Anode processes on Pt and ceramic anodes in chloride and oxide-chloride melts

Mullabaev, Albert; Ковров, В. А.; Kholkina, A. S.; Zaikov, Yu. P.

doi:10.1016/j.net.2021.08.034

Cited by 12 publications

(7 citation statements)

References 20 publications

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“…Dense cylindrical ceramic sample of the NiO-(2.5 wt%)Li 2 O composition (Ø10 mm) with an external current lead made of platinum wire was used as a counter electrode. [29][30][31] This ceramic anode material is one of the most promising for the electrolysis of LiCl-Li 2 O melts due to its relative availability and corrosion resistance. The content of Li 2 O in the anode, which provides the required conductivity, was selected empirically.…”

Section: Methodsmentioning

confidence: 99%

“…The content of Li 2 O in the anode, which provides the required conductivity, was selected empirically. 29,30 In order to reduce side reactions of the lithium interaction with the anode material and to maximize the removal of oxygen evolving at the anode, the anode space was shielded with MgO tube. [29][30][31] The measurements were performed using a PGSTAT AutoLab device and Nova 1.11 software (The MetrOhm, Netherlands).…”

Section: Methodsmentioning

confidence: 99%

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Reduction of ZrO₂ in LiCl-Li₂O Melt During Electrolysis

Shishkin¹,

Shishkin²,

Nikolaev³

et al. 2022

J. Electrochem. Soc.

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Reduction of spent nuclear fuel (SNF) components to metals during the electrolysis of the LiCl-Li2O melt at 650°C is extremely important in the framework of the development of fuel reprocessing technology. Here, ZrO2 reduction by lithium during the electrolysis of the LiCl-Li2O melt at 650°C was studied. Cathode processes on a molybdenum substrate in contact with different ZrO2 samples (powder, pressed pellet, dense ceramic) were analyzed using cyclic voltammetry and electrolysis. It was shown that the appearance of ZrO2 near the molybdenum cathode leads to increasing cathode currents and decreasing lithium oxidation current. Both effects indicate the consumption of reduced lithium for the reduction of ZrO2 samples. In order to analyze the reduction products X-ray phase analysis and scanning electron microscopy were used, and to estimate the reduction degree of ZrO2 samples three methods were tested: dissolution of samples in inorganic acid solution, dissolution of samples in EtOAc/Br2 solution, and carbothermal reduction. It was shown that during the electrolysis of dense samples only the lithium zirconate (Li2ZrO3) was formed at their surfaces, whereas the electrolysis of ZrO2 powder samples resulted in the formation of Li2ZrO3, Zr3O, and ZrO phases.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Reduction of ZrO₂ in LiCl-Li₂O Melt During Electrolysis

Shishkin¹,

Shishkin²,

Nikolaev³

et al. 2022

J. Electrochem. Soc.

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“…However, a number of researchers have reported on the significant (about 60% or greater) reduction of REM oxides, including lanthanum and neodymium, to metals in SNF [ 10 , 11 ]. This contradiction may be explained by the erroneous interpretation of the “bromine method” used for the determination of the mass fraction of the REM oxides reduced by metallic lithium [ 12 , 13 , 14 , 15 ]. The analysis of the metallic phase in the simulated nuclear fuel requires a reasonable approach to select an appropriate method for the samples analysis, because the analyzed product is normally composed of a number of metal oxides, which imitate the SNF fission products.…”

Section: Introductionmentioning

confidence: 99%

“…From then on, a dense ceramic anode based on nickel oxide doped by lithium oxide was used in the oxide-chloride melt [ 15 , 16 ], and small amounts of lithium oxide (1.0–1.5 wt.%) were added to the melt. Therefore, the anode reaction acquired the following form: 2O 2− − 4e → O 2(g) …”

