Nanostructured CarbideDerived Carbons

1
Nanostructured Carbide-Derived Carbons for
Energy-Related and Biomedical Applications Yury
Gogotsi Director, A.J. Drexel Nanotechnology
Institute Trustee Chair Professor of Materials
Science EngineeringDrexel University,
Philadelphia, PA 19104, USA gogotsi_at_drexel.edu
2
Major Research Activities

• Nanotubes, Nanocones, and Nanowires
• Y. G., J.A. Libera, N. Kalashnikov, M.
  Yoshimura, Science, v. 290, 317 (2000)
• Nanotube-Based Nanofluidic Devices
• Y. G., J. Libera, A. Yazicioglu, et al., Appl.
  Phys. Letters,v. 79, p.1021 (2001) N. Naguib, H.
  Ye, Y. G., et al. Nano Letters, v. 4, 2237 (2004)
  
• Nanotube-Reinforced Polymers
• F. Ko, Y. G., A. Ali, et al., Advanced
  Materials, 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)
  
• Indentation Induced Phase Transformations 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, v.362, 2289 (2004)
• Carbide-Derived Carbons for Energy-Related and
  Other Applications
• Y. G, M. Yoshimura, Nature, v. 367, 628-630
  (1994)
• 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
Nanotube-Tipped Multifunctional Cellular Probes
v
Carbon Nanotube
Electrical. Fluorescence. Optical,
SERS, Electrochemical measurements
mitochondria
Glass pipette
nucleus
Nanotube
J. R. Freedman, et al. Appl. Phys. Lett. 90,
103108 (2007) D. Staack, et al, Angewandte Chemie
Int. Ed., 47, 8020 (2008) M. G. Schrlau, et al,
Nanotechnology 19, 325102 (2008)
4
Carbide-Derived Carbon (CDC)
SiC(s) 2Cl2(g) ?SiCl4(g) C(s)
Carbide
Carbide Derived Carbon
Etching Agent
Cl2, F2 ,Br2, I2, HCl, HBr, HI, Supercritical H2O
Vcarbide VCDC
Temperature
2 nm
200-1200oC
Carbide Porosity 0
Nanoporous Carbon Porosity gt50
O. Hutchins, US Patent, 1271713 (1918) W.A.
Mohun, US Patent, 3066099 (1962) S.K. Gordeev et
al., J.Appl. Chem. (USSR) 64, 1178 (1991) N.F.
Fedorov, Russ. Chem. J. 39, 73 (1995) Y. Gogotsi,
M. Yoshimura, Nature, 367, p. 628 (1994) A.
Kravchik et al., Russ. J. Appl. Chem. 72, 2159
(1999) Y. Gogotsi, et al, Nature, 411, p. 283
(2001) J. Leis, et al. Carbon, 39, 2043 (2001)

• Process Features
• Network of open pores
• Precise control over structure and pore size
• Coating, free standing monolith or powder
• Numerous carbides can be used
• Linear kinetics

5
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 Nanomaterials Handbook, CRC
Press (2006)
6
Carbide Lattice Template for CDC
Ti3SiC2-CDC (1200C)
SiC-CDC (1200C)
Ar sorption at 77 K Autosorb-1
Pore-size distributions calculated using NL DFT
model
G. Yushin, A. Nikitin, Y. Gogotsi, in
Nanomaterials Handbook, ed. by Y. Gogotsi (CRC
Press, 2006)
7
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/oC, or /- 10o C temperature
control - better than 0.1 Å pore control.
T300C

• High surface area
• Uniform pores

Gogotsi, Y., et al., Nature Materials, v. 2, 591
(2003)
8
Formation of Graphite and Nanotubes

• Vacuum decomposition of SiC produces ordered
  nanostructures
• Graphene, graphite or CNTs
• Factors affecting
• CDC structure
• Temperature
• Crystal face
• Oxygen P
• Surface state (roughness)
• Surface chemistry
• Heating rate

Z. G. Cambaz, G. Yushin, S. Osswald, V. Mochalin,
Y. Gogotsi, Carbon (2008) 46, 841
M. Kusunoki at al. Applied Physics Letters 77,
424, 2000 Chemical Physics Letters, 366, 458,
2002
9
CDC Powders, Films, Fibers, Bulk
CDC coated SiC Tyranno fabric
CDC coated dynamic seals
Bulk CDC from sintered SiC
Powder
d3 cm
10
Efficiency of Energy Technologies
Input
Output
Liquefied hydrogen 400
Useful energy
Compressed hydrogen 312
Primary renewable energy
Compressed air 156
Pumped water 130
Lead acid batteries 120
Lithium-ion batteries 116
100
Supercapacitors 109
0
Energy Distribution Today 80 chemical, 20
physical Future 20 chemical, 80 physical

