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It is deemed as a tough yet profound project to comprehensively cope with a range of detrimental problems of lithium-sulfur batteries (LSBs), mainly pertaining to the shuttle effect of lithium polysulfides (LiPSs) and sluggish sulfur conversion. Herein, a Co2P-Fe2P@N-doped carbon (Co2P-Fe2P@NC) Mott-Schottky catalyst is introduced to enable bidirectionally stimulated sulfur conversion. This catalyst is prepared by simple carbothermal reduction of spent LiFePO4 cathode and LiCoO2. The experimental and theoretical calculation results indicate that thanks to unique surface/interface properties derived from the Mott-Schottky effect, full anchoring of LiPSs, mediated Li2S nucleation/dissolution, and bidirectionally expedited "solidâliquidâsolid" kinetics can be harvested. Consequently, the S/Co2P-Fe2P@NC manifests high reversible capacity (1569.9 mAh g-1), superb rate response (808.9 mAh g-1 at 3C), and stable cycling (a low decay rate of 0.06% within 600 cycles at 3C). Moreover, desirable capacity (5.35 mAh cm-2) and cycle stability are still available under high sulfur loadings (4-5 mg cm-2) and lean electrolyte (8 µL mg-1) conditions. Furthermore, the as-proposed universal synthetic route can be extended to the preparation of other catalysts such as Mn2P-Fe2P@NC from spent LiFePO4 and MnO2. This work unlocks the potential of carbothermal reduction phosphating to synthesize bidirectional catalysts for robust LSBs.
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Replacing the oxygen evolution reaction with thermodynamically more favorable alternative oxidation reactions offers a promising alternative to reduce the energy consumption of hydrogen production. However, questions remain regarding the economic viability of alternative oxidation reactions for industrial-scale hydrogen production. Here, we propose an innovative cost-effective, environment-friendly and energy-efficient strategy for simultaneous recycling of spent LiFePO4 (LFP) batteries and hydrogen production by coupling the spent LFP-assisted ferricyanide/ferrocyanide ([Fe(CN)6 ]4- /[Fe(CN)6 ]3- ) redox reaction. The onset potential for the electrooxidation of [Fe(CN)6 ]4- to [Fe(CN)6 ]3- is low at 0.87â V. Operando Raman and UV/Visible spectroscopy confirm that the presence of LFP in the electrolyte allows for the rapid reduction of [Fe(CN)6 ]3- to [Fe(CN)6 ]4- , thereby completing the [Fe(CN)6 ]4- /[Fe(CN)6 ]3- redox cycle as well as facilitating the conversion of spent LiFePO4 into LiOH â H2 O and FePO4 . The electrolyzer consumes 3.6â kWh of electricity per cubic meter of H2 produced at 300â mA cm-2 , which is 43 % less than conventional water electrolysis. Additionally, this recycling pathway for spent LFP batteries not only minimizes chemical consumption and prevents secondary pollution but also presents significant economic benefits.
RESUMO
Efficient and clean extraction lithium (Li) from spent LiFePO4 batteries (LIBs) still remains a challenge. In this paper, a green deep eutectic solvent (DES) based on ethylene glycol (EG) and choline chloride (CC), combined with ozone (O3) from air source, realized highly selective leaching Li from LiFePO4 in situ for the first time. The influence of experimental parameters on Li and Fe leaching efficiencies (ηLi, ηFe) were studied by orthogonal and single-factor tests, and ηLi ≥ 92.2% while ηFe ≤ 1.6% were obtained under the optimal conditions (6 h, 20 g/L, 8EG:1CC, 40 °C). The impurity Fe in the filtrate was completely precipitated as amorphous FePO4·3H2O after heating (150 °C, 0.5 h), achieving a pure Li-solution. The leaching mechanism elucidated that the synergistic effect (acidification, replacement and oxidation reaction) between the DES and O3 determined the phase transition of Li and Fe, promoting the efficient selective extraction of Li and in-situ separation of Fe (FePO4). The average ηLi and ηFe were separately 85.4% and 2.0% after ten cycles of the 8EG:1CC, indicative of its' excellent reusability. Meanwhile, LiCl was recovered from the filtrate. This process avoided the use of strong acid/alkali and discharge of waste water, providing fresh perspectives on the green recovery of spent LiFePO4 batteries.
