Search Results (90)

The high-voltage spinel ${\mathrm{LiNi}}_{0.5}{\mathrm{Mn}}_{1.5}{\mathrm{O}}_4$ (LNMO) is a promising cobalt-free cathode material for lithium-ion batteries, yet its integration as a binder-free thin film on metallic current collectors via simple solution routes remains underexplored. Here, LNMO films were synthesized on 304 stainless steel (SS304) by metal–organic decomposition (MOD) from metal–acetate precursors in ethanol, followed by spin-coating and annealing at 500, 600, and 700 °C under flowing ${\mathrm{O}}_2$. The films were characterized by XRD, FESEM–FIB cross-sectioning, EDS, and XPS, and tested as binder-free cathodes by cyclic voltammetry and galvanostatic charge/discharge. All samples are dense, approximately 1.9 μm thick, and crystallize in the disordered spinel phase. The LNMO crystallite size increases from 21.9 to 43.8 nm between 500 and 700 °C, while the grain size also shows a temperature dependence, increasing the average size from 25 up to 56 nm in diameter. XPS confirms ${\mathrm{Mn}}^{4+}$ as the dominant manganese surface species (45–49%) across all samples. The films deliver reversible discharge capacities of 92, 92, and 70 mAh ${\mathrm{g}}^{-1}$ at 0.1 C for LNMO500, LNMO600, and LNMO700, respectively, with well-defined ${\mathrm{Ni}}^{2+}{\mathrm{/Ni}}^{3+}$ and ${\mathrm{Ni}}^{3+}{\mathrm{/Ni}}^{4+}$ redox peaks at 4.7 and 4.8 V. DFT calculations independently predict a voltage plateau at ∼4.7 V for $0.2\le x\le 1$, in agreement with the experimental profiles. These findings establish MOD as a viable, vacuum-free route to the synthesis of nanostructured LNMO cathodes. Full article

This study investigates the leaching behavior of the LiNi_0.65Co_0.25Mn_0.10O₂ cathode material in a phosphoric acid medium, with metallic copper recycled from spent battery components serving as a reducing agent. The aim was to develop an efficient approach for the recovery of Li, Ni, Co, and Mn while providing a mechanistic understanding. Leaching experiments were performed by varying key parameters, including copper addition, acid concentration (0.2–0.8 mol·L⁻¹), cathode mass (0.2–1.0 g), stirring rate (0–600 rpm), and temperature (35–80 °C). Thermodynamic analysis, supported by Pourbaix and species distribution diagrams, was used to interpret metal behavior. The results show that lithium is readily dissolved, whereas the extraction of Ni, Co, and Mn depends on the presence of copper, which enables their reduction and dissolution. Optimal conditions (0.4 mol·L⁻¹ H₃PO₄, 0.2 g Cu, 600 rpm, 80 °C) enabled rapid extraction, exceeding 90% within 30 min, while near-complete extraction (~100%, 99%, 99%, and 97% for Li, Ni, Co, and Mn) was achieved after 60 min. Structural analysis revealed a transformation from the layered structure to spinel-like intermediates, followed by their dissolution and formation of copper phosphate phases. The proposed system represents an efficient approach for the sustainable recycling of NMC cathodes. Full article

Both Co-free and lithium- and manganese-rich layered oxide Li(Li_0.2Mn_xNi_yFe_z)O₂ (MNF) cathodes have recently attracted attention in lithium-ion battery (LIB) research due to their high capacities of over 250 mAhg⁻¹, as well as being more eco-friendly and inexpensive than commercial NMC and LiCoO₂. However, they still suffer from lower experimental capacity as well as capacity decay, voltage fade, poor rate capability, and thermal instability. In this paper, fluorine (F)-doped Li_1.2(Mn_0.5Ni_0.2Fe_0.1)O_2(1−x)F_2x (MNF502010, x = 0, 0.025, 0.05, 0.075, 0.1) cathode materials have been synthesized in the nanoscale via sol–gel and subsequent solid-phase calcination to address some of these problems. The resulting 5% F-doped MNF502010 cathode demonstrates the advantage of fluorine doping, which makes a significant contribution to the formation of a well-ordered layer structure with a minimal LiM₂O₄ spinel phase as an impurity. This composition achieves an initial discharge capacity of 252 mAhg⁻¹ (1C = 250 mAhg⁻¹) and a 156 mAhg⁻¹ discharge capacity at 0.3 C on the 100th discharge, with an average voltage fade of 0.24 V. The optimization of fluorine composition results in an enhancement in the activation of the Li₂MnO₃-type monoclinic phase, as well as an increase in the electronic conductivity compared to the fluorine-free cathode. To understand the structural origin of this improved performance, X-ray absorption spectroscopy (XAS) measurements were carried out on pristine and cycled MNF electrodes. Full article

