Overcoming Anode Instability in Solid-State Batteries through Control of the Lithium Metal Microstructure

Enabling the lithium metal anode (LMA) in solid-state batteries (SSBs) is the key to developing high energy density battery technologies. However, maintaining a stable electrode–electrolyte interface presents a critical challenge to high cycling rate and prolonged cycle life. One such issue is the interfacial pore formation in LMA during stripping. To overcome this, either higher stack pressure or binary lithium alloy anodes are used. Herein, it is shown that fine-grained (d = 20 µm) polycrystalline LMA can avoid pore formation by exploiting the microstructural dependence of the creep rates. In a symmetric cell set-up, i.e., LiǀLi_6.25Al_0.25La₃Zr₂O₁₂(LLZO)ǀLi, fine-grained LMA achieves > 11.0 mAh cm⁻² compared to ≈ 3.6 mAh cm⁻² for coarse-grained LMA (d = 295 µm) at 0.1 mA cm⁻² and at moderate stress of 2.0 MPa. Smaller diffusion lengths (≈ 20 µm) and higher diffusivity pathway along dislocations (D_d ≈ 10⁻⁷ cm² s⁻¹), generated during cell fabrication, result in enhanced viscoplastic deformation in fine-grained polycrystalline LMA. The electrochemical performances corroborate well with estimated creep rates. Thus, microstructural control of LMA can significantly reduce the required stack pressure during stripping. These results are particularly relevant for “anode-free” SSBs wherein both the microstructure and the mechanical state of the lithium are critical parameters.     

Manipulation of matter by electric and magnetic fields: Toward novel synthesis and processing routes of inorganic materials

The use of external electric and magnetic fields for the synthesis and processing of inorganic materials such as metals and ceramics has seen renewed interest in recent years. Electromagnetic energy can be utilized in different ways to improve or accelerate phase formation and stabilization, chemical ordering, densification and coarsening of particle-based materials (pore elimination and grain growth), and mechanical deformation (plasticity and creep). In these new synthesis and processing routes, the resulting microstructures and macroscopic material behavior are determined by the interaction of the applied fields with defects such as single or clustered point defects, dislocation networks, and interfaces. Multiscale experimental investigations and modeling are necessary to unveil the mechanisms underlying this field-assisted manipulation of matter.     

Oxide dispersion strengthening of nickel electrodeposits for microsystem applications

Oxide dispersion strengthened nickel (ODS-Ni) electrodeposits were fabricated to net shape using the lithography, electroforming, and molding (LIGA) process in a nickel sulfamate bath containing a suspension of 10 nm diameter Al₂O₃ particulates. Mechanical properties were compared to baseline specimens fabricated using an identical sulfamate bath chemistry without the particulates. Results revealed that the as-deposited ODS-Ni exhibited significantly higher yield strength and ultimate tensile strength (∼50 pct) than the baseline material. This increase in as-deposited strength was attributed to Orowan strengthening. The ODS-Ni also showed improved retention of room-temperature strength after annealing over a range of temperatures up to 600 °C. Nanoindentation measurements revealed that the properties of the dispersion-strengthened deposit were uniform through its thickness, even in narrow, high aspect ratio structures. Microscopy revealed that this resistance to anneal softening was due to an inhibition of grain growth in the presence of the oxide dispersion. At elevated temperatures, the strength of the ODS-Ni was approximately 3 times greater than that of the baseline material although with a significant reduction in hot ductility.     

Terahertz time-domain spectroscopy response of amines and amino acids intercalated smectites in far-infrared region

Layered clay minerals from the smectite group with different chemical composition and resulting layer charge (e.g. pyrophyllite, illite, hectorite and montmorillonite) were characterised for their dielectric properties in the far-infrared region using terahertz-time domain spectroscopy (THz-TDS). Samples with distinct cation exchange capacity such as hectorite and montmorillonite were modified using cation exchange reaction with alkylamines or amino acids. The presence of these species in 2D gallery was proved by X-ray diffraction and Fourier transform infrared spectroscopy. The frequency-dependent refractive index of these minerals was determined in the experimentally accessible range of 0.1–3.0 THz (3–100 cm⁻¹) using THz-TDS. Pristine samples revealed their refractive indices to be 1.82–2.15 at about 1 THz while the modified montmorillonite samples had their refractive indices changed by organic molecules used for their modification to 1.70–2.35 for amines and 1.97–2.36 for amino acids. The presence of organic substances in 2D gallery of clays was detectable despite the relatively high absorption of smectites with magnitude of 100 cm⁻¹.     