Assuntos
Lítio , Ozônio , Reciclagem/métodos , Fontes de Energia Elétrica , SolventesRESUMO
The large-scale implementations of lithium iron phosphate (LFP) batteries for energy storage systems have been gaining attention around the world due to their quality of high technological maturity and flexible configuration. Unfortunately, the exponential production of LFP batteries is accompanied by an annual accumulation of spent batteries and a premature consumption of the lithium resource. Recycling souring critical battery materials such as Li2CO3 is essential to reduce the supply chain risk and achieve net carbon neutrality goals. During the recovery of Li2CO3, impurity removal is the most crucial step in the hydrometallurgy process of spent LiFePO4, which determines the purity of Li2CO3. By investigating and comparing the results of impurity elimination from the purified Li+-containing liquids with strong and weak alkalis under identical pH conditions, respectively, a strategy based on an alkali mixture has been proposed. The purified Li+-containing liquid was, thereafter, concentrated and sodium carbonate was added in order to precipitate Li2CO3. As a result, a high purity Li2CO3 (99.51%) of battery grade was obtained. LiFePO4 prepared with the recovered Li2CO3 and FePO4 as raw materials also displayed a comparative high capacity and stable cycle performance to the commercial product and further verified the electrochemical activity of the recovered materials.
RESUMO
With the large-scale application of LiFePO4 (LFP) in energy storage and electric vehicles, the recycling of spent lithium LFP batteries has gained more attention. However, recycling spent LFP is less economically feasible owing to the poor economic value of Fe products, which causes a problem for both the efficiency and economy. This work proposes a highly economical acid-free mechanochemical approach for the efficient and selective extraction of lithium (Li) from spent LFP battery cathode materials. The selective release of 98.9 % of Li from the LFP crystal structure is achieved at a reaction time of 5 h, a rotational speed of 500 rpm, and sodium citrate (Na3Cit) to LFP mass ratio of 10. Meanwhile, Fe is reserved in the form of FePO4 in the olivine structure. The use of Na3Cit as a co-milling agent ensures a pollution-free recovery process and efficient extraction of Li+. The chelation of Li+ with organic ligands (Cit3-) is the key to the efficient selective recovery of Li+ from the olivine LFP structure via the mechanochemical process. The economic analysis indicates that the method is feasible and ensures industrial viability. The acid-free mechanochemical (MC) process reported in this work provides a novel route to selectively recover Li from spent LFP efficiently and highly economically.
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Mild-temperature (<1000 °C) carbothermic reduction has been proven as an effective way to recover Li and transition metals by converting lithium transition metal oxides to transition metals/alloys and Li2CO3. However, LiFePO4 cannot be reduced by carbon because of its thermodynamically stable olivine structure. Herein, LiFePO4 is converted to Fe and lithium salts by carbon with the assistance of Na2CO3 that acts as an activating agent to break down the chemical bonds of LiFePO4 and thereby enable the carbothermic reduction. Using Na2CO3 as the activating agent, LiFePO4 was reduced to Fe, NaLi2PO4, and LiNa5(PO4)2 which can be separated by magnetic separation with a Li recovery rate of 99.2%. Using NaOH as the activating agent, LiFePO4 was oxidized to Fe3O4, NaLi2PO4 and LiNa5(PO4)2 at 600 °C, and the roasted products can be separated by magnetic separation process with a Li recovery rate of 92.7%. Various sodium salts were tested to screen proper salts for the reduction process, and a 400-g scale roasting-separation process has been demonstrated. Overall, the salt-assisted roasting is a promising way to recycle spent LiFePO4 batteries without using strong mineral acids and shows great potential for the industrial-scale implementation.
RESUMO
Recovery of battery-grade FePO4 from Al-bearing spent LiFePO4 batteries (LFPs) is important for both prevention of environmental pollution and recycling of resources for LFPs industries. The premise for FePO4 recovery from spent LFPs is the separation of Al, because Al readily co-precipitates with FePO4 and lowers the electrochemical performance of the regenerated LiFePO4. In this work, an efficient approach involving sulfuric acid leaching followed by solvent extraction was developed to separate Al from spent LiFePO4/C powder. Di-(2-ethylhexyl) phosphoric acid (D2EHPA) in sulfonated kerosene was used as the extractant. The results showed that 96.4% of aluminum was extracted while the loss of iron was only 1.1% under the optimal conditions. The mass fraction of Al in the iron phosphate obtained from the extraction raffinate was only 0.007%, meeting the standard for preparing battery-grade FePO4. The extracted Al can be easily stripped by diluted H2SO4 solution and the extractants can be reused. Additionally, slope analysis method, FTIR spectroscopy, and ESI-MS analysis revealed that the extraction of Al in D2EHPA can be ascribed to the ion exchange between hydrogen ion of -PO(OH) and Al3+. This work may provide an economically feasible method for the recycling of valuable components from spent Al-bearing LiFePO4/C powder.
