Investigation of supercapacitors with carbon electrodes obtained from argon-acetylene arc plasma ; Superkondensatorių su anglies elektrodais, suformuotais iš elektrolankinio išlydžio argono-acetileno plamos, tyrimas

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Vytautas Magnus University Žydr ūnas Kavaliauskas INVESTIGATION OF SUPERCAPACITORS WITH CARBON ELECTRODES OBTAINED FROM ARGON-ACETYLENE ARC PLASMA Summary of Doctoral Dissertation Physics (02P) Kaunas, 2010 Doctoral dissertation was prepared in 2006-2010 at Vytautas Magnus University. Part of this research was performed in collaboration with Lithuanian Energy Institute. Scientific supervisor: Prof. habil. dr. Liudvikas Pranevi čius (Vytautas Magnus University, Physical sciences, Physics – 02P). Scientific advisor: Dr. Darius Mil čius (Lithuanian Energy Institute, Physical sciences, Physics – 02P). Doctoral Dissertation will be defended in the Council of Physics of Vytautas Magnus University. Chairman: Prof. habil. dr. Julius Dudonis (Kaunas University of Technology, Physical sciences, Physics – 02P). Members: Doc. dr. Valdas Girdauskas (Vytautas Magnus University, Physical sciences, Physics – 02P). Doc. dr. Aleksandras Iljinas (Kaunas University of Technology, Physical sciences, Physics – 02P). Dr. Vitas Valin čius (Lithuanian Energy Institute, Technological science, Power and thermal engineering – 06T). Dr. Viktorija Grigaitien ė (Lithuanian Energy Institute, Technological science, Power and therma Opponents: Doc. dr. Arvydas Kanapickas (Vytautas Magnus University, Physical sciences, Physics – 02P). Prof. habil. dr.

Sujets

• Capacity
• Physics
• Plasma
• Electric double-layer capacitor

Informations

• Publié par: vytautas_magnus_university
• Publié le: 01 janvier 2010
• Nombre de lectures: 62

Extrait

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Vytautas Magnus University

 ydrnas Kavaliauskas

INVESTIGATION OF SUPERCAPACITORS WITH CARBON ELECTRODES OBTAINED FROM ARGON- ACETYLENE ARC PLASMA 

Summary of Doctoral Dissertation Physics (02P)

Kaunas, 2010

Doctoral dissertation was prepared in 2006-2010 at Vytautas Magnus University. Part of this research was performed in collaboration with Lithuanian Energy Institute.  Scientific supervisor:  Prof. habil. dr. Liudvikas Pranevičius (Vytautas Magnus University, Physical sciences, Physics  02P).  Scientific advisor:  Dr. Darius Milčius (Lithuanian Energy Institute, Physical sciences, Physics  02P).  Doctoral Dissertation will be defended in the Council of Physics of Vytautas Magnus University.  Chairman: Prof. habil. dr. Julius Dudonis (Kaunas University of Technology, Physical sciences, Physics 02P).   Members: Doc. dr. Valdas Girdauskas (Vytautas Magnus University, Physical sciences, Physics  02P). Doc. dr. Aleksandras Iljinas (Kaunas University of Technology, Physical sciences, Physics  02P). Dr. Vitas Valinčius (Lithuanian Energy Institute, Technological science, Power and thermal engineering  06T). Dr. Viktorija Grigaitien Energy Institute, Technological science, (Lithuanian Power and thermal engineering  06T).  Opponents: Doc. dr. Arvydas Kanapickas (Vytautas Magnus University, Physical sciences, Physics  02P). Prof. habil. dr. Giedrius Laukaitis (Kaunas University of Technology, Physical sciences, Physics  02P).   The official defense of Dissertation will be held at 12 p.m on 9 December 2010

in 220 auditorium at Faculty of Natural Sciences of Vytautas Magnus University, Vileikos 8, LT-44404 Kaunas, Lithuania.  Summary of the Doctoral Dissertation has been distributed on 5 November 2010. The Dissertation is available at the libraries of Vytautas Magnus University, Institute of Physics, Martynas Mavydas National Library of Lithuania.    

