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Carbide-Derived Carbons for Energy-Related and Biomedical Applications Yury Gogotsi A.J. Drexel Nanotechnology Institute.

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Presentation on theme: "Carbide-Derived Carbons for Energy-Related and Biomedical Applications Yury Gogotsi A.J. Drexel Nanotechnology Institute."— Presentation transcript:

1 Carbide-Derived Carbons for Energy-Related and Biomedical Applications Yury Gogotsi A.J. Drexel Nanotechnology Institute and Dept. Materials Science & Engineering, Drexel University, Philadelphia Polytechnic U, April 23, 2007 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 Composites S. Osswald, G. Yushin, V. Mochalin, S. Kucheyev, Y. G., J. American Chemical Society, v. 128, (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 Nanomaterials: Ternary Bonding Diagram Nanodiamond Nanotubes Fullerenes Hydrocarbons sp n Corannulene Cumulene Adamantane Carbyne (sp 1 )Diamond (sp 3 ) Graphite (sp 2 ) Adapted from M. Inagaki, New Carbons, 2000 Heimann et al., Carbon, 1997 sp 3 +sp 2 +sp amorphous carbon, DLC, glassy carbon, carbon black, etc. sp 3 +sp 2 +sp amorphous carbon, DLC, glassy carbon, carbon black, etc. sp n, (1

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 TiC(s) + 2 Cl 2 (g) = TiCl 4 (g) + C(s) (  Gº = kJ/mol at 950°) ; M = metal (or Si or B) Carbide-Derived Carbon (CDC) Process 2 nm SiC 2 nm Carbide: Porosity = 0 %CDC: Porosity = 57 % Cl 2 ( o C) 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) Reaction valid for most carbides - huge number of possible precursors 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 Cl 2 HCl Ar 1 Flowmeters 2 Resistance furnace 3 Quartz reaction tube 4 Quartz boat with sample 5 Sulfuric acid T= °C; Ambient pressure Chlorination Set-up Large-scale production alternatives: Fluidized-bed furnace or rotary kiln reactor

8 CDC: Powders, Films, Fibers, Bulk CDC coated SiC Tyranno fabric Bulk CDC from sintered SiC CDC coated dynamic seals d=3 cm Amorphous Carbon Whisker 200nm CDC from SiC whisker Powder 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 Positions and spatial distribution of carbon atoms in the carbide affect the structure and pore size/shape of CDC Carbide Lattice – Template for CDC G. Yushin, A. Nikitin, Y. Gogotsi, Carbide Derived Carbon, in Nanomaterials Handbook., Y. Gogotsi, Editor. 2006, CRC Press

11 G. Yushin, A. Nikitin, Y. Gogotsi, in Nanomaterials Handbook, ed. by Y. Gogotsi (CRC Press, 2005) Carbide Lattice – Template for CDC Ti 3 SiC 2 -CDC (1200°C)SiC-CDC (1200°C) Pore-size distributions calculated using DFT model Ar sorption at 77 K Autosorb-1

12 Gogotsi, Y., et al., Nature Materials, 2, 591 (2003) dD/dT ~ nm/ o C, or: +/- 10 o C temperature control - better than 0.1 Å pore control. Tunable Pore Size in CDC Choice of starting material and synthesis conditions gives an almost unlimited range of porosity distributions High surface area Uniform pores Ti 3 SiC 2 -CDC

13 R.E. Smalley MRS Bulletin 30, (2005)

14 H 2 liquid at 20K 105 liters H 2 gas at 1 atm. pressure, 25 o C > 48,000 liters 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 DOE Target (by 2010) 6.5 wt.% 60 kg/m 3 Note: DOE target is system target and will include the density of accessories depending on the materials requirement CDC for H 2 Storage H 2 at 5,000psi 200 liters A hydrogen fuel cell (internal combustion engine) car will require 4 (8) kg or 225 (450) liters of hydrogen to travel 400 km.

15 CDC for H 2 Storage: Cryo-adsorption   Weak interaction between H 2 and adsorbent (e.g. isosteric heat of H 2 adsorption is ~ 5 kJ/mole on plan graphite and 5-7 kJ/mole on MOF, which is too weak for RT adsorption) Challenges:   MOF*   Nanoporous Carbon Candidates: * O. Yaghi, et al., J. Am. Chem. Soc., 128, 3494 (2006) Y. Gogotsi, et al., J. Am. Chem. Soc., 127, (2005)

16 “Hydrogen storage is proportional to specific surface area” Schlapbach et al. Nature 2001, Agarwal et al. Carbon 1987, Nijkamp et al. Applied Physics A K 1 atm CDC for H 2 Storage: Cryo-adsorption   Specific surface area of ~5750 m2/g will be required for reaching 6.5 wt.%.