The critical role of lithium in powering the new energy economy necessitates prioritizing efficient extraction methods. This study investigates a novel zeolitic imidazolate frame work (ZIF-8)-coated manganese-based lithium-ion sieve (LIS) for enhanced lithium recovery. The precursor of LIS, Li_1.6Mn_1.6O_4, was synthesized via the hydrothermal method, followed by acid pickling to obtain the spinel lithium-ion sieve H_1.6Mn_1.6O₄. The material was then immersed in a 2-methylimidazole/Zn(NO₃)₂ solution, undergoing ultrasonic-assisted hydrothermal growth to form H_1.6Mn_1.6O₄@ZIF-8 composites. Under optimized conditions (30 °C, pH = 11, 24 h), the composite demonstrated superior lithium extraction performance compared to single-phase adsorbents, reaching 26.62 mg/g in the solution with 250 mg/L Li⁺. The adsorption capacity of the composite increased with Li⁺ concentration and reaction time. The adsorption kinetics followed a pseudo-second-order kinetic model and were dominated by chemisorption. The H_1.6Mn_1.6O₄@ZIF-8 composite exhibited an enhanced Li⁺ partition coefficient K_d of 118.3 in a mixed solution containing ions such as Li⁺, Mg²⁺, K⁺, and Ca²⁺, each with a concentration of 250 mg/L (pH = 12); good structural stability with manganese dissolution of 1.6%; and a capacity retention of approximately 79.5% after five cycles (C_Li⁺ = 250 mg/L). Full article

Lithium-rich manganese-based cathode materials (LRMs, Li_1.2Mn_0.54Ni_0.13Co_0.13O₂) are promising prospects for subsequent-generation lithium-ion batteries owing to their elevated operating voltage, large specific capacity, and affordability. Nonetheless, their actual implementation is significantly impeded by irreversible lattice-oxygen redox reactions, surface structural disorder, and interfacial phase collapse, leading to low initial Coulombic efficiency (ICE), inadequate rate capability, and sluggish Li⁺ transport. Herein, we report a simple and mild glycolic acid-assisted surface-engineering strategy to enhance the electrochemical performance of LRM. Glycolic acid treatment induces controlled H⁺/Li⁺ ion exchange at the particle surface and anchors surface transition metals through the formation of transition metals (TM)–OH and TM–O–C=O bonds. Subsequent calcination constructs an in situ carbon layer-spinel-layered heterostructure, accompanied by the generation of coupled anionic and cationic vacancies. This reconstructed surface provides fast Li⁺ diffusion pathways and stabilized ion-transport channels, while the dual-vacancy configuration enhances lattice-oxygen reversibility and suppresses structural disorder. Consequently, the modified LRM delivers a high initial discharge capacity of 285.3 mAh⋅g⁻¹ with an ICE of 89.9%, while maintaining 81% capacity retention after 100 cycles. Notably, it exhibits a significantly suppressed voltage decay of only 1.7 mV/cycle at 3C, markedly outperforming the pristine LRM. Density Functional Theory (DFT) calculations reveal that the surface-modified sample possesses enhanced electronic conductivity, as evidenced by the improved Density of States (DOS), and achieves superior structural stability through increased binding energies. This environmentally benign surface-engineering strategy offers a practical and efficient route toward the industrial application of LRM. Full article

