Search Results (229)

O3-type layered transition-metal oxides are widely regarded as promising cathode materials for sodium-ion batteries due to their intrinsically high sodium content and favorable energy density. Nevertheless, their practical rate capability is hindered by sluggish Na⁺ transport and relatively high diffusion barriers. To address this issue, elemental substitution has emerged as an effective modification strategy. In this work, fluorine (F), characterized by strong electronegativity and a small ionic radius, is introduced to partially substitute oxygen in the bulk lattice of O3-type NaNi_1/3Fe_1/3Mn_1/3O₂ (NNFM). First-principles calculations demonstrate that F incorporation leads to an expansion of the interlayer spacing along the c-axis and a weakening of Na–O interactions, both of which facilitate Na⁺ migration. Among the considered configurations, Mn-adjacent substitution exhibits the lowest formation energy, indicating enhanced thermodynamic stability. Furthermore, electronic structure analysis reveals a reduced band gap (from 0.515 eV to 0.342–0.356 eV) and strengthened O-2p/Mn-3d orbital hybridization, contributing to improved electronic conductivity. These findings provide atomistic insights into F-induced modulation mechanisms and suggest an effective pathway for optimizing Na⁺ transport in O3-type cathodes. Full article

Recycling spent lithium-ion batteries (LIBs) is critical for resource sustainability and carbon neutrality. This work presents a green strategy in which NaA zeolite is used to preferentially recover lithium from leachate of spent NCM111 batteries, combined with temperature-regulated stepwise separation of transition metals. Benefiting from the distinct hydrated ionic radii and charge density between Li⁺ and divalent metal ions, NaA zeolite selectively adsorbs Ni²⁺, Co²⁺ and Mn²⁺, leaving Li⁺ in the raffinate. Under optimized conditions, two-stage adsorption achieves 95.6%, 96.7% and 99.7% removal of Ni²⁺, Co²⁺ and Mn²⁺, respectively, with 11% Li⁺ co-adsorption. Thermodynamic analysis reveals that the adsorption process is endothermic and thermodynamically spontaneous. The interaction strength between metal ions and NaA zeolite follows the order Ni²⁺ > Co²⁺ > Mn²⁺, and ion exchange is identified as the dominant mechanism. It is determined that 96.8% of Mn²⁺ can be recovered at 0 °C, followed by the desorption of 93.5% of Co²⁺ at 90 °C, and the sequential separation of Mn, Co and Ni is realized. Three consecutive adsorption–desorption cycles demonstrate the acceptable reusability of the Ni-loaded NaA adsorbent. High-purity Li₂CO₃ (purity 96.7%, yield 93.5%), MnO₂ (purity 99.3%, yield 98.4%) and Co₃O₄ (purity 98.8%, yield 97.6%) are obtained from the corresponding solutions. This approach provides a scalable closed-loop pathway for full-component recovery of valuable metals from spent LIBs. Full article

Sodium-ion batteries (SIBs) represent a compelling alternative to lithium-ion batteries for grid-scale energy storage, owing to the high natural abundance and low cost of sodium resources, as well as their strategic alignment with national energy security priorities. Nevertheless, the sluggish Na⁺ diffusion kinetics and limited specific capacity of anode materials continue to impede practical deployment. Herein, nitrogen-doped carbon-coated TiO₂ nanofibers (TiO₂/C-N) were rationally engineered through a facile electrospinning route integrated with synergistic defect and coating engineering. The in situ-formed N-doped carbon shell establishes a continuous, high-conductivity electron-transport network while simultaneously buffering volumetric strain during repeated (de)sodiation, thereby preserving long-term structural integrity. Electrochemical assessments demonstrate that the TiO₂/C-N electrode delivers a reversible specific capacity of 233.64 mAh g⁻¹ at 0.1 A g⁻¹ (initial Coulombic efficiency 54.13%). Quantitative kinetic analysis reveals a pronounced pseudocapacitive contribution of 41.4% at 1.2 mV s⁻¹, confirming a surface-controlled Na⁺ storage pathway that markedly enhances rate capability. Moreover, the electrode retains 245.5 mAh g⁻¹ after 150 cycles at 1 A g⁻¹, underscoring exceptional cycling stability. This work elucidates the synergistic regulation of N-doped carbon coating and pseudocapacitive kinetics in TiO₂-based anodes, offering a robust design strategy for high-rate, long-cycle-life SIB anodes. Full article