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Vytauto Didiojo Universitetas

 ydrnas Kavaliauskas    SUPERKONDENSATORISU ANGLIES ELEKTRODAIS, SUFORMUOTAIS I ELEKTROLANKINIO ILYDIO ARGONO-ACETILENO PLAZMOS, TYRIMAS   Daktaro disertacijos santrauka

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Fiziniai mokslai, fizika (02P)

 Kaunas, 2010

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Disertacija rengta 2006-2010 metais Vytauto Didiojo Universitete. Dalis eksperimentatlikta Lietuvos energetikos institute.  Mokslinis vadovas:  Prof. habil. dr. Liudvikas Pranevičius (Vytauto Didiojo universitetas, fizika  02P).  Konsultantas:  Dr. Darius Milčius (Lietuvos energetikos institutas, fiziniai mokslai, fizika  02P).  Disertacija ginama Vytauto Didiojo Universiteto Fizikos krypties taryboje.  Pirmininkas: Prof. habil. dr. Julius Dudonis (Kauno tecnologijos universitetas, fiziniai mokslai, fizika  02P).  Nariai: Doc. dr. Valdas Girdauskas (Vytauto Didiojo Universitetas, fiziniai mokslai, fizika  02P). Doc. dr. Aleksandras Iljinas (Kauno tecnologijos universitetas, fiziniai mokslai, fizika 02P).  Dr. Vitas Valinčius (Lietuvos energetikos institutas, technologijos mokslai, energetika ir termoininerija  06T). Dr. Viktorija Grigaitien(Lietuvos energetikos institutas, technologijos mokslai, energetika ir termoininerija  06T).  Oponentai: Doc. dr. Arvydas Kanapickas (Vytauto Didiojo Universitetas, fiziniai mokslai, fizika  02P). Prof. habil. dr. Giedrius Laukaitis (Kauno tecnologijos universitetas, fiziniai mokslai, fizika  02P).   Disertacija bus ginama vieame Fizikos mokslo krypties tarybos posdyje 2010 m. gruodio 9 d. 12 val. Vytauto Didiojo Universiteto Gamtos moksl fakulteto 220 auditorijoje. Adresas: Vileikos gt. 8 LT44404 Kaunas, Lietuva.  Disertacijos santrauka isiuntinta 2010 m. lapkričio mn. 5 d. Disertacijągalima perirti Vytauto Didiojo universiteto bibliotekoje, Fizikos instituto bibliotekoje bei Lietuvos nacionalinje Martyno Mavydo bibliotekoje. 

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Acknowledgment

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I feel thankful to many people for their assistance, contribution and support. I am

deeply grateful to all of them.

First of all, I would like to thank to my scientific supervisor prof. habil. dr.

Liudvikas Pranevičius for leadership and knowledge about nanomaterials physics. I am

also grateful for his patience and encouragement.

Also I want thank to the chief of Centre for Hydrogen Energy Technologies dr.

Darius Milčius for ideas and suggestions for scientific investigations and for the

availability of modern equipment.

I am grateful to the chief of Plasma processing laboratory dr. Vitas Valinčius for

valuable comments and granted access to experimental laboratory equipment.

I am grateful, to professor of Vytautas Magnus University Liudas Pranevičius and

to associate professor of Kaunas University of Technology Liutauras Marcinauskas for

assistance analyzing results and valuable observations.

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Introduction

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Electrochemical capacitors have been known since many years. First patents date

back to 1957 where a capacitor based on high surface area carbon was described by

Becker. Later in 1969 first attempts to market such devices were undertaken by

company SOHIO. However, only in the nineties electrochemical capacitors became

famous in the context of hybrid electric vehicles.

Electrochemical capacitors fill in the gap between batteries and conventional

capacitors such as electrolytic capacitors or metallized film capacitors. In terms of

specific energy as well as in terms of specific power this gap covers several orders of

magnitude [1].

Batteries and low temperature fuel cells are typical low power devices whereas conventional capacitors may have a power density of >10 6 watts per dm 3  very low at  energy density. Thus, electrochemical capacitors may improve battery performance in

terms of power density or may improve capacitor performance in terms of energy

density when combined with the respective device. In addition, electrochemical

capacitors are expected to have a much longer cycle life than batteries because no or

negligibly small chemical charge transfer reactions are involved [2].

