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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 AnSourangsu 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-preparedgraphene oxide/PVA thin film
Graphene oxide paper
Outline
aqueous graphene oxide
dispersion
Hot-pressedgraphene/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-preparedgraphene oxide/PVA thin film
Graphene oxide paper
Outline
aqueous graphene oxide
dispersion
Hot-pressedgraphene/PS thin film
NASA URETI: Bio-Inspired Materials
H2SO4
KMnO4
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 1-2graphiteoxide
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
CO2
• 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-preparedgraphene oxide/PVA thin film
Graphene oxide paper
Outline
aqueous graphene oxide
dispersion
Hot-pressedgraphene/PS thin film
NASA URETI: Bio-Inspired Materials
Graphene
in DMF with PS
Graphene–PS
nanocomposite powder
Graphene–PS
thin film
PS
thin filmSEM 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-preparedgraphene oxide/PVA thin film
Graphene oxide paper
Outline
aqueous graphene oxide
dispersion
Hot-pressedgraphene/PS thin film
NASA URETI: Bio-Inspired Materials
Graphene oxide paper via vacuum-assisted self-
assembly (VASA)
Vacuum
Membrane
filter
Graphene oxide
paper
FiltrationGraphene
oxide
sheets
5 10 15 20 25
Inte
ns
ity
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 MCl2
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
Flo
w d
ire
ctio
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 oxide0 wt% PVA
spacing = 8.7 Å spacing = 16.4 Å
51 wt% graphene oxide49 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 readilyoccurs 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-preparedgraphene oxide/PVA thin film
Graphene oxide paper
Outline
aqueous graphene oxide
dispersion
Hot-pressedgraphene/PS thin film
NASA URETI: Bio-Inspired Materials
vacuum
filtration
graphene oxidedispersion
graphene oxidepaper
vacuum
filtration
graphene paperreduction
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 currentcollector (Cu foil)
Polymer separator
Cathode currentcollector (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 LiPF6 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), 12800–12804
NASA URETI: Bio-Inspired Materials
CO2
• 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 MaterialsCompton, 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 oxidedispersion
graphene oxidepaper
Add polymer
vacuumfiltration
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 Li–O2 batteries
Xiao, Liu, Zhang, and coworkers Nano Lett., 2011, 11 (11), 5071–5078
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 (Jessup, 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 O’zyilmaz5,
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?