First-principles calculations based on density functional theory (DFT) are a powerful tool in data-oriented materials research. The choice of approximation for the exchange-correlation functional is crucial, as it strongly affects the accuracy of DFT calculations. This study compares the performance capabilities of three approximations on the energetics, mechanical and electronic properties, and crystal structure of NaAlP₂O₇, which is an insulator with a wide band gap that suppresses its electronic conductivity. Two of these approximations are based on Perdew–Burke–Ernzerhof (PBE) generalized gradient approximation (GGA) and the other on the strongly constrained and appropriately normed (SCAN) meta-GGA. We explore these materials as a contribution to the development of new solid electrolytes (SEs) for sodium-ion batteries (NIBs), which have the potential to mitigate challenges related to lifecycle, safety, and low ionic conductivity. The performance of these batteries largely emanates from the extraordinary demand for high-performing energy storage technologies. This study revealed that PBEsol accurately predicted lattice parameters that closely aligned with experimental values. However, r2SCAN provided the most reliable predictions of the structural and electronic properties of the NaAlP₂O₇ solid electrolyte compared to PBE and PBEsol. Findings demonstrated that the material is structurally, mechanically, electronically, and thermodynamically stable, but exhibits vibrational instability, which may scatter ions and reduce ionic conductivity due to the presence of imaginary frequencies. Our results highlight the importance of selecting appropriate functionals for solid electrolyte DFT computations. The r2SCAN functional appears to be a promising choice for calculating NaAlP₂O₇ properties. Full article

The valorization of biomass waste into advanced electrode materials presents a promising pathway toward sustainable electrochemical energy storage. Herein, a silicon-doped carbon material (Si-CTS-Carbon) is synthesized from chitosan via an in situ reaction with silicon tetrachloride (SiCl₄) and subsequent controlled pyrolysis. When evaluated as an anode for lithium-ion batteries (LIBs), Si-CTS-Carbon exhibits a high reversible capacity of 509.2 mAh g⁻¹ with 99% capacity retention after 100 cycles at 0.05 A g⁻¹. For sodium-ion battery (SIB) applications, it achieves a stable reversible capacity of 155.4 mAh g⁻¹ under identical conditions. Structural and electrochemical analyses reveal that the robust C–O–Si covalent network effectively accommodates volume variation of silicon and enhances structural integrity during cycling. Furthermore, the hierarchically porous architecture shortens ion diffusion pathways, leading to improved Li⁺/Na⁺ transport kinetics. This work demonstrates a viable strategy for fabricating high-performance battery anodes by synergistically doping silicon into biomass-derived carbon, enabling practical biowaste valorization for energy storage. Full article

Layered sodium transition-metal oxides are promising cathode materials for sodium-ion batteries due to their high theoretical capacity; however, their practical application is often limited by sluggish Na⁺ diffusion kinetics and structural instability during cycling. P2/O3 phase coexistence has been proposed as an effective strategy to balance capacity and stability, yet it is typically achieved through precise Na-content tuning or complex synthesis conditions, which restrict compositional flexibility. Herein, we demonstrate a phase-engineering approach that induces stable P2/O3 phase coexistence without adjusting the overall Na stoichiometry by controlling the dopant incorporation pathway. Using Na_0.8(Ni_0.25Fe_0.33Mn_0.33Cu_0.07)O₂ (NaNFMC) as a model system, Mg doping via a wet chemical route enables homogeneous dopant distribution, which triggers local stacking rearrangement and the formation of prismatic Na⁺ diffusion channels characteristic of the P2 phase. In contrast, dry-doped samples with identical Mg content retain a predominantly O3-type structure, highlighting the decisive role of dopant incorporation in governing phase evolution. As a result of the phase-engineered P2/O3 coexisting framework, the Mg wet-doped cathode exhibits enhanced initial reversibility, superior rate capability, and improved long-term cycling stability compared to pristine and dry-doped counterparts. Voltage-resolved dQ/dV and cyclic voltammetry analyses reveal stabilized redox behavior with reduced polarization, while electrochemical impedance spectroscopy confirms suppressed impedance growth and improved Na⁺ transport kinetics after cycling. This study establishes that phase engineering through controlled dopant incorporation provides an effective alternative to conventional Na-content tuning strategies for layered sodium cathodes. The findings offer a scalable and versatile design principle for optimizing the electrochemical performance and structural durability of next-generation sodium-ion battery cathode materials. Full article

