One-dimensional composites based on carbon nanotubes and conjugated polymers for applications in energy storage and optoelectronic devices field


Project Director: Dr. Mihaela Baibarac
Project ID:  150/05.10.2011 Code: PN-II-ID-PCE-2011-3-0623
Project Director:  Dr. Mihaela Baibarac
Project Type: National
Project Program: IDEAS
Funded by: Romanian National Authority for Scientific Research, UEFISCDI
Contractor: National Institute of Materials Physics
Start Date: Saturday, 1 October, 2011
End Date: Saturday, 1 October, 2016
Project Abstract:

One-dimensional composites based on carbon nanotubes (CNTs) and conjugated polymers (CPs) or co-polymers (COP) will be synthesized for applications in the energy storage and optoelectronics devices field. Using chemical and electrochemical synthesis adapted for the nanoscale templates, composites based on single walled carbon nanotubes (SWNTs) and CPs or COP of the type poly(p-phenylene-vinylene) (PPV), poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-viny-lene) (MEH-PPV), poly(2,5-bisoctyloxy)-1,4-phenylenevinylene) (BPPV), poly(3,4-ethylenedioxy thiophene-co-pyrene)(PEDOT-Py) and poly(bithiophene-co-pyrene) (PBth-Py) with the fibers, rods and wires morphological structure will be obtained. The morphological and structural characterization of these composites by HRTEM, SEM, UV-VIS-NIR, FTIR, Raman spectroscopy, photoluminescence and conductivity will be carried out to establish the type of interaction between the two constituents and the role of these in the core/shell structure of co-axial wires. Additional data concerning the role of polymers and CNTs and the orientation of composites vs. metallic surface will be revealed by optical methods assisted of surface plasmons as the anti-Stokes/Stokes surface enhanced Raman scattering, surface enhanced infrared absorption spectroscopy and surface enhanced photoluminescence. Electrochemical studies concerning the doping process of one-dimensional composites will be carried out to improve the performances of these materials in some applications at laboratory level.

Project Objectives: 

A prospective analysis of the results estimated to be obtained in this project reveals as novelty, the following elements: i) in the frame of the fundamental researchers focused on materials science, is envisaged the elaboration of new protocols for new one-dimensional composites of the type PPv/CNTs, MEH-PPV/CNTs, B-PPV/CNTs, PEDOT-Py/CNTs and PBTh-Py with fibers, rod and core-shell wires structure as well as evaluation of the optical and electrochemical properties of onedimensional composites in order to establish new strategies for applications in the energy storage and optoelectronics devices; ii) in the frame of the experimental techniques is envisaged the development of new optical methods assisted by surface plasmons which induce surface enhanced process such as SEIRA and SEPL, experimental methods which will be demonstrate that are valuable tools to characterization of composites based on CNTs and CPs with fibers, rod and coreshell wire structure, iii) in the frame of the applicative researcher is envisaged the development at laboratory level of high performed electrodes for supercapacitors and Li rechargeable batteries having as active materials one- dimensional composites of the type PEDOT-Py/CNTs and PBTh-Py/CNTs with fibers, rod and core-shell wire structure and the evaluation of their performances and iv) another purpose is the optimization of optical properties of one-dimensional composites for applications in the solar cells and optical switches -a special attention will be given to the influence of doped anions on one-dimensional composites for applications as hole conductors.

Team

Name, first name Position & scientific title
Baibarac Aneta Mihaela Project Director
Baltog Ioan Senior Researcher
Mihut Lucian Senior Researcher
Velula Timucin Senior Researcher
Stroe Malvina PhD Student
Smaranda Ion Master Student
Popa Cristina Master Student
Bucur Ioana Technical Assistant
Lutea Ion Technical assistant
Ghica Corneliu Senior Researcher
Ilie Mirela Master Student
Matea Adelina Master Student

 

Stages Activities   Deadline
Stage

I

One-dimensional composites of the type PEDOT-Py/CNTs with fiber structure synthesized in the presence of hard template and their optical properties. Synthesis and optical properties of the PEDOT-Py/CNTs one-dimensional composites with fiber structure.

