Functionalized Graphene and Graphene Oxide: Materials Synthesis ...

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

Sourangsu Sarkar

Zhi An

Owen Compton

Collaborators

• 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) NASA URETI: Bio-Inspired Materials

Outline •

Synthesis and functionalization of graphene oxide and graphene

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Nanocomposites with graphene oxide and graphene

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Vacuum-assisted self-assembly (VASA) fabrication of graphene oxide paper and nanocomposites

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aqueous graphene oxide dispersion

Graphene-based structures for energy storage and electronic applications

Graphene oxide paper

VASA-prepared graphene oxide/PVA thin film


Hot-pressed graphene/PS thin film

Outline •


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Synthesis and characterization of graphene oxide graphite

• Bulk quantities attainable only via chemical route • Oxygenation expands interlayer gallery H2SO4 KMnO4

graphite oxide

• Sonication exfoliates structure into individual nm-thick sheets • C/O ratio from 1-2

sonication

graphite oxide suspension Hummers, W.S.; Offeman, R.E., J. Am. Chem. Soc. 1958, 80, 1339-1339. NASA URETI: Bio-Inspired Materials


with Ruoff group

Characterization of graphene oxide TGA

FT-IR

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Thermogravimetric analysis (TGA) reveals pyrolysis of oxygen-containing functional groups

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Fourier transform-infrared (FT-IR) and Xray photoelectron spectroscopy (XPS) identify functional groups


XPS

with Ruoff group

Surface functionalization •

Thermal reduction can tune C/O ratio in the 2-10 range

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Nanosheets can be coated with surfactants to maximize interaction between nanofiller and polymer

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Isocyanates and amines can react to cover the basal plane and sheet edge with nearly limitless number of functional groups

CO2

TEM image of phenyl isocyanatefunctionalized graphene 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. NASA URETI: Bio-Inspired Materials

with Ruoff group

Surface functionalization •

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

TEM image of phenyl isocyanatefunctionalized graphene 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. NASA URETI: Bio-Inspired Materials

with Ruoff group

Outline •


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Fabricating thin film of nanocomposites

Isocyanate-treated graphene oxide in DMF with PS

hydrazine

precipitate

90 °C

MeOH

Graphene in DMF with PS

Graphene–PS nanocomposite powder

Powder is amenable to melt-processing

SEM image of graphene dispersed in PS matrix


Graphene–PS thin film

PS thin film

PS/Graphene Composite (1 wt%)

• The reduced sheets have a crumpled morphology • Even at 1 wt% loading the polymer matrix appears to be completely filled with sheets Stankovich, S. et al., Graphene-based Composite Materials. Nature 2006, 442, 282-286.


Enhanced conductivity, mechanical, and thermal properties in PS-graphene nanocomposites

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Graphene transforms insulating polystyrene matrix into electrically conductive composite

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Mechanical and thermal properties of parent matrix enhanced by addition of 1 wt% graphene

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Percolation threshold of only 0.1 vol% due to excellent dispersion of functionalized graphene in PS matrix

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CNTs afford similar improvement, but can cost $250 per gram

Stankovich, S. et al., Nature 2006, 442, 282-286.

Ramanathan, T. et al., Nat. Nanotechnol. 2008, 3, 327-331. NASA URETI: Bio-Inspired Materials

Outline •


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Graphene oxide paper via vacuum-assisted selfassembly (VASA)

Graphene oxide sheets

Filtration


Membrane filter

Intensity

Vacuum

5 Stankovich, S. et al. Nature 2006, 448, 457-460.


10

15 20 2q (deg)

25

with Ruoff group

VASA in the presence of metal ions

Rinsing if necessary

graphene oxide paper


Mg-modified graphene oxide paper

with Ruoff group

Lateral crosslinking of graphene oxide sheet by MCl2

Park et al., ACS Nano 2008, 2(3), 572-578

Tightly bound, still remain after rinsing

Weakly bound, can

be rinsed away

Edge-linked M-carboxylate works agains tensile force to enhance mechanical properties


with Ruoff group

Covalent cross-linking with borate

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Hydrogen bonding is weak link in cross-linking network

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Annealing drives condensation reactions between borate and surface-bound hydroxyls

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Covalent linkage increases mechanical stiffness up to 120 GPa

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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. NASA URETI: Bio-Inspired Materials

Flow direction

VASA in the presence of polymer additives

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Composite solution loaded into vacuum filtration reservoir

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Vacuum applied to initiate flow over a membrane

