Functionalized Graphene and Graphene Oxide: Materials Synthesis ...

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Functionalized Graphene and Graphene. Oxide: Materials Synthesis and Electronic. Applications. Zhi An, Sourangsu Sarkar, Owen C. Compton, SonBinh T.

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



Nanocomposites with graphene oxide and graphene



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



aqueous graphene oxide dispersion

Graphene-based structures for energy storage and electronic applications

Graphene oxide paper

VASA-prepared graphene oxide/PVA thin film

NASA URETI: Bio-Inspired Materials

Hot-pressed graphene/PS thin film

Outline •

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



aqueous graphene oxide dispersion

Graphene-based structures for energy storage and electronic applications

Graphene oxide paper

VASA-prepared graphene oxide/PVA thin film

NASA URETI: Bio-Inspired Materials

Hot-pressed graphene/PS thin film

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

aqueous graphene oxide dispersion

with Ruoff group

Characterization of graphene oxide TGA

FT-IR



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



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

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XPS

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

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 •

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



aqueous graphene oxide dispersion

Graphene-based structures for energy storage and electronic applications

Graphene oxide paper

VASA-prepared graphene oxide/PVA thin film

NASA URETI: Bio-Inspired Materials

Hot-pressed graphene/PS thin film

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

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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.

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



Graphene transforms insulating polystyrene matrix into electrically conductive composite



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



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



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 •

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



aqueous graphene oxide dispersion

Graphene-based structures for energy storage and electronic applications

Graphene oxide paper

VASA-prepared graphene oxide/PVA thin film

NASA URETI: Bio-Inspired Materials

Hot-pressed graphene/PS thin film

Graphene oxide paper via vacuum-assisted selfassembly (VASA)

Graphene oxide sheets

Filtration

Graphene oxide paper

Membrane filter

Intensity

Vacuum

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

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10

15 20 2q (deg)

25

with Ruoff group

VASA in the presence of metal ions

Rinsing if necessary

graphene oxide paper

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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

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with Ruoff group

Covalent cross-linking with borate



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. NASA URETI: Bio-Inspired Materials

Flow direction

VASA in the presence of polymer additives



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

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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



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. NASA URETI: Bio-Inspired Materials

Relating structure and property •

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

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

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

Partial summary •

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



Filler-matrix compatibilization affords unprecedented property enhancements in properties



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

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Outline •

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



aqueous graphene oxide dispersion

Graphene-based structures for energy storage and electronic applications

Graphene oxide paper

VASA-prepared graphene oxide/PVA thin film

NASA URETI: Bio-Inspired Materials

Hot-pressed graphene/PS thin film

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

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• 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



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.

NASA URETI: Bio-Inspired Materials

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

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

Composite electrodes •

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 charge-discharge profiles

cell cyclability

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

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.

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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

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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