Some industries usually reduce the concentration of protons in acidic wastewater by conducting neutralization reactions and/or adding seawater to industrial effluents. This work proposes a novel electrochemical system that can harvest energy originating from entropic changes due to alteration in the concentration of sodium ions along wastewater treatment. Preparation of a self-assembled material from nickel Prussian blue analogue (NPBA) was the first step to obtain such electrochemical system. Investigation into the electrochemical properties of this material helped to evaluate its potential use in neutralization and mixing entropy batteries. Assessment of parameters such as the potentiodynamic profile of the current density as a function of the concentration of protons and sodium ions, charge capacity, and cyclability as well as the reversibility of the sodium ion electroinsertion process aided estimation of the energy storage efficiency of the system. Frequency-domain measurements and models and the proposed charge compensation mechanism provided the rate constants at different dc potentials. After each charge/discharge cycle, the NPBA electrode harvested 12.4 kJ per mol of intercalated sodium ion in aqueous solutions of NaCl at concentrations of 20 mM and 3.0 M. The full electrochemical cell consisted of an NPBA positive electrode and a negative electrode of silver particles dispersed in a polypyrrole electrode. This cell extracted 16.8 kJ per mol of intercalated ion after each charge/discharge cycle. On the basis of these results, the developed electrochemical system should encourage wastewater treatment and help to achieve sustainable growth.
We propose novel pseudocapacitors that can store energy related to the partial entropy change associated with proton concentration variations following neutralization reactions. In this situation, it is possible to obtain electrochemical energy after the complete charge/discharge cycle conducted in electrolytic solutions with different proton concentrations. To this end, we prepared modified electrodes from phosphomolybdic acid (PMA), poly(3,4-ethylenedioxythiophene/poly(styrenesulfonate) (PEDOT-PSS), and polyallylamine (PAH) by the layer-by-layer (LbL) method and investigated their electrochemical behavior, aiming to use them in these neutralization pseudocapacitors. We analyzed the potentiodynamic profile of the current density at several scan rates, to evaluate the reversibility of the proton electroinsertion process, which is crucial to maximum energy storage efficiency. On the basis of the proposed reaction mechanism and by using frequency-domain measurements and models, we determined rate constants at different potentials. Our results demonstrated that the conducting polymer affects the self-assembled matrixes, ensuring that energy storage is high (22.5 kJ mol(-1)). The process involved neutralization of a hydrochloric acid solution from pH = 1 to pH = 6, which corresponds to 40% of the neutralization enthalpy.
This study proposes a thermodynamic machine that operates between acid and basic reservoirs in four stages. Two of these stages are buffered isothermal steps. The other two stages constitute an open system and allow the passage of acid and base. The machine consists of a neutralization pseudocapacitor that, after a full cycle, carries out work generated from partial change in entropy associated with a change in the hydrogen potential after the neutralization process. Thermodynamic formalism is presented under reversible stages. This presentation enables determination of the maximum efficiency, related to the difference between the hydrogen potential of the acid reservoir and of the resulting solution after neutralization in the machine. Hence, the hydrogen potential scale can be defined as a function of the efficiency of the reversible acid−base machine regardless of the electrochemical cell composition. Electroactive thin films formed from phosphomolybdic acid and poly(3,4ethylenedioxythiophene) have been investigated as proof of concept in electrolytic solutions at several pH values; their efficiency was close to the efficiency predicted by the thermodynamic approach. Therefore, this model allows one to estimate the maximum energy harvesting of neutralization pseudocapacitors and financial return for the treatment of acid wastewater, contributing to sustainable growth.
We have developed an electrochemical system that performs electrical work due to changes in alkaline ion and proton activities associated with acidic solution neutralization. This system can be used to treat wastewater, contributing to sustainable growth. The system includes an electrochemical machine that operates between an acidic and a basic reservoir to produce work in cycles comprising four stages: two isothermal ionic insertion/de-insertion steps and two steps involving acid and base injection. On the basis of the mixing free energy associated with the reaction free energy, we have developed the thermodynamic formalism by considering reversible electrochemical processes to determine the maximum work performed by this acid-base machine and the efficiency. Electrochemical methods in the time and frequency domains helped in investigating the kinetics of sodium ions and proton insertion in host matrices consisting of copper hexacyanoferrate and phosphomolybdic acid, respectively, to improve our understanding of the factors underlying dissipation as a function of pH and pNa. The full cell composed of these insertion electrodes was used as a proof of concept. It performed a maximum work of 26.4 kJ per mol of electro-inserted ion from HCl solution neutralization with the addition of NaOH, to simulate acidic wastewater treatment in a profitable and sustainable way.
We prepared self-assembled materials consisting of TiO 2 nanoparticles, N,O-carboxymethylchitosan (NOCMCh), and poly(ethylene oxide) (PEO) by the layer-by-layer (LbL) technique, aiming to employ them as modified electrodes under high lithium ion electroinsertion rate. Electrostatic interaction between the components promoted growth of visually uniform TiO 2 /NOCMCh films with highly controlled thickness. We used NOCMCh to produce a polymeric mixture with PEO to incorporate the polyether into the self-assembled structure during the preparation of the LbL TiO 2 /NOCMCh/PEO films. Scanning electron microscopy (SEM) and contact angle measurements between the electrolytic solution and the thin films surface suggested that the polymers affected the mean size of the aggregates and the permeation of the electrolytic solution into the host matrix, leading to greater electrolytic connection between the TiO 2 sites. Chronopotentiometric curves and the differential capacities recorded as a function of the potential under several applied current densities indicated higher charge capacity and absorbance changes (ΔA) for the TiO 2 /NOCMCh/PEO electrode. We employed the potentiostatic intermittent titration technique (PITT) to determine the chemical diffusion coefficient (D c ) associated with electron and lithium ion diffusion in the host matrices. To investigate the independent motion of these charge carriers in the absence of an internal electrical field, we also obtained the Wagner factor (W) and the lithium (D Li ) and electron (D e ) self-diffusion coefficients. Spectroelectrochemical measurements also indicated higher coloration front rate due to lithium ion transport in the TiO 2 /NOCMCh/PEO electrodes. The electrochemical impedance spectroscopy (EIS) measurements suggested trapping effects and anomalous diffusion, which contributed to a better understanding of the role that polymeric components play in charge transport within the self-assembled materials under high electroinsertion rate.
Ever-rising energy demand, fossil fuel dependence, and climate issues have harmful consequences to the society. Exploring clean and renewable energy to diversify the world energy matrix has become an urgent matter. Less explored or unexplored renewable energy sources like the salinity and proton gradient energy are an attractive alternative with great energy potential. This paper discusses important electrochemical systems for energy conversion from natural and artificial concentration gradients, namely capacitive mixing (CapMix), mixing entropy batteries (MEB), and neutralization batteries (NB); the working principle and thermodynamic formalism of these systems; and the materials employed in the assembly of these systems.
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