Activities:

1. Purifications of CNTs and establishment of all parameters of the electrochemical synthesis of the PEDOT-Py fibers and the PEDOT-Py/CNTs one-dimensional composite using "hard-templates" (the ratio of concentration of the two monomers: 3,4-ethylene dioxythiophene (EDOT) and pyrene (Py), influence of electrolyte concentration and sweep rate on cyclic voltammograms, co-functionalization of SWNTs with EDOT and Py, etc.);

2. Photoluminescence and UV-VIS-NIR absorption studies on PEDOT-Py fibers and the PEDOT-Py/CNTs one-dimensional composite;

3. Vibrational studies using anti-Stokes/Stokes surface enhanced Raman scattering (aS/S - SERS) and FTIR/SEIRA spectroscopy on PEDOT-Py fibers and the PEDOT-Py/CNTs one-dimensional composite;

4. Preparation of the metallic supports for SERS and SEIRA studies;

5. HRTEM and SEM studies on PEDOT-Py fibers and the PEDOT-Py/CNTs one-dimensional composite;

6. Evaluation of the orientation of PEDOT-Py fibers and the PEDOT-Py/CNTs one-dimensional composite on the metallic supports;

7. Studies of UV-VIS-NIR absorption spectroscopy on PEDOT-Py fibers and the PEDOT-Py/CNTs one-dimensional composite;

8. Writing of a raport of activities carried out during this stage.

15.12.2011
Stage

II

Molecular strategies for the manufacturing of one-dimensional composites of the type PPV/CNTs, MEH-PPV/CNTs, BPPV/CNTs, PBTh-Py/CNTs with fiber structure synthesized in the presence of hard template and their optical properties. Synthesis and optical properties of the one-dimensional composites of the type PPV/CNTs, MEH-PPV/CNTs, BPPV/CNTs, PBTh-Py/CNTs with fiber structure.

Activities:

1. Synthesis of precursor solution for PPV, MEH-PPV and BPPV, the functionalization of CNTs with precursor and thermal conversion of precursor and precursor functionalized CNTs in polycarbonate membranes;

2. Establishment of all parameters of the electrochemical synthesis of the PBTh-Py fibers and the PBTh-Py/CNTs one-dimensional composite using "hard-templates" (the ratio of concentration of the two monomers: bithiophene (BTh) and pyrene (Py), influence of electrolyte concentration and sweep rate on cyclic voltammograms, co-functionalization of SWNTs with PBTh-Py, etc.);

3. SEPL properties in Stokes and anti-Stokes range of the PPV, MEH-PPV and B-PPV fibers and one-dimensional composites of the type PPV/CNTs, MEH-PPV/CNTs and BPPV/CNTs using the excitation wavelengths in VIS range; PL studies with excitation wavelengths in NIR range;

4. Surface enhanced resonant Raman scattering studies on the PPV, MEH-PPV, B-PPV and PBTh-Py fibers and the PPV/CNTs, MEH-PPV/CNTs, BPPV/CNTs and PBTh-Py/CNTs one-dimensional composites as depending on the CNTs type, weight ratio of the two constituents, conversion temperature, etc.;

5. Preparation of the metallic supports for SERS and SEIRA studies;

6. HRTEM/SEM studies on CPs fibers and the CPs/CNTs one-dimensional composite;

7. FTIR/SEIRA studies on CPs fibers and the CPs/CNTs one-dimensional composites in polarized light and evaluation of the orientation of the PPV, MEH-PPV, B-PPV and PBTh-Py fibers and one-dimensional composites of the type PPV/CNTs, MEH-PPV/CNTs, BPPV/CNTs and PBTh-Py/CNTs on the metallic suports; the influence of the metallic support on SEIRA spectra of PPV, MEH-PPV and BPPV fibers and one-dimensional composites of the type PPV/CNTs, MEH-PPV/CNTs and BPPV/CNTs;

8. Writing of 2 articles that will be sent for publication at an ISI journal, preparation of a presentation for an international conference (www.diamond-conference.elsevier.com) and a raport of activities carried out during this stage.

15.12.2012
 

Stage

III

Electrochemical properties of PPV/CNTs, MEH-PPV/CNTs and BPPV/CNTs composites with fiber structure. Doping process of the one-dimensional composites of PPV/CNTs, MEH-PPV/CNTs and BPPV/CNTs with fiber structure in order to establish new strategies in the field of optoelectronics.

Activities:

1.  The influence of electrochemical doping of carbon nanotubes (CNTs) based composites and conjugated polymers PPV, MEH-PPV/CNTs and BPPV/CNTs with ClO4- ions on the vibrational properties.

