Thermodynamics and Efficiency of a CuCl(aq)/HCl(aq) Electrolyzer

被引：36

作者：

Hall, Derek M. ^{[1
,2
]}

Akinfiev, Nikolay N. ^{[3
]}

LaRow, Eric G. ^{[1
,2
]}

Schatz, Richard S. ^{[1
,2
]}

Lvov, Serguei N. ^{[1
,2
,4
]}

机构：

[1] Penn State Univ, EMS Energy Inst, University Pk, PA 16802 USA

[2] Penn State Univ, Dept Energy & Mineral Engn, University Pk, PA 16802 USA

[3] Russian Acad Sci, Inst Geol Ore Deposits Petrog Mineral & Geochem, Moscow 119017, Russia

[4] Penn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA

来源：

ELECTROCHIMICA ACTA | 2014年 / 143卷

关键词：

Copper-chlorine (Cu-Cl) hybrid thermochemical cycle; CuCl(aq)/HCl(aq) electrolytic cell; Decomposition potential; Voltage; Current; Thermodynamic and overall efficiencies; GIBBS ENERGY MINIMIZATION; HYDROGEN-PRODUCTION; ACTIVITY-COEFFICIENTS; CUCL ELECTROLYZER; HIGH-PRESSURES; THEORETICAL PREDICTION; AQUEOUS-ELECTROLYTES; TEMPERATURES; MOLAL; STANDARD;

D O I：

10.1016/j.electacta.2014.08.018

中图分类号：

O646 [电化学、电解、磁化学];

学科分类号：

081704 ;

摘要：

The high ionic strength and complex speciation of the anolyte solution within the CuCl(aq)/HCl(aq) electrolytic cell have impeded predictions of the energy requirements for the cell's electrolytic reaction at 25 degrees C and 1 bar. After collecting experimental open circuit potential (OCP) data and comparing the values obtained with predictions from prospective thermodynamic models, an approach to predict thermodynamic values and the overall efficiency was formulated. The compositions of the experimental measurements ranged from 2-2.5 mol of CuCl(aq) with 8-9 mol of HCl(aq) per kilogram of water in anolyte solution and 8-9 mol of HCl(aq) per kilogram of water in catholyte solution. From the OCP data, it was found that activity coefficient and speciation effects were critical in predicting the Gibbs energy, entropy and thermodynamic (intrinsic maximum) efficiency of the electrolytic cell. At equilibrium, all thermodynamic functions of the anolyte redox reactions were the same after activity coefficients and speciation effects were taken into account. The electrochemical reactions' Gibbs energy and entropy were found to be 9700 J/mol and 2.18 J/(mol K) at 25 degrees C and 1 bar, which indicated that the reactions required a small amount of electrical and thermal energy to proceed. With thermodynamic values for the electrolytic reaction and experimental data from a CuCl(aq)/HCl(aq) electrolytic cell, the voltage, current, thermodynamic and overall efficiency were calculated. The overall efficiency ranged from 15 to 95% depending on the current density. (C) 2014 Elsevier Ltd. All rights reserved.

引用

页码：70 / 82

页数：13

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