TY - JOUR

T1 - Revealing the causes of degradation of an asymmetric ionic liquid supercapacitor with a composite polyaniline/carbon electrode

AU - Lebedeva, Marina V.

AU - Gribov, Evgenii N.

N1 - The synthesis and electrochemical study of Pani-C was carried out with the financial support of Ministry of Science and Higher Education of the Russian Federation within the governmental order for Novosibirsk State University (project FSUS-2022-0022 ). Investigation of physico-chemical characteristics was carried out with the financial support of Ministry of Science and Higher Education of the Russian Federation within the governmental order for Boreskov Institute of Catalysis (project АААА-А21–121011390006–0 ).

PY - 2023/11/15

Y1 - 2023/11/15

N2 - The extended window of electrochemical stability of ionic liquids and the high specific capacitance values of activated carbon (AC)/conductive polymer (polyaniline, Pani) composite materials are promising approaches to improve the performance of supercapacitors (SC). In this work, we studied the stability of an asymmetric AC//Pani-C cell with 1 M solution of 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) in acetonitrile as an electrolyte. Pani-C (56 wt% of Pani) composite was prepared by oxidative polymerization of aniline in the presence of high surface area AC (SBET = 2300 m2‧g−1). Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission and scanning electron microscopies data confirmed the formation of Pani-C composite. Combination of cyclic voltammetry, galvanostatic charge/discharge method, and electrochemical impedance spectroscopy in 2- and 3-electrode cell configurations gave information about anodic (1 V vs. Ti) and cathodic (−1.8 V vs. Ti) potential limits of electrochemical stability, and potential of zero charge of Pani-C and AC. From these data, optimal mass ratio of Pani-C and AC electrodes was obtained for asymmetric SC assembly. It was found that after 500 charge/discharge cycles, the capacitance of the asymmetric AC//Pani-C SC decreased by 15% from 46.8 to 39.9 F·g−1 as a result of Pani-C degradation. The specific capacitance of AC remained virtually unchanged (decreased from 144 to 141 F·g−1), while that of Pani-C decreased by 8.7% from 230 to 210 F·g−1. Electrochemical measurements showed that degradation is accompanied by an increase in the working potential window of Pani-C (from 0.85 V to 0.97 V) and a shift in Emin…Emax working potentials from 0.15 … 1 to 0.52 … 1.49 V vs. Ti in the beginning and in the end of stability test, respectively. The last region is related to the potential for non-conductive pernigraniline formation (1.3 V vs. Ti). It was shown that the main reason of AC//Pani-C SC capacitance decay is a gradual increase in the operating potential window with a constantly shifts towards anodic values of positive Pani-C electrode, which resulted in accumulation of nonconductive polymer form that does not participate in charge accumulation.

AB - The extended window of electrochemical stability of ionic liquids and the high specific capacitance values of activated carbon (AC)/conductive polymer (polyaniline, Pani) composite materials are promising approaches to improve the performance of supercapacitors (SC). In this work, we studied the stability of an asymmetric AC//Pani-C cell with 1 M solution of 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) in acetonitrile as an electrolyte. Pani-C (56 wt% of Pani) composite was prepared by oxidative polymerization of aniline in the presence of high surface area AC (SBET = 2300 m2‧g−1). Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission and scanning electron microscopies data confirmed the formation of Pani-C composite. Combination of cyclic voltammetry, galvanostatic charge/discharge method, and electrochemical impedance spectroscopy in 2- and 3-electrode cell configurations gave information about anodic (1 V vs. Ti) and cathodic (−1.8 V vs. Ti) potential limits of electrochemical stability, and potential of zero charge of Pani-C and AC. From these data, optimal mass ratio of Pani-C and AC electrodes was obtained for asymmetric SC assembly. It was found that after 500 charge/discharge cycles, the capacitance of the asymmetric AC//Pani-C SC decreased by 15% from 46.8 to 39.9 F·g−1 as a result of Pani-C degradation. The specific capacitance of AC remained virtually unchanged (decreased from 144 to 141 F·g−1), while that of Pani-C decreased by 8.7% from 230 to 210 F·g−1. Electrochemical measurements showed that degradation is accompanied by an increase in the working potential window of Pani-C (from 0.85 V to 0.97 V) and a shift in Emin…Emax working potentials from 0.15 … 1 to 0.52 … 1.49 V vs. Ti in the beginning and in the end of stability test, respectively. The last region is related to the potential for non-conductive pernigraniline formation (1.3 V vs. Ti). It was shown that the main reason of AC//Pani-C SC capacitance decay is a gradual increase in the operating potential window with a constantly shifts towards anodic values of positive Pani-C electrode, which resulted in accumulation of nonconductive polymer form that does not participate in charge accumulation.

KW - Activated carbon

KW - Asymmetric supercapacitor

KW - BMIMBF4

KW - Composite material

KW - Ionic liquid

KW - Polyaniline

KW - Potential of zero charge

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85171845702&origin=inward&txGid=1fae8ac4f7b45a3dcfe182802382d065

UR - https://www.mendeley.com/catalogue/39071547-e6a6-3f9d-9fa7-b36b6ac926db/

U2 - 10.1016/j.ssi.2023.116353

DO - 10.1016/j.ssi.2023.116353

M3 - Article

VL - 401

JO - Solid State Ionics

JF - Solid State Ionics

SN - 0167-2738

M1 - 116353

ER -