A review on liquid metals as cathodes for molten salt/oxide electrolysis

Compared with solid metals,liquid metals are considered more promising cathodes for molten slat/oxide electrolysis due to their fascinating advantages,which include strong depolarization effect,strong alloying effect,excellent selective separation,and low operating temperature.In this review,we briefly introduce the properties of the liquid metal cathodes and their selection rules,and then summarize development in liquid metal cathodes for molten salt electrolysis,specifically the extraction of Ti and separation of actinides and rare-earth metals in halide melts.We also review recent attractive progress in the preparation of liquid Ti alloys via molten oxide electrolysis by using liquid metal cathodes.Problems related to high-quality alloy production and large-scale applications are cited,and several research directions to further improve the quality of alloys are also discussed to realize the industrial applications of liquid metal cathodes.

Enhanced electrodeposition and separation of metallic Cr from soluble K2CrO4 on a liquid Zn cathode

Carbon contamination and the formation of low-valence oxides limit the preparation of refractory metals by molten salt electrolysis.In this paper,a liquid Zn cathode is adopted for the electrochemical reduction of soluble K2CrO4 to metallic Cr in CaCl2-KCl molten salt.It is found that CrO4^2-can be directly electrochemically reduced to Cr via a six-electron-transfer step and low-valence Cr oxides is hardly produced.The reduction rate is obviously increased from 16.7 mgCrh^-1cm^-2 on the solid Mo cathode to58.7 mgCrh-1cm-2on liquid Zn cathode.The electrodeposited Cr is distributed in liquid Zn cathode.Carbon contamination is effectively avoided due to the negligible solubility of carbon in the liquid Zn cathode.Furthermore,Cr can be effectively separated and enriched to the bottom of liquid Zn under supergravity field,realizing the efficient acquisition of metallic Cr and recycling of liquid Zn.The method herein provides a promising route for the preparation of refractory metals with high-purity by molten salt electrolysis.

Development of a novel electrolytic process for producing high-purity magnesium metal from magnesium oxide using a liquid tin cathode

The current electrolytic processes for magnesium(Mg)metal have several disadvantages,such as anhydrous magnesium chloride(MgCl_(2))preparation and generation of harmful chlorine(Cl_(2))gas.To overcome these drawbacks,a novel Mg production process to produce high-purity Mg metal directly from magnesium oxide(MgO)was investigated in this study.The electrolysis of MgO was conducted using a liquid tin(Sn)cathode and a carbon(C)anode in the eutectic composition of a magnesium fluoride(MgF_(2))-lithium fluoride(LiF)molten salt under an applied voltage of 2.5 V at 1053-1113 K.Under certain conditions,the Mg-Sn alloys with Mg_(2)Sn and Mg(Sn)phases were obtained with a current efficiency of 86.6%at 1053 K.To produce high-purity Mg metal from the Mg-Sn alloy,vacuum distillation was conducted at 1200-1300 K for a duration of 5-10 h.Following the vacuum distillation,the concentration of Mg in the Mg-Sn alloy feed decreased from 34.1 to 0.17 mass%,and Mg metal with a purity of 99.999%was obtained at 1200 K.Therefore,the electrolytic process developed here is feasible for the production of high-purity Mg metal from MgO using an efficient method.

Preparation of CTS Coatings Containing Calcium and Phosphorus on Titanium Surface by the Cathode Liquid Phase Plasma Technology

Chitosan （CTS） coatings contained calcium （Ca） and phosphorus （P） on titanium （Ti） surface are prepared by the cathode liquid phase plasma technology （CLPT）, in a certain concentration electrolyte solution with selective additions of ammonium dihydrogen phosphate and calcium nitrate. It is indicated that the parameters for a stable discharge are voltage of 400 V, frequency of 100 Hz, duty cycle of 30% based on a large amount of experiment data. The morphology, structure and composition of the coated samples are studied by SEM, FTIR, XRD, XPS. The results demonstrate that the composite coatings are uniform, and some solid particles of inorganic salt containing calcium and phosphorus dispersed on the coatings. CA tests show that the samples treated by the liquid plasma became less hydrophilic. The variation of hydrophilicity on the CLPT treated titanium is attributed to the change of the function groups on the sample surface. Meanwhile, a possible formation mechanism of the composite coatings is discussed.

Electroextraction of neodymium from LiCl-KCl melt using binary liquid Ga-Al cathode

The electrochemical behaviour of Nd(Ⅲ)ion was investigated on inert W,active Ga and Ga-AI cathodes.It is established that the reduction of Nd(Ⅲ)ion on the inert electrode is a consecutive two-step process while that on the active electrodes is a one-step process.The apparent standard potential of the Nd(Ⅲ)/Nd redox couple at different temperatures was determined by open-circuit chronopotentiometry and semi-differential method,and the relationship between temperature and apparent standard potential was further discussed.The thermodynamic properties of Nd in Ga and Ga-Al electrodes such as activity coefficient and activity were evaluated via intermittent coulomb titration and temperature dependence test,and the effect of temperature on activity coefficient was verified.Finally,Nd was successfully extracted in form of alloy from molten salt by galvanostatic electrolysis,in which the current efficiency of91.7%for the electroextraction indicates that the binary liquid Ga-Al electrode has favorable performance.

An amorphous carbon-graphite composite cathode for long cycle life rechargeable aluminum ion batteries

Natural graphite is investigated as the cathode for aluminum ion batteries in recent years. However, some drawbacks of the natural graphite such as severe volume swelling shorten its lifetime, In this work, we prepared a composite material by depositing an amorphous carbon on the graphite paper, The composite was used as a cathode to study the electrochemical performance in aluminum ion batteries. The charge/discharge results showed that the composite could exhibit a longer cycle life than the graphite paper, Electrochemical analyses demonstrated that the interface between the amorphous carbon and the graphite paper made a major contribution to the improvement of the cycling stability.