http://nano.materials.drexel.edu carbide-derived carbons for energy-related and biomedical...

http://nano.materials.drexel.eduDANOTECHNOLOGY

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Carbide-Derived Carbons for Energy-Related and Biomedical Applications

Yury GogotsiA.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.


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Current Research Projects

• Nanotubes, Nanocones, and Nanowires Y. G., et al, Science, v. 290, 317 (2000)

• Nanotube-Based Nanofluidic DevicesY. G., J. Libera, A. Yazicioglu, et al., Appl. Phys. Lett.,v. 79, p.1021 (2001)

• Nanotube-Reinforced PolymersF. 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 MicroscopyP.H. Tan, S. Dimovski, Y.G., Phil. Trans. Royal Soc. Lond. A, 362, 2289 (2004)

• Carbide-Derived Carbons for Energy-Related and Other ApplicationsY. 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)


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Carbon Nanomaterials: Ternary Bonding Diagram

Nanodiamond

Nanotubes

Fullerenes

Hydrocarbons

spn

Corannulene

CumuleneAdamantane

Carbyne (sp1)Diamond (sp3)

Graphite (sp2)

Adapted from M. Inagaki, New Carbons, 2000Heimann et al., Carbon, 1997

sp3+sp2+spamorphous carbon,DLC, glassy carbon,

carbon black, etc.

sp3+sp2+spamorphous carbon,DLC, glassy carbon,

carbon black, etc.

spn, (1<n<3, n=2)

Classification based on:-hybridization type of C atoms -characteristic size of clusters

Classification based on:-hybridization type of C atoms -characteristic size of clusters

Fullerene family

sp2 +

Csp + 2sp3

=C=C=

Nanosizedmorphology of graphite-based

materials

Ovalene

Car

bon

whi

sker

s,

cone

s an

d

poly

hedr

al

crys

tals


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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


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TiC(s) + 2 Cl2(g) = TiCl4(g) + C(s) (Gº = - 434.1 kJ/mol at 950°)

c(g)22c

ba MClaCbClCM ; M = metal (or Si or B)

Carbide-Derived Carbon (CDC) Process

2 nmSiC 2 nm

Carbide: Porosity = 0 % CDC: Porosity = 57 %

Cl2

( 200 - 1200oC)

2 methods of pore size control:1.) Precursor choice2.) 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)


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2

Cl2HCl

Ar

1 Flowmeters2 Resistance furnace3 Quartz reaction tube4 Quartz boat with sample5 Sulfuric acid

T=200-1200°C; Ambient pressure

Chlorination Set-up

Large-scale production alternatives: Fluidized-bed furnace or rotary kiln reactor


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CDC: Powders, Films, Fibers, Bulk

CDC coated SiC Tyranno fabric

Bulk CDCfrom sintered

SiC

CDC coateddynamic 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)


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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


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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


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G. Yushin, A. Nikitin, Y. Gogotsi, in Nanomaterials Handbook, ed. by Y. Gogotsi (CRC Press, 2005)

Carbide Lattice – Template for CDC

0 1 2 3 4 5 6 70.0

0.1

0.2

0.3

0.4

Por

e vo

lum

e (c

c/nm

/g)

Pore size (nm)

Ti3SiC2-CDC (1200°C) SiC-CDC (1200°C)

0 1 2 3 4 5 6 7

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Por

e vo

lum

e (c

c/nm

/g)

Pore size (nm)

Pore-size distributions calculated using DFT model

Ar sorption at 77 KAutosorb-1


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Gogotsi, Y., et al., Nature Materials, 2, 591 (2003)

0.1 1 10 100

Dm=0.51 nm

Dm=0.58 nm

300 400 500 600 700 8000.5

0.6

0.7

0.8

P

ore

siz

e (

nm

)

Temperature of synthesis (°C)

Po

re v

olu

me

(a

.u.)

Pore size (nm)

Dm=0.64 nm (T=700oC) dD/dT ~ 0.0005 nm/o C,

or: +/- 10o 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

Ti3SiC2 -CDC


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R.E. Smalley MRS Bulletin 30, 412-417 (2005)


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H2 liquid at 20K

105 liters

H2 gas at 1 atm.

pressure,25oC

> 48,000 liters

DOE target67 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/m3

Note: DOE target is system target and will include the density of accessories depending on the materials requirement

CDC for H2 Storage

H2 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.