Fig. 1 shows a schematic diagram of an electrochemical double-layer capacitor

consisting of a single cell with a high surface-area electrode material, which is loaded

with electrolyte. The electrodes are separated by a porous separator, containing the same electrolyte as the active material. Concentrated potassium alkali (KOH) (10 mol dm -3 ,

40 mL) is used as electr

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Fig. 1. Principle of a single-cell double-layer capacitor

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In previous studies it was shown that ruthenium oxide (RuO 2 ) is the most suitable material for the production of supercapacitors. Though ruthenium oxide has many

advantages  such as high specific capacitance, high conductivity  new materials as

alternatives to its cost and certain technological problems of its production started to be

searched for. One of the alternative materials is an activated carbon, which is used for

the production of electrodes of supercapacitors. Activated carbon suits well for the

production of supercapacitors due to its large surface area, which directly influences

capacitance. Activated carbon also is characterised by superb temperature stability and

relatively low cost. Together with carbon, nickel oxide (NiO) is also used for the

production of electrodes of supercapacitors. Nickel oxide acts as catalyst and increases the area of active surface [3, 4]. Concentrated potassium alkali (KOH) (10mol dm -3 ,

40mL) is used as electrolyte in supercapacitors. Many methods are used for the

production of activated carbon electrodes: anodic deposition, chemical reactions,

electrochemical deposition, magnetron sputtering deposition, thermal evaporation

method, pulsed laser deposition and plasma spray.

In this study, the two-stage electrode formation method is used, encompassing the

methods of plasma spray and magnetron sputtering deposition [5, 6]. The method

plasma spray is used for the deposition of activated carbon while magnetron sputtering

technique is used to deposit nickel oxide on the top of carbon layer. Using these

electrodes, supercapacitors have been fabricated and their characteristics analyzed.

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Main objectiveis to:

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Investigation of structure and electrical

characteristics

of

supercapacitors

electrodes produced by atmospheric pressure plasma torch has been done.

Determination of thin layer nickel oxide deposited on carbon and influence of plasma-

chemical etching on material structure an

performed.

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d electrical characteristics of electrodes was

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Main tasks:

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3. 

4. 

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To form carbon electrodes by plasma torch at atmospheric pressure To deposit nanometer thick NiO layers on the surface of carbon electrodes by magnetron sputtering.

To investigate the influence of plasma properties on the structure and surface topography of carbon electrodes.

To evaluate the influence of NiO deposited quantity and plasma-chemical etching of carbon on the properties of supercapacitors.

To optimize the electrical characteristics of resulting supercapacitors.

Innovations of this work:

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For the production of carbon electrodes for supercapacitorsAr/C 2 H 2  atmospheric plasma was used. Though, the data concerning the carbon coatings deposited using

acetylene gas are sufficiently explored, but information on application for electrode production is not found in scientific publications. The influence of Ar/C 2 H 2 plasma parameters on the electrical and physical characteristics of electrodes of supercapacitors

was investigated. The magnetron deposition method was employed to form NiO thin

layer on carbon surface. The influence of nanometer thick NiO layers on the electrical

parameters of supercapacitors was investigated.

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Positions to defend:

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Experimental data and numerical modeling results suggest that the electrical parameters of supercapacitors and carbon electrode structure depend on the

plasmatron power and acetylene content in the atmospheric pressure plasma jet.

Increasing the quantity of acetylene, the size of generated micropores on electrode surface increases. Increasing the amount of sp 2 bonds, the capacity of the capacitor increases. Changing the quantity of the acetylene in the plasma flow, the

supercapacitor voltage stability changes slightly (in the range from 0.5 to 0.55 V).

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From the theoretical and experimental results it was determined that the deposition of a small amount (12-240 µg/ 2 ) of nickel oxide on the carbon electrode surface cm increases the capacity of supercapacitor and changes the surface microstructure.

Three-dimensional dispersive surface structure disappears when the quantity of nickel oxide deposited on carbon electrode exceeds 48 µg/cm 2 . Maximum capacity of supercapacitor is obtained for 48 µg/cm 2 of NiO. The mean stability voltage of

carbon electrode with NiO - 0.35 V and it is about 1.5 times less than for

supercapacitor with electrodes made of carbon.

It was estimated that the irradiation of carbon electrodes with oxygen plasma

allows to change the surface microstructure and to increase the capacity of

supercapacitor. The interaction of carbon electrode surface with oxygen plasma

leads to the etching of isotropic microbeads. The mean capacity of carbon

electrodes with the surface affected by oxygen plasma is larger than electrodes

without etching, but smaller than those with small amount of nickel oxide

vaporized on the surface. Meanwhile, the carbon electrodes etched by oxygen

plasma have no influence to the supercapacitor stability voltage.

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Approbation:

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The results presented in this thesis are published in 7 international scientific papers:

3 of them are the published in the ISI-rated journals. Also the results were presented at 8

International Conferences.

