I) Exfoliated Graphite Nano Platelets and II) Metal Nano Particles as Multifunctional Materials for Polymers and Energy Storage

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1 I) Exfoliated Graphite Nano Platelets and II) Metal Nano Particles as Multifunctional Materials for Polymers and Energy Storage Lawrence T. Drzal Dept of Chemical Engineering and Materials Science Composite Materials and Structures Center Michigan State University East Lansing, MI

2 NANO Material Portfolio Carbon Nanotubes.3 nm Boron Nitride Nanotubes Nanoclay Vapor Grown Carbon Fibers NanoGraphite Platelets Boron Nitride NanoPlatelets Cellulose Nanowhiskers Halloysite Nanotubes

3 Graphite NanoPlatelets xgnp Carboxyl C OH O Layered Natural Mineral 3.35 Å NH2 Amine C O O O Lactone Pyrone OH OH Hydroxyl O NH Carbonyl Imine 7nm Layers can be intercalated and exfoliated into nanosize platelets with high aspect ratio Basal Plane is inert (sp 2 + π) Existence of functional groups at the edges can lead hydrogen or covalent bond with polymer matrix Nanocomposite properties mechanical, electrical, thermal and barrier properties Estimated Cost <$1/lb

4 Nanoreinforcements & Properties Exfoliated Clay Carbon Nanotube VGCF Exfoliated h-bn BN Nanotubes Cellulose Nanowhisker Graphite NanoPlatelets PHYSICAL STRUCTURE Platelet ~1nm x 1nm Cylinder NT ~1nm X 1nm Platelet Cylinder Needle-Whisker Platelet ~1nm X 1nm VGCF ~2nm X 1um CHEMICAL STRUCTURE SiO2, Al2O3, MgO, Graphene (chair, zigzag, chiral) Boron Nitride Cellulose Graphene K2O, Fe2O3 INTERACTIONS Hydrogen bond π - π Hydrogen bond Hydrogen Bond π - π Dipole-Dipole TENSILE MODULUS.17 TPa NT TPa VGCF TPa ~1 TPa ~ 13 GPa ~1. TPa TENSILE STRENGTH ~1 GPa (NT 18 GPa) VGCF 3-7 GPa? 1 GPa ~(1-2 GPa) ELECTRICAL RESISTIVITY Ω cm NT ~ 5 x 1-6 Ω cm VGCF 5-1x1-3 Ω cm insulator insulator 1 1 Ω cm ~ 5x1-6 Ω cm ~ 1 Ω cm THERMAL CONDUCTIVITY 6.7 x 1-1 W/m K 3 W/m K (NT) 2-2 W/m K (VGCF) conductor ~3W/m K insulator 3 W/m K 6 W/m K COEF. THERMAL EXP x x 1-6 ~1 x x x x 1-6 DENSITY g/cm 3 NT g/cm 3 ~2. g/cm g/cm 3 ~2. g/cm 3 VGCF g/cm 3

5 Multifunctionality Attainable with xgnp Mass Reduction (low density, low concentration) Increased Stiffness (high aspect ratio) Increased Toughness (engineered interfacial adhesion) Electrical Conductivity (electrostatic dissipation, electrostatic painting, electromagnetic shielding) Thermal Conductivity (lower C.T.E., higher T ult ) Improved Appearance (scratch resistance) Barrier to Permeants (platelet morphology) Reduced Flammability (less combustible material) Surface Conductivity (controlled deposition and alignment) Intra and Interlaminar Strengthening and Toughening Composite Transverse Properties

6 xgnp + Thermoset & Thermoplastics [MPa] [MPa] Flexural Modulus of Nylon 6 Composites xgnp-1 xgnp-15 CF GF VGCF Nanomer I34.TCN Cloisite 93A [Vol%] Flexural Strength of Nylon 6 Composites xgnp-1 xgnp-15 CF GF VGCF Nanomer I34.TCN Cloisite 93A [Vol%] [cm3/m2*day*atm] Å NH2 Amine O NH Imine O Pyrone Permeability of Nylon 6 Films Carboxyl Lactone OH Carbonyl C C O O OH OH O Hydroxyl Control N6 3v%xGnP-15um/N6 3v%xGnP-1um/N6 3v%CF/N6 3v%GF 3v%VGCF/N6 3v%Nanomer/N6 3v%Cloisite/N6 (W/g*K) Log(Z/ohm*cm) Control Epoxy Thermal Conductivity 3 vol% MW Ex.Gr Log(Freq/Hz) Control Epoxy 1.Vol% Exfoliated Gr 2.Vol% Exfoliated Gr 3.Vol% Exfoliated Gr Static Dissipation Electrostatic Painting EMI/RFI Shielding 3 vol% CF 3 vol% VGCF 3 vol% CB [Hour]

7 xgnp Nanoparticles Applied to Carbon Fiber Surfaces in Epoxy Composites Short Beam Shear Strength [MPa] Control xgnp Coated sample 11 Flexural Modulus in Transverse Direction Flexural Strength in Transverse Direction [GPa [MPa] Control xgnp Coated sample Control xgnp Coated sample

