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Carbide-Derived Carbons for Energy-Related and Biomedical Applications Yury Gogotsi

Polytechnic U, April 23, 2007. Carbide-Derived Carbons for Energy-Related and Biomedical Applications Yury Gogotsi A.J. Drexel Nanotechnology Institute and Dept. Materials Science & Engineering, Drexel University, Philadelphia. nano.drexel.edu.

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Carbide-Derived Carbons for Energy-Related and Biomedical Applications Yury Gogotsi

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  1. Polytechnic U, April 23, 2007 Carbide-Derived Carbons for Energy-Related and Biomedical Applications Yury Gogotsi A.J. Drexel Nanotechnology Institute and Dept. Materials Science & Engineering, Drexel University, Philadelphia nano.drexel.edu The A.J. Drexel Nanotechnology Institute oversees education, research, collaboration, commercialization, and communication activities in the interdisciplinary field of nanotechnology for Drexel University.

  2. Current Research Projects • Nanotubes, Nanocones, and Nanowires • Y. G., et al, Science, v. 290, 317 (2000) • Nanotube-Based Nanofluidic Devices • Y. G., J. Libera, A. Yazicioglu, et al., Appl. Phys. Lett.,v. 79, p.1021 (2001) • Nanotube-Reinforced Polymers • F. Ko, Y. G., A. Ali, et al., Adv. Mater., v. 15, 1161(2003) • Nanodiamond Powders and CompositesS. Osswald, G. Yushin, V. Mochalin, S. Kucheyev, Y. G., J. American Chemical Society, v. 128, 11635 (2006) • Nanoindentation Testing Y. G., A. Kailer, K.G. Nickel, Nature, v. 401, 663 (1999) • Raman Spectroscopy and Electron Microscopy • P.H. Tan, S. Dimovski, Y.G., Phil. Trans. Royal Soc. Lond. A, 362, 2289 (2004) • Carbide-Derived Carbons for Energy-Related and Other Applications • Y. G., S. Welz, D. Ersoy, M.J. McNallan, Nature, v. 411, 283 (2001) • J. Chmiola, G. Yushin, Y.G., et al., Science, v. 313, 1760 (2006)

  3. Business Week, February 14, 2005

  4. Carbon whiskers, cones and polyhedral crystals C spn, (1<n<3, n=2) Carbon Nanomaterials: Ternary Bonding Diagram Graphite (sp2) • Classification based on: • hybridization type of C atoms • characteristic size of clusters Nanosized morphology of graphite-based materials Adapted from M. Inagaki, New Carbons, 2000 Heimann et al.,Carbon, 1997 Ovalene Fullerene family Nanotubes sp2 +p spn sp3+sp2+sp amorphous carbon, DLC, glassy carbon, carbon black, etc. Corannulene sp +2p sp3 Fullerenes =C=C= Adamantane Cumulene Hydrocarbons Nanodiamond Diamond (sp3) Carbyne (sp1)

  5. Nanotechnology A new material, process, or device must offer a net increase in economic utility if it is to be considered successful. John J. Gilman, Mater. Res. Innov., v. 5, 12 (2001) • “Ideal” Nanotechnology Process: • Control over the structure on the atomic level • Ability to generate desirable structures • Self-assembly • Low-cost/high-volume production

  6. Cl2 ( 200 - 1200oC) 2 nm 2 nm SiC Carbide:Porosity = 0 % CDC:Porosity = 57 % Carbide-Derived Carbon (CDC) Process ; M = metal (or Si or B) TiC(s) + 2 Cl2(g) = TiCl4(g) + C(s) (Gº = - 434.1 kJ/mol at 950°) Reaction valid for most carbides - huge number of possible precursors 2 methods of pore size control: 1.) Precursor choice 2.) Synthesis conditions G. Yushin, A. Nikitin, Y. Gogotsi, in Nanomaterials Handbook Y. Gogotsi, Ed. (CRC Press, 2006) B.D. Shaninaa, S.K. Gordeev , A.V. Grechinskaya et al., Carbon (2003) J. Leis, A. Perkson, M. Arulepp, M. Kaarik, G. Svensson, Carbon (2001)

