Li Mn Research Articles

A process for preferential recovery of lithium and manganese from spent NCM by vacuum carbothermal reduction method

In this study, a process was developed for the preferential recovery of lithium and manganese from spent ternary lithium batteries using the vacuum carbothermal reduction method. Firstly, the electrolyte and PVDF in the cathode and anode wafers of the spent ternary lithium batteries were removed. Subsequently, lithium in the cathode powder was preferentially recovered under vacuum conditions using the anodic powder as a reducing agent. The findings show that at 1623 K and 25 %for 2 h, the reduction process generates Li2O, (NiO)m-(MnO)n, Ni, and Co as the ultimate products. Reduction roasting enables the preferential extraction of 99.99 % Li and 99.82 % Mn, which condense on the condensation tray as Li2O and MnOx, while Ni and Co are present in the residue as oxides and monomers. In summary, the whole process of the vacuum carbothermal reduction method achieves efficient extraction of Li and Mn while avoiding the subsequent recovery of Ni, Co, and Mn. It also minimizes Li loss and Mn contamination during the recovery of Ni and Co. Additionally, by utilizing the cathode material from waste LIBs. This process realises the use of waste for waste management, resulting in significant cost savings in recycling and reducing environmental harm.

The high strength and ductility mechanism of Zn-0.45Mn-0.8Li alloys with heterogeneous lamellar structure

The high strength and ductility Zn–Mn–Li alloys with heterogeneous lamellar (HL) structure were prepared by rotary swaging. Li(Mn,Zn)4 phase was identified as the matrix phase. Grain refinement and hetero-deformation induced strengthening. Grain sliding and activation of more pyramidal slip system increase the strain.

Towards a State of Health Definition of Lithium Batteries through Electrochemical Impedance Spectroscopy

In the era of Industry 4.0, achieving optimization in production and minimizing environmental impact has become vital. Energy management, particularly in the context of smart grids, plays a crucial role in ensuring sustainability and efficiency. Lithium-ion batteries have emerged as a leading technology for energy storage due to their versatility and performances. However, accurately assessing their State of Health (SOH) is essential for maintaining grid reliability. While discharge capacity and internal resistance (IR) are commonly used SOH indicators, battery impedance also offers valuable insights into aging degradation. This article explores the use of Electrochemical Impedance Spectroscopy (EIS) to define the SOH of lithium batteries. By analyzing impedance spectra at different frequencies, a comprehensive understanding of battery degradation is obtained. A life cycle analysis is conducted on cylindrical Li–Mn batteries under various discharge conditions, utilizing EIS measurements and an Equivalent Circuit Model (ECM). This study highlights the differential effects of aging on battery characteristics, emphasizing the variations at different life stages and the behavior changes on each region of the impedance spectrum. Furthermore, it demonstrates the efficacy of EIS and the advantages of this technique compared to the solely IR measurements used in tracking SOH over time. This research contributes to advancing the understanding of lithium battery degradation and underscores the importance of EIS in defining their State of Health for Smart Grids applications.

Phase equilibria in the quasi–ternary Li<sub>2</sub>O–Mn<sub>2</sub>O<sub>3</sub>–Eu<sub>2</sub>O<sub>3</sub> system

Series of samples of quasi–ternary Li2O–Mn2O3 – Eu2O3 system, synthesized from of precursors subjected to preliminary mechanochemical activation and annealed in air at temperatures of 700–1100°C have been systematically studied by powder X–ray diffraction(pXRD) and thermal analysis (TG–DSC) methods. The possibility of substituting Mn for Eu for the LiMn2–xEuxO4 spinel phase is estimated. Within the framework of the Li–Mn–Eu concentration triangle, a subsolidus isobaric diagram and a projection of the liquidus surface of the Li–Mn–Eu–O system were constructed using models of polythermal phase diagrams of the LiEuO2–LiMnO2 and LiEuO2–LiMn2O4 sections. The temperatures of eutectic equilibria with the participation of three crystalline phases and a melt were determined.