17   Large variation for similar surface area   H 2 storage is NOT proportional to SSA Linear fit 77K 1 atm CDC for H 2 Storage: Cryo-adsorption Y. Gogotsi, et al., J. Am. Chem. Soc., 127, (2005)

18 TiC-CDC ZrC-CDC SiC-CDC B 4 C-CDC H 2 wt.% per unit SSA, Pore size, nm.10 3 m 2 wt%.g   Small pores are more efficient than large ones for a given SSA   SSA of ~3000 m 2 /g will be needed for 7wt% storage - FEASIBLE! Empty symbols: H 2 treated samples Y. Gogotsi, et al., J. Am. Chem. Soc., 127, (2005) CDC for H 2 Storage: Cryo-adsorption 77K 1 atm

19 CDC for H 2 storage: Cryo-adsorption 77K 1 atm   Large volume of pores < 1 nm needed for high storage capacity Density of gaseous H 2 in nano-pores can be higher than density of liquid H 2 J. Jagiello et al., J. Phys. Chem. B, in press (2006), Q. Wang et al., J. Chem. Phys. 110, (1999)   Samples with modest SSA ( 2300 m 2 /g but having wider PSD if all these pores filled with liquid H 2

20 CDC for H 2 storage: Cryo-adsorption Obtained from 77, 88, and 300K using Clausius-Clapeyron Equation   Small pores increase the interaction with H 2 and thus result in higher H 2 coverage of the sorbent surface   CDC demonstrate stronger interaction with H 2 than CNT and MOF G. Yushin et al., Advanced Functional Materials, 16, p (2006)

21 S.K. Bhatia, A.L. Myers, Langmuir (22) (2006) 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, P delivery, P storage ) = where: n = number of sorb. sites; equilibrium constant -ΔH o = heat of adsorption; ΔS o = entropy change relative to standard pressure (1 atm) Max Delivery: P storage =30 atm, P delivery =1.5 atm; ΔS o ~8R: -ΔH o optimum = 15.1 kJ/mol

22 CDC for Protein Adsorption Grand challenge - Sepsis   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 Hydrogen TNF- α 9.4 x 9.4 x 11.7 nm

23 CDC for Protein Adsorption PSD in the nm range obtained from N 2 sorption isotherms: commercial carbons and CDC from MAX phase ternary carbides G. Yushin, et al. Biomaterials, 27, 5755, 2006

24 CDC for Cytokine* Adsorption * 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. TNF-α IL-6 CDC outperformed commercial carbons in the efficiency of cytokine’s removal

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

26 CDC for Cytokine Adsorption proteins adsorbed on the surfaceproteins adsorbed on the surface and in the mesopores 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. *Halper, M.S., & Ellenbogen, J.C., MITRE Nanosystems Group, March 2006 Ragone plot of energy storage systems*

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

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

31 (CH 3 CH 2 ) 4 N Å diameter BF Å diameter 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 (CH 3 CH 2 ) 4 N BF 4 in CH 3 CN (most conventional) Tests: Cyclic Voltammetry (CV), EIS, Galvanostatic cycling Characterization : Ar and N 2 adsorption, TEM, SEM, XRD, SAXS (Prof. Fischer, Dr. Laudisio), four-probe conductivity measurements, Raman spectrometry Our Study: Experimental Details

32   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. CDC: Galvanostatic and Potentiostatic Tests 700 o C 20 mA/cm 2 20 mV/s

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, (2006)

34 Sub-nanometer pore size control shows a new direction for research!!! Electrolyte: 1.5 M (CH 3 CH 2 ) 4 N BF 4 in CH 3 CN (most conventional)

35   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 CDC for Supercapacitors J. Chmiola, G. Yushin, Y. Gogotsi, et al., Science, 313, (2006)

36 Conclusions   Extraction of metals from carbides produces carbon with tunable: Structure Pore size; Pore volume and Specific surface area   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   CDC process allows one to perform fundamental studies of the effects of porous carbon parameters on adsorption- and transport related phenomena

37 G. Yushin, Y. Gogotsi, and A. Nikitin, Carbide Derived Carbon, in Nanomaterials Handbook, Y. Gogotsi, Editor. 2006, CRC Press. p Book chapter on CDC 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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