8 Mechanical and Electrical Properties of Glass fiber/caco 3 /UPE Flexural strength stress (MPa) Strength Stress Modulus A B C D E F Flexural modulus (GPa) log (Resistivity) (R in Ohms.m) Volume resistivity Surface resistivity xgnp-1 wt.% log (Resistivity) (R in Ohms/sq) Impact strength (J/m) A B C D E F A= 28%(glass fiber) + 47% (CaCO 3 ) + 23%(UPE)= composite (xgnp %) B= 28% (glass fiber /1.% xgnp 1) + 47% (CaCO 3 ) +23%(UPE)= composite (xgnp.3%) C= 28% (glass fiber) + 47% (CaCO 3 /2.1% xgnp 1) +23%(UPE)= composite (xgnp 1.%) D= 28% (glass fiber) + 47% (CaCO 3 /3.2% xgnp 1) +23%(UPE)= composite (xgnp 1.5%) E= 28% (glass fiber) + 47% (CaCO 3 /4.3% xgnp 1) +23%(UPE)= composite (xgnp 2.%) F= 28% (glass fiber) + 38% (CaCO 3 /1% xgnp 1) +29%(UPE)= composite (xgnp 3.8%)

9 Metal NANO Particles + Nanographite Platelets xgnp Size Surface Chemistry Dispersion Metal Nanoparticles Size (.5 1nm) Composition Concentration Dispersion xgnp + Nanoparticle Size Utilization Composition Distribution xgnp-supported Pt catalysts in various sizes produced by MSU techniques (3-5um) (3-5 um) (15-1 um) ( < 1um) 3~4nm 2~3nm Surface chemistry control hydrophobic/hydrophilic xgnp dispersed in water 6wt.% Pt 6wt.% Pt 1~2nm < 1nm Conventional Drzal Group method

10 Metal NANO Particles on Graphene Freq uency (% ) Pt Ru 1.~ ~2. 2.~ ~3. 3.~ ~4. Particle size (nm) Pd PtRu Au

11 Metal Nanoparticles on Graphene and other Surfaces Commercial Pt/CB Pt/CB-MSU Pt/SWNT-MSU Pt/GNF-MSU Pt/MWNT-MSU MSU synthesize smaller particles with better dispersion on any carbon surface without a harsh pretreatment

12 Advantages of MSU process Advantages of xgnp over other state of the art carbon materials? The highest oxidation resistance and the highest crystallinity The low impurities The most cost effective The morphology to enhance contact with reactants + Advantages of MSU technique in depositing nanosized metals and oxides? Simple, fast and economical process Easy to tune the size / dispersion of metals Versatile to apply for any solid support, Highly active, large surface to volume ratio and easily accessible

13 Applications of xgnp: Energy Devices* Fuel Cells Supercapacitors Batteries Hydrogen Storage 1. Pt, Pd on xgnp 1. Pseudocapacitors 1. Non Li Battery 1. Direct application Metal oxide/xgnp conductive 2. Pillared xgnp 2. PtM alloys on xgnp (RuO2, CuO, ) enhancer in 3. M/xGnP (M=Pd, Ni.) CP/xGnP cathode 3. AuAg on xgnp * CP: conducting 4. AuM alloys on xgnp 2. EDLC polymers 2. Li Battery Anode CNF/xGnP * combined with metals 5. WC/xGnP Hybrid Increase surface composite area Metal oxide/xgnp of xgnp (MnO2, SnO2, Oxidation of xgnp SiO2.) Nano metals/xgnp

14 Fuel Cell High performance, inexpensive xgnpsupported electrocatalysts for hydrogenoxygen fuel cells Reduction of Pt usage Pt-free catalysts Li Ion Battery Nanosized metal oxide coated and surface modified xgnp for anode and cathode in Li Ion batteries Superior long-term stability of anode material and battery recharging performance Cell housing - + Current collector cathode separator Al foil nanocomposite anode Current collector e.g. Al or Cu foil xgnp Pt Liquid/polymer electrolyte Gas supply & current collector PEM H H oxidation H Lithiation H H COOLi COOLi OLi OLI OLi xgnp anode Li ionmetal element Li + Electrolyte

15 Glass slide coated with xgnp with ~8% transmission in visible spectrum Transmittance (%) nm 1 nm 2 nm Wavelength (nm) Monolayer of graphene covering a glass slide. Transmission ~75% from 5 to 2nm. Conductivity ~1 S/cm

16 xgnp Exfoliated Graphite Nano Platelets rd W a w A 7 2 r inne MSU Spin-off Company: XG Sciences, Inc. Michael R. Knox, CEO DRZAL xgnp Group Sanjib Biswas Huang Wu Xian Jiang Jinglei Jiang Anchita Monga Hiroyuki Fukushima, PhD InHwan Do, PhD Hwan Man Park, PhD Wanjun Liu, PhD Xiaobing Li, PhD

17 Applications of Graphite NanoPlatelets (xgnp) with Nanosized Metals and Metal oxides Fuel Cell Li Battery Sensors Solar Cells H 2 Production Bioproducts Chemical Industry H2 Storage Supercapacitor Polymer Multifunctional Additive