. Nantechnol.
2010, DOI:
10.1038/NNANO.2010.132
NASA URETI: Bio-Inspired Materials
Update on commercial scale-up
A worker at XG Sciences (East Lansing,
MI) operates equipment that produces
graphene at the multi-kilogram-per-day
scale.
Credit: Lawrence T. Drzal/XG Science
NASA URETI: Bio-Inspired Materials
Conclusions
Graphene oxide and graphene are versatile
nanomaterials that can be assembled into a wide range
of macroscopic structures and objects
Chemical modifications can greatly improve the
properties of the resulting carbon-based assembled
materials
Thank you for your attention
Questions?