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Electrophysical behavior of ion-conductive organic-inorganic polymer system based on aliphatic epoxy resin and salt of lithium perchlorate.

Matkovska L, Iurzhenko M, Mamunya Y, Matkovska O, Demchenko V, Lebedev E, Boiteux G, Serghei A - Nanoscale Res Lett (2014)

Bottom Line: The effect of LiClO4 content on the electrophysical properties of epoxy polymers has been studied by differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS).The effect of LiClO4 content on the structure has been studied by wide-angle X-ray scattering (WAXS).The presence of ether oxygen in DEG macromolecules provides a transfer mechanism of the lithium cations with the ether oxygen similar to polyethylene oxide (PEO).

View Article: PubMed Central - PubMed

Affiliation: Institute of Macromolecular Chemistry of National Academy of Sciences of Ukraine, Kyiv, 02160, Ukraine, LOVEMK@ukr.net.

ABSTRACT

Unlabelled: In the present work, ion-conductive hybrid organic-inorganic polymers based on epoxy oligomer of diglycide aliphatic ester of polyethylene glycol (DEG) and lithium perchlorate (LiClO4) were synthesized. The effect of LiClO4 content on the electrophysical properties of epoxy polymers has been studied by differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS). The effect of LiClO4 content on the structure has been studied by wide-angle X-ray scattering (WAXS). It was found that LiClO4 impacts on the structure of the synthesized hybrid epoxy polymers, probably, by formation of coordinative complexes {ether oxygen-lithium cations-ether oxygen} as evidenced from a significant increase in their glass transition temperatures with increasing LiClO4 concentration and WAXS studies. The presence of ether oxygen in DEG macromolecules provides a transfer mechanism of the lithium cations with the ether oxygen similar to polyethylene oxide (PEO). Thus, the obtained hybrid polymers have high values of ionic conductivity σ' (approximately 10(-3) S/cm) and permittivity ϵ' (6 × 10(5)) at elevated temperatures (200°С). On the other hand, DEG has higher heat resistance compared to PEO that makes these systems perspective as solid polymer electrolytes able to operate at high temperature.

Pacs: 81.07.Pr; 62.23.St; 66.30.hk.

No MeSH data available.


Related in: MedlinePlus

Scheme of the DEG/LiClO4system. DEG/LiClO4 system consists of DEG polymer chains with coordinative bonds between lithium cations and ether oxygen.
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Fig2: Scheme of the DEG/LiClO4system. DEG/LiClO4 system consists of DEG polymer chains with coordinative bonds between lithium cations and ether oxygen.

Mentions: The DSC results are shown in Figure 1a. The values of the glass transition temperature derived from the curves of the obtained composites depending on the content of LiClO4 in the reaction mixture are shown in Figure 1b. It is obvious that the increase of LiClO4 amount in reactive mixture from 0 to 20 phr leads to a linear increase of the glass transition temperature from −10°C to 25°C. This can be a result of the electrostatic interactions between lithium cations Li+ and the macromolecular r chain of DEG with immediate forming of coordinative complexes, such as {ether oxygen-lithium cations-ether oxygen} (Figure 2), which are accompanied by displacement of electron density of the oxygen atoms and their partial polarization [5, 21, 25]. The result is a substantial reduction of segmental mobility of DEG chains within the complexes formed that shows up in a glass transition temperature rise of polymer matrix. The linear dependence of Tg on the salt content testifies that all the lithium ions participate in the formation of coordination bonds.Figure 1


Electrophysical behavior of ion-conductive organic-inorganic polymer system based on aliphatic epoxy resin and salt of lithium perchlorate.

Matkovska L, Iurzhenko M, Mamunya Y, Matkovska O, Demchenko V, Lebedev E, Boiteux G, Serghei A - Nanoscale Res Lett (2014)

Scheme of the DEG/LiClO4system. DEG/LiClO4 system consists of DEG polymer chains with coordinative bonds between lithium cations and ether oxygen.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4493850&req=5

Fig2: Scheme of the DEG/LiClO4system. DEG/LiClO4 system consists of DEG polymer chains with coordinative bonds between lithium cations and ether oxygen.
Mentions: The DSC results are shown in Figure 1a. The values of the glass transition temperature derived from the curves of the obtained composites depending on the content of LiClO4 in the reaction mixture are shown in Figure 1b. It is obvious that the increase of LiClO4 amount in reactive mixture from 0 to 20 phr leads to a linear increase of the glass transition temperature from −10°C to 25°C. This can be a result of the electrostatic interactions between lithium cations Li+ and the macromolecular r chain of DEG with immediate forming of coordinative complexes, such as {ether oxygen-lithium cations-ether oxygen} (Figure 2), which are accompanied by displacement of electron density of the oxygen atoms and their partial polarization [5, 21, 25]. The result is a substantial reduction of segmental mobility of DEG chains within the complexes formed that shows up in a glass transition temperature rise of polymer matrix. The linear dependence of Tg on the salt content testifies that all the lithium ions participate in the formation of coordination bonds.Figure 1

Bottom Line: The effect of LiClO4 content on the electrophysical properties of epoxy polymers has been studied by differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS).The effect of LiClO4 content on the structure has been studied by wide-angle X-ray scattering (WAXS).The presence of ether oxygen in DEG macromolecules provides a transfer mechanism of the lithium cations with the ether oxygen similar to polyethylene oxide (PEO).

View Article: PubMed Central - PubMed

Affiliation: Institute of Macromolecular Chemistry of National Academy of Sciences of Ukraine, Kyiv, 02160, Ukraine, LOVEMK@ukr.net.

ABSTRACT

Unlabelled: In the present work, ion-conductive hybrid organic-inorganic polymers based on epoxy oligomer of diglycide aliphatic ester of polyethylene glycol (DEG) and lithium perchlorate (LiClO4) were synthesized. The effect of LiClO4 content on the electrophysical properties of epoxy polymers has been studied by differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS). The effect of LiClO4 content on the structure has been studied by wide-angle X-ray scattering (WAXS). It was found that LiClO4 impacts on the structure of the synthesized hybrid epoxy polymers, probably, by formation of coordinative complexes {ether oxygen-lithium cations-ether oxygen} as evidenced from a significant increase in their glass transition temperatures with increasing LiClO4 concentration and WAXS studies. The presence of ether oxygen in DEG macromolecules provides a transfer mechanism of the lithium cations with the ether oxygen similar to polyethylene oxide (PEO). Thus, the obtained hybrid polymers have high values of ionic conductivity σ' (approximately 10(-3) S/cm) and permittivity ϵ' (6 × 10(5)) at elevated temperatures (200°С). On the other hand, DEG has higher heat resistance compared to PEO that makes these systems perspective as solid polymer electrolytes able to operate at high temperature.

Pacs: 81.07.Pr; 62.23.St; 66.30.hk.

No MeSH data available.


Related in: MedlinePlus