Department of Inorganic Chemistry I, Dresden … · Evolution of Porosity in Carbide-Derived Carbon Aerogels Introduction Carbide-derived Carbons Department of Inorganic Chemistry

Department of Inorganic Chemistry I, Dresden University of Technology

Design of Carbon Materials with Hierarchical Pore Architecture for

Electrochemical Energy Storage Dr. Martin Oschatz, Prof. Dr. Stefan Kaskel

1st German-Chinese-Symposium, Germany „Development and Technology of Carbon Materials“ 13.11.2016–16.11.2016, Harnack House, Berlin

Evolution of Porosity in Carbide-Derived Carbon Aerogels

Motivation and Outline

2

Well-defined carbon nanomaterials with hierarchical pore architecture.

Catalysis Gas Storage/ Gas Purification

Li-S Batteries

Electrical Double-Layer Capacitors

Surface Area

Pore Structure

Materials Transport

CDCs by Nanocasting

CDC Aerogels

CDCs from Emulsions

CDC Nanoparticles


Introduction Carbide-derived Carbons


3

Microporous Activated Carbons

SiC(s) + 2 Cl2(g) SiCl4(g) + C(s)

Carbide-Derived Carbons (CDCs)

V. Presser, M. Heon , Y. Gogotsi, Adv. Funct. Mater. 2011, 21, 810

Y. Gogotsi, A. Nikitin, H. Ye, W. Zhou, J. E. Fischer, B. Yi, H. C. Foley and M. W. Barsoum, Nat. Mater. 2003, 2, 591.

© Starfire Systems

“Nanocarbons”

Graphene Fullerenes Carbon

Nanotubes

xCKCOKKOHCx 226)2( 32

xCCOHOHCx gg )()(22)1(



4

Synthesis of CDC-Mesofoams by Nanocasting

CDC Mesofoams Synthesis and Structure

M. Oschatz, L. Borchardt, K. Pinkert, S. Thieme, M. R. Lohe, C. Hoffmann, M. Benusch, F. M. Wisser, C. Ziegler, L. Giebeler, M. H. Rümmeli, J. Eckert, A. Eychmüller, S. Kaskel, Adv. Energy Mater. 2014, 4, 1300645/1.

Transmission Electron Microscopy

SiC Foam

SiO2 Foam CDC Foam

CDC Foam p/p0

N2 Physisorption, -196°C

0

N2 a

dso

rbed

(cm

3/g

)

0.2 0.4 0.6 0.8 1.0

0

200

1000

1200

1400

1600

1800

400

600

800

CDC-Mesofoam SSABET: 2900 m2/g

VPore: 2.6 cm3/g

Mesoporous SiC Foam SSABET: 650 m2/g VPore: 0.7 cm3/g

Chlorine Treatment



5

CDC Mesofoams Electrochemical Energy Storage Material

Electrode Material in EDLCs

~ 250 F/g in 1 M H2SO4 Electrolyte

Electrode Material in Li-S Batteries

~ 1150 mAh/gSulfur ~ 700 mAh/gCathode

F. Beguin, V. Presser, A. Balducci, E. Frackowiak, Adv. Mater. 2014, 26, 2219.

M. Oschatz, L. Borchardt, K. Pinkert, S. Thieme, M. R. Lohe, C. Hoffmann, M. Benusch, F. M. Wisser, C. Ziegler, L. Giebeler, M. H. Rümmeli, J. Eckert, A. Eychmüller, S. Kaskel, Adv. Energy Mater. 2014, 4, 1300645/1.



6

CDC PolyHIPEs Synthesis

Pulko and P. Krajnc, Macromol. Rapid Commun., 2012, 33, 1731. R. Frind, M. Oschatz, S. Kaskel, J. Mater. Chem. 2011, 21, 11936.

High Internal Phase Emulsions

Synthesis of PolyHIPE-CDCs

M. Oschatz, L. Borchardt, M. Thommes, K. A. Cychosz, I.Senkovska, N. Klein, R. Frind, M. Leistner, V. Presser, Y. Gogotsi, S. Kaskel, Angew. Chem. Int. Ed. 2012, 51, 7577.

M. Oschatz, L. Borchardt, I. Senkovska, N. Klein, M. Leistner, S. Kaskel, Carbon 2013, 56, 139.



7

CDC PolyHIPEs Structure

M. Oschatz, L. Borchardt, M. Thommes, K. A. Cychosz, I.Senkovska, N. Klein, R. Frind, M. Leistner, V. Presser, Y. Gogotsi, S. Kaskel, Angew. Chem. Int. Ed. 2012, 51, 7577.