Enhanced mechanical properties and microstructural stability of ultrafine-grained biodegradable Zn–Li–Mn–Mg–Cu alloys produced by rapid solidification and high-pressure torsion

Zinc alloys have emerged as promising candidates for biodegradable materials due to their remarkable biocompatibility and favorable mechanical characteristics. The incorporation of alloying elements plays an essential role in advancing the tensile strength of Zn alloys. Nevertheless, achieving uniform dispersion of these elements poses challenges due to chemical segregation during solidification. In this study, rapid solidification followed by high-pressure torsion was successfully employed to fabricate Zn–Li–Mn–Mg–Cu alloys characterized by ultrafine-grained microstructures with evenly distributed nanometric intermetallic phases. A comprehensive examination, including phase composition, microstructural evolution, tensile properties and deformation mechanisms, was conducted. The impact of varying annealing temperatures on microstructural stability was systematically examined. The combined implementation of rapid solidification and high-pressure torsion yielded alloys with an average grain size below 360 nm, thereby demonstrating exceptional mechanical properties including yield stress (YS), ultimate tensile strength (UTS), and elongation to failure (Ef) equal to at least 325 ± 6 MPa, 350 ± 8 MPa and 40 ± 11 %, respectively. Heat treatment notably augmented the mechanical properties, resulting in a YS = 440 ± 11 MPa and UTS = 491 ± 6 MPa, while preserving plasticity (Ef = 23 ± 4 %) in the Zn-0.33Li-0.27Mn-0.14Mg-0.1Cu alloy. Nanoindentation strain rate jump tests identified thermally activated mechanisms and grain boundary sliding as dominant deformation mechanisms.

Entropic Stabilization in Lithium Rich Transition Metal Oxide Cathodes

It is well known that lithium rich transition metal oxide cathodes (LRM) experience voltage fade and capacity loss over the course of cycling, and it is generally known that these are a result of the LRM materials’ general instability 1–7. However, the mechanisms behind these losses are still unknown, due in large part to the structural ambiguity and controversy associated with the LRM material structure. In this perspective we consider the role entropy plays in LRM materials’ structural stability and electrochemical properties. With this mind set we argue that due to their metastability LRM cathodes’ structure and properties are not synthesis agnostic, and therefore establishment of consistent synthetic procedures is of paramount importance. We also propose that LRM materials could be categorized as entropically stabilized oxides through exploring their configurational entropies, phase behaviors, and thermal responses. The entropic stabilization of LRM materials is also found to be consistent with the ordering behaviors of LRM cathode transitional metal layers, with this ordering presenting both compositional, thermal, and electrochemical dependencies. The impact of these behaviors on the redox and electrochemical structure and activation of LRM materials is also explored. Finally, we seek to put these findings into the context of the wider battery field. Fell, C. R. et al. Correlation Between Oxygen Vacancy, Microstrain, and Cation Distribution in Lithium-Excess Layered Oxides During the First Electrochemical Cycle. Chem. Mater. 1621–1629 (2013) doi:10.1021/cm4000119.Lu, Z., Beaulieu, L. Y., Donaberger, R. A., Thomas, C. L. & Dahn, J. R. Synthesis, Structure, and Electrochemical Behavior of Li [Ni x Li(1/2-2x/3) Mn(2/3-x/3)]O2. J. Electrochem. Soc. 149, A778–A791 (2002).Wu, Y. & Manthiram, A. High Capacity, Surface-Modified Layered Li†Li„1−x.../3Mn„2−x.../3Nix/3Cox/3‡O2 Cathodes with Low Irreversible Capacity Loss. Electrochem. Solid-State Lett. 9, A221–A224 (2006).Dupré, N., Cuisinier, M., Legall, E., War, D. & Guyomard, D. Contribution of the oxygen extracted from overlithiated layered oxides at high potential to the formation of the interphase. J. Power Sources 299, 231–240 (2015).Jarvis, K. A. et al. Formation and effect of orientation domains in layered oxide cathodes of lithium-ion batteries. Acta Mater. 108, 264–270 (2016).Jiang, M., Key, B., Meng, Y. S. & Grey, C. P. Electrochemical and Structural Study of the Layered, ‘Li-Excess’; Lithium-Ion Battery Electrode Material Li[Li 1/9 Ni 1/3 Mn 5/9 ]O 2. Chem. Mater. 21, 2733–2745 (2009).Hy, S. et al. Performance and design considerations for lithium excess layered oxide positive electrode materials for lithium ion batteries. Energy Environ. Sci. 9, 1931–1954 (2016).

