RESUMEN
Lithium-metal batteries offer substantial advantages over lithium-ion batteries in terms of gravimetric and volumetric energy densities. However, their widespread practical use is hindered by safety concerns, often attributed to the poor stability of the metallic lithium interface, where electrochemical impedance spectroscopy (EIS) can provide crucial information. The EIS spectra of metallic lithium electrodes proved to be more complex than expected, especially when studying thin lithium metal foils. Here, it is identified that charge-transfer impedance becomes one of the main components of the EIS spectra, the magnitude of which is found to be strongly dependent on the native passivation layer of metallic lithium and on the nature of electrolyte. "Asymmetricity" of the EIS spectra in symmetric cells when separated the working and counter electrode contributions to the total impedance using three-electrode cells is also identified.
RESUMEN
Lithium-ion batteries based on single-crystal LiNi1- x - y Cox Mny O2 (NCM, 1-x-y ≥ 0.6) cathode materials are gaining increasing attention due to their improved structural stability resulting in superior cycle life compared to batteries based on polycrystalline NCM. However, an in-depth understanding of the less pronounced degradation mechanism of single-crystal NCM is still lacking. Here, a detailed postmortem study is presented, comparing pouch cells with single-crystal versus polycrystalline LiNi0.60 Co0.20 Mn0.20 O2 (NCM622) cathodes after 1375 dis-/charge cycles against graphite anodes. The thickness of the cation-disordered layer forming in the near-surface region of the cathode particles does not differ significantly between single-crystal and polycrystalline particles, while cracking is pronounced for polycrystalline particles, but practically absent for single-crystal particles. Transition metal dissolution as quantified by time-of-flight mass spectrometry on the surface of the cycled graphite anode is much reduced for single-crystal NCM622. Similarly, CO2 gas evolution during the first two cycles as quantified by electrochemical mass spectrometry is much reduced for single-crystal NCM622. Benefitting from these advantages, graphite/single-crystal NMC622 pouch cells are demonstrated with a cathode areal capacity of 6 mAh cm-2 with an excellent capacity retention of 83% after 3000 cycles to 4.2 V, emphasizing the potential of single-crystalline NCM622 as cathode material for next-generation lithium-ion batteries.
RESUMEN
Developing a simple, cheap, and scalable synthetic method for the fabrication of functional nanomaterials is crucial. Carbon-based nanowire nanocomposites could play a key role in integrating group IV semiconducting nanomaterials as anodes into Li-ion batteries. Here, we report a very simple, one-pot solvothermal-like growth of carbonaceous germanium (C-Ge) nanowires in a supercritical solvent. C-Ge nanowires are grown just by heating (380-490 °C) a commercially sourced Ge precursor, diphenylgermane (DPG), in supercritical toluene, without any external catalysts or surfactants. The self-seeded nanowires are highly crystalline and very thin, with an average diameter between 11 and 19 nm. The amorphous carbonaceous layer coating on Ge nanowires is formed from the polymerization and condensation of light carbon compounds generated from the decomposition of DPG during the growth process. These carbonaceous Ge nanowires demonstrate impressive electrochemical performance as an anode material for Li-ion batteries with high specific charge values (>1200 mAh g-1 after 500 cycles), greater than most of the previously reported for other "binder-free" Ge nanowire anode materials, and exceptionally stable capacity retention. The high specific charge values and impressively stable capacity are due to the unique morphology and composition of the nanowires.
RESUMEN
Ni-rich layered oxides, in a general term of Li(NixCoyMn1-x-y)O2 (x > 0.5), are widely recognized as promising candidates for improving the specific energy and lowering the cost for next-generation Li-ion batteries. However, the high surface reactivity of these materials results in side reactions during improper storage and notable gas release when the cell is charged beyond 4.3 V vs Li+/Li0. Therefore, in this study, we embark on a comprehensive investigation on the moisture sensitivity of LiNi0.85Co0.1Mn0.05O2 by aging it in a controlled environment at a constant room-temperature relative humidity of 63% up to 1 year. We quantitatively analyze the gassing of the aged samples by online electrochemical mass spectrometry and further depict plausible reaction pathways, accounting for the origin of the gas release. Transmission electron microscopy reveals formation of an amorphous surface impurity layer of ca. 10 nm in thickness, as a result of continuous reactions with moisture and CO2 from the air. Underneath it, there is another reconstructed layer of ca. 20 nm in thickness, showing rock salt/spinel-like features. Our results provide insight into the complex interfacial degradation phenomena and future directions for the development of high-performance Ni-rich layered oxides.
