Microporous Carbons For Electrochemical Double Layer Capacitors

Microporous Carbons for Electrochemical Double
Layer Capacitors
Patrice Simon
Univ. Paul Sabatier de Toulouse, CIRIMAT, UMR 5085, 118 route de Narbonne, 31062 Toulouse FRANCE simon@chimie.ups-tlse.fr
AABC Europe, ECCAP symposium, June7-8 2011
1. Electrochemical Capacitors (ECs)

ECs (supercapacitors):
- high power (10-20 kW/kg) - medium energy (5 Wh/kg) - time constant:1 5 s
performance between capacitors and batteries Complement to batteries
ECs:
- Oxide-based (pseudocapacitors)
- Carbon-based (EDLCs)
P. Simon and Y. Gogotsi, Nature Materials 7 (2008) 845-854
1. Charge storage in EDLC: electrostatic

Electrochemical Double Layer Capacitor: no redox reaction
Electrolyte
Electrode
Cdl10-20
F/cm
Double Layer Capacitance Electrolyte dielectric constant
Approaching distance Surface
High-surface area Carbon SSA 1500 m.g-1 100 150 F.g-1 of AC Electrostatic (NO REDOX) Using non aqueous electrolyte Emax = 2.5 V
1.2 EDLC (Challenges) Next Challenges for Supercapacitors

Increase the energy density to >10 Wh/kg (E=1/2 C.V) 1.Hybrid (asymmetric) systems
Combination of a battery-like electrode with a SC electrode combines energy (faradic) and power (SC)
2. Pseudo-capacitive charge storage

pseudo-intercalation reactions in mesoporous oxides (B. Dunn, S. Tolbert groups)
3. EDLCs: Carbons with controlled Pore Size Distribution

Control the pore size to increase C
2. Carbide-Derived Carbons
Collaboration with Prof Y. Gogotsi, Drexel university in Philadelphia (USA)
Selective dissolution of a metal carbide (TiC, SiC, ZrC) TiC(s) + 2 Cl2(g) TiCl4(g) + C(s) (Tsynthesis, H2 annealing) Why CDCs? fine tuning of the pore size and pore size distribution TiC: pores from 0.6 to 1.1 nm
1700 1600 1.2 1.1
1.1 nm 8.1 7.6 7.4 7.0 6.8

Average pore size (nm)
(m /g)
1500 1400
600C
1.0 0.9
BETSSA
1300 1200 1100 1000 500 600 700 800 900 1000 0.8 800C 0.7 0.6
Chlorination temperature ( C)
1000C
2.1 CDCs in Organic Liquid Electrolyte 4 cm Lab Cells

Electrolyte (C2H5)4N+,BF4- 1.5M in ACN
Et 4 N +
BF4 -
95% CDC, 5% PTFE cast onto Al foils 4cm2 electrode area, 15 mg/cm
2.1 CDCs: Anomalous capacitance increase in 1M (C2H5)4N+,BF4- in AN electrolyte

Pores smaller than the solvated ion size are accessible to the ions
High capacitance in micropores; 50% increase
Hypothesis: micropores accessible thanks to the distortion of the ion solvation shell
J. Chmiola, G. Yushin, Y. Gogotsi, C. Portet, P.L. Taberna and P. Simon, Science 313, 1760-1763 (2006)
2.1 Cavity
-electrode (CME) in TEABF4 electrolyte
How to evaluate from dynamic measurements (high-rate CV): - the effective ion size seen by the carbon? - the extent of solvation?
use Cavity
-Electrode / CDCs combination to study electrochemical behavior

V. Vivier, C. Cachet-Vivier, et al., Electrochem. Solid-State Lett. V. 2, 385 (1999)
2.
-electrode cell in TEABF4 in AN

Scan rate = 100 mV/s
NEt4+ adsorption
BF4- adsorption
CV distorsion for Pore size < 1 nm
No CV distorsion
Effective size of ion: - BF4- size 0.68 nm (bare ion = 0.48 nm; solvated = 1 nm) - 1nm NEt4+ size 0.76nm (bare ion = 0.67 nm; solvated = 1.2 nm) Solvation shell partially stripped off
J. Chmiola. C. Largeot, P.L. Taberna, P. Simon and Y. Gogotsi, Angewandte Chemie Int. 120 (18), 2008, 3440
-electrode + CDC
in-situ measurement of the effective ion size

2011
R. Lin, P.L. Taberna, J. Chmiola, D. Guay, Y. Gogotsi and P. Simon, JECS 158 (2009) A7-A12 AABC Europe, ECCAP symposium, June7-8
2. CDCs: High power capability in 1M (C2H5)4N+,BF4- in AN electrolyte

B 150
0.72 nm
140
Specific capacitance (F/g)
130 120 110 100 90 80 CDC 500 CDC 600 CDC 700 CDC 800 CDC1000 NMAC SMAC C C C C C
0.76 nm 0.64 nm 1.1 nm
Activated Carbons
0 20 40 60 80 100
2
Current density (mA/cm
Microporous CDCs: high capacitance and high power capability

