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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
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Introduction Carbide-derived Carbons
Department of Inorganic Chemistry I, Dresden University of Technology
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(
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Department of Inorganic Chemistry I, Dresden University of Technology
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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
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Department of Inorganic Chemistry I, Dresden University of Technology
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.
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Department of Inorganic Chemistry I, Dresden University of Technology
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.
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Department of Inorganic Chemistry I, Dresden University of Technology
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
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Department of Inorganic Chemistry I, Dresden University of Technology
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
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Department of Inorganic Chemistry I, Dresden University of Technology
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
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Department of Inorganic Chemistry I, Dresden University of Technology
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
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Department of Inorganic Chemistry I, Dresden University of Technology
11
CDC Aerogels Synthesis and Structure
Scanning Electron Microscopy
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.
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
)
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Department of Inorganic Chemistry I, Dresden University of Technology
12
CDC Aerogels Electrochemistry
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.
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
Department of Inorganic Chemistry I, Dresden University of Technology
13
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Polymer-based CDCs Model Substances for Adsorption and Structural Investigations
Department of Inorganic Chemistry I, Dresden University of Technology
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
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Summary
Department of Inorganic Chemistry I, Dresden University of Technology
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
Evolution of Porosity in Carbide-Derived Carbon Aerogels
Acknowledgements
Department of Inorganic Chemistry I, Dresden University of Technology
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)