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Herein, we converted spent LiFePO4 battery to the sea urchin-like material (SULM) with a highly efficient and environment-friendly method, which can contribute to building a zero-waste city. With SULM as a Fenton-like catalyst, a highly-efficient degradation process was realized for organic pollutants with interface and solution synergistic effect. In our SULM+NH2OH+H2O2 Fenton-like system, NH2OH can effectively promote the interface iron (Fe(â ¢)/Fe(â ¡)) and solution iron (Fe(â ¢)/Fe(â ¡)) redox cycle, thus promoting the generation of reactive oxygen species (ROS). However, the ROS generation process and organic pollutants degradation pathway with the presence of NH2OH remains a puzzle. Here the detailed ROS generation mechanism and pollutants degradation pathway have been illustrated carefully based on experimental exploration and characterization. Therein, hydroxyl radicals (·OH) and singlet oxygen (1O2) are the main ROS for oxidizing and degrading organic pollutants. Notably, 1O2 can be converted from superoxide radicals (·O2) in SULM+NH2OH+H2O2 system. This study not only demonstrates the strategy of "trash-to-treasure" and "waste-to-control-waste" to simultaneously reduce the hazardous release from industrial solid waste and organic wastewater, it also provides new mechanistic insights for NH2OH mediated Fenton-like redox system.
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Search for simple and efficient recycling methods to utilize spent lithium-ion batteries is crucial for achieving sustainable resource development and reducing the hazardous materials released from the spent batteries. Herein, we have developed a new strategy to utilize the spent LiFePO4 batteries by utilizing the cathode plate as raw material to synthesize mesoporous core-shell adsorbent Mm@SiO2 (Mm denoted as the magnetic material) through a simple alkaline leaching process. The as-converted material exhibits excellent adsorption capacity when it has been used to remove heavy metal ions in heavy metal polluted water. The adsorption capacities for Cu2+, Cd2+, and Mn2+ have been achieved up to 71.23, 80.31 and 68.73 mg g-1, respectively. The detailed adsorption mechanism has been elucidated with comprehensive characterization techniques, including TEM, XPS, NEXAS, and EXAFS, the edge shared [Cu2O8] bipyramids can be fit against the EXAFS data to represent the atomic-scale local structure after Mm@SiO2 adsorbs Cu2+. The present work demonstrates a novel routine to reutilize the spent lithium batteries, which is of great importance to achieve sustainable development based on the "waste-to-treasure" and "waste-to-control-waste" strategy for simultaneously reducing the hazardous release from industrial solid waste and heavy metal polluted water.
RESUMO
Recovery of high-content and valuable elements including phosphorus (P) is critical for recycling of spent LiFePO4 battery, but P recovery is challengeable due to the poor solubility of lithium phosphate and iron phosphate. This study compared two strategies to recover P by adopting sulfide salt to induce P dissolution, i.e., recovery of P directly from LiFePO4, and step-by-step recovery of Li then P. The results revealed that the second strategy was more efficient because of the higher recovering efficiency and selectivity. Accordingly, an acid-free process to recover P was successfully demonstrated. Li-recovery efficiency of 97.5 % was reached at a leaching time of 65â¯min, and nearly 100 % P-recovery efficiency was reached at 5â¯h. Mechanism analysis revealed that the transforming of delithiated LiFePO4 crystal to NaFeS2 was mainly responsible for P dissolution. Thermodynamic analysis and density functional theory calculation further proved the transformation reaction, and a stepwise-transformation mechanism was proposed. In addition, P was reclaimed in the form of soluble phosphate salts. The process is especially appealing due to its environmental and economic benefits for recycling spent LiFePO4 batteries.
RESUMO
In spent lithium iron phosphate batteries, lithium has a considerable recovery value but its content is quite low, thus a low-cost and efficient recycling process has become a challenging research topic. In this paper, two methods about using the non-oxidizing inorganic iron salt - Fe2(SO4)3 to recover lithium from LiFePO4 are proposed. The method-1 is theoretical-molar Fe2(SO4)3 (Fe2(SO4)3 : LiFePO4 =1:2) dosage is added and more than 97% of lithium can be leached in just 30 min even under a pretty high solid-liquid ratio of 500 g/L. Spectrophotometry provides the evidence of Fe2+/Fe3+ substitution in the leaching process. In the method-2, the generated Fe2+ originating from LiFePO4 is fully utilized with the addition of H2O2, and the dosage of Fe2(SO4)3 is decreased by two thirds (Fe2(SO4)3 : LiFePO4 =1:6). Several sulphates (CuSO4, NiSO4, MgSO4) are employed to explore the leaching mechanism. All the results reveal that the reaction of Fe3+ substituting Fe2+ has a powerful driving force. In addition, these two leaching processes simultaneously present superior selectivity for the impurities. The Fe2(SO4)3 in two methods does not cause pollution and is easily regenerated by adding H2SO4. The proposed rapid, efficient and selective leaching thought would be a competitive candidate for recycling spent LiFePO4 batteries.