  7. 2 1 Flowmeters 2 Resistance furnace 3 Quartz reaction tube 4 Quartz boat with sample 5 Sulfuric acid Ar Cl2 HCl Chlorination Set-up T=200-1200°C; Ambient pressure Large-scale production alternatives: Fluidized-bed furnace or rotary kiln reactor

  8. CDC: Powders, Films, Fibers, Bulk Powder CDC coated SiC Tyranno fabric CDC coated dynamic seals Amorphous Carbon Whisker Bulk CDC from sintered SiC 200nm CDC from SiC whisker d=3 cm Z.G. Cambaz, G. Yushin, Y. Gogotsi, J. Am. Ceram. Soc., 89, 509 (2005)

  9. Market Opportunities* • Supercapacitors – up to $ 2B • Gas storage (hydrogen, methane, chlorine, etc.) - $1-50B • Adsorption/separation of proteins (bio-fluids’ purification / blood cleansing etc.) - $0.2-10B • Poisoning treatment - $0.04-1B • Protective respiratory equipment and suits – up to $4B • Water purification / desalination membranes - up to $2B • Portable desalination units • Filters (gas separation / indoor air quality/ etc.) - up to $2B • Others (tribological applications, catalyst support, etc.) * Addressable (not necessarily current) market. Data taken from Frost & Sullivan and other business databases

  10. Carbide Lattice – Template for CDC Positions and spatial distribution of carbon atoms in the carbide affect the structure and pore size/shape of CDC G. Yushin, A. Nikitin, Y. Gogotsi, Carbide Derived Carbon, in NanomaterialsHandbook., Y. Gogotsi, Editor. 2006, CRC Press

  11. Carbide Lattice – Template for CDC Ti3SiC2-CDC (1200°C) SiC-CDC (1200°C) Ar sorption at 77 K Autosorb-1 Pore-size distributions calculated using DFT model G. Yushin, A. Nikitin, Y. Gogotsi, in Nanomaterials Handbook,ed. by Y. Gogotsi (CRC Press, 2005)

  12. Tunable Pore Size in CDC Choice of starting material and synthesis conditions gives an almost unlimited range of porosity distributions Ti3SiC2 -CDC dD/dT ~ 0.0005 nm/o C, or: +/- 10o C temperature control - better than 0.1 Å pore control. • High surface area • Uniform pores Gogotsi, Y., et al., Nature Materials, 2, 591 (2003)

  13. R.E. Smalley MRS Bulletin30, 412-417 (2005)

  14. CDC for H2 Storage DOE Target (by 2010) 6.5 wt.% 60 kg/m3 H2 gas at 1 atm. pressure, 25oC > 48,000 liters A hydrogen fuel cell (internal combustion engine) car will require 4 (8) kg or 225 (450) liters of hydrogen to travel 400 km. H2 at 5,000psi 200 liters H2 liquid at 20K 105 liters Note: DOE target is system target and will include the density of accessories depending on the materials requirement DOE target 67 liters Volume of 4 kg of hydrogen stored in different ways L. Schlapbach and A.Zuttel, Nature, 2001, v.,414, p. 353

  15. CDC for H2 Storage: Cryo-adsorption Candidates: • MOF* • Nanoporous Carbon Challenges: • Weak interaction between H2 and adsorbent (e.g. isosteric heat of H2 adsorption is ~ 5 kJ/mole on plan graphite and 5-7 kJ/mole on MOF, which is too weak for RT adsorption) * O. Yaghi, et al. , J. Am. Chem. Soc., 128, 3494 (2006) Y. Gogotsi, et al. , J. Am. Chem. Soc., 127, 16006 (2005)

  16. CDC for H2 Storage: Cryo-adsorption 77K 1 atm • Specific surface area of ~5750 m2/g will be required for reaching 6.5 wt.%. “Hydrogen storage is proportional to specific surface area” Schlapbach et al. Nature 2001, Agarwal et al. Carbon 1987, Nijkamp et al. Applied Physics A 2001

  17. CDC for H2 Storage: Cryo-adsorption Linear fit • Large variation for similar surface area • H2 storage is NOT proportional to SSA 77K 1 atm Y. Gogotsi, et al. , J. Am. Chem. Soc., 127, 16006 (2005)