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Filtered solution can be aqueous or organic solvent

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Process is amenable to hydrophilic and hydrophobic polymers

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Fabrication speed peaks near 0.1 min layer-1


with Brinson group

Tuning interlayer gallery

100 wt% graphene oxide 0 wt% PVA

51 wt% graphene oxide 49 wt% PVA

spacing = 8.7 Å

spacing = 16.4 Å

Putz, K.W.; Compton, O.C.; Palmeri, M.J.; Nguyen, S.T.; Brinson, L.C., Adv. Funct. Mater. 2010, 20, 3322-3329. NASA URETI: Bio-Inspired Materials

Mechanical enhancement graphene oxide/PVA

graphene oxide/PMMA

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PVA-based composites improve stiffness by 1000% in comparison to pure polymer, well above the rule of mixtures (ROM)

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Stiffness of PMMA-based composites is in line with the ROM, while tensile strength increases over 1100% above the pristine polymer


Relating structure and property •

Composition of interlayer gallery affects mechanical properties

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Hydrogen bonding readily occurs between nanosheet and polymer within interlayer gallery

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Carbon backbone introduces covalent aspect to cross-linking network

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Resulting hybrid network of covalent and hydrogen bonds stiffens the composite thin film

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. NASA URETI: Bio-Inspired Materials

Relating structure and property

graphene oxide film prepared from water

graphene oxide film prepared from DMF

graphene oxide/PVA composite film prepared from water

graphene oxide/PMMA composite film prepared from DMF


Partial summary •

Concentration of polymer in graphene oxide-polymer nanocomposites can be tuned from near trace quantities (70 wt%)

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Filler-matrix compatibilization affords unprecedented property enhancements in properties

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Modifying intersheet gallery composition drastically improves mechanical and storage properties of thin films


Outline •


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Anode assembly graphene oxide dispersion

graphene oxide paper vacuum filtration

reduction hydrazine

graphene paper vacuum filtration

Abouimrane, A.; Compton, O.C.; Amine, K.; Nguyen, S.T., J. Phys. Chem. C 2010, 114, 12800-12804. NASA URETI: Bio-Inspired Materials

LIB Cell assembly

Cathode current collector (Al foil)

• Graphene paper is loaded into coin cell without any polymer binder or additive • Graphene powder cells require PVDF binder and acetylene black

Li metal Polymer separator

• Electrolyte solution containing LiPF6 in NMP is added between separator and electrodes

Graphene paper Anode current collector (Cu foil)

Coin cell scheme


• Cells are prepared and sealed in a He-filled glove box

• Electrochemical measurements made using a Maccor battery cycler

Performance of graphene-based anode graphene paper

graphene powder

Abouimrane, A.; Compton, O. C.; Nguyen, S. T.;Materials Amine, K. J. Phys. Chem. C, 2010, 114(29), 12800–12804 NASA URETI: Bio-Inspired

Anode modification •

Functional groups can be covalently bound to the nanosheet surface

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Isocyanates yield carbamate moieties on the basal plane, similar to the carbonate ions that can facilitate SEI layer formation

CO2

TEM image of phenyl isocyanatefunctionalized graphene

Stankovich, S.; Piner, R.D.; Nguyen, S.T.; Ruoff, R.S., Carbon 2006, 44, 3342-3347.


Anode modification

Compton, O.C.; Jain, B; Abouimrane, A; Dikin, D.A.; Amine, K.; Nguyen, S.T., ACS Nano 2011, 5(6), 4380-4391 NASA URETI: Bio-Inspired Materials

Anode assembly graphene oxide dispersion

graphene oxide paper vacuum filtration

reduction hydrazine

Graphenepolymer paper Add polymer vacuum filtration


Composite electrodes •

Lithium ion batteries poses some explosion hazards due to high potential in proximity to flammable organic electrolytes

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Polymers with high ionic conductivity for Li+ ions (i.e., PEO) are candidates to replace these electrolytes charge-discharge profiles

cell cyclability


Ternary metal oxide-graphene composites for LIBs

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.


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 Liu, Zhang, and coworkers Nano Lett., 2011, 11 (11), 5071–5078 NASA URETI: Bio-InspiredXiao, Materials

Substrates for flexible LEDs

Hong and coworkers, Mater. 2011, 23, 4614-4619 DOI: 10.1002/adma.201102407 NASA URETI:Adv. Bio-Inspired Materials

Electrically conductive graphene-based ink for printedcircuit 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, JaeSung 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

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? NASA URETI: Bio-Inspired Materials