Structural Reversibility of Nanoscaled Sn Anodes.

Alloying-type anode materials provide high capacity for lithium-ion batteries; however, they suffer pulverization problems resulting from the volume change during cycling. Realizing the cycling reversibility of these anodes is therefore critical for sustaining their electrochemical performance. Here, we investigate the structural reversibility of Sn NPs during cycling at atomic-level resolution utilizing in situ high-resolution TEM. We observed a surprisingly near-perfect structural reversibility after a complete cycle. A three-step phase transition happens during lithiation, accompanied by the generation of a significant number of defects, grain boundaries, and up to 202% volume expansion. In subsequent delithiation, the volume, morphology, and crystallinity of the Sn NPs were restored to their initial state. Theoretical calculations show that compressive stress drives the removal of vacancies generated within the NPs during delithiation, therefore maintaining their intact morphology. This work demonstrates that removing vacancies during cycling can efficiently improve the structural reversibility of high-capacity anode materials.

Molybdenum-Doped Cobalt-Free Cathode Realizing the Electrochemical Stability by Enhanced Covalent Bonding.

The doping strategy effectively enhances the capacity and cycling stability of cobalt-free nickel-rich cathodes. Understanding the intrinsic contributions of dopants is of great importance to optimize the performances of cathodes. This study investigates the correlation between the structure modification and their performances of Mo-doped LiNi0.8Mn0.2O2 (NM82) cathode. The role of doped Mo's valence state has been proved functional in both lattice structural modification and electronic state adjustment. Although the high-valence of Mo at the cathode surface inevitably reduces Ni valence for electronic neutrality and thus causes ion mixing, the original Mo valence will influence its diffusion depth. Structural analyses reveal Mo doping leads to a mixed layer on the surface, where high-valence Mo forms a slender cation mixing layer, enhancing structural stability and Li-ion transport. In addition, it is found that the high-valence dopant of Mo6+ ions partially occupies the unfilled 4d orbitals, which may strengthen the Mo─O bond through increased covalency and therefore reduce the oxygen mobility. This results in an impressive capacity retention (90.0% after 200 cycles) for Mo-NM82 cathodes with a high Mo valence state. These findings underscore the valence effect of doping on layered oxide cathode performance, offering guidance for next-generation cathode development.

Surface Lattice Modulation Enables Stable Cycling of High-Loading All-solid-state Batteries at High Voltages.

Halide solid electrolytes, known for their high ionic conductivity at room temperature and good oxidative stability, face notable challenges in all-solid-state Li-ion batteries (ASSBs), especially with unstable cathode/solid electrolyte (SE) interface and increasing interfacial resistance during cycling. In this work, we have developed an Al3+-doped, cation-disordered epitaxial nanolayer on the LiCoO2 surface by reacting it with an artificially constructed AlPO4 nanoshell; this lithium-deficient layer featuring a rock-salt-like phase effectively suppresses oxidative decomposition of Li3InCl6 electrolyte and stabilizes the cathode/SE interface at 4.5 V. The ASSBs with the halide electrolyte Li3InCl6 and a high-loading LiCoO2 cathode demonstrated high discharge capacity and long cycling life from 3 to 4.5 V. Our findings emphasize the importance of specialized cathode surface modification in preventing SE degradation and achieving stable cycling of halide-based ASSBs at high voltages.

In Situ Transmission Electron Microscopy Methods for Lithium-Ion Batteries.

In situ Transmission Electron Microscopy (TEM) stands as an invaluable instrument for the real-time examination of the structural changes in materials. It features ultrahigh spatial resolution and powerful analytical capability, making it significantly versatile across diverse fields. Particularly in the realm of Lithium-Ion Batteries (LIBs), in situ TEM is extensively utilized for real-time analysis of phase transitions, degradation mechanisms, and the lithiation process during charging and discharging. This review aims to provide an overview of the latest advancements in in situ TEM applications for LIBs. Additionally, it compares the suitability and effectiveness of two techniques: the open cell technique and the liquid cell technique. The technical aspects of both the open cell and liquid cell techniques are introduced, followed by a comparison of their applications in cathodes, anodes, solid electrolyte interphase (SEI) formation, and lithium dendrite growth in LIBs. Lastly, the review concludes by stimulating discussions on possible future research trajectories that hold potential to expedite the progression of battery technology.