Concentration Tetrahedron of the Li–Mn–Eu–O System

Concentration Tetrahedron of the Li–Mn–Eu–O System

Phase Equilibria in the Li–Mn–Eu–O System

Phase Equilibria in the Li–Mn–Eu–O System

PHASE EQUILIBRIA IN THE Li–Mn–Eu–O SYSTEM

Phase equilibria in the Li–Mn–Eu–O system were studied for the first time in the temperature range 700–1000°С, and a concentration diagram was plotted within the Li–Mn–Eu triangle at an oxygen partial pressure of 21 kPa. It is shown that the LiEuO2–Li2MnO3 system is quasi-binary, unlike the sections LiEuO2–LiMnO2 and LiEuO2–LiMn2O4. It has been established that, for spinel LiMn2O4 (Fd\(\bar {3}\)m), a homogeneous introduction of 2 mol % Eu is possible, while in the case of Li2MnO3 (C2/m), the single-phase state decays.

Phase States in the Li–Mn–Eu–O System

Phase States in the Li–Mn–Eu–O System

CONCENTRATION TETRAHEDRON OF THE Li–Mn–Eu–O SYSTEM

Based on fragmentary experimental data, an isothermal concentration tetrahedron of the Li–Mn–Eu–O system was constructed for the first time by the method of topological modeling, which describes possible solid-state transformations in the system occurring at a constant temperature with a change in pressure. Thirty-two equilibria involving four crystalline phases have been identified.

Characterization of trace and heavy metal concentration in groundwater: A case study from a tropical river basin of southern India

This study investigates the hydrogeochemistry of groundwater samples collected from the Shiriya River Basin (SRB), a tropical watershed located in Kasaragod, Kerala, southern India, with a special focus on trace elements. Fifty-four groundwater samples were collected from deep aquifers, which constitute weathered and fractured granitoids and mafic rocks, and the groundwater is tapped by bore wells from a fractured zone at a depth range of 60–100 m. Concentrations of Sr, Li, Ba, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Cd, Ag, Au, Te, Pb, Re, and PGEs in groundwater were determined by using Q-ICPMS. Out of the 25 analysed trace elements in groundwater, only Sr (489.6 μg/L), Ba (226 μg/L), Li (11.76 μg/L) Mn (396.8 μg/L), Ni (68 μg/L) and Fe (2438.5 μg/L) show anomalous values. The PGEs and the majority of trace elements show values within the permissible limit. Raman spectral studies reveal the presence of celsian in aquifer rocks and are the source of Ba in groundwater. Further, XRF data of the rocks show a high enrichment of Fe and Mn in mafic dyke, basalt, and syenite, and Ba and Sr in granite, pegmatite, and granitic gneiss. Therefore, this study proved that the source of these elements is geogenic, i.e., they are released from the crystalline aquifer through rock-water interaction under alkaline conditions. The results of this study show that the groundwater of the basin has enough metals such as Na, K, Mg, Ca, Mn, Fe, Co, Cu, and Zn, which are good for health. Nevertheless, a few metals (Fe, Mn, Ba, Sr, Li, Ni) that may exert toxic effects on humans are also present in the groundwater of the SRB. As groundwater is found to be a dependable source of drinking water in such watersheds, a comprehensive study on the hydrogeochemistry of all watersheds in tropical regions is recommended.

Precipitates strengthening mechanism of a new squeeze-cast Al–Cu–Li–Mn alloy with high strength and ductility