RESUMO
A simple, green and effective method, which combined lithium iron phosphate battery charging mechanism and slurry electrolysis process, is proposed for recycling spent lithium iron phosphate. Li and FePO4 can be separation in anionic membrane slurry electrolysis without the addition of chemical reagent. The leaching efficiency of Li can reach to 98% and over 96% of Fe are recycled as FePO4/C. Kinetics analysis indicates that the surface chemical reaction is the control step during the slurry electrolysis. Additionally, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Electrochemical Impedance Spectroscopy (EIS) characterization and thermodynamic analysis are employed to investigate the leaching mechanism. It is found that the spent LiFePO4 is delithiated and oxidized to FePO4 by the function of e-, which is similar as the LiFePO4 battery charging process. EIS analysis also verify the kinetics results, the charge transfer resistance controlled the leaching process. Finally, a novel process for recovery of spent LiFePO4 is proposed. The recovered Li2CO3 and FePO4/C can be used for resynthesize LiFePO4, and the resynthesized LiFePO4 exhibits reversible capacities of 143.6 mAh g-1 at 1C and high current efficiency, stable cycle performances at 0.1 and 0.5C which meets the basic requirements for reuse.
Assuntos
Carbono , Lítio , Fontes de Energia Elétrica , Eletrodos , Eletrólise , Ferro , FosfatosRESUMO
To recycle the sharply growing spent lithium-ion batteries and alleviate concerns over shortages of resources, particularly Li, is still an urgent issue. In this work, an organic acids based leaching approach at room temperature is proposed to recover Li and FePO4 from spent LiFePO4 cathode powder. The coexistent metal ions, Cu and Al, have also been investigated. Citrus fruit juices, rich in organic acids, such as citric acid and malic acid, have been used as leaching agents in this work. Among lemon, orange and apple, lemon juice shows the best leaching effect based on its suitable pH of the reaction system. Under the optimized conditions, the leaching rates of Li, Cu and Al can reach up to 94.83%, 96.92% and 47.24%, while Fe and P remain as low as 4.05% and 0.84%, respectively. Li2CO3 and FePO4 can be recovered from the leachate and the leaching residue, respectively. The recovered FePO4 was used to prepare new cathode material LiFePO4. The crystalline carbon, present in the spent LiFePO4 cathode scraps, has a significant effect on the electrochemical performances of the regenerated LiFePO4. The regenerated LiFePO4 cathode material delivered a comparable discharge capacity of 155.3 mAh g-1 at 0.1C and rate capacity to the fresh LiFePO4. For the cycling stability, it displays capacity retention of 98.30% over 100 cycles at 1 C with a fading rate of 0.017% per cycle. The proposed organic acids-based recycling strategy is much benign for recycling the spent LiFePO4 cathode materials.
Assuntos
Fontes de Energia Elétrica , Lítio , Eletrodos , Íons , ReciclagemRESUMO
In this study, a novel process consisting of pyrolysis and physical separation was proposed to comprehensively recycle spent lithium ion batteries (LIBs). The discharge and pyrolysis behaviors of spent LIBs, the recovery of electrolyte from the spent LIBs by low-temperature volatilization, and the recovery of valuable materials from the pyrolytic residues through physical separation were studied in detail. The results indicated that approximately 99.91% of the organic electrolytes was recycled, and the lithium salt (LiPF6) in the batteries was disposed by pyrolysis process. The active materials could be effectively separated from current collectors after the pyrolysis under N2 at 550⯰C for 2â¯h. The pyrolytic gas was mainly composed of light alkenes, and the pyrolytic tar was mainly composed of aromatic long chain alkenes and light alcohols. Pyrolytic residues were recycled by color sorting, high-pressure water cleaning and flotation processes, and about 99.34% of Al, 96.25% of Cu, and 49.67% of cathode active materials were recovered from the spent LIBs. Finally, electrochemical tests indicate that the cathode active materials obtained by the process can be used to produce new batteries.