Si-Based High-Entropy Anode for Lithium-Ion Batteries.

Up to now, only a small portion of Si has been utilized in the anode for commercial lithium-ion batteries (LIBs) despite its high energy density. The main challenge of using micron-sized Si anode is the particle crack and pulverization due to the volume expansion during cycling. This work proposes a type of Si-based high-entropy alloy (HEA) materials with high structural stability for the LIB anode. Micron-sized HEA-Si anode can deliver a capacity of 971 mAhg-1 and retains 93.5% of its capacity after 100 cycles. In contrast, the silicon-germanium anode only retains 15% of its capacity after 20 cycles. This study has discovered that including HEA elements in Si-based anode can decrease its anisotropic stress and consequently enhance ductility at discharged state. By utilizing in situ X-ray diffraction and transmission electron microscopy analyses, a high-entropy transition metal doped Lix (Si/Ge) phase is found at lithiated anode, which returns to the pristine HEA phase after delithiation. The reversible lithiation and delithiation process between the HEA phases leads to intrinsic stability during cycling. These findings suggest that incorporating high-entropy modification is a promising approach in designing anode materials toward high-energy density LIBs.

Lattice pinning in MoO3 via coherent interface with stabilized Li+ intercalation.

Large lattice expansion/contraction with Li+ intercalation/deintercalation of electrode active materials results in severe structural degradation to electrodes and can negatively impact the cycle life of solid-state lithium-based batteries. In case of the layered orthorhombic MoO3 (α-MoO3), its large lattice variation along the b axis during Li+ insertion/extraction induces irreversible phase transition and structural degradation, leading to undesirable cycle life. Herein, we propose a lattice pinning strategy to construct a coherent interface between α-MoO3 and η-Mo4O11 with epitaxial intergrowth structure. Owing to the minimal lattice change of η-Mo4O11 during Li+ insertion/extraction, η-Mo4O11 domains serve as pin centers that can effectively suppress the lattice expansion of α-MoO3, evidenced by the noticeably decreased lattice expansion from about 16% to 2% along the b direction. The designed α-MoO3/η-Mo4O11 intergrown heterostructure enables robust structural stability during cycling (about 81% capacity retention after 3000 cycles at a specific current of 2 A g-1 and 298 ± 2 K) by harnessing the merits of epitaxial stabilization and the pinning effect. Finally, benefiting from the stable positive electrode-solid electrolyte interface, a highly durable and flexible all-solid-state thin-film lithium microbattery is further demonstrated. This work advances the fundamental understanding of the unstable structure evolution for α-MoO3, and may offer a rational strategy to develop highly stable electrode materials for advanced batteries.

Regulation of Surface Defect Chemistry toward Stable Ni-Rich Cathodes.

Surface reconstruction of Ni-rich layered oxides (NLO) degrades the cycling stability and safety of high-energy-density lithium-ion batteries (LIBs), which challenges typical surface-modification approaches to build a robust interface with electrochemical activity. Here, a strategy of leveraging the low-strain analogues of Li- and Mn-rich layered oxides (LMR) to reconstruct a stable surface on the Ni-rich layered cathodes is proposed. The new surface structure not only consists of a gradient chemical composition but also contains a defect-rich structure regarding the formation of oxygen vacancies and cationic ordering, which can simultaneously facilitate lithium diffusion and stabilize the crystal structure during the (de)lithiation. These features in the NLO lead to a dramatic improvement in electrochemical properties, especially the cyclability under high voltage cycling, exhibiting the 30% increase in capacity retention after 200 cycles at the current density of 1 C (3.0-4.6 V). The findings offer a facile and effective way to regulate defect chemistry and surface structure in parallel on Ni-rich layered structure cathodes to achieve high-energy density LIBs.