High-energy Ni-rich layered cathodes are critical for next-generation lithium-ion batteries yet remain limited by severe interfacial degradation and thermal vulnerability under high-voltage operation. In this work, a robust spinel-layered heterostructure is constructed by encapsulating LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) with a LiNi_0.5Mn_1.5O₄ (LNMO) spinel shell via a scalable sol–gel route. Structural characterizations confirm that the coating maintains the secondary-particle architecture, while X-ray photoelectron spectroscopy reveals a chemically reconditioned interface, achieved by the scavenging residual lithium species and suppressing of rock-salt-like surface reconstruction. Consequently, the optimized 4 wt% LNMO@NCM811 electrode demonstrates significantly enhanced high-voltage (2.8–4.4 V) stability, maintaining 41.84% of its initial capacity after 200 cycles compared to only 15.75% for the pristine sample. Crucially, thermogravimetric-differential scanning calorimetry (TG-DSC) uncovers the kinetic origin of this safety improvement: the spinel shell alters the thermal decomposition pathway, delaying the 10% mass loss temperature (T_10%) from 515.2 °C to 716.6 °C and suppressing the total exothermic heat release from 208.3 J g⁻¹ to 81.5 J g⁻¹. Collectively, these results demonstrate that the co-free spinel encapsulation is a dual-functional strategy to simultaneously stabilize surficial chemistry and intrinsically enhance the thermal safety of Ni-rich cathodes for carbon-neutral energy storage applications. Full article

Spinel LiNi_0.5Mn_1.5O₄ (LNMO) has emerged as a highly competitive cobalt-free cathode material for higher-energy-density lithium-ion batteries. However, its practical application is hindered by severe capacity degradation, particularly under high-voltage operation. To solve this problem, we put forward a surface modification strategy employing a Li_0.4La_0.54TiO₃ (LLTO) coating. The LLTO coating forms a protective cathode–electrolyte interphase that helps to inhibit interfacial side reactions, enabling enhanced electrochemical performance up to 5 V. As a result, the optimized 1 wt% LLTO-coated LNMO exhibits a remarkable capacity retention of 96.5% after 200 cycles at 0.1 C and delivers a high-rate capacity of 103.5 mAh g⁻¹ at 2 C, significantly outperforming its pristine counterpart (86.8% and 89.6 mAh g⁻¹, respectively). This work provides a viable and efficient surface modification approach for achieving robust high-voltage LNMO cathode material, underscoring its great potential for next-generation energy storage systems. Full article

The development of lithium-ion batteries necessitates cathode materials that possess excellent mechanical and thermal properties in addition to electrochemical performance. As a prominent functional ceramic, the properties of spinel LiMn₂O₄ are governed by its atomic-level structure. This study systematically investigates the impact of Ni doping concentration on the mechanical and thermal properties of spinel LiNi_xMn_2−xO₄ via first-principles calculations combined with the bond valence model. The results suggest that when x = 0.25, the LiNi_xMn_2−xO₄ shows excellent mechanical properties, including a high bulk modulus and hardness, due to the favorable ratio of bond valence to bonds length in octahedra. Furthermore, this optimized composition shows a lower thermal expansion coefficient. Additionally, Ni doping concentration has a very minimal influence on the maximum tolerable temperature of the cathode material during rapid heating. Therefore, from the perspective of mechanical and thermal properties, this composition could be beneficial for improving the cycling life of the battery, since comparatively inferior mechanical properties and a higher thermal expansion coefficient make it prone to microcrack formation during charge–discharge cycles. Full article

The compounds LiCo_1−xMn_xO₂ (x = 0.5, 0.7) were synthesized via the solid-state method and exhibited crystallization in the cubic spinel structure (space group Fd-3m). UV–Vis spectroscopy reveals strong visible-light absorption and a reduction in the indirect optical band gap from 1.85 eV (x = 0.5) to 1.60 eV (x = 0.7) with increasing Mn content, which is consistent with semiconducting behavior. This narrowing arises from Mn³⁺/Mn⁴⁺ mixed valence, which introduces mid-gap states and enhances Co/Mn 3d–O 2p orbital hybridization within the spinel framework. In contrast, the Urbach energy increases from 0.55 eV to 0.65 eV, indicating greater structural and energetic disorder in the Mn-rich composition which is attributed to the Jahn–Teller distortions and valence heterogeneity associated with Mn³⁺. Impedance and dielectric modulus analyses confirm two distinct non-Debye relaxation processes related to grains and grain boundaries. AC conductivity is governed by the Correlated Barrier Hopping (CBH) model, with bipolaron hopping identified as the dominant conduction mechanism. The x = 0.7 sample displays significantly enhanced conductivity due to increased Mn³⁺/Mn⁴⁺ mixed valence, lattice expansion, efficient 3D electronic connectivity of the spinel lattice, and reduced interfacial resistance. These findings highlight the potential of these two spinels compounds as narrow-gap semiconductors for optoelectronic applications including visible-light photodetectors, photocatalysts, and solar absorber layers extending their utility beyond conventional battery cathodes. Full article

