Ion dynamics into different pore size distributions in supercapacitors under compression

Compressing supercapacitor(SCs)electrode is essential for improving the energy storage characteristics and minimizing ions’distance travel,faradaic reactions,and overall ohmic resistance.Studies comprising the ion dynamics in SC electrodes under compression are still rare.So,the ionic dynamics of five aqueous electrolytes in electrodes under compression were studied in this work for tracking electrochemical and structural changes under mechanical stress.A superionic state is formed when the electrode is compressed until the micropores match the dimensions with the electrolyte’s hydrated ion sizes,which increases the capacitance.If excessive compression is applied,the accessible pore regions decrease,and the capacitance drops.Hence,as the studied hydrated ions have different dimensions,the match between ion/pore sizes differs.To the LiOH and NaClO4electrolytes,increasing the pressure from 60 to 120 and 100 PSI raised the capacitance from 13.5 to 35.2 F g^(-1)and 30.9 to 39.0 F g^(-1),respectively.So,the KOH electrolyte with the lowest and LiCl with the biggest combination of hydrated ion size have their point of maximum capacitance(39.5 and 36.7F g^(-1))achieved at 140 and 80 PSI,respectively.To LiCl and KCl electrolytes,overcompression causes a drop in capacitance higher than 23%.

Boosting energy-storage capability in carbon-based supercapacitors using low-temperature water-in-salt electrolytes

Supercapacitors(SCs) are high-power energy storage devices with ultra-fast charge/discharge properties.SCs using concentrated aqueous-based electrolytes can work at low temperatures due to their intrinsic properties, such as higher freezing point depression(FPD) and robustness. Besides the traditional organic-and aqueous-based(salt-in-water) electrolytes used in SCs, water-in-salt(WISE) sodium perchlorate electrolytes offer high FPD, non-flammability, and low-toxicity conditions, allowing the fabrication of safer, environmentally friendly, and more robust devices. For the first time, this work reports a comprehensive study regarding WISE system’s charge-storage capabilities and physicochemical properties under low-temperature conditions(T < 0 ℃) using mesoporous carbon-based electrodes. The effect of temperature reduction on the electrolyte viscosity and electrical properties was investigated using different techniques and the in-situ(or operando) Raman spectroscopy under dynamic polarization conditions.The cell voltage, equivalent series resistance, and specific capacitance were investigated as a function of the temperature. The cell voltage(U) increased ~ 50%, while the specific capacitance decreased ~20%when the temperature was reduced from 25 ℃ to -10 ℃. As a result, the maximum specific energy(E = CU^(2)/2) increased ~ 100%. Therefore, low-temperature WISEs are promising candidates to improve the energy-storage characteristics in SCs.

Raman probing carbon&aqueous electrolytes interfaces and molecular dynamics simulations towards understanding electrochemical properties under polarization conditions in supercapacitors

Raman probing of carbon electrode and electrolyte under dynamic conditions is performed here using different aqueous electrolytes to elucidate the fundamental events occurring in electrochemical supercapacitor during charge–discharge processes.The areal capacitance ranges from 1.54 to 2.31μF cm^(-2)μm and it is determined using different techniques.These findings indicate that the Helmholtz capacitance governs the overall charge-storage process instead of the space charge(quantum)capacitance commonly verified for HOPG electrodes in the range of~3 to 7μF cm^(-2).Molecular dynamics simulations are employed to elucidate the origin of the reversible Raman spectral changes during the charge–discharge processes.A correlation is verified between the reversible Raman shift and the surface excesses of the different ionic species.A theoretical framework is presented to relate the effect of the applied potential on the Raman shift and its correlation with the surface ionic charge.It is proposed that the Raman shift is governed by the interaction of solvated cations with graphite promoted by polarization conditions.It is the first time that a comparative study on different aqueous electrolyte p H and cation ion size has been performed tracking the Raman spectra change under dynamic polarization conditions and contrasting with comprehensive electrochemistry and dynamic molecular simulations studies.This study shines lights onto the charge-storage mechanism with evidence of Kohn anomaly reduction in the carbon electrode during the reversible adsorption/desorption and insertion/extraction of ionic species.

Direct observation of the CO_(2) formation and C–H consumption of carbon electrode in an aqueous neutral electrolyte supercapacitor by in-situ FTIR and Raman

Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their overall energy storage capabilities.Therefore,the stability of the EDLCs’materials is the primary focus of this study.Since energy storage depends on the specific capacitance,and also on the square of the maximum capacitive cell voltage(UMCV).Thus,electrodes with high specific surface area(SSA)and electrolytes with excellent electrochemical stability are commonly reported in the literature.Aqueous electrolytes are safer and green devices compared to other organic-based solutions.On the other hand,their UMCVis reduced compared to other electrolytes(e.g.,organic-based and ionic liquids).In this sense,spanning the UMCVfor aqueous-based electrolytes is a’hot topic’research.Unfortunately,the lack of protocols to establish reliable UMCVvalues has culminated in the publishing of several conflicting results.Herein,we confirm that multiwalled carbon nanotubes(MWCNTs)housed in cells degrade and produce CO_(2) under abusive polarisation conditions.It is probed by employing electrochemical techniques,in-situ FTIR and in-situ Raman spectroscopies.From these considerations,the current study uses spectro-electrochemical techniques to support the correct determination of the electrode and electrolyte stability conditions as a function of the operating electrochemical parameters.