  18. 3 .10 2 wt%.g m wt.% per unit SSA, 2 H CDC for H2 Storage: Cryo-adsorption 77K 1 atm T i C - C D C 2 . 6 • Small pores are more efficient than large ones for a given SSA • SSA of ~3000 m2/g will be needed for 7wt% storage - FEASIBLE! Z r C - C D C 2 . 4 S i C - C D C B C - C D C 2 . 2 4 2 . 0 1 . 8 1 . 6 1 . 4 1 . 2 1 . 0 Empty symbols: H2 treated samples 0 . 8 0 . 6 0 . 7 0 . 8 0 . 9 1 . 0 1 . 1 1 . 2 1 . 3 1 . 4 1 . 5 1 . 6 P o r e s i z e , n m Y. Gogotsi, et al. , J. Am. Chem. Soc., 127, 16006 (2005)

  19. CDC for H2 storage: Cryo-adsorption 77K 1 atm if all these pores filled with liquid H2 • Large volume of pores < 1 nm needed for high storage capacity • Density of gaseous H2 in • nano-pores can be higher • than density of liquid H2 J. Jagiello et al., J. Phys. Chem. B, in press (2006), Q. Wang et al., J. Chem. Phys. 110, 577-586 (1999) • Samples with modest SSA (< 1300 m2/g) but with small pores substantially outperformed others with SSA > 2300 m2/g but having wider PSD

  20. CDC for H2 storage: Cryo-adsorption • Small pores increase the interaction with H2 and thus result in higher H2 coverage of the sorbent surface • CDC demonstrate stronger interaction with H2 than CNT and MOF Obtained from isotherms @ 77, 88, and 300K using Clausius-Clapeyron Equation G. Yushin et al., Advanced Functional Materials, 16, p. 2288-2293 (2006)

  21. Optimum Isosteric Heat of Hydrogen Adsorption Assumptions: (1) homogeneous adsorbent and Langmuir isotherm (2) delivery and storage at the same temperature (RT) (3) minimal storage in adsorbent-free volume (justified at RT) Delivery (K, Pdelivery, Pstorage) = where: n = number of sorb. sites; equilibrium constant -ΔHo = heat of adsorption; ΔSo = entropy change relative to standard pressure (1 atm) Max Delivery: Pstorage=30 atm, Pdelivery=1.5 atm; ΔSo~8R: -ΔHooptimum= 15.1 kJ/mol S.K. Bhatia, A.L. Myers, Langmuir (22) 1688-1700 (2006)

  22. CDC for Protein Adsorption Grand challenge -Sepsis Hydrogen • Severe sepsis kills 1,500 people/day (comparable to lung and breast cancer (~ 2,700 and ~ 1,100 people /day, respectively) • Sepsis > $ 17 billion / year in the US • Inflammatory response is driven by a complex network of cytokines, inflammatory mediators • Cytokine removal from blood brings under control the unregulated pro- and anti-inflammatory processes driving sepsis TNF-α 9.4 x 9.4 x 11.7 nm

  23. CDC for Protein Adsorption PSD in the 1.5 - 36 nm range obtained from N2 sorption isotherms: commercial carbons and CDC from MAX phase ternary carbides G. Yushin, et al. Biomaterials, 27, 5755, 2006

  24. CDC for Cytokine* Adsorption • CDC outperformed commercial carbons in the efficiency of cytokine’s removal TNF-α IL-6 * cytokines are regulatory proteins that are released by cells of the immune system and need to be removed from the blood in case of an autoimmune disease.

  25. CDC for Cytokine Adsorption • Adsorption depends on the SSA of adsorbents accessible by cytokines G. Yushin, et al. Biomaterials, 27, 5755, 2006

  26. proteins adsorbed on the surface proteins adsorbed on the surface and in the mesopores CDC for Cytokine Adsorption G. Yushin, et al. Biomaterials, 27, 5755, 2006

  27. Store charge electrostatically as charged ions “adsorbed” to oppositely charged surfaces No charge transfer reactions take place, eliminating many shortcomings of traditional batteries High specific surface area that is accessible to the electrolyte is crucial - porosity control is a requisite for high performance ELECTRODE OPTIMIZATION CRUCIAL FOR MAXIMIZING PERFORMANCE Supercapacitors Supercap schematic • B. E. Conway, Electrochemical Capacitors: Scientific • Fundamentals and Technological Applications, Kluwer, (1999).

