Maletin cesep2013

N-Doped Nanoporous Carbons for High Power Supercapacitors

CESEP-2013,Mülheim an der Ruhr, Sep. 23-26

Yurii Maletin, Volodymyr Strelko

ISPE NASU

Table of Contents

1. Institute for Sorption & Problems of Endoecology (ISPE),

National Academy of Science of Ukraine

2. YUNASKO LLC

3. Supercapacitors: energy storage due to nanoporous

carbons

4. Supercapacitors: technology challenges

5. ISPE-YUNASKO joint efforts to improve SC performance

6. SC prototypes – most recent test results

7. Conclusions and acknowledgements

ISPE NASU

Nanoporous carbons for high powersupercapacitors

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Institute for Sorption & Problems of Endoecology

ISPE NASU


• 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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YUNASKO LLC is registered in the UK since 2010 and has two subsidiaries: YUNASKO-Ukraine and YUNASKO-Latvia.

The core R&D team has 24 years of experience in supercapacitor technology.

Previous R&D cooperation projects included:- Idaho National Lab (1996-1997)- Skeleton Technologies AG (1996-2002)- Ener1 Group (2004-2005)- APowerCap Technologies (2006-2009)

YUNASKO LLC

ISPE NASU


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For batteries:~ 102 W.h/kg

d++

++ _

_

__ C =

QU

=A

d

E = 12 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

ISPE NASU


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Why the SC technologyis of interest?

First patents: H.E. Becker, US Patent 2 800 616 (General Electric Co.) 1957R.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:

dC =

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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Why SUPER capacitor?

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Pore size distribution in some carbon materials (DFT analysis of N2 sorption/desorption isotherms)

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1

2

3

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1 and 2 look more promising than 3

TEM image of carbon powder

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Slit-shaped pores or just shear cracks of graphene layers


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• 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).

Quantum-chemical study of carbons

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Effect of N-heteroatom location on HOMO level and ΔE

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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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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 -6.41DE, eV 4.70 2.72 3.81

Effect of O-heteroatom location on HOMO level and ΔE

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ISPE NASU


Effect of N,O-heteroatom location on HOMO level and ΔE

Maximum EHOMO value can be achieved in C92N3O cluster. This results in the highest electron donor ability.

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Comparison of energy storage technologies

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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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Another approach to compare SC and batteries(taken from Dr. John R. Miller presentation)

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Low internal resistance, Rin

- key advantage of SC devices in various applications

Heat generation = ʃI2RintEfficiency = RLoad/(RLoad + Rin)

Power output ~ 1/ Rin

Also MASS and COST reduction!

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Quick response (low RC-constant)


ISPE NASU

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)

Yunasko approach to reduce Rin

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Electrolyte mobility in nanopores – MD study

O.N.Kalugin, et al. Nanoletters, 8 (2008) 2126-2130: confinement results in slow diffusion of AN molecules in carbon nanotubes (by a factor of ca. 4)


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Correlation of in-pore diffusion coefficients with SC resistance

2 4 6 8 10 12 14 161

1.1

1.2

1.3

1.4

1.5

1.6

1.7

Diffusion coefficient, D, 10-10 m2/s

ED

LC

res

isti

vity

, R

, O

hm

.cm

2

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 )


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1 1.2 1.4 1.6 1.8 2 2.20.5

0.7

0.9

1.1

1.3

1.5

1.7

Diffusion coefficient, D, 10-10 m2/s

ED

LC

res

isti

vity

, R

, O

hm

.cm

2

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 )



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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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CV curves: A - 3-electrode cell B - SC prototype

A

B


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40 50 60 70 80 90 100 110 120-10

0

10

20

30

40

50

60

70

DC=2.7V AC= 5mV Freq --> 0.1Hz to 10 kHz

1- poor

2- typical

3- optimized

SC design:

Impedance spectroscopy (Nyquist plots)

1

2

3

23

1

22


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Two SC devices: which one has higher capacitance?


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YUNASKO single SC cells and combined modules (Li-ion battery and SC stack in parallel)

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Module: 14 VMax.current: 1200 AMass: 2.8 kg

Single cells:480 F1200 F1500 F


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15 ÷ 45 V, 4 ÷ 6 kg (spot welding: current up to 7 kA; stud welding: stud 12mm)

SC modules for portable welding machines(tested in the Paton Institute of Electric Welding, Kiev)

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Recent Yunasko SC modules

48 V, 165 F:

Max surge voltage: 52 V DC pulse resistance: <4 mΩMass: 12 kg

equipped with a proprietary voltage balancing system and temperature sensor


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Recent Yunasko SC modules

16 V, 200 F:

Max surge voltage: 18 V DC pulse resistance: 0.6 mΩMass: 2.5 kg

equipped with a proprietary voltage balancing system and temperature sensor


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Yunasko competitive advantage: low heat generation

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


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Test results

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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).


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Conclusions

1. YUNASKO SC devices provide the lowest internal resistance and highest power density.

2. Electrolyte mobility in nanopores is the major contributor to SC internal resistance.

3. A way to further improve the SC performance lies in reducing the interaction of electrolyte with the carbon matrix. This can probably be achieved due to N-doping the carbon surface.

4. We are open to cooperation with the carbon community.

ISPE NASU


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Ukraine Ultracap is number one(cited from: BEST Battery Briefing – 29 July 2013)

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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)

ISPE NASU


http://us1.campaign-archive1.com/?u=84cc935cd75c22a368d1cd12e&id=31a3699821&e=193f657ac6



Many thanks to CESEP2013 organizers: for their kind invitation to take part in this conference

Special thanks to YUNASKO-ISPE R&D team: Dr. N. Stryzhakova, Dr. S. Zelinsky, Dr. N. Davydenko, V. Trykhlib,V. Goba, O. Gozhenko, S. Tychina, D. Drobny, and A. Maletin

To our partners: Financial support from FP7 Project # 286210 (Energy Caps) is very much

acknowledged

Financial support from Project # 6.22.5.26 of Nanotechnology and Nanomaterials Program (Ukraine) is very much acknowledged

Special thanks to Dekarta Capital Fund for their financial support of YUNASKO supercapacitor project

Acknowledgements


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THANKS FOR YOUR ATTENTION! Please visit us at: www.yunasko.com

Maletin cesep2013

Technology

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