Progress of international hydrogen production network for the thermochemical Cu–Cl cycle

Naterer, G.F.; Suppiah, S.; Stolberg, L.; Lewis, Michele A.; Wang, Z.; Dinçer, İbrahim; Rosen, Marc A.; Gabriel, Kamiel; Secnik, E.; Easton, E. Bradley; Pioro, Igor; Lvov, Serguei N.; Jiang, Jin; Mostaghimi, J.; Ikeda, B.M.; Rizvi, Ghaus; Lu, Lixuan; Odukoya, A.; Spekkens, P.; Fowler, Michael; Avsec, Jurij

doi:10.1016/j.ijhydene.2012.10.023

Cited by 62 publications

(30 citation statements)

References 45 publications

(21 reference statements)

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“…The large difference in Cu I bulk concentrations in combination with the observed high current densities and limiting currents suggested that this species was a likely candidate as an electrochemically active species. Given the high concentrations of CuCl 3 2− (aq) and CuCl 3 − (aq) from thermodynamic speciation calculations, Equation 3 is the simplest form of a possible anode reaction, written in its reduction form:…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Kinetics of CuCl(aq)/HCl(aq) Electrolyzer for Hydrogen Production via a Cu-Cl Thermochemical Cycle

Hall

LaRow

Schatz

et al. 2014

J. Electrochem. Soc.

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An electrochemical kinetics investigation of the CuCl(aq)/HCl(aq) electrolyzer identified methods to significantly reduce the platinum loadings required to achieve a high cell current density of 0.5 A/cm 2 at 0.7 V. As the CuCl(aq)/HCl(aq) electrolyzer is a key component of the Cu-Cl thermochemical cycle, the economic viability of the Cu-Cl thermochemical cycle was significantly improved by reducing the loading required to achieve 0.5 A/cm 2 . Electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) with a rotating disc electrode were employed to investigate the kinetics of the aqueous Cu II /Cu I chloride complexes reaction on platinum and glassy carbon using a three-electrode cell. It was found that the standard exchange current density of the anodic Cu II /Cu I electrochemical reaction on platinum, 4-12 A/cm 2 , was significantly larger than the values reported for the HER cathodic reaction thus far. In addition, SEM was used to observe the effectiveness of different catalyst application techniques. Through SEM observations, and electrochemical data analysis, the amount of platinum used in a laboratory scale CuCl(aq)/HCl(aq) electrolyzer was reduced from 0.8 mg/cm 2 applied to both electrodes to 0.4 mg/cm 2 on the cathode and zero at the anode while still maintaining a current density of 0.5 A/cm 2 at 0.7 V of applied potential difference. As interest in an energy storage option capable of storing both thermal and electrical energy produced via solar resources increases, low temperature hybrid thermochemical cycles are becoming an attractive candidate to fill this role. In particular, the Cu-Cl hybrid thermochemical cycle's high efficiency and moderate temperature requirements have established itself as a promising option for inexpensive hydrogen generation through harnessing excess thermal and electrical energy from solar resources.1 In addition to utilizing excess energy, the Cu-Cl thermochemical cycle provides a means of efficiently producing hydrogen gas not reliant on fossil fuels.The Cu-Cl hybrid thermochemical cycle uses a number of intermediate compounds, heat, and a small amount of electrical energy, within a series of physical and chemical reactions to split water into hydrogen and oxygen.2-10 One of the most important components in the hybrid cycle is the CuCl(aq)/HCl(aq) electrolytic cell. 11 In the electrolytic step of this cycle, the general electrochemical reaction consists of an anode reaction in which aqueous Cu I chloride complex species are oxidized to aqueous Cu II chloride complex species, and a cathode reaction in which HCl(aq) is reduced to H 2 (aq) with transfer of H + (aq) through a cation conductive membrane. This process is usually simplified as follows:To increase the solubility of CuCl(s) in the anolyte, a high concentration of HCl(aq) is typically used. Similarly, the catholyte comprises of highly concentrated HCl(aq) to avoid copper deposition at the cathode. 9Previous research established an electrolytic cell design that employed membrane electrode assemb...