RESUMEN
Control of electrode-electrolyte interfacial reactivity at high-voltage is a key to successfully obtain high-energy-density lithium-ion batteries. In this study, 2-aminoethyldiphenyl borate (AEDB) is investigated as a multifunctional electrolyte additive in stabilizing surface and bulk of both Ni-rich LiNi0.85 Co0.1 Mn0.05 O2 (NCM851005) and graphite electrodes in a cell operated with elevated upper cutoff voltage of 4.4â V vs. Li+ /Li. The presence of AEDB in a full-cell inhibits structural degradation of both cathode and anode materials, suppressing crack formation, and reduces metal dissolution at the cathode and metal deposition at the anode. As a consequence, the interfacial resistance is significantly reduced. Moreover, this is a case where "the whole is greater than the sum of the parts": the effect of AEDB in half-cells is rather modest, whereas in full-cells its addition results in tremendous performance improvement. The graphiteâNCM851005 full-cell in the presence of AEDB has a capacity retention of 88 % after 100 cycles, even when the upper cutoff voltage is set to 4.35â V, corresponding to 4.4â V vs Li+ /Li, whereas with standard electrolyte under the same conditions it is only 21 %. The study shows a simple and easy approach to using Ni-rich cathodes in an extended voltage window and demonstrates the importance of full-cell testing for electrolyte additive selection.
RESUMEN
Carbon inverse opals (IOs) were prepared via a facile synthesis approach using a sucrose-based precursor and polystyrene (PS) spheres as a sacrificial template. During IO preparation, polymer spheres are typically removed by dispersion in organic solvents, such as toluene or tetrahydrofuran. In this study, carbon IOs are prepared with and without removal of PS spheres by toluene to determine the influence of template removal prior to high-temperature treatment on the morphology and chemistry of the resulting carbons. Properties of samples are compared through a systematic investigation by electron microscopy, Fourier-transform infrared spectroscopy and Raman spectroscopy. We demonstrate that a commonly used processing step-polymer sphere template chemical removal-does not make any significant difference to the IO morphology. A correlation of Raman spectroscopy with SEM imaging and TGA analysis indicates that carbon IOs prepared without the solvent-treatment step are more ordered than samples prepared with this processing step. The key finding of this report is the simplified IO synthesis procedure, which can be adapted to the preparation of IOs of other materials besides carbon.
RESUMEN
High-energy-density lithium-rich materials are of significant interest for advanced lithium-ion batteries, provided that several roadblocks, such as voltage fade and poor energy efficiency are removed. However, this remains challenging as their functioning mechanisms during first cycle are not fully understood. Here we enlarge the cycling potential window for Li1.2Ni0.13Mn0.54Co0.13O2 electrode, identifying novel structural evolution mechanism involving a structurally-densified single-phase A' formed under harsh oxidizing conditions throughout the crystallites and not only at the surface, in contrast to previous beliefs. We also recover a majority of first-cycle capacity loss by applying a constant-voltage step on discharge. Using highly reducing conditions we obtain additional capacity via a new low-potential P" phase, which is involved into triggering oxygen redox on charge. Altogether, these results provide deeper insights into the structural-composition evolution of Li1.2Ni0.13Mn0.54Co0.13O2 and will help to find measures to cure voltage fade and improve energy efficiency in this class of material.
RESUMEN
Asymmetric separators with polysulfide barrier properties consisting of porous polypropylene grafted with styrenesulfonate (PP-g-PLiSS) were characterized in lithium-sulfur cells to assess their practical applicability. Galvanostatic cycling at different C-rates with and without an electrolyte additive and cyclic voltammetry were used to probe the electrochemical performance of the cells with the PP-g-PLiSS separators and to compare it with the performance of the cells utilizing state-of-the-art separator, Celgard 2400. Overall, it was found that regardless of the applied cycling rate, the use of the grafted separators greatly enhances the Coulombic efficiency of the cell. An appropriate Li-exchange-site (-SO3(-)) concentration at and near the surface of the separator was found to be essential to effectively suppress the polysulfide shuttle without sacrificing the Li-ion mobility through the separator and to improve the practical specific charge of the cell.