Probing the Ni(OH)2 Precursor for LiNiO2 at the Atomic Scale: Insights into the Origin of Structural Defect in a Layered Cathode Active Material

In lithium ion batteries (LIBs), the layered cathode materials of composition LiNi_1−x−yCo_xMn_yO₂ are critical for achieving high energy densities. A high nickel content (>80%) provides an attractive balance between high energy density, long lifetime, and low cost. Consequently, Ni-rich layered oxides cathode active materials (CAMs) are in high demand, and the importance of LiNiO₂ (LNO) as limiting case, is hence paramount. However, achieving perfect stoichiometry is a challenge resulting in various structural issues, which successively impact physicochemical properties and result in the capacity fade of LIBs. To better understand defect formation in LNO, the role of the Ni(OH)₂ precursor morphology in the synthesis of LNO requires in-depth investigation. By employing aberration-corrected scanning transmission electron microscopy, electron energy loss spectroscopy, and precession electron diffraction, a direct observation of defects in the Ni(OH)₂ precursor preparedis reported and the ex situ structural evolution from the precursor to the end product is monitored. During synthesis, the layered Ni(OH)₂ structure transforms to partially lithiated (non-layered) NiO and finally to layered LNO. The results suggest that the defects observed in commercially relevant CAMs originate to a large extent from the precursors, hence care must be taken in tuning the co-precipitation parameters to synthesize defect-free Ni-rich layered oxides CAMs.     

Crystal structure of the bacterial ribosomal decoding site complexed with a synthetic doubly functionalized paromomycin derivative: a new specific binding mode to an a-minor motif enhances in vitro antibacterial activity

The crystal structure of the complex between oligonucleotide containing the bacterial ribosomal decoding site (A site) and the synthetic paromomycin analogue 1, which contains the gamma-amino-alpha-hydroxybutyryl (L-haba) group at position N1 of ring II (2-DOS ring), and an ether chain with an O-phenethylaminoethyl group at position C2' of ring III, is reported. Interestingly, next to the paromomycin analogue 1 specifically bound to the A site, a second molecule of 1 with a different conformation is observed at the crystal packing interface which mimics the A-minor interaction between two bulged-out adenines from the A site and the codon-anticodon stem of the mRNA-tRNA complex. Improved antibacterial activity supports the conclusion that analogue 1 might affect protein synthesis on the ribosome in two different ways: 1) specific binding to the A site forces maintenance of the "on" state with two bulged out adenines, and 2) a new binding mode of 1 to an A-minor motif which stabilizes complex formation between the ribosome and the mRNA-tRNA complex regardless of whether the codon-anticodon stem is of the cognate or near-cognate type.     

Electrically Produced Standard Aerosols in a Wide Size Range

Non-uniformly charged particles cause a major problem in electrical methods for producing standard aerosols, imposing strict limitations on the usability of the obtained standard aerosols. This article gives a quick overview of this problem, examining the ways how differently charged particles affect the generation of standard aerosols, and presenting a new method for producing standard aerosols and avoiding the effects of multiply charged particles, with the key idea that the probability for small particles to have more than one charge is very low. A two-stage aerosol generator is used. Small silver particles (d< 40 nm) generated by homogeneous nucleation of silver vapors obtain in bipolar charger not more than one elementary charge. These condensation nuclei are enlarged by a condensational growth device. Big particles are now also not more than singly charged, and narrow size distribution can be obtained by electrical separation. Properties of standard aerosols produced experimentally by both the conventional and the new method, are compared and the validity of the new idea behind the new method is confirmed.     

Applicability of ToF-SIMS for monitoring compositional changes in bone in a long-term animal model

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a well-established technique in material sciences but has not yet been widely explored for implementation in life sciences. Here, we demonstrate the applicability and advantages of ToF-SIMS analysis for the study of minerals and biomolecules in osseous tissue. The locally resolved analysis of fragment ions deriving from the sample surface enables imaging and differentiation of bone tissue and facilitates histology on non-stained cross sections. In a rat model, bilateral ovariectomy combined with either a multi-deficiency diet or steroid treatment was carried out to create osteoporotic conditions. We focused our study on the Ca content of the mineralized tissue and monitored its decline. Calcium mass images of cross sections show the progressive degenerative changes in the bone. We observed a decreased Ca concentration in the edge region of the trabeculae and a decline in the Ca/P ratio. Additionally, we focused on the non-mineralized matrix and identified fragment ions that are characteristic for the collagen matrix. We observed trabeculae with wide ranges of non-mineralized collagen for the diet group owing to an impaired mineralization process. Here, the advantage of coeval monitoring of collagen and minerals indicated an osteomalacic model rather than an osteoporotic one.