In this paper, aging precipitates and their high effects on mechanical properties of squeeze-cast Al–5Cu-0.6Li-0.5Mn-0.3Mg-0.15Ti alloy (a novel Al–Cu–Li–Mn alloy) were investigated to reveal strengthening & toughening mechanism. After T6 heat treatment (i.e., solution treatment at 530 °C for 10 h + aging at 180 °C for 8 h), its ultimate tensile strength (UTS), yield strength (YS) and elongation (El.) are 465 MPa, 310 MPa and 16.5%, respectively. Compared with the as-cast Al–Cu–Li–Mn alloy, the UTS and YS are increased by 55% and 63.2%, respectively, with almost no loss in ductility. Interestingly, the product of UTS and El. (i.e., UTS•El.) of the T6-treated Al–Cu–Li–Mn alloy reaches 7.67 GPa%, which is 50.4% higher than that of the as-cast Al–Cu–Li–Mn alloy and better than that of most third-generation or fourth-generation Al–Li and Li-free 2xxx alloys prepared by casting or plastic deformation followed by heat treatment. The uniformly dispersed submicron-sized T (AlxMnyCuz), nano-sized T1 (Al2CuLi) and much smaller θ' (Al2Cu) phases precipitated in the T6-treated Al–Cu–Li–Mn alloy are coherent or semi-coherent with aluminum matrix, which not only enhances strength but also delays strain localization and fracture. In addition, the actual average thickness of T1 and θ′ precipitates are about 2 nm and 3.5 nm, which are much larger than their critical values for the conversion of their strengthening mechanisms. Therefore, the main strengthening mechanism of the squeeze-cast Al–Cu–Li–Mn alloy is the Orowan bypassing mechanism rather than the shearing mechanism.

Mapping of geological complexity and analyzing its relationship with the distribution of gold deposits in the Guangxi Gold Ore Province, Southern China

The Guangxi gold ore province contains >370 gold deposits with total resources of >260 t Au. Factor analysis (FA) of geochemical data, and calculation of lineament density within 10 km, 20 km, and 30 km circular search grids across a geological map, were applied in Guangxi to highlight geological complexity and to analyze its relationships with the distribution of gold deposits. The FA of stream sediment geochemical data for 42 elements, subjected first to center logarithmic transformation (clr), yield several element combinations that allowed distinction of metallogenic signatures from geological backgrounds. The element combinations of the first and second factors were Cd–Co–Cr–Cu–Li–Mn–Ni–P–Sb–Y–Zn–Mg and Be–Bi–La–Nb–Pb–Sn–Th–U–W–Zr–Al, and the spatial distributions of their factor scores overlap the Devonian to Permian strata and granite, respectively. The distribution of factor scores of mineralization-related element combination, Ag–As–Au–Mo, coincides with 70 % of gold deposits. The lineament density mapping can highlight different-scale faults and lithological contacts by using circular search grids with different diameters. The C–A fractal modeling for lineament density has indicated four populations, namely low, moderate-low, moderate-high, and high lineament densities. About ∼80 to ∼90 % of the known gold deposits exist in areas with moderate-low to moderate-high lineament densities. This highlights the importance of distinguishing geological complexity based on faults and lithological contacts, which are commonly the pathways for the focused fluid flow and gold ore formation. The deposit-scale geological complexity mapping has predicted several exploration targets, where high-grade gold orebodies have been prospected successfully by drilling in 2018. The geological complexity mapping is a kind of geochemical and geological complementation for resource potential assessment.

Direct Electrochemical Leaching Method for High-Purity Lithium Recovery from Spent Lithium Batteries.

Recovering lithium from lithium batteries (LIBs) is a promising approach for sustainable ternary lithium battery (T-LIB) development. Current lithium recovery methods from spent T-LIBs mainly concentrated on chemical leaching methods. However, chemical leaching relying on the additional acid seriously threatens the global environment and nonselective leaching also leads to low Li recovery purity. Here, we first reported a direct electro-oxidation method for lithium leaching from spent T-LIBs (Li0.8Ni0.6Co0.2Mn0.2O2); 95.02% of Li in the spent T-LIBs was leached under 2.5 V in 3 h. Meanwhile, nearly 100% Li recovery purity was also achieved, attributed to no other metal leaching and additional agents. We also clarified the relationship between lithium leaching and other metals during the electro-oxidation of spent T-LIBs. Under the optimized voltage, Ni and O maintain the electroneutrality in the structure assisting Li leaching, while Co and Mn maintain their valence states. A direct electro-oxidation Li leaching approach achieves high Li recovery purity and meanwhile overcomes the secondary pollution problem.

