Search Results (17)

High-nickel ternary LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) is a promising cathode material for lithium-ion batteries due to its high discharge-specific capacity and energy density. However, problems of NCM622 materials, such as unstable surface structure, lithium–nickel co-segregation, and intergranular cracking, led to a decrease in the cycling performance of the material and an inability to fully utilize high specific capacity. Surface coating was the primary approach to address these problems. The effect of TiO₂ coating prepared by the sol–gel method on the performance of LiNi_0.6Co_0.2Mn_0.2O₂ was studied, mainly including the morphology, cell structure, and electrochemical properties. LiNi_0.6Co_0.2Mn_0.2O₂ was coated by TiO₂ with a thickness of about 5 nm. Compared with the pristine NCM622 electrode, the electrochemical performance of the TiO₂-coated NCM622 electrodes is improved. Among all TiO₂-coated NCM622, the NCM622 cathode with TiO₂ coating content of 0.5% demonstrates the highest capacity retention of 89.3% and a discharge capacity of 163.9 mAh g⁻¹, in contrast to 80.9% and145 mAh g⁻¹ for the pristine NCM622 electrode, after 100 cycles at 0.3 C between 3 and 4.3 V. The cycle life of the 5 wt% TiO₂-coated NCM622 electrode is significantly improved at a high cutoff voltage of 4.6 V. The significantly enhanced cycling performance of TiO₂-coated NCM622 materials could be attributed to the TiO₂ coating layer that could block the contact between the material surface and the electrolyte, reducing the interface side reaction and inhibiting the transition metal dissolution. At the same time, the coating layer maintained the stability of layered structures, thus reducing the polarization phenomenon of the electrode and alleviating the irreversible capacity loss in the cycle process. Full article

High Ni-content LiNi_xMn_yCo_zO₂ (NMC) cathodes (with x ≥ 0.8, x + y + z = 1) have gained attention recently for their high energy density in electric vehicle (EV) Li-ion batteries. However, Ni-rich cathodes pose challenges in capacity retention due to inherent structural and surface redox instabilities. One promising strategy is to make the Ni-rich NMC material in the form of single-crystal micron-sized particles, as they resist intergranular and surface degradation during cycling. Among various methods to synthesize single-crystal NMC (SC-NMC) particles, molten-salt-assisted calcination offers distinct processing advantages but at present, is not yet optimized or mechanistically clarified to yield the desired control over crystal growth and morphology. In this project, molten-salt-mediated transformation of Ni_0.85Mn_0.05Co_0.15(OH)₂ precursor (P-NMC) particles to LiNi_0.85Mn_0.05Co_0.15O₂ particles is investigated in terms of the crystal growth mechanism and its electrochemical response. Unlike previous studies that involved large volumes of molten salt, using a smaller volume of molten KCl is found to result in larger primary particles with improved cycling performance achieved via partial reactive dissolution and heterogeneous nucleation growth, suggesting that the ratio of molten salt volume to NMC mass is an important parameter in the synthesis of single-crystal Ni-rich NMC materials. Full article

This article presents a novel aging-coupled predictive thermo-electrical dynamic modeling tool tailored for primary lithium manganese dioxide ($Li\text{-}Mn{O}_2$) batteries in active implantable medical devices (AIMDs). The aging mechanisms of rechargeable lithium batteries are well documented using computationally intensive physics-based models, unsuitable for real-time onboard monitoring in AIMDs due to their high demands. There is a critical need for efficient, less demanding modeling tools for accurate battery health monitoring and end-of-life prediction as well as battery safety assessment in these devices. The presented model in this article simulates the battery terminal voltage, remaining capacity, temperature, and aging during active discharge, making it suitable for real-time health monitoring and end-of-life prediction. We incorporate a first-order dynamic for internal resistance growth, influenced by time, temperature, discharge depth, and load current. By adopting Arrhenius-type kinetics and polynomial relationships, this model effectively simulates the combined impact of these variables on battery aging under diverse operational conditions. The simulation handles both the continuous micro-ampere-level demands necessary for device housekeeping and periodic high-rate pulses needed for therapeutic functions, at a constant ambient temperature of 37 °C, mimicking human body conditions. Our findings reveal a gradual, nonlinear increase in internal resistance as the battery ages, rising by an order of magnitude over a period of 5 years. Sensitivity analysis shows that as the battery ages and load current increases, the terminal voltage becomes increasingly sensitive to internal resistance. Specifically, at defibrillation events, the ${\displaystyle \frac{\partial V}{\partial R}}$ trajectory dramatically increases from ${10}^{-12}$ to ${10}^{-8}$, indicating a fourth-order-of-magnitude enhancement in sensitivity. A model verification against experimental data shows an R² value of 0.9506, indicating a high level of accuracy in predicting the $Li\text{-}Mn{O}_2$ cell terminal voltage. This modeling tool offers a comprehensive framework for effectively monitoring and optimizing battery life in AIMDs, therefore enhancing patient safety. Full article