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CDC for H2 Storage: Cryo-adsorption

50 55 60 65 70 75 800

2

4

6

8

10

12

14

assuming liquid H2

filling all the pores

Max

. H2 s

tora

ge p

ossi

ble,

wt.%

Carbon pore volume, %

assuming solid H2

filling all the pores

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)

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, 16006 (2005)


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0 300 600 900 1200 1500 1800 2100 24000.0

0.4

0.8

1.2

1.6

2.0

2.4

2.8

Linear fit (y = 0.00118x +0.1053) R = 0.93

Activated carbon Activated carbon fibers Carbon nanotubes Carbon nanofibers

Gra

vim

etric

den

sity

, wt%

H2

Specific surface area, m2/g

“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

77K1 atm


Specific surface area of ~5750 m2/g will be required for reaching 6.5 wt.%.


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0 300 600 900 1200 1500 1800 21000.0

0.4

0.8

1.2

1.6

2.0

2.4

2.8

3.2 TiC-CDC ZrC-CDC SiC-CDC B

4C-CDC

Activated carbon Carbon nanotubesG

ravi

met

ric d

ensi

ty, w

t% H

2

Specific surface area, m2/g

Large variation for similar surface area

H2 storage is NOT proportional to SSA

Linear fit

77K1 atm




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0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

2.2

2.4

2.6 TiC-CDC ZrC-CDC SiC-CDC B4C-CDC

H2

wt.

% p

er u

nit

SS

A,

Pore size, nm

.103

m2

wt%

.g Small pores are more efficient than large ones for a given SSA

SSA of ~3000 m2/g will be needed for 7wt% storage - FEASIBLE!

Empty symbols: H2 treated samples


CDC for H2 Storage: Cryo-adsorption77K

1 atm


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CDC for H2 storage: Cryo-adsorption

0.1 0.2 0.3 0.4 0.5

1.0

1.5

2.0

2.5

3.0

Gra

vim

etr

ic c

ap

aci

ty,

wt.

% H

2

Volume of pores below 1 nm, cc/g

large volume and SSA of pores above 1 nm

0.0 0.2 0.4 0.6 0.8

1.0

1.5

2.0

2.5

3.0

Gra

vim

etr

ic c

ap

aci

ty,

wt.

% H

2

Volume of pores above 1 nm, cc/g

77K1 atm

Large volume of pores < 1 nm needed for high storage capacityDensity of gaseous H2 innano-pores can be higherthan 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

if all these poresfilled with liquid H2


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CDC for H2 storage: Cryo-adsorption

20 40 60 80 100 120

5

6

7

8

9

10

11

TiC-CDC (1000oC)

TiC-CDC (800oC)

SWCNT

Isot

eric

Hea

t of

ads

orpt

ion,

KJ/

mol

Volume adsorbed, cc/g

MOF

stQRT

P

)(

)(ln12

)(ln

RT

H

T

P vap

Obtained from isotherms @ 77, 88, and 300K using Clausius-Clapeyron Equation

6.2 6.4 6.6 6.8 7.0 7.2 7.41.0

1.2

1.4

1.6

1.8

2.0

2.2

Heat of adsorption, kJ/mol

wt%

.g.1

0-3

m2

H2 w

t.% p

er B

ET

SS

A,

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)


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S.K. Bhatia, A.L. Myers, Langmuir (22) 1688-1700 (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, Pdelivery, Pstorage) = storage

storage

delivery

delivery

KP

nKP

KP

nKP

11

where: n = number of sorb. sites; equilibrium constant 0

00 1)exp()exp(

PRTH

RSK

-ΔHo = heat of adsorption; ΔSo = entropy change relative to standard pressure (1 atm)

Max Delivery:

20

00 ln2 P

PPRTSTH storagedelivery

optimum

Pstorage=30 atm, Pdelivery=1.5 atm; ΔSo ~8R:

-ΔHooptimum= 15.1 kJ/mol 10 100 1000

6

8

10

12

14

16

18

1000 atm.Opt

imum

Hea

t of

Hyd

roge

n A

dsor

ptio

n

Storage pressure, atm.

storage and delivery at room temperature (298 K) delivery at 1.5 atm

30 atm.