Stabilizing a Li–Mn–O Cathode by Blocking Lattice O Migration through a Nanoscale Phase Complex

Among all intercalation cathodes for Li-ion batteries, Li–Mn–O layered oxides offer the highest initial energy density at the lowest cost, due to the joint contribution from cationic and anionic redox chemistry. However, the poor cycling capability, resulting from the continuous lattice O loss at high potentials (>4.5 V), hinders practical applications. Herein, we employed phase complex engineering to obtain a new Li–Mn–O nanohybrid cathode featuring the uniform and coherent integration of layered nanodomains and spinel nanodomains. The combination of DFT calculations, synchrotron-based transmission X-ray microscopy, in situ differential electrochemical mass spectrometry, in situ synchrotron XRD, and electrochemical tests demonstrated that the O migration path in layered nanodomains was blocked by the neighboring spinel nanodomains with a higher oxygen vacancy migration energy, thus effectively suppressing the irreversible lattice O loss at high potentials and enhancing the cycling stability in both capacity and average voltage. The strategy is experimentally demonstrated to be effective and it leads to a new path for developing stable high-energy-density cathode materials.

Li–Mn–O Li-rich cation disordered rock-salt cathode materials do not undergo reversible oxygen redox during cycling

A comprehensive study of Li4Mn2O5 (LMO) shows that it does not undergo reversible oxygen redox when charged in lithium cells. The electrochemical properties can be substantially improved by modification with spinel (LMO-s).

In-depth structural characterization of the influence of Li+ excess on spherical, Co-free layered LiMn0.5Ni0.5O2 cathode material using correlative Raman–SEM microscopy

Structural evidence of a Li+ induced phase segregation on particle level in Co-free layered Li–Mn–Ni-oxide cathode materials for Li-ion batteries is presented, illustrating the importance of correlative SEM–Raman microscopy in battery research.

Evaluating the theoretical elastic properties of Li-Mn ferrites: A new approach

The ability to select the most suited ferrite materials for a given application necessitates understanding of their elastic characteristics. In the present communication, the elastic properties of Li–Mn–Co, Li–Mn–Ni and Li–Mn–Cu ferrite series were evaluated and predicted in terms of compositional parameters, for the first time. This has been carried out on the basis of Makishima-Mackenzie's theory, Rocherulle et al. model as well as Abd El-Moneim and Alfifi's approach. The compositional factors that are most important were assessed and correlated with experimental elastic properties. Moreover, the theoretically calculated values of elastic moduli, micro-hardness, and Poisson's ratio were compared with those determined experimentally from ultrasonic velocities and density measurements. It has been found that Abd El-Moneim and Alfifi's approach can be applied successfully to predict changes in bulk modulus of the investigated ferrite series. The calculated packing densities from Makishima-Mackenzie's theory and Rocherulle et al. model are suitable for predicting the data of experimental Poisson's ratio. A reasonable agreement between theoretical and experimental data of elastic moduli, and micro-hardness was achieved on the basis of Makishima-Mackenzie's theory.

A second nearest-neighbor modified embedded-atom method combined with a charge equilibration interatomic potential for the Li–Ni–O ternary system and Li diffusion in lithium-ion battery cathode structure

Ni is a key element, especially in layered cathodes, to achieve a large capacity and a reduced cost. To analyze and gain insight into such cathode materials, large-scale atomistic simulations such as molecular dynamics (MD) are a suitable method. In this paper, a Li–Ni–O interatomic potential has been developed on the basis of the second nearest-neighbor modified embedded-atom method (2NNMEAM) formalism combined with a charge equilibration (Qeq) concept. This potential reproduces fundamental properties (thermodynamic, structural, elastic) of lithium-nickel and nickel oxide binary systems as well as the lithium-nickel oxide ternary system in good agreement with experiments and first-principles calculations. Lithium diffusion properties such as the activation energy for lithium migration and diffusion coefficients in Li1-xNiO2 layered structures are also calculated by a MD simulation and found to show the same tendency as observed in experiments. The potential can be utilized for simulating various material phenomena in the Li-ion battery (LIB) system and can be easily extended to the mainly used Li-[Ni,Mn,Co]-O quinary system, in combination with already developed Li–Mn–O and Li–Co–O ternary potentials based on the same formalism.