2.1 CDCs Structure

Quenched Molecular Dynamics modelling of CDCs
CDC 600C (0.74 nm) CDC 1200C (1.2 nm)
4 nm
4 nm
4 nm
Highly disordered structures (no graphitic plans, no slit pores) interconnected, open porous structure
J. C. Palmer, Y. Gogotsi et al, Carbon, 48. 1116-1123 (2010)
Limitation in ion adsorption

CDC 0.68nm in NEt4,BF4 in AN
0.008 0.006 0.004 Current / mA 0.002 0 -0.002 -0.004 -0.006 -1.5 100 mV/s
CDC 0.68nm in EMI,TFSI in AN

0.01 100 mV/s
Current / mA
EMI+
?
NEt4+ BF4-
0.005
+ BF4- ?
EMI+ TFSI-
-0.005
-0.01
-1 -0.5 0 E/V vs. Ag ref 0.5 1
-1
-0.5
Limited NEt4+ adsorption
Limited
0 0.5 1 E/V vs. Ag ref TFSI - adsorption
Limited pore accessibility: steric effect or surface saturation?
Addition of EMIBF4
Limited pore accessibility or surface saturation?
Addition of EMIBF4
NEt4BF4 1.5M in ACN + addition of EMIBF4
1
Normalized current
EMI,TFSI 2M in ACN + addition of EMIBF4

1.5 100 mV/s CDC 0.68 nm 1 Normalized current 0.5 0 -0.5 -1
0.5 0 -0.5 -1
[EMIBF ]:
4
[EMIBF ] in EMITFSI 2M+ACN:

4
0.68 nm 20 mV/sCDC
0.00 M 0.2 M 0.5 M
1M 2M
0M 0.2M
0.5M 1M
2M
-1.5 -1.5
-1
-0.5
0.5
-1.5 -1 -0.5 0 0.5 E/V vs. Ag ref 1
E/V vs. Ag ref
Current increase with EMI,BF4 additions
no C surface saturation
1. Pore size/ion size relationship drives the capacitance 2. Selective ion adsorption AABC Europe, ECCAP symposium, June7-8 2011
Limited pore accessibility or surface saturation?
1 Normalized current 0.5 0 -0.5 -1
20 mV/s
1.5 Normalized current 1 0.5 0 -0.5 -1 -1.5
100 mV/s
EMI,TFSI 1.5M+ACN NEt BF 4 4

EMIBF 2M+ACN
4
NEt BF 1.5M + ACN

4 4
-1.5 -1.5 -1
EMIBF 2M + ACN
4
-0.5 0 E/V vs. Ag ref
0.5
-1
-0.5
0 0.5 E/V vs. Ag ref
EMI,BF4
no limitation, ideal capacitive behavior
No surface charge saturation, only steric (size) effect

2.2
3-electrode cell in neat Ionic Liquid

Electrolyte Ethyl-MethylImmidazolium-TriFluoro -methane-SulfonylImide (EMI-TFSI)
4 cm Cell
Galva. +
EMI
TFSI-
EMI+: 0.76 nm (longest dimension) TFSI-: 0.79 nm (longest dimension)

Same size Temp. 60C; Active materials: CDCs
2.2
180 160 C (F/g) 140 120 100 80 60 0.6
3-electrode cell in EMI-TFSI

Positive Electrode (F/g) Cell Capacitance (F/g) Negative Electrode (F/g)
TFSI-
EMI+
YP17 AC
0.7 0.8 0.9 Pore Size (nm) 1 1.1
1. +50% increase capacitance vs YP17 AC 2. Maximum at 0.72 nm when ion size ~ pore size!!! Ions aligned into the pores!
P. Simon, Y. Gogotsi Nature Materials, 7 (2008) 845-854 R. Lin, P. Huang, J. Segalini, C. Largeot, PL Taberna, Y. Gogotsi and P. Simon., Electrochimica Acta 54 (2009)
3-electrode cell in neat Ionic Liquids

Electrolyte Ethyl-MethylImmidazolium-TriFluoro-methane-SulfonylImide (EMI-TFSI)
Maximum Capacitance when pore size ~ ion size Ions aligned in pores capacitance increase
- potential well (K. Kaneko, Carbon 2010)? - screening effect (Kornyshev et al., 2011)? - exclusion of counter ions (Shim et al., 2010)? Combining Modelling with in-situ experiment are needed to understand ion adsorption in nanopores
2.2
3-electrode cell in PYR14-TFSI
High temperature EDLC in PYR14,TFSI

2.5V supercapacitor cell operating at 100C
70 F.g-1 130 F.g-1
80 F.g-1
0.64 nm 5mV.s-1
0.8 nm 5mV.s-1
1.1 nm 5mV.s-1
Small pore size: CV distortion
Medium pore size: Ideal CV, high C
Larger pore size: Ideal CV, low C
Adapt the carbon pore size to the ion size is the key to reach high C in-situ NMR (Prof C. Grey) and modelling (K. Kaneko) on-going
3. From powder to bulk films

Bulk CDC films
TiC bulk (ceramic)
1. Chlorination
@ 500C
TiC derived carbon film
Monolithic TiC
2. Cell
TiC plate
CDC film
No binder, dense electrode
Teflon plates Electrolyte + separator
3.2 Electrochemistry (CVs)
Organic electrolyte (NEt4BF4 + ACN)
Aqueous electrolyte (H2SO4)
Similar capacitive behavior as for powder CDCs vol. capacitance ?