Nanoparticles have many advantages as active materials, such as a short diffusion length, low charge transfer resistance, or a reduced probability of cracking. However, their low packing density makes them unsuitable for commercial battery applications. Hierarchically structured microparticles are synthesized from nanoscale primary particles by targeted aggregation. Due to their open accessible porosity, they retain the advantages of nanomaterials but can be packed much more densely. However, the intrinsic porosity of the secondary particles leads to limitations in processing properties and increases the overall porosity of the electrode, which must be balanced against the improved rate stability and increased lifetime. This is demonstrated for an established cathode material for lithium-ion batteries (LiNi_0.33Co_0.33Mn_0.33O₂, NCM111). For active materials with low electrical or ionic conductivity, especially post-lithium systems, hierarchically structured particles are often the only way to produce competitive electrodes. Full article

An innovative cryo-mechano-hydrometallurgical process (named LIBAT) was demonstrated at pilot scale for the treatment of EOL lithium primary batteries with chemistry Li(0)-MnO₂. The process allowed the recycling of steel scraps from external cases after cryomechanical dismantling, and the recovery of Mn and Li products after hydrometallurgical processing. During demonstration activities, about nine tons of batteries were treated in the cryomechanical section, and one ton of black mass was treated in the hydrometallurgical section for the recovery of Mn hydroxides and Li₂CO₃. The environmental impacts of the process were evaluated in comparison with an innovative pyrometallurgical approach allowing Li recovery, confirming the benefits of the proposed process due to a reduction in energy consumption. Process simulations were performed considering different mixture feeds (only Li primary, or mixture with Li-ion batteries) and process options (only the cryomechanical section of the integral process) to assess the lower limits of potentiality that would ensure economic sustainability. Full article

Environmental concerns push for a reduction in greenhouse gas emissions and technologies with a low carbon footprint. In the transportation sector, this drives the transition toward electric vehicles (EVs), which are nowadays mainly based on lithium-ion batteries (LIBs). As the number of produced EVs is rapidly growing, a large amount of waste batteries is expected in the future. Recycling seems to be one of the most promising end-of-life (EOL) methods; it reduces raw material consumption in battery production and the environmental burden. Thus, this work introduces a comprehensive pre-recycling material characterization of waste nickel-manganese-cobalt (NMC) LIB cells from a fully electric battery electric vehicle (BEV), which represents a basis for cost-effective and environmentally friendly recycling focusing on the efficiency of the implemented technique. The composition of the NCM 622 battery cell was determined; it included a LiNi_0.6Co_0.2Mn_0.2O₂ spinel on a 15 μm Al-based current collector (cathode), a graphite layer on 60 μm copper foil (anode), 25 μm PE/PVDF polymer separator, and a LiPF₆ salt electrolyte with a 1:3 ratio in primary solvents DMC and DEC. The performed research was based on a series of X-ray, infrared (IR) measurements, gas chromatography–mass spectrometry (GC-MS), and inductively coupled plasma–optical emission spectrometry (ICP-OES) characterization of an aqueous solution with dissolved electrolytes. These results will be used in subsequent works devoted to optimizing the most suitable recycling technique considering the environmental and economic perspectives. Full article

The lack of suitable lightweight current collectors is one of the primary obstacles preventing the energy density of aqueous lithium-ion batteries (ALIBs) from becoming competitive. Using silver nanowire (AgNW) films as current collectors and a molecular crowding electrolyte, we herein report the fabrication of ALIBs with relatively good energy densities. In the 2 m LiTFSI–94% PEG–6% H₂O solution, the AgNW films with a sheet resistance of less than 1.0 ohm/square exhibited an electrochemical stability window as broad as 3.8 V. The LiMn₂O₄//Li₄Ti₅O₁₂ ALIBs using AgNW films as the current collectors demonstrated an initial energy density of 70 Wh/kg weighed by the total mass of the cathode and anode, which retained 89.1% after 50 cycles. Full article