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Papers from the Master List of the Institute for Scientific Information:

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1. . Kavaliauskas, L. L. Pranevičius, L. Marcinauskas, P. Valatkevičius. Deposition of carbon electrodes for supercapacitors using atmospheric plasma torch.

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Mediagotyra, Vol. 15, No. 2, pp. 99-102 (2009).

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Presentations at conferences:

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4. 

. Kavaliauskas, L. Marcinauskas. Electrical characteristics of double-layer supercapacitors. Jaunoji energetika, pp. 433-437 (2010).

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technologijos, Kaunas, 2008 m. 01-31 02-01 d. Oral presentation. 2. . Kavaliauskas, L.L. Pranevičius, L. Marcinauskas  P. Valatkevičius,The role of thin nio 2  on the top of carbon electrode on the parameters of supercapacitors, film Jaunoji energetika, Kaunas, 2008 m. May 29 d. Oral presentation.

dang atmosferinio sl formavimasgio plazmos sraute, ilumos energetika ir

1. . Kavaliauskas, L. Marcinauskas, L.L. Pranevičius. Suprekondensatori elektrod

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2. 

3. 

92-94 (2010).

stability of supercapacitor. High temperature material processes. Vol. 14, No. 3 pp.

. Kavaliauskas, L. Pranevičius, L. Marcinauskas, P. Valatkevičius. Atmospheric Plasma Carbon Materials for Supercapacitor Electrodes. Electrical review, No 7 pp.

Papers published in the others scientific journals:

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237-244 (2010).

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3. . Kavaliauskas, L. Marcinauskas, L. Pranevičius, A. Baltunikas. Properties of supercapacitors fabricated by plasma technologies. Jaunoji energetika, pp. 1-5

(2009).

1. . Kavaliauskas, L. Marcinauskas, L.L. Pranevičius. Suprekondensatori elektrod dang formavimas atmosferinio slgio plazmos sraute, ilumos energetika ir

technologijos, pp. 25-27 (2008). 2. . Kavaliauskas, L.L. Pranevičius, L. Marcinauskas  P. Valatkevičius,The role of thin nio 2  film on the top of carbon electrode on the parameters of supercapacitors, Jaunoji energetika, pp. 10-15 (2008).

. Kavaliauskas, L. Marcinauskas, L.L. Pranevičius, L. Pranevičius, P. Valatkevicius. Influence of nickel oxide amount on electrical parameters and

3. 

. Kavaliauskas, L.L. Pranevičius, L. Marcinauskas, L. Pranevičius, P. Valatkevičius, Effects of thin NiO film on plasma spray deposited carbon electrodes

for supercapacitors, Ion implantation and other applications of ions and electrons,

Kazimierz Dolny Lenkija, 2008 m. June 16-19 d. Poster presentation.

4. . Kavaliauskas, L. Marcinauskas, L. Pranevičius, A. Baltunikas. Properties of supercapacitors fabricated by plasma technologies. Jaunoji energetika, Kaunas, 2009

m. May 28 d. Oral presentation.

5. . Kavaliauskas, L. Marcinauskas. Electrical characteristics of double-layer supercapacitors. Jaunoji energetika, Kaunas, 2010 m. May 27 d. Oral presentation.

6. . Kavaliauskas, L.L. Pranevičius, L. Marcinauskas, P. Valatkevičius, Atmospheric Plasma Carbon materials for supercapacitor electrodes. New electrical and

electronic technologies and their industrial implementation, Zakopan, Lenkija,

2009 m. June 13-26 d. Poster presentation.

7. . Kavaliauskas, L. Pranevičius, P. Valatkevičius. Studies of carbon nanotopography effects the capacity of supercapacitor. Systems with Fast Ionic

8. 

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Transport, Ryga, Latvija, 2010 m. June 1  5 d. Poster presentation.

. Kavaliauskas, L. Marcinauskas, P. Valatkevičius. Enhanced capacitance of porous carbon electrodes through deposition of small amounts of NiO. Ion

Implantation and other Applications of Ions and Electrons, Kazimierz Dolny,

Lenkija, 2010 m. June 14  17 d. Poster presentation

Authors contributions:

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The author of thesis contributed in all experiments and experimental measurements,

preparation of experimental methodic and partly in numerical calculations, processing

of experimental results, their interpretations and publishing.

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The outline of main results

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The thesis consists: introduction, experimental results, modeling and conclusions

and a list of references.

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