Calorimetry can detect the early onset of hydrolysis in hybrid supercapacitors with aqueous electrolytes

Frajnkovič, Matevž; Likitchatchawankun, Ampol; Douard, Camille; Zhou, Yucheng; Baek, Sun Woong; Catton, Ivan; Crosnier, Olivier; Brousse, Thierry; Pilon, Laurent

doi:10.1016/j.jpowsour.2022.232069

Calorimetry can detect the early onset of hydrolysis in hybrid supercapacitors with aqueous electrolytes

Journal Article · Fri Sep 16 00:00:00 EDT 2022 · Journal of Power Sources

DOI:https://doi.org/10.1016/j.jpowsour.2022.232069· OSTI ID:2421229

^[1]; Likitchatchawankun, Ampol ^[2]; Douard, Camille ^[3]; Zhou, Yucheng ^[4]; Baek, Sun Woong ^[4]; Catton, Ivan ^[4]; Crosnier, Olivier ^[3]; Brousse, Thierry ^[3]; ^[4]

Univ. of California, Los Angeles, CA (United States); OSTI
King Mongkut's University of Technology, Bangkok (Thailand)
Nantes Université (France); Centre National de la Recherche Scientifique (CNRS) (France); Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amiens (France)
Univ. of California, Los Angeles, CA (United States)

This study investigates the effect of cation species on the onset of electrolyte hydrolysis in hybrid supercapacitors with aqueous electrolytes using isothermal operando calorimetry. The cells consisted of a positive α-MnO₂ cryptomelane electrode and a negative activated carbon (AC) electrode with either 0.5 M K₂SO₄ or 0.5 M Cs₂SO₄ aqueous electrolytes. They were characterized using cyclic voltammetry and galvanostatic cycling. In addition, the instantaneous heat generation rate at each electrode was measured using a custom isothermal operando calorimeter. Heat generation associated with resistive losses (Joule heating) and reversible ion adsorption/desorption was clearly identified. For larger potential windows, an endothermic dip, attributed to the onset of hydrolysis, was observed at the positive α-MnO₂ electrode where K⁺ and Cs⁺ ions engaged in fast surface redox reactions. Interestingly, this endothermic dip appeared at 1.8 V and 2.0 V for K₂SO₄ and Cs₂SO₄ aqueous electrolytes, respectively. The difference in the stable operating potential window was attributed to thinner solvation shell around Cs⁺ cation than for K⁺ thus reducing the amount of water present near the electrodes as ions partially shed their solvation shells during adsorption. The early onset of hydrolysis could be observed by isothermal operando calorimetry before it could be observed with conventional electrochemical methods.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019381

OSTI ID:: 2421229

Journal Information:: Journal of Power Sources, Journal Name: Journal of Power Sources Vol. 548; ISSN 0378-7753

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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42 ENGINEERING
Aqueous electrolyte
Hybrid supercapacitor
Hydrolysis
Isothermal operando calorimetry
MnO2 cryptomelane

Calorimetry can detect the early onset of hydrolysis in hybrid supercapacitors with aqueous electrolytes

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