Silicon has become an integral negative electrode component for lithium-ion batteries in numerous applications including electric vehicles and renewable energy sources. However, its high capacity and low cycling stability represent a significant trade-off that limits its widespread implementation in high fractions in the negative electrode. Herein, we assembled high-capacity (1.8 Ah) cells using a nanoparticulate silicon–graphite (1:7.1) blend as the negative electrode material and a LiFePO₄–LiNi_0.5Mn_0.3Co_0.2O₂ (1:1) blend as the positive electrode. Two types of cells were constructed: cylindrical 18650 and pouch cells. These cells were subjected both to calendar and cycling aging, the latter exploring different working voltage windows (2.5–3.6 V, 3.6–4.5 V, and 2.5–4.5 V). In addition, one cell was opened and characterised at its end of life by means of X-ray diffraction, scanning electron microscopy, and further electrochemical tests of the aged electrodes. Si degradation was identified as the primary cause of capacity fade of the cells. This work highlights the need to develop novel strategies to mitigate the issues associated with the excessive volumetric changes of Si. Full article

Compared with the polycrystalline system, the single-crystalline ternary cathode material has better cycle stability because the only primary particles without grain boundaries effectively alleviate the formation of micro/nanocracks and retain better structural integrity. Therefore, it has received extensive research attention. There is no consistent result whether tungsten oxide acts as doping and/or coating from the surface modification of the polycrystalline system. Meanwhile, there is no report on the surface modification of the single-crystalline system by tungsten oxide. In this paper, multirole surface modification of single-crystalline nickel-rich ternary cathode material LiNi_0.6Co_0.2Mn_0.2O₂ by WO₃ is studied by a simple method of adding WO₃ followed by calcination. The results show that with the change in the amount of WO₃ added, single-crystalline nickel-rich ternary cathode material can be separately doped, separately coated, and both doped and coated. Either doping or coating effectively enhances the structural stability, reduces the polarization of the material, and improves the lithium-ion diffusion kinetics, thus improving the cycle stability and rate performance of the battery. Interestingly, both doping and coating (for SC-NCM622-0.5%WO₃) do not show a more excellent synergistic effect, while the single coating (for SC-NCM622-1.0%WO₃) after eliminating the rock-salt phase layer performs the most excellent modification effect. Full article

In order to examine the effect of excessive sulfate in the leachate of spent Li-ion batteries (LIBs), LiNi_1/3Co_1/3Mn_1/3O₂ (pristine NCM) and sulfate-containing LiNi_1/3Co_1/3Mn_1/3O₂ (NCMS) are prepared by a co-precipitation method. The crystal structures, morphology, surface species, and electrochemical performances of both cathode active materials are studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and charge-discharge tests. The XRD patterns and XPS results identify the presence of sulfate groups on the surface of NCMS. While pristine NCM exhibits a very dense surface in SEM images, NCMS has a relatively porous surface, which could be attributed to the sulfate impurities that hinder the growth of primary particles. The charge-discharge tests show that discharge capacities of NCMS at C-rates, which range from 0.1 to 5 C, are slightly decreased compared to pristine NCM. In dQ/dV plots, pristine NCM and NCMS have the same redox overvoltage regardless of discharge C-rates. The omnipresent sulfate due to the sulfuric acid leaching of spent LIBs has a minimal effect on resynthesized NCM cathode active materials as long as their precursors are adequately washed. Full article

Composite positive electrode materials (1−x) LiNi_0.8Mn_0.1Co_0.1O₂∙xLi₂SO₄ (x = 0.002–0.005) for Li-ion batteries have been synthesized via conventional hydroxide or carbonate coprecipitation routes with subsequent high-temperature lithiation in either air or oxygen atmosphere. A comparative study of the materials prepared from transition metal sulfates (i.e., containing sulfur) and acetates (i.e., sulfur-free) with powder X-ray diffraction, electron diffraction, high angle annular dark field transmission electron microscopy, energy-dispersive X-ray spectroscopy, and electron energy loss spectroscopy revealed that the sulfur-containing species occur as amorphous Li₂SO₄ at the grain boundaries and intergranular contacts of the primary NMC811 crystallites. This results in a noticeable enhancement of rate capability and capacity retention over prolonged charge/discharge cycling compared to their sulfur-free analogs. The improvement is attributed to suppressing the high voltage phase transition and the associated accumulation of anti-site disorder upon cycling and improving the secondary agglomerates’ mechanical integrity by increasing interfacial fracture toughness through linking primary NMC811 particles with soft Li₂SO₄ binder, as demonstrated with nanoindentation experiments. As the synthesis of the (1−x) LiNi_0.8Mn_0.1Co_0.1O₂∙xLi₂SO₄ composites do not require additional operational steps to introduce sulfur, these electrode materials might demonstrate high potential for commercialization. Full article

