TY - JOUR

T1 - Electrochemical synthesis and characterization of poly [Ni(CH3Osalen)] with immobilized poly(styrenesulfonate) anion dopants

AU - Apraksin, R. V.

AU - Volosatova, Y. A.

AU - Volkov, A. I.

AU - Vlasov, P. S.

AU - Lukyanov, D. A.

AU - Kulikov, I. R.

AU - Eliseeva, S. N.

AU - Levin, O. V.

N1 - Funding Information: The synthetic work, electrochemical and conductivity tests were made with financial support of Russian Science Foundation , grant number 19-19-00175 . The research was partially conducted in the Interdisciplinary Resource Centre for Nanotechnology, the Centre for Physical Methods of Surface Investigation, the Centre for Geo-Environmental Research and Modelling, the Chemical Analysis and Materials Research Centre, the Chemistry Educational Centre, the Magnetic Resonance Research Centre and the Cryogenic department of Research Park of SPbSU. IRK is grateful for the financial support of academic exchange between Saint Petersburg State University and Freie Universität Berlin by Joint Seed Project of SPbSU and FUB, grant # 39855834, which allowed developing mathematical models for separation of electronic and ionic conductivity. Publisher Copyright: © 2020 Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2021/2/1

Y1 - 2021/2/1

N2 - Intrinsically conductive polymer poly(N,N′-bis(3-methoxysalicylidene)ethylenediamine nickel(II)) (poly[Ni(CH3Osalen)]:PSS) has been synthesized by electrochemical polymerization from the [Ni(CH3Osalen)] solution containing tetrabutylammonium poly(styrenesulfonate) (TBAPSS). Cyclic voltammetry and in situ EQCM data demonstrated that electrochemical properties of poly[Ni(CH3Osalen)]:PSS are highly dependent on the nature of electrolyte solutions. A wider range of electrochemical activity, higher values of conductance and binary diffusion coefficient in TBAPSS solution are observed than in LiClO4, but the capacity values of films are higher in LiClO4 solution. The introduction of PSS− polyanion during synthesis of polymer film induced cationic mode of charge transport for poly[Ni(CH3Osalen)]. This type of PSS− doped polymers can be used as ion-exchange membranes. The combined electrochemical impedance spectroscopy and in situ conductance measurements on interdigitated electrodes were analyzed using the model concepts of Matthias and Haas, and Einstein relation. This novel approach allowed separating the diffusion coefficient into its ionic and electronic constituents. The ionic diffusion was found to be the limiting factor. Strong association of lithium cation with both the PSS− polyanion and methoxy-groups may be the cause of lower values of diffusion coefficients in LiClO4 solutions. The proposed model is suitable for further studies of similar systems.

AB - Intrinsically conductive polymer poly(N,N′-bis(3-methoxysalicylidene)ethylenediamine nickel(II)) (poly[Ni(CH3Osalen)]:PSS) has been synthesized by electrochemical polymerization from the [Ni(CH3Osalen)] solution containing tetrabutylammonium poly(styrenesulfonate) (TBAPSS). Cyclic voltammetry and in situ EQCM data demonstrated that electrochemical properties of poly[Ni(CH3Osalen)]:PSS are highly dependent on the nature of electrolyte solutions. A wider range of electrochemical activity, higher values of conductance and binary diffusion coefficient in TBAPSS solution are observed than in LiClO4, but the capacity values of films are higher in LiClO4 solution. The introduction of PSS− polyanion during synthesis of polymer film induced cationic mode of charge transport for poly[Ni(CH3Osalen)]. This type of PSS− doped polymers can be used as ion-exchange membranes. The combined electrochemical impedance spectroscopy and in situ conductance measurements on interdigitated electrodes were analyzed using the model concepts of Matthias and Haas, and Einstein relation. This novel approach allowed separating the diffusion coefficient into its ionic and electronic constituents. The ionic diffusion was found to be the limiting factor. Strong association of lithium cation with both the PSS− polyanion and methoxy-groups may be the cause of lower values of diffusion coefficients in LiClO4 solutions. The proposed model is suitable for further studies of similar systems.

KW - Electrochemical quartz crystal microbalance

KW - Immobilized dopants

KW - In situ conductance

KW - Nickel salen complexes

KW - Poly(styrenesulfonate)

KW - BEHAVIOR

KW - COMPLEXES

KW - FILMS

KW - NICKEL

KW - CONDUCTIVITY

KW - POLYANILINE

KW - SALEN

KW - ENERGY-STORAGE

KW - ELECTRODE

KW - INDUCED CHARGE

UR - http://www.scopus.com/inward/record.url?scp=85098168021&partnerID=8YFLogxK

U2 - 10.1016/j.electacta.2020.137637

DO - 10.1016/j.electacta.2020.137637

M3 - Article

AN - SCOPUS:85098168021

VL - 368

JO - Electrochimica Acta

JF - Electrochimica Acta

SN - 0013-4686

M1 - 137637

ER -