Hard carbon (HC) was considered as a promising anode candidate for Na-ion batteries, due to its ability of efficient Na-ion storage. Bamboo-derived HC has the advantages of sustainability, environmental benefits and low cost, which are crucial for advancing the commercialization of SIBs technology. Precarbonization has been reported as a method to improve the electrochemical performance of HC anodes derived from various precursors, while the underlying mechanism behind why precarbonization improved the electrochemical performance of bamboo-derived HC has not been studied in detail. Herein, the effect of precarbonization on electrochemical behavior, bulk and surface structure, and surface composition was comprehensively explored. The results revealed that the improved reversible capacity was attributed to the increased closed pores for extra Na-ion storage, increased surface N content and decreased oxygen content for Na-ion absorption/desorption; the improved cycling stability was ascribed to the reduced surface oxygen and C-O content leading to suppressed side reactions, while the improved surface graphitization degree contributed to rate capability enhancement. This work clarified the role of precarbonization in improving the hard carbon anode for Na-ion batteries, which will be helpful to the commercialization of hard carbon materials. Full article

P2/O3-type Ni/Mn-based layered oxides are regarded as promising cathode materials for sodium-ion batteries (SIBs) because of their high energy density. However, their practical application is limited by low initial Coulombic efficiency, sluggish Na⁺ kinetics, transition-metal dissolution/migration and irreversible phase transitions during cycling. Herein, a controlled P2 phase was achieved through elemental ratio regulation, enabling systematic synthesis of a series of Na_xNi_0.4Co_0.1Mn_0.5O₂(x-NCMO) materials with tailored P2/O3 ratios. The optimized composition (x = 0.8), containing 16.6% P2 and 83.4% O3 phases, achieves an optimal phase equilibrium, thereby maximizing the synergistic coupling between the two layered polymorphs. This biphasic architecture demonstrates significantly enhanced Na⁺ transport kinetics and exceptional electrochemical performance, high initial capacity of 168.65 mAh g⁻¹ and excellent rate performance, maintaining 84.88 mAh g⁻¹ at 10 C, outperforming most reported P2/O3 biphasic cathodes. Structural analysis and electrochemical analysis reveal that elemental ratio regulation modulates the TM–O electronic structure, promotes electronic transport, and accelerates Na⁺ migration. These effects collectively reduce polarization, stabilize the structure, and thereby improve rate capability and long-term cycling capacity retention. This work provides an effective design strategy for designing high-performance layered oxide cathodes with improved structural and interfacial stability. Full article

Sodium metal batteries (SMBs) are promising energy storage systems, yet their practical application is hindered by unstable solid electrolyte interphases (SEIs) and safety issues associated with flammable electrolytes. Although the flame-retardant solvent trimethyl phosphate (TMP) is widely used in rechargeable batteries, its application in SMBs remains constrained due to uncontrolled and accumulated parasitic reactions with sodium metal anodes. Here, we propose a novel synergistic strategy that combines a fluorinated additive (FEC) with a low-cost, high-concentration NaClO₄ to stabilize the electrode–electrolyte interface in TMP-based electrolytes. This approach enables the formation of a robust, NaF-rich SEI while restructuring the Na⁺ solvation sheath to coordinately trap TMP molecules, thereby suppressing parasitic reactions between sodium metal and TMP. As a result, the Na|Na₃(VOPO₄)₂F cell achieves exceptional cycling stability with 89.04% capacity retention over 1000 cycles at 1C. This work provides a cost-effective and practical pathway toward safe and long-lasting SMBs using non-flammable phosphate electrolytes. Full article