Section: Introductionmentioning

confidence: 99%

Electrochemical Reduction of La2O3, Nd2O3, and CeO2 in LiCl-Li2O Melt

et al. 2022

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The reduction of pellets composed of individual CeO2, Nd2O3 and a La2O3-Nd2O3-CeO2 mixture by lithium extracted on a cathode during lithium chloride electrolysis at 650 °C was studied. The methods of cyclic voltammetry, electron microscopy, including determination of the elemental composition of the studied objects, and X-ray diffraction analysis were applied for the present study. The reduction degree of rare-earth metal (REM) oxides was determined using both the bromine method and reduction melting of the samples in the graphite crucible. The formation of the metallic phase composed of the rare-earth elements (REEs) was not observed even at the cathode potentials, corresponding to the formation of the liquid alkali metal phase, and lithium extraction, which, in the quantitative ratio, exceeds greatly the values needed for the reduction reaction. CeO2 was found to reduce to Ce2O3.

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“…Generally, the anode material needs to meet certain requirements, such as good conductivity, stability in molten salt, good electrochemical stability, resistance to corrosion from chlorine gas, oxygen, and oxygen ions, high current density for oxygen ions, good mechanical and thermal stability, low cost, no pollution, and easy assembly. 2,3 Currently, platinum is the most commonly used anode material, [4][5][6][7][8][9][10] followed by graphite. [11][12][13][14][15][16] Other materials include glassy carbon electrode, 17,18 TiN, 19 SnO 2 , 10 BDD, 20 La 0.33 Sr 0.67 MnO 3 , 21,22 NiO, 9,18 nickel ferrite, 2 Inconel 600 and 700, 23 stainless steel alloy 316, 23 W, 23 Mo, 23 Ni, 24 Fe-36Ni, 25 Ti, 23 Sb, 26 Rh, 6 Pd, 6 Ir, 4,6 Au 6 and etc.…”

mentioning

confidence: 99%

A Liquid Alloy Anode for the Electrolytic Reduction of Uranium Oxide in Molten Lithium Chloride

Yao,

Xiao,

Jia

et al. 2024

J. Electrochem. Soc.

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A cost-effective anode material for uranium oxide electrolytic reduction in lithium chloride is still in deficiency. In this work, the application of liquid lithium-bismuth alloy anode was investigated. In the LiCl electrolyte at 923 K, UO2 was reduced electrochemically in cathode, while Li-Bi alloy served as counter electrode. Partial reduction of UO2 was verified by X-ray powder diffraction when the cathode potential was intentionally controlled above the lithium reduction potential. In contrast, when the precipitation of lithium metal was intentionally controlled, the reduction of UO2 was significantly improved. The charge transfer coefficient of UO2/U reaction was also calculated. Regeneration of Li-Bi alloy in LiCl-Li2O through electrolysis was proposed. Carbon, gold, and platinum had been investigated as anode materials. According to the potential variation curve, lithium was not effectively reduced into bismuth as in pure LiCl when oxygen ion was present in the molten salt. These three materials failed to demonstrate advantage in the regeneration of Li-Bi alloy.

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Anode processes on Pt and ceramic anodes in chloride and oxide-chloride melts

Cited by 12 publications

References 20 publications

Reduction of ZrO₂ in LiCl-Li₂O Melt During Electrolysis

Reduction of ZrO₂ in LiCl-Li₂O Melt During Electrolysis

Electrochemical Reduction of La2O3, Nd2O3, and CeO2 in LiCl-Li2O Melt

A Liquid Alloy Anode for the Electrolytic Reduction of Uranium Oxide in Molten Lithium Chloride

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Anode processes on Pt and ceramic anodes in chloride and oxide-chloride melts

Cited by 12 publications

References 20 publications

Reduction of ZrO2 in LiCl-Li2O Melt During Electrolysis

Reduction of ZrO2 in LiCl-Li2O Melt During Electrolysis

Electrochemical Reduction of La2O3, Nd2O3, and CeO2 in LiCl-Li2O Melt

A Liquid Alloy Anode for the Electrolytic Reduction of Uranium Oxide in Molten Lithium Chloride

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Reduction of ZrO₂ in LiCl-Li₂O Melt During Electrolysis

Reduction of ZrO₂ in LiCl-Li₂O Melt During Electrolysis