2. The influence of electrochemical doping of carbon nanotubes (CNTs) based composites and conjugated polymers PPV, MEH-PPV/CNTs and BPPV/CNTs with ClO4- ions studied by aid of UV-VIS-NIR and photoluminescence spectroscopies.

3. Electrochemical studies regarding the doping of carbon nanotubes (CNTs) based composites and PEDOT-Py copolymer with ClO4- ions.

4. Writing of one article that will be sent for publication in a ISI journal and a raport of activities carried out during this stage.

15.12.2013
 

Stage

IV

Chemical synthesis and the optical properties of uni-dimensional   PEDOT-Py/CNT and PBTh-Py/CNTs composites

Activities:

1. The chemical synthesis of the PEDOT-Py/CNTS and PBTh-Py/CNTs composites using “soft-template” method.

2. Studies of  the SERS, FTIR/SEIRA and UV-VIS-NIR spectroscopy on the PEDOT-Py/CNTs and PBTH-Py/CNTs  chemically synthesized composites.

3. Photoluminescence studies on the PEDOT-Py/CNTs and PBTh-Py/CNTs  chemically synthesized composites.

4. Writing an article to be submitted for publication in a ISI journal.

15.12. 2014
 

 

 

 

Stage

V

Demonstration applications in the field of energy storage using as active materials  PEDOT - Py / CNTs and PBTh - Py / CNTs  composites

Activities:

1. Studies of HR-TEM/SEM on the PEDOT - Py / CNTs and PBTh - Py / CNTs chemically synthesized composites; evaluation of conductive properties of PEDOT- Py copolymer and PEDOT / CNTs composite . Tests of charge / discharge and cyclic voltammetry for supercapacitors using PEDOT - Py / CNTs and PBTh - Py / CNTs composites.

2. Performances evaluation of  composite materials as electrode in supercapacitors field.

3. Tests of charge / discharge and cyclic voltammetry for lithium rechargeable batteries  using as active materials PEDOT - Py / CNTs and PBTh - Py / CNTs  composites.

4. Performances evaluation of composite materials as electrode in lithium rechargeable batteries.

Writing of two articles to be submitted for publication in a ISI journal.

 

 

 

 

 

 

05.10.2015

List of Publications:

 

Raman scattering and anti-Stokes luminescence in poly-paraphenylene vinylene/carbon nanotubes composites

M. Baibarac, F. Massuyeau, J. Wery, I. Baltog, S. Lefrant

Journal of Applied Physics 111 (8),  083109, (2012)

Abnormal anti-Stokes Raman emission and infrared dichroism studies on poly(p-phenylenevinylene)/single-walled carbon nanotube composites

M. Baibarac, I. Baltog, J. Wery, S. Lefrant, J. Y. Mevellec

The Journal of Physical Chemistry C 116 (48), 25537-25545, (2012)

Abnormal Anti-Stokes Raman scattering and surface-enhanced infrared absorbtion spectroscopy studies of carbon nanotubes electrochemically functionalized with copolymer poly (2,2’-bithiophene-co-pyrene)

M. Baibarac, I. Baltog, I. Smaranda, M. Scocioareanu, J.Y. Mevellec, S.Lefrant

Applied Surface Science, 309,11-21, (2014)

New features in the anti-Stokes and Stokes Raman spectra of single-walled carbon nanotubes that are highly separated into their semiconducting and metallic nanotube components

M. Baibarac, I. Baltog, L. Mihut, S. Lefrant

Journal of Raman Spectroscopy, 45 (5), 323–331, (2014)

Nonlinear features of surface-enhanced Raman scattering revealed under non-resonant and resonant optical excitation

M. Baibarac, I. Baltog, L. Mihut, A. Matea, S. Lefrant

Journal of Optics, 16 (3) (2014)

Spectroelectrochemical properties of the poly[(2,5-bisoctyloxy)-1,4-phenylenevinylene]/single-walled carbon nanotube  composite

M. Baibarac, I. Baltog, I. Smaranda, M.Ilie, M.Scocioreanu, J.Y. Mevellec, S. Lefrant

 Synthetic Metals, 195, 276-285 (2014)

Optical Properties of Single-Walled Carbon Nanotubes Functionalized with Poly(2,2’-bithiophene-co-pyrene) Copolymer