The pursuit of high-energy-density cathode materials has positioned LiNiO₂ as a promising candidate due to its high theoretical capacity. However, its practical application is hindered by structural instability, cation mixing, and sluggish Li-ion mobility. This study presents a strategic co-doping approach to enhance the electrochemical performance of R3m-structured LiNiO₂ by introducing Na at the Li site and Nb/Al/W at the Ni site. First-principles calculations based on density functional theory (DFT), combined with the bond valence sum energy (BVSE) method, were employed to evaluate the structural, electronic, and transport properties of the doped systems. The optimized lattice parameters reveal that co-doping induces lattice expansion and suppresses cation disorder, thereby improving structural integrity. Formation energy validates the thermodynamics of the modified structures. Furthermore, BVSE-based ion migration mapping shows that Na/Nb and Na/Al co-doping significantly broadens Li-ion diffusion pathways and lowers migration barriers compared to pristine LiNiO₂. These results demonstrate that dual-site doping is an effective strategy to overcome intrinsic limitations of Ni-rich layered oxides, offering a rational design route cathode for next-generation Li-ion battery. Full article

The rapid increase in end-of-life lithium-ion batteries demands sustainable recycling routes for lithium recovery. This work presents a novel integrated hydrometallurgical–electrodialysis process designed specifically for recovering lithium from off-specification NMC cathode materials while enabling full reagent recyclability. Selective leaching with oxalic acid was optimised by setting the water-to-oxalic acid dihydrate ratio (H₂O/OA·2H₂O) to 7.3:1 w/w, achieving 81% lithium extraction at room temperature within 2 h while limiting the co-dissolution of Ni, Co and Mn to 0.2%, 1.6% and 1.7% by weight, respectively. The resulting leachate was processed in a four-chamber electrodialysis cell equipped with two Nafion 117 cation-exchange membranes and one Neosepta AMX-fmg anion-exchange membrane operating at −1.6 V versus Ag/AgCl, enabling 96% lithium recovery and 98% oxalic acid recovery. The regenerated oxalic acid stream (41.8 g L⁻¹) was fully restored to its initial concentration and reused in successive cycles without performance loss. Subsequent precipitation of lithium with Na₂CO₃ yielded 99.3%-pure Li₂CO₃. This combined leaching–electrodialysis–precipitation presents a high selectivity, low-waste, circular recovery system, offering a scientifically original approach that integrates reagent regeneration with high-purity lithium production. Full article

This study presents a sustainable, battery-free UV (ultraviolet) dose sensor designed for intelligent food packaging applications. The device integrates laser-induced graphene (LIG) electrodes, a ZnO-CNT (carbon nanotube) UV-active composite, and a bio-derived ionochromic cell composed of blueberry anthocyanins and a NaCl electrolyte. This work advances the platform by introducing a quantitative and predictive dose–color mapping framework for cumulative UV detection under zero-bias operation. A controlled charge-injection protocol was employed to emulate UV-generated photocurrent, enabling systematic investigation of charge-transfer-driven ionochromic kinetics across five current levels (0.2–3 mA). HSB (hue–saturation–brightness)-based colorimetric analysis was performed to quantify the time-dependent chromatic evolution, and a numerical fitting model was developed to map charge accumulation to color shifts. Using this calibration, the color response at microampere-level photocurrents—corresponding to real zero-bias UV operation—can be predicted. The resulting model enables estimation of the cumulative time required for the ionochromic cell to transition from red to purple under realistic UV intensities. By combining self-powered sensing with predictive colorimetric modeling, this work significantly enhances the functionality of battery-free UV indicators, enabling quantitative dose measurement without external electronics for safer food-supply-chain monitoring. Full article

