Due to the ability of LiFePO4 (LFP) to be charged with large currents, LFP batteries are widely used in household appliances and electric vehicles, so the recycling of spent LFP batteries becomes an urgent need. First, they contain toxic components of electrolyte that cannot be buried in landfills; secondly, the cost of lithium which contains in the electrode material continuously increases, and therefore its return to circulation is profitable and expedient. To achieve this goal, much attention is paid to hydrometallurgical processing based on the chemical extraction of Li2CO3 and FePO4 during the regeneration of the electrode material. Here we report on the wet chemistry recycling of used LFP batteries. The main task of the work was to simplify the LiFePO4 regeneration process by leaching with a solution of citric acid due to the elimination of the stage of isolation of Li2CO3 and FePO4, i.e. without selective separation of the filtrate components. The source of spent LiFePO4 was an industrial lithium iron phosphate battery failed due to an internal short circuit. It was found that using citric acid in the ratio H3Cit:LiFePO4=0.5:1, it is possible to efficiently and quickly separate the electrode material from the aluminum current collector. Further pyrolysis and heat treatment of the citrate solution makes it possible to obtain a high-purity LiFePO4/C composite material without extraneous impurities, except for amorphous carbon, which is formed during the pyrolysis of iron (II) and lithium citrates and the thermal decomposition of the binding material in an inert atmosphere. The specific capacity of the LiFePO4/C composite material recovered by the proposed method (145 mA∙h/g) insignificantly differs from that of commercial analogues. This, in our opinion, indicates good prospects of the lithium-iron phosphate regeneration method proposed in this paper.
The possibility of formation of an active interphase on iron particles in C/PVDF has been dictated by the thermochemical reactions of iron and iron oxides in the presence of carbon. The composition with polyvinylidene fluoride (PVDF) changed the redox activity of iron particles and decreased pure iron (Fe0) amount by 0,24 wt. %. The surface properties of various compositions have been characterized by scanning electron microscopy with the analytical mode for determining the relationship between the microstructure and local thermal reactions on the iron particle surface. A relationship between the surface composition, morphology and electrochemical behavior of the Fe/C/PVDF electrodes has been found. Electric current affects the surface morphology and changes it from a mosaic structure to a monolith in atmosphere oxygen. The electrochemical properties of Fe/C/PVDF electrodes have been tested using cyclic voltammetry (CVA). The long air contact (for more than 3 hours) during electrochemical cycling changes the surface structure in the direction of decreasing crystallinity. The Fe/C/PVDF electrode can be charge in neutral solutions (pH ~7).
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