I. Smaranda, M. Baibarac, M. Ilie, A. Matea, I. Baltog, S. Lefrant

Current Organic Chemistry, 19 (10), 652-661 (2015)

Optical properties of single-walled carbon nanotubes functionalized with copolymer poly(3,4-ethylene-dioxythiophene-co-pyrene)

I. Baltog, M. Baibarac, I. Smaranda, A. Matea, M. Ilie, J.Y. Mevellec, S. Lefrant

Optical Materials, 62, 604-611 (2016)

Electrochemical characterization of the Poly(2, 2’-Bithiophene-co-Pyrene) Functionalized Single-Walled Carbon Nanotubes and Their Applications in Supercapacitors Field

M. Baibarac, I. Baltog, M. Daescu

International Journal of Electrochemical Science, 12, 2013-2025 (2017)

The influence of single-walled carbon nanotubes on optical properties of the poly[(2, 5-bisoctyloxy)-1,4-phenylenevinylene] evidenced by infrared spectroscopy and anti-Stokes photoluminescence

M. Baibarac, I. Smaranda, I. Baltog, S. Lefrant, J.Y. Mevellec

Optical Materials, 67, 52-58 (2017)

 

Conferences:

Anti-Stokes photoluminescence and Raman scattering in poly[(2,5-bisoctyloxy)-1,4 phenylenevinylene]/single-walled carbon nanotubes composites

I. Baltog, M. Baibarac, I. Smaranda, S. Lefrant, J. Y. Mevellec

International Conference on Diamond and Carbon Materials, 2-6 september 2012, Granada, Spain (poster P 1.8, September 2, 2012)

Spectroelectrochemical properties of the single-walled carbon nanotubes functionalized with the copolymer poly(3,4-ethylenedioxithiophene-co-pyrene)

M. Baibarac, I. Baltog, T. Velula, M. Scocioreanu, J.Y. Mevellec, S. Lefrant

9th International Conference on Physics of Advanced Materials, 20-23 September 2012, Iasi, Romania (poster P-4)

Electrochemical functionalization of carbon nanotubes with copolymers based on 2.2'-bithiophene and pyrene evidence by Raman scattering and IR spectroscopy

M.Baibarac, I. Baltog, M.Scocioreanu, T. Velula, J.Y. Mevellec, and S. Lefrant

The Nanoscale and Electroanalysis: Surface Nanostructuration, Nanobiological Systems, Coupled Techniques, Microsystems,15th-17th May 2013, Bordeaux-France

SERS and SEIRA studies of carbon nanotubes electrochemically functionalized with poly (2,2'-bithiophen-co-pyrene)

I. Smaranda, M. Scocioreanu , M. Baibarac, I. Baltog, J.Y. Mevellec, S. Lefrant

The 8th International Conference on Advanced Materials, ROCAM, 7-10 July, 2015, Bucharest, Romania

 

Didactic Activities

PhD  thesis entitled:

"Optical properties of composites materials based on conductive polymers and carbon nanoparticles"

Author: Ion Smaranda, Faculty of Physics, University of Bucharest

Research report : " Abnormal Anti-Stokes Raman scattering and surface-enhanced infrared absorbtion spectroscopy studies of carbon nanotubes electrochemically functionalized with poly(2,2'-bithiophene-co-pyrene) (sep. 2014)

Research report: "Spectroelectrochemical properties of the poly[(2,5-bisoctyloxy)-1,4-phenylenevinylene]/single-walled carbon nanotube composite" (jun. 2015)

Research report: "Investigating the optical properties of composite materials based on copolymer poli(2,2’-bithiophen-co-pyrene) and SWNTs " (sep. 2015)

Author: Ion Smaranda

 

PhD  thesis entitled:“Optical properties of materials composites based on conjugated polymers as poly(p-phenylenevinylene) (PPV) and its derivatives with carbon nanotubes high separated and graphene”

Author: Mirela Ilie, Faculty of Physics, University of Bucharest

Semestrial report I  Synthesis methods of PPV and rGO ( 24.02.2015),

Semestrial report II  Optical properties of PPV and PPV/rGO composites ( 30.06.2015),

Final research report of the first year of PhD Comparation between optical properties of PPV-rGO composites synthetized by chemical and electrochemical methods   (02.10.2015)

Project Contact Person: Dr. Mihaela Baibarac

phone: +40-21369 0170 /112

Fax    : +40-21369 0177

e-mail: barac@infim.ro


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