N-Doped nanoporous carbons for high power supercapacitors

1. N-Doped Nanoporous Carbons
for High Power Supercapacitors
Mülheim an der Ruhr, Sep. 23-26
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2. ISPE
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Nanoporous carbons for high power
supercapacitors
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3. ISPE
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Nanoporous carbons for high power
supercapacitors
• Founded by Prof. V.V. Strelko in 1991.
• Main directions: sorption, ion exchange, catalysis, and
energy storage with the use of carbons and metal oxides.
• Nanoporous carbons to be used in advanced sorption
technologies for the extraction, separation, concentration,
and purification in industry, medicine, environment
protection and in energy storage.
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4. ISPE
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Nanoporous carbons for high power
supercapacitors
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5. For batteries:
~ 102
W.h/kg
d
+
+
+
+ _
_
_
_ C =
Q
U
=
A 
d
E =
1
2
CU2
Energy Power output
For capacitors:
~ 104
W/kg
For batteries:
~ 102
W/kg
For capacitors:
~ 10-2
W.h/kg
For SUPERCAPACITORS:
E ~ 100
 101
W.h/kg P ~ 104
W/kg
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Nanoporous carbons for high power
supercapacitors
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6. First patents:
H.E. Becker, US Patent 2 800 616 (General Electric Co.) 1957
R.A. Rightmire, US Patent 3 288 641 (SOHIO) 1966
bulk
electrolyte
-
-
-
-
+
+
+
+
_
_
_
_
+
+
+
+
equivalent
circuit:
Re
For activated carbons:
~~A 1200 m2/g
CDEL
~~ 12 F/cm2
~~d 1 nm ~~C = CDEL x A 150 F/g
C 10 F/cc~~For a SC device:
d
C =
A 
When a potential is applied to the electrodes, a
DEL forms at the electrode/electrolyte interface.
It is this layer that stores electrostatic energy
and functions as the double layer capacitor.
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Nanoporous carbons for high power
supercapacitors
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7. 7
1
2
3
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Nanoporous carbons for high power
supercapacitors
1 and 2 look more promising than 3

8. 8
Slit-shaped pores or
just shear cracks of
graphene layers
Nanoporous carbons for high power
supercapacitors
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9. • AM1 semi-empirical quantum-chemical method was used to
evaluate the energy parameters (EHOMO, ELUMO, electron work
function, and energy gap) of various carbons.
• In calculations, C96 carbon clusters containing 37 condensed
rings were used. To model N- and O- containing carbons, some
of C-atoms were substituted by N- and O- atoms. As another
option, heteroatoms were bonded with edge C-atoms.
V.V. Strelko. J. Energy Chem., 2013, 22, 174-182 (and refs therein).
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Nanoporous carbons for high power
supercapacitors
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10. ISPE
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Nanoporous carbons for high power
supercapacitors
Ehomo,eV
∆E, eV
-7.20
4.88
-7.47
4.91
-6.02
3.95
-5.93
3.81
C96 cluster Pyridine-N Centre-N Valley-N
Ehomo, eV
∆E, eV
-5.91
3.48
-6.18
3.66
-5.64
3.10
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Nanoporous carbons for high power
supercapacitors
c96o4 c94o4 C96O11
c96 c92o4 c96o4
EHOMO,eV -7.20
∆E, eV 4.88
-5.66
2.03
-6.40
2.29
EHOMO,eV -7.17 -6.32 -6.41
DE, eV 4.70 2.72 3.81
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12. ISPE
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Nanoporous carbons for high power
supercapacitors
Maximum EHOMO value can be achieved in C92N3O cluster. This results in
the highest electron donor ability.
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13. ISPE
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Nanoporous carbons for high power
supercapacitors
Batteries SC Flywheels
Specific energy stored, W.h/kg 30… 150 3… 6 4… 9
Specific power @ 95% eff., kW/kg 0.1… 1 1… 10 2… 4
Supercapacitors are NOT energy devices, they ARE power devices!
Key SC applications are related with covering the peaks of power, load
leveling the batteries, kinetic energy recovery, etc.
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14. ISPE
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Nanoporous carbons for high power
supercapacitors
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15. Rin
= ʃI2Rint
= RLoad/(RLoad + Rin)
~ 1/ Rin
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Nanoporous carbons for high power
supercapacitors
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16. rAl-C ≤ 0.01 (in Yunasko technology)
rC ~ 0.05
Thus: rEl ~ 0.75
“pore resistance” ~ 0.6
SC resistivity (in W.cm2)
total ~ 0.8
Though: rEl-in-bulk ~ 0.15 (electrode+separator thickness)
Rin
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Nanoporous carbons for high power
supercapacitors
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17. Nanoporous carbons for high power
supercapacitors
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18. 18
1
1.1
1.2
1.3
1.4
1.5
1.6
1.7
2 4 6 8 10 12 14 16
EDLCresistivity,R,Ohm.cm2
Diffusion coefficient, D, 10-10 m2/s
Diffusion coefficients of BF4
- anions in NP carbons
(pulsed field-gradient 19F NMR measurements, see: Y. Cohen,
L. Avram, L. Frish; Angew. Chem. Int. Ed., 2005, 44, p.520 )
Nanoporous carbons for high power
supercapacitors
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19. 19
0.5
0.7
0.9
1.1
1.3
1.5
1.7
1 1.2 1.4 1.6 1.8 2 2.2
EDLCresistivity,R,Ohm.cm2
Diffusion coefficient, D, 10-10 m2/s
Diffusion coefficients of EtMe3N+cations in NP carbons
(pulsed field-gradient 1H NMR measurements, see: Y. Cohen,
L. Avram, L. Frish; Angew. Chem. Int. Ed., 2005, 44, p.520 )
Nanoporous carbons for high power
supercapacitors
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20. 20
Diffusion coefficients of Fc+ cations in NP carbons
(Porous-C Rotating Disc Electrode measurements, see: (a) A.J.Bard, L.R.Faulkner;
Electrochemical Methods. Fundamentals and Applications (2nd ed.); Wiley, 2001, p.335 );
(b) Bonnecaze, R.T., Mano, N., Nam, B., Heller, A. On the behavior of the porous
rotating disk electrode. J Electrochem. Soc. 2007,154, F44-7.
NOTE: in bulk solution
Deff = 10.1×10-10 m2/s
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Nanoporous carbons for high power
supercapacitors