• Chemical Storage
• Capacitive Storage
• Cross-cutting panel

Ideal storage (no losses)
U. Bossel - European Fuel Cell Forum - July 2008
P. Simon, Y. Gogotsi, Nature Materials, v.7, 845
(2008)
11
Increase in Carbon Capacitance at pore size
below 1 nm
Cation (CH3CH2)4N Anion BF4-
Unexpected capacitance increase as pores decrease
below 1nm
Chmiola, J. Yushin, G. Gogotsi, Y. Portet, C.
Simon, P. Taberna, P.-L., Science, 2006, v.
313, 1760
12
TiC-CDC Electrochemistry
Ions MUST be desolvated!
J. Chmiola, C. Largeot, P.-L. Taberna, P. Simon,
Y. Gogotsi, Angew. Chemie Int. Ed. v. 47, 3395
(2008)
13
Carbon-Electrolyte Couples

• Question How to match a porous carbon (select
  from hundreds) with an electrolyte (select from
  thousands)?

• Need to increase energy (gt100W-h kg-1) to
  directly compete with batteries
• Larger voltage window that traditional
  electrolytes provides much greater energy density
• Still need to understand capacitance mechanisms
  and possibly increase the voltage window even more

P. Simon, Y. Gogotsi, Nature Materials, v.7, 845
(2008)
14
TiC-CDC Ionic Liquid

• Specific gravimetric and volumetric capacitances
  change versus the chlorination temperature for
  CDC electrodes tested in EMI-TFSI electrolyte at
  60C.
• A standard activated carbon (Kuraray) designed
  for organic electrolyte-based supercapacitors
  reached 90 F/g and 45 F/cm3 under the same
  experimental conditions.

C. Largeot, et al, J. Am. Chem. Soc. v. 130,
2730 (2008)
15
Cryo-adsorption of Hydrogen
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

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 at ambient
  pressure for 7wt storage - FEASIBLE!

Z
r
C
-
C
D
C
2
.
4

S
i
C
-
C
D
C
2
.
2

B
C
-
C
D
C
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)
17
CDC for H2 storage Cryo-adsorption
if all these pores filled with liquid H2

• Large volume of pores lt 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)

• 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

G. Yushin et al., Advanced Functional Materials,
16, p. 2288-2293 (2006)
18
Correlation of 60 bar 77K storage with SSA and
volume of small pores
The best pore size
max
Little or no contribution
Useful pores
Overall, linear dependence of storage
on BET SSA, similar to 1 atm.
Similar to 1 atm., small pores are overweighted
in the SSA/normalized storage.
Activation is effective if the increase in SSA
comes mainly from small pores. On this basis,
CDCs can outperform ACs.
Y. Gogotsi, et al, Importance of Pore Size in
High Pressure Hydrogen Storage by Porous Carbons,
Int. J.Hydrogen Energy (2008)
19
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 gt 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-a
9.4 x 9.4 x 11.7 nm
20
CDC for Cytokine Adsorption

• CDC outperformed commercial carbons in the
  efficiency of cytokines removal

TNF-a
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.
IL-6
G. Yushin, et al. Biomaterials, 27, 5755 , 2006
21
CDC for Cytokine Adsorption

• Adsorption depends on the SSA of adsorbents
  accessible by cytokines

G. Yushin, et al. Biomaterials, 27, 5755 , 2006
22
Conclusions

• CDC process enables design and fine tuning of
  porous carbons for improved performance in energy
  applications
• electrochemical capacitors, hydrogen storage,
  methane storage, fuel cell catalyst support, etc.
• Move from trial-and-error tests to
  science-driven design of nanostructured carbons
  for energy, biomedical and other applications

• Further reading
• G. Yushin, Y. Gogotsi, and A. Nikitin, Carbide
  Derived Carbon, in Nanomaterials Handbook, Y.
  Gogotsi, Editor. 2006, CRC Press. p. 237-280.

23
Acknowledgements
Students and post-docs at Drexel University J.
Chmiola, G. Yushin, C. Portet, E. Hoffman, R.
Dash, G. Cambaz and other Collaborators Prof. P.
Simon, Paul Sabatier University, Toulouse,
France Prof. J.E. Fischer, University of
Pennsylvania Prof. M. Barsoum, Drexel University,
Prof. M.J. McNallan, UIC Funding DOE, NSF, Arkema