M. Oschatz, L. Borchardt, I. Senkovska, N. Klein, M. Leistner, S. Kaskel, Carbon 2013, 56, 139.

N2 Physisorption, -196°C Mercury Intrusion Porosimetry

PolyHIPE-CDC SSABET: 2900 m2/g

VPore,Micro+Meso: 1.1 cm3/g VPore,Macro: 7.5 cm3/g



8

CDC Nanospheres Synthesis and Structure

Water

Surfactant (SDS)

Oil Phase (SMP-10 +

p-DVB + Hexadecane)

Miniemulsion

Ultrasound

Cross-

Linking+

Solvent

Evaporation

Pyrolysis

(Polycarbosilane

Decompositon)

Cross-Linked

Polycarbosilane

Nanospheres

Silicon Carbide

Nanospheres

High-Temperature

Chlorine Treatment

(Silicon Removal)

CDC Nanospheres

Synthesis of CDC Nanospheres by the Miniemulsion Technique

M. Oschatz, M. Zeiger, N. Jäckel, P. Strubel, L. Borchardt, R. Reinhold, W. Nickel, J. Eckert, V. Presser, S. Kaskel, J. Mater. Chem. A 2015, 3, 17983.

Electron Microscopy

0.0 0.2 0.4 0.6 0.8 1.00

50

100

150

200

250

Vo

lum

e a

t S

TP

(c

m3/g

)

P/P0

SiC-NS-50-50

SiC-NS-70-30

0.0 0.2 0.4 0.6 0.8 1.00

200

400

600

800

1000

1200

Vo

lum

e a

t S

TP

(c

m3/g

)

P/P0

CDC-NS-50-50

CDC-NS-70-30

N2 Physisorption, -196°C



9

CDC Nanospheres Electrochemical Properties

Synthesis of CDC Nanospheres by the Miniemulsion Technique

M. Oschatz, M. Zeiger, N. Jäckel, P. Strubel, L. Borchardt, R. Reinhold, W. Nickel, J. Eckert, V. Presser, S. Kaskel, J. Mater. Chem. A 2015, 3, 17983.

Water

Surfactant (SDS)

Oil Phase (SMP-10 +

p-DVB + Hexadecane)

Miniemulsion

Ultrasound

Cross-

Linking+

Solvent

Evaporation

Pyrolysis

(Polycarbosilane

Decompositon)

Cross-Linked

Polycarbosilane

Nanospheres

Silicon Carbide

Nanospheres

High-Temperature

Chlorine Treatment

(Silicon Removal)

CDC Nanospheres

0.0 0.5 1.0 1.5 2.0 2.5-200

-150

-100

-50

0

50

100

150

200

Cap

acit

an

ce (

Fg

-1)

Cell voltage (V)

CDC-NS-70-30

CDC-NS-50-50

CVs @ 10 mV/s

0.1 1 100

25

50

75

100

125

Ca

pa

cit

an

ce

(F

g-1)

Current (Ag-1)

0.1 1 100

25

50

75

100

125

Ca

pa

cit

an

ce

(F

g-1)

Current (A/g)

0.1 1 100

25

50

75

100

125

Cap

acit

an

ce (

F/g

)

Current (A/g)

0.1 1 100.6

0.7

0.8

0.9

1.0

C/C

0

Current (A/g)

CDC-NS-50-50

CDC-NS-70-300.1 1 10

0.6

0.7

0.8

0.9

1.0

CDC-NS-50-50

CDC-NS-70-30

C/C

0

Current (A/g)

0.0 0.5 1.0 1.5 2.0 2.5-200

-150

-100

-50

0

50

100

150

200

Cap

acit

an

ce (

F/g

)

Cell voltage (V)

CDC-NS-50-50

CDC-NS-70-30

C D

A B

0.0 0.2 0.4 0.6 0.8-150

-100

-50

0

50

100

150 CDC-NS-50-50

CDC-NS-70-30

Ca

pac

ita

nc

e (

F/g

)

Cell voltage (V)

E F

0 100 200 300 400 5000.0

0.2

0.4

0.6

0.8

Ce

ll v

olt

ag

e (

V)

0.1 A/g1 A/g

Time (s)

CDC-NS-50-50

CDC-NS-70-30

0 500 1000 1500 2000 2500 3000 35000.0

0.5

1.0

1.5

2.0

2.5

Ce

ll v

olt

ag

e (

V)

Time (s)

CDC-NS-50-50

CDC-NS-70-30

0.1 A/g

1 A/g

CDC Nanospheres as Electrode Material in EDLCs

~ 130 F/g in 1 M TEABF4 in ACN Electrolyte

Electron Microscopy



10

CDC Aerogels Synthesis and Structure

Synthesis of CDC Aerogels by Cross-Linking of Polycarbosilanes

M. Oschatz, W. Nickel, M. Thommes, K. A. Cychosz, M. Leistner, M. Adam, G. Mondin, P. Strubel, L. Borchardt, S. Kaskel, J. Mater. Chem. A 2014, 2, 18472.