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Nanoporous carbons for high power
supercapacitors
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22. -10
0
10
20
30
40
50
60
70
40 50 60 70 80 90 100 110 120
DC=2.7V AC= 5mV Freq --> 0.1Hz to 10 kHz
1- poor
2- typical
3- optimized
SC design:
1
2
3
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1
22
Nanoporous carbons for high power
supercapacitors
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Nanoporous carbons for high power
supercapacitors
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24. YUNASKO single SC cells and combined modules
(Li-ion battery and SC stack in parallel)
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Module: 14 V
Max.current: 1200 A
Mass: 2.8 kg
Single cells:
480 F
1200 F
1500 F
Nanoporous carbons for high power
supercapacitors
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25. 15 ÷ 45 V, 4 ÷ 6 kg
(spot welding: current up to 7 kA; stud welding: stud  12mm)
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Nanoporous carbons for high power
supercapacitors
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26. 26
48 V, 165 F:
Max surge voltage: 52 V
DC pulse resistance: <4 mΩ
Mass: 12 kg
equipped with a proprietary
voltage balancing system
and temperature sensor
Nanoporous carbons for high power
supercapacitors
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27. 27
16 V, 200 F:
Max surge voltage: 18 V
DC pulse resistance: 0.6 mΩ
Mass: 2.5 kg
equipped with a proprietary
voltage balancing system
and temperature sensor
Nanoporous carbons for high power
supercapacitors
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NASU

28. 28
Continuous cycling the 16V module over 8 hours
basic city duty cycle
ΔT:
cells in the centre
cells at the edge
Time, s
V
A, charge
A, discharge
Nanoporous carbons for high power
supercapacitors
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29. 29
Capacitance,
F
Internal
resistance,
mΩ
Time
constant,
s
Spec.
energy
(CU2
/2),
W.h/kg
Spec.
power
(95% eff.),
kW/kg
Max.
spec.
power,
kW/kg
SC power cells (2.7V)
480a
0.20 0.10 4.9 10.2 91
1200a,b
0.10 0.12 5.3 8.9 79
1500b
0.09 0.14 6.1 9.1 81
Hybrid cells (2.8 V)
6000a
1.0 6.0 37 4.5 NA
16 V module (6 “power” cells of 1200F in series)
200c,d
0.6 0.12 2.8 4.8 43
48 V module (18 “energy” cells of 3000F in series)
165d
4.0 0.65 4.4 1.4 12
a) Also tested in ITS, UC Davis, CA; b) Also tested in JME, Cleveland, OH;
c) Also tested in Wayne State University, Detroit, MI;
d) Equipped with a proprietary voltage balancing system (patent pending).
Nanoporous carbons for high power
supercapacitors
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30. ISPE
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Nanoporous carbons for high power
supercapacitors
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“During the recent ECCAP Symposium at AABC-2013 in Strasbourg
(June 24-26) a recognised specialist in the field of supercapacitor
research – Dr. John Miller from JME Inc. revealed testing results for
the six key ultracapacitor producers, including a market leader –
Maxwell Technologies. The results showed substantial advantage
of YUNASKO technology over the closest analogues.”
(http://us1.campaign-archive1.com/?u=84cc935cd75c22a368d1cd12e&id=31a3699821&e=193f657ac6)
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Nanoporous carbons for high power
supercapacitors

32. Financial support from FP7 Project # 286210 (Energy Caps) is very much
acknowledged
Nanoporous carbons for high power
supercapacitors
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