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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


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CDC for Protein Adsorption

5 10 15 20 25 30 350.0

0.1

0.2

Ti3AlC

2- CDC @ 600oC

dV, c

c/nm

/gdV

, cc/

nm/g

5 10 15 20 25 30 350.0

0.1

0.2

Ti3AlC

2 - CDC @ 800oC

5 10 15 20 25 30 350.0

0.1

0.2

0.3

0.4

Ti3AlC

2 - CDC @ 1200oC

5 10 15 20 25 30 350.0

0.1

0.2

Pore width, nmPore width, nmPore width, nm Pore width, nm

Ti2AlC - CDC @ 600oC

5 10 15 20 25 30 350.0

0.1

0.2

Adsorba

5 10 15 20 25 30 350.0

0.1

0.2

CXV

5 10 15 20 25 30 350.0

0.1

0.2


5 10 15 20 25 30 35 400.0

0.1

0.2

0.3

0.4


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


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CDC for Cytokine* Adsorption

100

1000

Control TNF-

TN

F-

con

cent

ratio

n, p

g/m

l initial 5 min 30 min 60 min

Adsorba CXV Ti3AlC

2 - CDC Ti

2AlC - CDC

1200oC600oC 800oC 1200oC600oC 800oC

100

1000

1200oC600oC

IL-6

con

cent

ratio

n, p

g/m

l

initial 5 min 30 min 60 min

Adsorba CXV Ti3AlC

2 - CDC

800oC

Control IL-6

1200oC600oC 800oC

Ti2AlC - CDC

* 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


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CDC for Cytokine Adsorption

Adsorption depends on the SSA of adsorbents accessible by cytokines



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CDC for Cytokine Adsorption

proteins adsorbed on the surface proteins adsorbed on the surface and in the mesopores



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• 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).


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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*


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Supercapacitors: Market Segmentation

Total addressable market size in 2012 ~$2 Billion The largest part – applications in Hybrid Electrical Vehicles

2005 2006 2007 2008 2009 2010 2011 2012 20130

200

400

600

800

1000

1200

1400

1600

1800

2000

EV Market Mobile Device Market UPS Market Military Market Specialty Market

Ma

rke

t ($

Mill

ion

s)

Year

Uninterruptible Power Supplies and Power Quality

Mobile devices

Aerospace applications

Defense applications

Vehicles with electrical or hybrid motors (EV)

CAGR = 50%


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Traditional View: Increasing Pore Size Increases Specific Capacitance

Energy ~ C

Power ~ RC

1

Car

bo

n

Ideal pore size (~ 3x solvated ion size)

Carbon2

Pore

Surface

3

Carbon

electrolyte ions + its solvation shells

Too large pore size

A3>A1; A3>A1

Too small pore size


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(CH3CH2)4N+

6.75 Å diameterBF4

-

3.25 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 (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

Our Study: Experimental Details


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0

0.5

1

1.5

2

2.5

3

0 50 100 150 200 250

Ce

ll vo

ltag

e (

V)

Time (s)

A

-0.08

-0.06

-0.04

-0.02

0

0.02

0.04

0.06

0.08

-0.5 0 0.5 1 1.5 2 2.5 3C

urr

en

t (A

)Voltage (V)

B

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 TestsTiC-CDC @ 700oC

20 mA/cm2

20 mV/s


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1000

1100

1200

1300

1400

1500

1600

1700

0.6

0.7

0.8

0.9

1.0

1.1

1.2

500 600 700 800 900 1000

BE

T S

SA

(m

2 /g)

Average

pore size (nm

)

Chlorination temperature (¼C)

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)


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Sub-nanometer pore size control shows a new direction for research!!!

Electrolyte: 1.5 M (CH3CH2)4N BF4 in CH3CN (most conventional)


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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, 313,1760-1763 (2006)


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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


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

Book chapter on CDC

AcknowledgementsStudents and post-docs at Drexel University: J. Chmiola, G. Yushin, C. Portet, E. Hoffman, R. DashProf. J.E. Fischer, University of PennsylvaniaProf. M. Barsoum, Drexel University, Prof. M.J. McNallan, UICProf. P. Simon, Paul Sabatier University, Toulouse, FranceProf. S. Mikhalovsky, U. Brighton, UKFinancial support: DOE, DARPA, NSF, Arkema

http://nano.materials.drexel.edu carbide-derived carbons for energy-related and biomedical...

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