3.3 Volummetric capacitance

ACN + 1M NEt4BF4
A
H2SO4 1M
B
CA
CA
Vol. Capacitance of 180 F/cm3 for e = 1 m (CA = 50 F/cm3) Thin films with high energy density (+300% !!!)
J. Chmiola, C. Largeot, P.L. Taberna, P. Simon and Y. Gogotsi, Science 328, 480-483 (2010)
3.4 Towards high energy

A
SiO2 Sputtered TiC thin film
SC integrated on Si?
B
SiO2 TiC-CDC thin film
Chlorination (500C<T<1000C)
Si waffer Si waffer
Masking and Au sputterring
D
Electrolyte SiO2
Au collectors
C
Au collector Au collector
CDC etching SiO2
Si waffer
Si waffer
CDC film
J. Chmiola, C. Largeot, P.L. Taberna, P. Simon and Y. Gogotsi, Science 328, 480-483 (2010)
4. Conclusions
Microporous Carbons (CDCs) for EDLCs

1. Capacitance increase thanks to partial desolvation twice volummetric capacitance; no power limitation 2. High capacitance when pore size ion size; mechanism? need for modelling coupled with in-situ experiments (NMR, XRD) 3. Thin-films high energy (x3) with bulk microporous carbons

Microporous Carbons For Electrochemical Double Layer Capacitors

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Microporous Carbons for Electrochemical Double

AABC Europe, ECCAP symposium, June7-8 2011

1. Electrochemical Capacitors (ECs)

performance between capacitors and batteries Complement to batteries

1. Charge storage in EDLC: electrostatic

Double Layer Capacitance Electrolyte dielectric constant

Approaching distance Surface

1.2 EDLC (Challenges) Next Challenges for Supercapacitors

2. Pseudo-capacitive charge storage

3. EDLCs: Carbons with controlled Pore Size Distribution

1.1 nm 8.1 7.6 7.4 7.0 6.8

Average pore size (nm)

2.1 CDCs in Organic Liquid Electrolyte 4 cm Lab Cells

2.1 CDCs: Anomalous capacitance increase in 1M (C2H5)4N+,BF4- in AN electrolyte

High capacitance in micropores; 50% increase

-electrode (CME) in TEABF4 electrolyte

-Electrode / CDCs combination to study electrochemical behavior

V. Vivier, C. Cachet-Vivier, et al., Electrochem. Solid-State Lett. V. 2, 385 (1999)

-electrode cell in TEABF4 in AN

CV distorsion for Pore size < 1 nm

in-situ measurement of the effective ion size

2. CDCs: High power capability in 1M (C2H5)4N+,BF4- in AN electrolyte

Specific capacitance (F/g)

0.76 nm 0.64 nm 1.1 nm

Current density (mA/cm

Microporous CDCs: high capacitance and high power capability

2.1 CDCs Structure

Limitation in ion adsorption

CDC 0.68nm in EMI,TFSI in AN

Limited NEt4+ adsorption

0 0.5 1 E/V vs. Ag ref TFSI - adsorption

Limited pore accessibility: steric effect or surface saturation?

Limited pore accessibility or surface saturation?

EMI,TFSI 2M in ACN + addition of EMIBF4

[EMIBF ] in EMITFSI 2M+ACN:

0.00 M 0.2 M 0.5 M

-1.5 -1 -0.5 0 0.5 E/V vs. Ag ref 1

E/V vs. Ag ref

Current increase with EMI,BF4 additions

Limited pore accessibility or surface saturation?

1 Normalized current 0.5 0 -0.5 -1

1.5 Normalized current 1 0.5 0 -0.5 -1 -1.5

EMI,TFSI 1.5M+ACN NEt BF 4 4

NEt BF 1.5M + ACN

-0.5 0 E/V vs. Ag ref

0 0.5 E/V vs. Ag ref

no limitation, ideal capacitive behavior

No surface charge saturation, only steric (size) effect

3-electrode cell in neat Ionic Liquid

EMI+: 0.76 nm (longest dimension) TFSI-: 0.79 nm (longest dimension)

3-electrode cell in EMI-TFSI

3-electrode cell in neat Ionic Liquids

3-electrode cell in PYR14-TFSI

High temperature EDLC in PYR14,TFSI

Small pore size: CV distortion

Medium pore size: Ideal CV, high C

Larger pore size: Ideal CV, low C

3. From powder to bulk films

TiC derived carbon film

No binder, dense electrode

Teflon plates Electrolyte + separator

AABC Europe, ECCAP symposium, June7-8 2011

3.2 Electrochemistry (CVs)