Li primary batteries are currently treated along with other Li batteries in several big pyro- metallurgical plants in Northern EU countries. Nevertheless, pyro-metallurgical processes do not allow for Mn and Li recycling and present negative environmental impacts, on the other hand hydrometallurgical processing can potentially ensure the integral recovery of all materials in Li primary batteries. In this work, preliminary experimental findings obtained in the LIFE-LIBAT project (LIFE16 ENV/IT/000389) are reported. In this project, end of life Li(0)-MnO₂ batteries were cryo-mechanically treated and then the metals were recovered by a hydrometallurgical process. Representative samples of end of life Li(0) batteries were characterized by type and composition. Batteries were stabilized in an N₂ bath and then crushed, sieved, and magnetically separated in the SEVal pilot units. Separated fractions (fine fraction, magnetic coarse fraction, and non-magnetic coarse fraction) were chemically characterized for target metal content (Li and Mn). Fractions were first treated for Li extraction and recovery, then the fine fraction was also leached for Mn recovery. Mass balances evidenced a 55% recycling rate and process simulations outlined profitability in the potentiality range in agreement with battery collection fluxes. Full article

In this work, an innovative hydrometallurgical recycling route for the recovery of all the materials composing Li-MnO₂ primary batteries was proposed. End-of-life batteries were mechanically treated in an innovative pilot plant where a cryogenic crushing was performed. The mechanical treatment allowed for the release of the electrodic powder contained in the batteries with the simultaneous recovery of 44 kg of steel and 18 kg of plastics from 100 kg of batteries. Electrodic powder was employed as the raw material for the synthesis of LiMnPO₄ nanoparticles. To obtain the synthesis precursors, selective sequential leaching of Li and Mn was performed. Li was extracted via water washing the electrodic powder and Li₂CO₃ and a purity of 99% was recovered. The black mass containing Mn oxides was leached using phosphoric acid, which gave a Mn-bearing precursor solution that was directly used for the hydrothermal synthesis of LiMnPO₄ nanoparticles. A preliminary materials balance of the process was presented, indicating that the proposed process should be an easy hydrometallurgical route for the recycling of primary lithium batteries. In addition, the simultaneous production of high-value-added products that could be reintroduced into the battery manufacturing chain could ensure the economic feasibility of the process. Full article

Understanding the capacity fading mechanism of the LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathode materials is crucial for achieving long-lasting lithium-ion batteries with high energy densities. In this study, we investigated the factors affecting the capacity fading of NCM811 during repeated cycling at high temperatures. We found that the change in the c-axis length during charging and discharging is the main cause of the formation and propagation of microcracks in the primary particles of NCM811. In addition, the electrolyte is decomposed on the microcrack surfaces and, consequently, by-products are formed on the particle surface, increasing the impedance and resulting in poor electronic and ionic connectivity between the primary particles of NCM811. In addition, the transition metals in the NCM811 cathode material are dissolved in the electrolyte from the newly formed microcrack surface between primary particles. Therefore, the electrolyte decomposition and transition metal dissolution on the newly formed surface are the major deteriorative effects behind the capacity fading in NCM811. Full article

Li_1.27Cr_0.2Mn_0.53O₂ layered cathodic materials were prepared by a nanomilling-assisted solid-state process. Whole-pattern refinement of X-ray diffraction (XRD) data revealed that the samples are solid solutions with layered α-NaFeO₂ structure. SEM observation of the prepared powder displayed a mesoporous nature composed of tiny primary particles in nanoscale. X-ray photoelectron spectroscopy (XPS) studies on the cycled electrodes confirmed that triple-electron-process of the Cr³⁺/Cr⁶⁺ redox pair, not the two-electron-process of Mn redox pair, dominants the electrochemical process within the cathode material. Capacity test for the sample revealed an initial discharge capacity of 195.2 mAh·g⁻¹ at 0.1 C, with capacity retention of 95.1% after 100 cycles. EIS investigation suggested that the high Li ion diffusion coefficient (3.89 × 10⁻¹⁰·cm²·s⁻¹), caused by the mesoporous nature of the cathode powder, could be regarded as the important factor for the excellent performance of the Li_1.27Cr_0.2Mn_0.53O₂ layered material. The results demonstrated that the cathode material prepared by our approach is a good candidate for lithium-ion batteries. Full article