This study investigates the hydrometallurgical purification of the acidic leachate from spent LiCoO₂-based lithium batteries, focusing on the selective removal of Cu, Mn, and Ni while monitoring co-precipitation of Fe and Al and minimizing Co and Li losses. Thermodynamic modelling using HSC Chemistry 10 and Hydra/Medusa guided the design of precipitation conditions. The optimal Cu precipitation was achieved using Na₂S (Na₂S:Cu = 4:1, 20 °C, 5 min, 300 rpm), yielding > 99% removal. Mn was efficiently precipitated as MnO₂ using KMnO₄ (KMnO₄:Mn = 1:1, 20 °C, pH ≈ 2, 10–15 min, ≈97% efficiency). Ni was recovered as [Ni(DMG)₂] under DMG:Ni = 5:1, 80 °C, 15 min, pH ≈ 5, achieving ≈99% removal. Sequential 2 L experiments (precipitation order: Cu → Mn → Ni) validated the scalability of the process. Cu and Ni removal remained high (>95%), while Mn efficiency slightly decreased (≈91%) due to kinetic and redox inhomogeneity. No significant precipitation of Co and Li was observed, leaving them in solution and concentrating from 12.9 to 18.8 g·L⁻¹ and 2.71 to 3.50 g·L⁻¹, respectively, with total losses of <1%. The resulting CuS, MnO₂, and [Ni(DMG)₂] precipitates exhibited moderate purity (46–63%) but represented valuable secondary raw materials. Overall, sequential precipitation under optimized conditions demonstrates robust, selective removal of accompanying metals while concentrating Co and Li, providing an efficient and scalable route for LIBs leachate valorisation. Full article

In this work, a method for leaching black mass from spent Li batteries using oxalic acid was developed and experimentally verified with the objective of selectively separating lithium and cobalt. Oxalic acid proved to be an efficient and selective leaching agent. Under 1 M C₂H₂O₄, 120 min, L:S = 20, 80 °C and 300 rpm, a lithium yield of 90% was achieved, while cobalt dissolution remained low at 1.57%. Subsequently, cobalt spontaneously precipitated from the leachate within several hours, and the solid phase was fully separated after 24 h. The leachate contained minor amounts of accompanying metals, with dissolution yields of 0.5% Mn, 8% Fe and 1.4% Cu. These impurities were removed from the leachate by controlled pH adjustment using NaOH at ambient temperature and 450 rpm, with complete precipitation at pH 12. This procedure generated a purified lithium-rich leachate, which was converted into lithium oxalate by crystallisation at 105 °C. Subsequent calcination of the resulting solid at 450 °C for 30 min produced Li₂CO₃ with a purity of 91%. Based on the experimental findings, a conceptual technological process for selective lithium leaching using oxalic acid was proposed, demonstrating the potential of this method for sustainable lithium recovery. Full article

The increasing demand for lithium-ion batteries (LIBs) has intensified the need for efficient lithium (Li) recovery from secondary sources. This study focuses on anti-solvent crystallization for the recovery of high-purity lithium hydroxide monohydrate (LiOH·H₂O) from a Li-rich leachate, derived from the flue dust of a pilot-scale pyrometallurgical process for LIB material recycling. To optimize product yield and purity, a series of experiments were performed, focusing on the influence of parameters such as solvent type, organic-to-aqueous (O/A) volumetric ratio, crystallization time, stirring rate, and anti-solvent addition rate. Acetone was identified as the most effective anti-solvent, producing rectangular cuboid crystals with approximately 90% Li recovery and around 95% purity, under optimized conditions (O/A = 4, 3 h, 150 rpm, and solvent flow rate of 5 mL/min). The flow rate influenced crystal morphology and impurity entrapment, with 5 mL/min favoring nucleation-dominated crystallization regime, producing ~20 μm of well-dispersed crystals with reduced impurity incorporation. SEM-EDS, surface washing, and gradual dissolution of obtained LiOH·H₂O crystals revealed that the impurities sodium (Na), potassium (K), aluminum (Al), calcium (Ca) and chromium (Cr) were crystallized as conglomerates. It was found that Na, K, Al, and Ca primarily crystallized as highly soluble conglomerates, while Cr was crystallized as a lowly soluble conglomerate impurity. In contrast Zn was distributed throughout the crystal bulk, suggesting either the entrapment of soluble zincate species within the growing crystals or the formation of mixed Li-Zn phase. Therefore, to achieve battery-grade purity, further purification measures are necessary. Full article