4LiF-MM’₂O₄ composites were synthesized via the mechanical milling of LiF and MM’₂O₄ (M = Mn, Mg, Zn; M’ = Mn Fe) for 72 h. In the obtained composites, the XRD peak broadened because of the milling, and the composites possessed a rock-salt-type structure. During charge–discharge measurements at 0.1 C, composites with spinel materials containing Mg showed particularly high discharge capacities; the discharge capacity of 4LiF-MMn₂O₄ and 4LiF-MFe₂O₄ was 310 mAh/g and 309 mAh/g, respectively. The discharge voltage was approximately 3.2 V for 4LiF-MgMn₂O₄ and approximately 2.8 V for 4LiF-MgFe₂O₄, and 4LiF-MgMn₂O₄ composites had the highest energy densities, exceeding 1000 Wh/kg. During cycle characteristic measurements with a cutoff voltage of 4.8 V and 4.4 V, the initial capacity retentions at the 100th cycle were 11% and 79%, respectively. The Coulombic efficiency was also better at a cutoff voltage of 4.4 V than that of 4.8 V, indicating that electrolyte decomposition has a significant influence on the cycle characteristics. Additionally, composites were synthesized via mechanical milling using various molar ratios of LiF and MgMn₂O₄. In xLiF-MgMn₂O₄ (x ≥ 3), the discharge potential was approximately 3.2 V, and the discharge capacity was higher than 250 mAh/g. The highest discharge capacity was observed for 4LiF-MgMn₂O₄ among xLiF-MgMn₂O₄ (x ≥ 3) composites. Full article

Near-complete (>99%) dissolution of lithium and cobalt was achieved by the leaching of black mass from spent (end-of-life) lithium-ion batteries (LiBs) using 4 M H₂SO₄ or HCl at 60 °C. Raising the temperature to 90 °C did not increase the overall extraction of lithium or cobalt, but it increased the rate of extraction. At 60 °C, 2 M H₂SO₄ or 2 M HCl performed similarly to the 4 M H₂SO₄/HCl solution, although extractions were lower using 1 M H₂SO₄ or HCl (~95% and 98%, respectively). High extractions were also observed by leaching in low pulp density (15 g/L) at 60 °C with 2 M CH₂ClCOOH. Leaching was much slower with hydrogen peroxide reductant concentrations below 0.5 mol/L, with cobalt extractions of 90–95% after 3 h. Pulp densities of up to 250 g/L were tested when leaching with 4 M H₂SO₄ or HCl, with the stoichiometric limit estimated for each test based on the metal content of the black mass. Extractions were consistently high, above 95% for Li/Ni/Mn/Cu with a pulp density of 150 g/L, dropping sharply above this point because of insufficient remaining acid in the solution in the later stages of leaching. The final component of the test work used leaching parameters identified in the previous experiments as producing the largest extractions, and just sulphuric acid. A seven-stage semi-continuous sulphuric acid leach at 60 °C of black mass from LiBs that had undergone an oxidising roast (2h in a tube furnace at 500 °C under flowing air) to remove binder material resulted in high (93%) extraction of cobalt and near total (98–100%) extractions of lithium, nickel, manganese, and copper. Higher cobalt extraction (>98%) was expected, but a refractory spinel-type cobalt oxide, Co₃O₄, was generated during the oxidising roast as a result of inefficient aeration, which reduced the extraction efficiency. Full article

