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Basic theory of Dielectric Relaxation Spectroscopy and Studies of Electrolyte Structure

유전체 이완 분광법의 원리 및 이를 이용한 전해액 미시구조 연구

  • 구본협 (대구경북과학기술원에너지공학전공) ;
  • 황순욱 (대구경북과학기술원에너지공학전공) ;
  • 이호춘 (대구경북과학기술원에너지공학전공)
  • Received : 2019.05.10
  • Accepted : 2019.05.21
  • Published : 2019.05.31

Abstract

To examine the solution structure of electrolytes, it is very important to understand ion-ion and ion-solvent interactions. In this review, we introduce the basic principle of dielectric relaxation spectroscopy (DRS) and studies of electrolyte structure. DRS is a type of impedance method, which measures the dielectric properties of electrolytes over a high frequency domain at levels of tens of GHz. Therefore, DRS provides information on the different polar chemical species present in the electrolyte, including the type and concentration of free solvents and ion pairs with dipole moments. The information of DRS is complementary to the information of conventional analytical techniques (Infrared/Raman spectroscopy, nuclear magnetic resonance (NMR), etc.) and thus enables a broad understanding of electrolyte structure.

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Fig. 1. Parallel plate capacitor with direct current (DC) voltage source.

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Fig. 2. Parallel plate capacitor with alternating current(AC) voltage source.

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Fig. 3. Frequency response of dielectric mechanisms.

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Fig. 4. Dipole rotation in electric field.

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Fig. 5. Permittivity, ε′ (v) spectra and dielectric loss, ε″ (v) spectra of water at 25oC.

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Fig. 6. Total permittivity, η″ (v) , permittivity, ε′ (v) spectra, and dielectric loss, ε″ (v) spectra of 0.1 M Fe(ClO4)2 at 25oC. The slashed areas show the contributions of the ion pair (IP) and free water molecule relaxation process to ε″ (v).

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Fig. 7. Permittivity, ε′ (v) , and dielectric loss, ε″ (v) of 1 M LiBF4-PC compared with the spectrum calculated with Debye equation. The slashed areas show the contributions of the SIP, CIP and free PC solvents (PC and PC') relaxation process to ε″ (v).

Table 1. Possible ionic species in non-aqueous system, and their activity for Raman spectroscopy and DRS.

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Acknowledgement

Supported by : 한국연구재단

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