+H2Si SiH

19

CH2

SiC

H

H2Si

HH

SiC

H2Si

CH2 H

H

H

Pt

Hydrosilylation Reaction

Pt Catalyst



11

CDC Aerogels Synthesis and Structure

Scanning Electron Microscopy



N2 Physisorption (-196°C)

N2 a

dso

rbed

(cm

3/g

)

0

1000

2000

3000

4000

5000

6000

p/p0

0 0.2 0.4 0.6 0.8 1.0

SSA

BE

T (

m2/g

)

1000

CDC-Aero-1000°C CDC-Aero-700°C

CDC-Aero-Act (CO2 Activated)

1500

2000

2500

0.4

0.5

0.6

0.7

VM

icro

po

re(c

m3/g

)



12

CDC Aerogels Electrochemistry



M. Oschatz, S. Boukhalfa, W. Nickel, C. Fischer, G. Yushin, S. Kaskel, Carbon 2016, submitted.

Time (s)

0 10 20 15 5

60 A/g 40 A/g

20 A/g 10 A/g

Voltage (V)

0 2.0 0.5 1.0 1.5

Spec

ific

cap

acit

ance

(F

/g)

150

-150

-50

50

CDC-Aero-Act

Spec

ific

cap

acit

ance

(F

/g)

50

70

90

130

110

0 20

Current density (A/g)

40 60

Vo

ltag

e (V

)

0

0.5

1.0

1.5

2.0

2.5

~ 120 F/g in 1 M TEABF4 in ACN Electrolyte

CDC-Aero-700°C

CDC-Aero-Act

CVs at 50 mV/s.

CDC-Aero-1000°C CDC-Aero-700°C

CDC-Aero-Act

CDC Aerogels as Electrode Material in EDLCs with Organic Electrolytes

Evolution of Porosity in Carbide-Derived Carbon Aerogels Polymer-based CDC Structures

Structural Variety


13


Polymer-based CDCs Model Substances for Adsorption and Structural Investigations


14

InfraSORP Technology

M. Oschatz, M. Leistner, W. Nickel, S. Kaskel, Langmuir 2015, 31, 4040.

L. Borchardt, M. Oschatz, S. Paasch, S. Kaskel, E. Brunner, Phys. Chem. Chem. Phys. 2013, 15, 15177.

MAS NMR (Ion Adsorption)

In Situ 129Xe NMR

n-Nonane Preadsorption

M. Oschatz, L. Borchardt, S. Rico-Frances, F. Rodriguez-Reinoso, S. Kaskel, J. Silvestre-Albero, Langmuir 2013, 29, 8133.

M. Oschatz, H. C. Hoffmann, J. Pallmann, J.Schaber, L. Borchardt, W. Nickel, I. Senkovska, S. Rico-Frances, J. Silvestre-Albero, S. Kaskel, E. Brunner, Chem. Mater. 2014, 26, 3280.

M. Oschatz, P. Pre, S. Dörfler, W. Nickel, P. Beaunier, J.-N. Rouzaud, C. Fischer, E. Brunner, S. Kaskel, Carbon 2016, 105, 314.

TEM Study of Carbon Microstructure


Summary


15

CDC Mesofoams prepared by Nanocasting as Versatile Electrochemical Energy Storage Materials

CDC Aerogels Synthesized from Cross-Linked PCS Aerogels as Electrode Materials in EDLCs

CDC Nanospheres and CDC PolyHIPEs

Overview over Polymer-Based CDC Materials and Adsorption Studies


Acknowledgements


16

Prof. Dr. Stefan Kaskel

Dr. Lars Borchardt (TU Dresden) W. Nickel (TU Dresden)

G. Yushin group (Georgia Tech) E. Brunner group (TU Dresden) M. Thommes (Quantachrome) J. Slivestre-Albero group (Alicante) M. Leistner (IWS Dresden) B. Smarsly group (Giessen) Y. Gogotsi group (Drexel) J. Eckert group (IFW Dresden) M. Biesheuvel (Wetsus) V. Presser (Saarbrücken)

http://upload.wikimedia.org/wikipedia/de/8/88/Logo_Universit%C3%A4t_Utrecht.svg

Documents

Department of Inorganic Chemistry I, Dresden … · Evolution of Porosity in Carbide-Derived Carbon Aerogels Introduction Carbide-derived Carbons Department of Inorganic Chemistry