  28. Capacitive Storage of Energy Supercapacitors bridge between batteries and conventional capacitors Supercapacitors are able to attain greater energy densities while still maintaining the high power density of conventional capacitors. Supercapacitors are a potentially versatile solution to a variety of emerging energy applications based on their ability to achieve a wide range of energy and power density. Ragone plot of energy storage systems* *Halper, M.S., & Ellenbogen, J.C., MITRE Nanosystems Group, March 2006

  29. Supercapacitors: Market Segmentation • Uninterruptible Power Supplies and Power Quality • Defense applications CAGR = 50% • Aerospace applications • Mobile devices • Vehicles with electrical or hybrid motors (EV) • Total addressable market size in 2012 ~$2 Billion • The largest part – applications in Hybrid Electrical Vehicles

  30. Energy ~ C Power ~ 2 Carbon 1 Pore Carbon Traditional View: Increasing Pore Size Increases Specific Capacitance Ideal pore size (~ 3x solvated ion size) Too small pore size Too large pore size 3 Carbon A3>A1; A3>A1 electrolyte ions + its solvation shells Surface

  31. (CH3CH2)4N+ 6.75 Å diameter BF4- 3.25 Å diameter Our Study: Experimental Details Cell: 2-electrode cells (3-electrode cell experiments are in progress) Electrode Preparation: 95% CDC (TiC-CDC initially), 5% PTFE cast onto treated Al current collectors Electrolyte: 1.5 M (CH3CH2)4N BF4 in CH3CN (most conventional) Tests: Cyclic Voltammetry (CV), EIS, Galvanostatic cycling Characterization: Ar and N2 adsorption, TEM, SEM, XRD, SAXS (Prof. Fischer, Dr. Laudisio), four-probe conductivity measurements, Raman spectrometry

  32. CDC: Galvanostatic and Potentiostatic Tests TiC-CDC @ 700oC 20 mA/cm2 20 mV/s • Charge-Discharge: linear profile and identical slopes: non Faradic response. • CV: identical response and non-Faradic behavior. • This shows CDC electrode cells stable up to at least 2.7 V.

  33. CDC: SSA and pore size vs. synthesis T • Higher SSA and Pore size at higher temperature • Specific capacitance should increase with synthesis temperature J. Chmiola, G. Yushin, Y. Gogotsi, et al., Science, 313,1760-1763 (2006)

  34. Sub-nanometer pore size control shows a new direction for research!!! Electrolyte: 1.5 M (CH3CH2)4N BF4 in CH3CN (most conventional)

  35. CDC for Supercapacitors • Decreasing pore size allowed a 50% increase in specific capacitance above the most advanced activated carbons commercially available • The decrease in capacitance for small pore samples at high current densities is negligible - ion transport in small pores is still fast J. Chmiola, G. Yushin, Y. Gogotsi, et al., Science, 313,1760-1763 (2006)

  36. Conclusions • Extraction of metals from carbides produces carbon with tunable: • Structure • Pore size; Pore volume and Specific surface area • CDC process allows one to perform fundamental studies of the effects of porous carbon parameters on adsorption- and transport related phenomena • CDC process enables design and fine tuning of porous carbons for improved performance in applications • Move from trial-and-error tests to design of nanoporous carbons

  37. Book chapter on CDC G. Yushin, Y. Gogotsi, and A. Nikitin, Carbide Derived Carbon, in Nanomaterials Handbook, Y. Gogotsi, Editor. 2006, CRC Press. p. 237-280. Acknowledgements Students and post-docs at Drexel University: J. Chmiola, G. Yushin, C. Portet, E. Hoffman, R. Dash Prof. J.E. Fischer, University of Pennsylvania Prof. M. Barsoum, Drexel University, Prof. M.J. McNallan, UIC Prof. P. Simon, Paul Sabatier University, Toulouse, France Prof. S. Mikhalovsky, U. Brighton, UK Financial support: DOE, DARPA, NSF, Arkema

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