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Section: Resultsmentioning

confidence: 99%

Electrochemical Kinetics of CuCl(aq)/HCl(aq) Electrolyzer for Hydrogen Production via a Cu-Cl Thermochemical Cycle

Hall

LaRow

Schatz

et al. 2014

J. Electrochem. Soc.

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“…In the Cu-Cl cycle, water is decomposed into hydrogen and oxygen through intermediate Cu-Cl compounds [1,2]. Nuclear-based ''water splitting'' requires an intermediate heat exchanger between the nuclear reactor and hydrogen plant, which transfers heat from the reactor coolant to the thermochemical cycle.…”

Section: Thermochemical Hydrogen Production Cyclementioning

confidence: 99%

“…The dilute gas dynamic viscosity for CLS model is written as [2,3,[14][15][16][17][18][19][20][21][22][23]:…”

Section: Thermodynamic and Transport Properties Of Statementioning

confidence: 99%

“…(2) is extended to account for the effects of temperature and pressure by developing an empirically correlated function of density and temperature as shown below [2,3,[18][19][20][21][22][23]:…”

Section: Thermodynamic and Transport Properties Of Statementioning

confidence: 99%

“…We used the Taxman theory [2,3,[22][23][24] which solved the problem of influence of internal degrees of freedom on the basis of WCUB theory [8] and the approximations given by Mason and Moschick [22]. The presented expression is more accurate than the Eucken correction, and the equation is supported with theory.…”

Section: Thermodynamic and Transport Properties Of Statementioning

confidence: 99%

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Thermodynamic and transport properties of fluids and solids in a Cu–Cl solar hydrogen cycle

Avsec

Wang

Naterer

2016

J Therm Anal Calorim

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Sustainable methods of clean fuel production are needed in the face of depleting oil reserves and to reduce carbon dioxide emissions. The technology of fuel cells for electricity production or the transport sector is already developed. However, a key missing element is a large-scale economical method of hydrogen production. The Cu-Cl thermochemical cycle is a promising thermochemical cycle to produce hydrogen. This paper focuses on a copper-chlorine (Cu-Cl) cycle and solar hydrogen production technology and describes the models how to calculate thermodynamic and transport properties. This paper discusses the mathematical model for computing the thermodynamic properties for pure substances and their mixtures such as CuCl in the solid phase with an aid of statistical thermodynamics and kinetic theory. The developed mathematical model takes into account vibrations of atoms in molecules and intermolecular forces. This mathematical model can be used for the calculation of thermodynamic properties of polyatomic crystals on the basis of the Einstein and Debye equations. We developed the model in the lowtemperature and high-temperature region. All analytical data are compared with experimental results, and these show good agreement. For the transport properties, we have used kinetic theory. For fluid phase, we have calculated viscosity and thermal conductivity on the basis of the Chung-LeeStarling kinetic model; for the solid phase, we have developed a model for calculations of thermal conductivity on the basis of electron and phonon contributions.

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Thermal spray coatings for molten salt facing structural parts and enabling opportunities for thermochemical cycle electrolysis

Faisal,

Rajendran,

Prathuru

et al. 2024

Engineering Reports

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Thermochemical water splitting stands out as the most efficient techniques to produce hydrogen through electrolysis at a high temperature, relying on a series of chemical reactions within a loop. However, achieving a durable thermochemical cycle system poses a significant challenge, particularly in manufacturing suitable coating materials for reaction vessels and pipes capable of enduring highly corrosive conditions created by high‐temperature molten salts. The review summarizes thermally sprayed coatings (deposited on structural materials) that can withstand thermochemical cycle corrosive environments, geared towards nuclear thermochemical copper–chlorine (CuCl) cycles. An assessment was conducted to explore material composition and selection (structure–property relations), single and multi‐layer coating manufacturing, as well as corrosion environment and testing methods. The aim was to identify the critical areas for research and development in utilizing the feedstock materials and thermal spray coating techniques for applications in molten salt thermochemical applications, as well as use lessons learnt from other application areas (e.g., nuclear reaction vessels, boilers, waste incinerators, and aero engine gas‐turbine) where other types of molten salt and temperature are expected. Assessment indicated that very limited sets of coating‐substrate system with metallic interlayer is likely to survive high temperature corrosive environment for extended period of testing. However, within the known means and methods, as well as application of advanced thermal spray manufacturing processes could be a way forward to have sustainable coating‐substrate assembly with extended lifetime. Spraying multi‐layered coating (nano‐structured or micro‐structured powder materials) along with the application of modern suspension or solution based thermal spray techniques are considered to result in dense microstructures with improved resistance to high temperature thermochemical environment.

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Progress of international hydrogen production network for the thermochemical Cu–Cl cycle

Cited by 62 publications

References 45 publications

Electrochemical Kinetics of CuCl(aq)/HCl(aq) Electrolyzer for Hydrogen Production via a Cu-Cl Thermochemical Cycle

Electrochemical Kinetics of CuCl(aq)/HCl(aq) Electrolyzer for Hydrogen Production via a Cu-Cl Thermochemical Cycle

Thermodynamic and transport properties of fluids and solids in a Cu–Cl solar hydrogen cycle

Thermal spray coatings for molten salt facing structural parts and enabling opportunities for thermochemical cycle electrolysis

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