High-voltage spinel (LiNi_0.5Mn_1.5O₄; LNMO) has been a prospective cathode material that may exploit the maximal voltage of 5 V for lithium-ion batteries. However, the practical application has been hindered by the severe electrochemical instability of the Ni²⁺/Ni⁴⁺ redox couple at such a high voltage. Herein, we coated lithium phosphate (Li₃PO₄) on the surface of the LNMO by a wet-coating method to improve the electrochemical stability. The coating layer provided an effective cathode–electrolyte interphase, which prevented the excessive decomposition of the electrolyte on the surface of LNMO cathode. The Li₃PO₄-coated LNMO exhibited enhanced rate capability in accordance with the lowered solid-electrolyte interphase (SEI) and charge-transfer resistance values from electrochemical impedance spectroscopy. Full article

Li-rich Mn-based cathode materials are considered potential cathode materials for next-generation lithium-ion batteries due to their outstanding theoretical capacity and energy density. Nonetheless, challenges like oxygen loss, transition metal migration, and structural changes during cycling have limited their potential for commercialization. The work in this study employed a straightforward heat treatment to generate oxygen vacancies. This process led to the development of a spinel phase on the surface, which improved Li⁺ diffusion and boosted the electrochemical performance of Li-rich Mn-based oxides. The results demonstrate that the treated Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ exhibits an initial specific capacity of 247 mAh·g⁻¹ at 0.2C, as well as a reversible capacity of 224 mAh·g⁻¹ after 100 cycles, with a capacity retention of 90.7%. The voltage decay is 1.221 mV per cycle under 1C long-term cycling conditions, indicating excellent cycling stability and minimal voltage drop. Therefore, this strategy of engineering through nanoscale oxygen vacancies provides a new idea for the development of high-stability layered oxide anodes and provides a reference for the development and application of new energy materials. Full article

A simple and cost-effective route based on a KOH-assisted molten salt method is designed here to synthesize LiNi_0.5Mn_1.5O₄ spinel. Pure-phase LiNi_0.5Mn_1.5O₄ can be successfully prepared using chlorides as raw materials and adding KOH at 700 °C. The structure, morphology, and performance are discussed in detail. The measurements reveal that using KOH-assisted synthesis can optimize the crystal structure of the obtained LiNi_0.5Mn_1.5O₄ samples, resulting in grain refinement while maintaining the predominantly octahedral structure that grows along the (111) crystal plane. This new synthesis pathway provides excellent performance in terms of cycle life. Electrochemical tests show that the KOH-assisted sample exhibits higher initial specific capacities (124.1 mAh·g⁻¹ at 0.2 C and 111.4 mAh·g⁻¹ at 3 C) and superior cycling performances (capacity retention of 85.0% after 200 cycles at 0.2 C and 95.70% after 100 cycles at 3 C). This provides a potential solution for the practical application of high-voltage LiNi_0.5Mn_1.5O₄ lithium-ion batteries. Full article

LiMn₂O₄, a significant cathode material for lithium-ion batteries, has garnered considerable attention due to its low cost and environmental friendliness. However, its widespread application is constrained by its rapid capacity degradation and short cycle life at elevated temperatures. To enhance the electrochemical performance of LiMn₂O₄, we employed a liquid-phase co-precipitation and calcination method to incorporate Cr³⁺ into the LiMn₂O₄ cathode material, successfully synthesizing a series of LiCr_xMn_2−xO₄ (x = 0~0.06). The prepared Cr-doped samples exhibited an excellent spinel structure and a unique truncated octahedral morphology. Additionally, the substitution of Mn³⁺ in LiMn₂O₄ by Cr³⁺, coupled with the significantly higher Cr-O bond energy compared to Mn-O bond energy, enhanced the stability of the crystal structure and inhibited the Jahn–Teller effect. Experimental results demonstrated that the optimized LiCr_0.04Mn_1.96O₄ displayed superior electrochemical performance, with a capacity retention rate of 93.24% after 500 cycles under a 0.5C current density; even at 50 °C, the capacity retention rate remained at 86.46% after 350 cycles under a 0.5C current density. The polyhedral morphology formed by Cr doping in LiMn₂O₄ offers an effective approach to achieving high-performance LiMn₂O₄ cathode materials. Full article