Functionalized Graphene and Graphene Oxide: Materials Synthesis and Electronic Applications

Transcription

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

2 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)

3 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 Hot-pressed graphene/ps thin film

5 Synthesis and characterization of graphene oxide graphite graphite oxide H 2 SO 4 KMnO 4 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 sonication Hummers, W.S.; Offeman, R.E., J. Am. Chem. Soc. 1958, 80, graphite oxide suspension aqueous graphene oxide dispersion with Ruoff group

6 Characterization of graphene oxide TGA FT-IR XPS Thermogravimetric analysis (TGA) reveals pyrolysis of oxygen-containing functional groups Fourier transform-infrared (FT-IR) and X- ray photoelectron spectroscopy (XPS) identify functional groups with Ruoff group

7 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 CO 2 TEM image of phenyl isocyanatefunctionalized graphene Stankovich, S.; Piner, R.D.; Nguyen, S.T.; Ruoff, R.S., Carbon 2006, 44, Compton, O.C.; Dikin, D.A.; Putz, K.W.; Brinson, L.C.; Nguyen, S.T., Adv. Mater. 2010, 22, with Ruoff group

8 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, Compton, O.C.; Dikin, D.A.; Putz, K.W.; Brinson, L.C.; Nguyen, S.T., Adv. Mater. 2010, 22, with Ruoff group

10 Fabricating thin film of nanocomposites hydrazine 90 C precipitate MeOH Isocyanate-treated graphene oxide in DMF with PS 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

11 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,

12 Enhanced conductivity, mechanical, and thermal properties in PS-graphene nanocomposites Graphene transforms insulating polystyrene matrix into electrically conductive composite Percolation threshold of only 0.1 vol% due to excellent dispersion of functionalized graphene in PS matrix Mechanical and thermal properties of parent matrix enhanced by addition of 1 wt% graphene CNTs afford similar improvement, but can cost $250 per gram Stankovich, S. et al., Nature 2006, 442, Ramanathan, T. et al., Nat. Nanotechnol. 2008, 3,

14 Graphene oxide paper via vacuum-assisted selfassembly (VASA) Intensity Graphene oxide sheets Filtration Graphene oxide paper Vacuum Membrane filter Stankovich, S. et al. Nature 2006, 448, q (deg) with Ruoff group

15 VASA in the presence of metal ions Rinsing if necessary graphene oxide paper Mg-modified graphene oxide paper with Ruoff group

16 Lateral crosslinking of graphene oxide sheet by MCl 2 Park et al., ACS Nano 2008, 2(3), 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

17 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.

18 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 with Brinson group

19 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,

20 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,

21 Relating structure and property Composition of interlayer gallery affects mechanical properties graphene oxide film prepared from water 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/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,

22 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,

23 Partial summary 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

25 Anode assembly graphene oxide dispersion graphene oxide paper reduction graphene paper vacuum filtration hydrazine vacuum filtration Abouimrane, A.; Compton, O.C.; Amine, K.; Nguyen, S.T., J. Phys. Chem. C 2010, 114,

26 LIB Cell assembly Li metal Graphene paper Cathode current collector (Al foil) Polymer separator Anode current collector (Cu foil) 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 Coin cell scheme Electrochemical measurements made using a Maccor battery cycler

27 Performance of graphene-based anode graphene paper graphene powder Abouimrane, A.; Compton, O. C.; Nguyen, S. T.; Amine, K. J. Phys. Chem. C, 2010, 114(29),

28 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 CO 2 TEM image of phenyl isocyanatefunctionalized graphene Stankovich, S.; Piner, R.D.; Nguyen, S.T.; Ruoff, R.S., Carbon 2006, 44,

29 Anode modification Compton, O.C.; Jain, B; Abouimrane, A; Dikin, D.A.; Amine, K.; Nguyen, S.T., ACS Nano 2011, 5(6),

30 Anode assembly graphene oxide dispersion graphene oxide paper reduction Graphenepolymer paper vacuum filtration hydrazine Add polymer vacuum filtration Abouimrane, A.; Compton, O.C.; Amine, K.; Nguyen, S.T., J. Phys. Chem. C 2010, 114,

31 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,

32 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,

33 Li-air battery based on porous 3-D graphene structures Discharge capacity ~ 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 O 2 batteries Xiao, Liu, Zhang, and coworkers Nano Lett., 2011, 11 (11),

34 Substrates for flexible LEDs Hong and coworkers, Adv. Mater. 2011, 23, DOI: /adma

35 Electrically conductive graphene-based ink for printedcircuit labels Vorbeck Materials (Jessup, MD)

36 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: /NNANO

37 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

38 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?