RESUMEN
Traditional sulfide metallurgy produces harmful sulfur dioxide and is energy intensive. To this end, we develop an anode electrolysis approach in molten salt by which sulfide is electrochemically split into sulfur gas at a graphite inert anode while releasing metal ions that diffuse toward and are deposited at the cathode. The anodic splitting dictates the "sulfide-to-metal ion and sulfur gas" conversion that makes the reaction recur continuously. Using this approach, Cu2S is converted to sulfur gas and Cu in molten LiCl-KCl at 500 °C with a current efficiency of 99% and energy consumption of 0.420 kWh/kg-Cu (only considering the electricity for electrolysis). Besides Cu2S, the anode electrolysis can extract Cu from Cu matte that is an intermediate product from the traditional sulfide smelting process. More broadly, Fe, Ni, Pb, and Sb are extracted from FeS, CuFeS2, NiS, PbS, and Sb2S3, providing a general electrochemical method for sulfide metallurgy.
Asunto(s)
Electrólisis , Sulfuros , Electrodos , Electrólisis/métodos , Grafito , Metales/síntesis química , Sulfuros/química , Azufre/químicaRESUMEN
Reactive metals hydrolysis offers significant advantages for hydrogen storage and production. However, the regeneration of common reactive metals (e.g., Mg, Al, etc.) is energy-intensive and produces unwanted byproducts such as CO2 and Cl2. Herein, we employ Zn as a reactive mediator that can be easily regenerated by electrolysis of ZnO in an alkaline solution with a Faradaic efficiency of >99.9 %. H2 is produced in the same electrolyte by constructing a Zn-H2O hydrolysis battery consisting of a Zn anode and a Raney-Ni cathode to unlock the Zn-H2O reaction. The entire two-step water splitting reaction with a net energy efficiency of 70.4 % at 80 °C and 50â mA cm-2. Additionally, the Zn-H2O system can be charged using renewable energy to produce H2 on demand and runs for 600 cycles only sacrificing 3.76 % energy efficiency. DFT calculations reveal that the desorption of H* on Raney-Ni (-0.30â eV) is closer to zero compared with that on Zn (-0.87â eV), indicating a faster desorption of H* at low overpotential. Further, a 24â Ah electrolyzer is demonstrated to produce H2 with a net energy efficiency of 65.5 %, which holds promise for its real application.
RESUMEN
A reducing agent can reduce Co3+ to Co2+ in LiCoO2, thus increasing the leaching efficiency and extraction rate of Co-based cathode materials from spent lithium-ion batteries (LIBs). Herein, ethanol was employed as the reducing agent to leach LiCoO2 obtained from LIBs in a sulfuric acid solution. The effects of operating temperatures (50-90⯰C), dosage of ethanol (0-20â¯vol%), concentration of sulfuric acid (2-6â¯mol/L), and solid/liquid ratio (10-40â¯â¯g/L) on the leaching efficiency of LiCoO2 were investigated. By adding 5â¯vol% ethanol in a 6â¯mol/L sulfuric acid solution at 90⯰C, the extraction efficiency of Co and Li are both over 99%, meaning that ethanol can reduce Co3+ to Co2+ while the ethanol was oxidized to acetic acid. The dissolution of LiCoO2 obeys the residue layer diffusion control model. Although ethanol is a promising reducing agent, future efforts should pay to the management of the secondary wastewater. Overall, the ethanol can be used as a reducing agent to assist the leaching of cathode materials from spent LIBs.
Asunto(s)
Cobalto , Suministros de Energía Eléctrica , Litio , Reciclaje/métodos , Electrodos , EtanolRESUMEN
Improving cycling stability while maintaining a high initial Coulombic efficiency (ICE) of the antimony (Sb) anode is always a trade-off for the design of electrodes of sodium-ion batteries (SIBs). Herein, we prepare a carbon-free Sb8Bi1 anode with an ICE of 87.1% at 0.1 A g-1 by a one-step electrochemical reduction of Sb2O3 and Bi2O3 in alkaline solutions. The improved ICE of the Sb8Bi1 anode is due to the alloying of bismuth (Bi) that prevents irreversible interfacial reactions during the sodiation process. Unlike carbon buffers, the use of Bi will reduce the number of side reactions between the carbon buffer and sodium. Moreover, Bi2O3 can promote the reduction of Sb2O3 and reduce the particle size of Sb from â¼20 µm to below 300 nm. The electrolytic products can be modulated by controlling the cell voltages and electrolysis time. The electrolytic Sb8Bi1 anode delivered a capacity of 625 mAh g-1 after 200 cycles with an ICE of 87.1% at 0.1 A g-1 and even 625 mAh g-1 at 1 A g-1 over 100 cycles. Hence, alloying Bi into Sb is an effective way to make a long-lasting Sb anode while maintaining a high Coulombic efficiency.
RESUMEN
An environmentally benign vacuum pyrolysis (VP) approach is employed to recover Li and Co from spent LiCoO2-based lithium-ion batteries (LIBs). First, the electroactive materials were separated from the current collector by the VP method from 623 to 823â¯K with an attempt to choose an appropriate temperature. Then, the as-received cathode materials were mixed with different amounts of graphite from the anode to selectively convert LiCoO2 to Co or CoO and Li2CO3 by carbothermic reduction under vacuum and at 873 to 1273â¯K. After carbothermic reduction, the pyrolyzed powder was leached in water to separate Li2CO3 from Co/CoO. By alternating the C/LiCoO2 mass ratio and the pyrolysis temperature, a recovery rate reaches over 93% for Li and 99% for Co. Finally, the recovered CoO and Li2CO3 were used to regenerated LiCoO2 that delivered a specific capacity of 145â¯mAhâ¯g-1 at 1C and retaining 93% of the initial capacity after 100 cycles. Overall, a multi-vacuum-pyrolysis approach offers a closed-loop route for the management of spent LIBs without using any hazardous chemicals.
Asunto(s)
Litio , Pirólisis , Suministros de Energía Eléctrica , Reciclaje , VacioRESUMEN
Recycling of the spent LIBs to extract Li and Co not only offers raw materials for batteries but also lays a sustainable way for battery development. Herein, we adopt a route combining hydrometallurgical and pyro-electrochemical routes to extract Li2CO3 and Co powder from the spent LIBs of cell phones. The LiCoO2-based cathode materials were firstly dissolved in H2SO4 solution containing H2O2 as the reductant, and the optimal conditions for attaining a high extraction rate of 99% were studied. After that, the precipitated Co(OH)2 was calcinated in air under 500 °C to generate Co3O4 which was thereafter electrochemically converted into Co powder and oxygen in molten Na2CO3-K2CO3. Overall, the hybrid method employing both hydro- and pyro-route provides an effective pathway to recover both Li2CO3 and Co powder from spent LIBs.