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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

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Page 1: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

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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

Page 3: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

Page 4: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

Page 5: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

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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

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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

Page 8: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

Page 9: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

Page 10: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

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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

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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

Page 13: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

Page 14: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

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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

Page 16: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

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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

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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

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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

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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

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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

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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

Page 23: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

Page 24: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

Page 25: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

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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

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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

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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

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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

Page 30: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

Page 31: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

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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

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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

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NASA URETI: Bio-Inspired Materials

Substrates for flexible LEDs

Hong and coworkers, Adv. Mater. 2011, 23, 4614-4619 DOI: 10.1002/adma.201102407

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NASA URETI: Bio-Inspired Materials

Electrically conductive graphene-based ink for printed-

circuit labels

Vorbeck Materials (Jessup, MD)

Page 36: Functionalized Graphene and Graphene Oxide: …nseresearch.org/2011/presentations/Day1_SonBinh... · Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic

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

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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

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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?