Search Results (162)

In this study, commercial Ospray-2507 super-duplex stainless steel powder was investigated for the first time as a potential metal support material for solid oxide cells. Initially, metal supports were fabricated and processed in air using various sintering profiles, followed by comprehensive mechanical, structural and electrochemical characterization. The optimal sintering condition was identified as 900 °C for 5 h. Subsequently, sintering under a H₂ atmosphere was explored, and its effects on the microstructural and functional properties of the metal supports were systematically to assessed to evaluate the influence of the sintering atmosphere on material performance. Although X-ray diffraction patterns showed no phase changes between the two sintering atmospheres, notable improvements were observed in mechanical, electrochemical, and microstructural properties under H₂ sintering. XPS spectra reveal that both air- and hydrogen-treated surfaces remain rich in chromium (Cr) and Manganese (Mn), which together dominate the surface and consequently attenuate the signal from the underlying iron. The thickness of the Cr- and Mn-based oxide layer decreases when sintering MS in H₂ atmosphere. Specifically, mechanical strength, as measured by three-point bending tests, increased by a factor of 12.5, and hardness rose from 500.3 to 523.5 HV. Furthermore, electrical conductivity also improved significantly, exhibiting an approximately 2.3–2.4 fold increase under H₂-sintered conditions. Full article

Both Co-free and lithium- and manganese-rich layered oxide Li(Li_0.2Mn_xNi_yFe_z)O₂ (MNF) cathodes have recently attracted attention in lithium-ion battery (LIB) research due to their high capacities of over 250 mAhg⁻¹, as well as being more eco-friendly and inexpensive than commercial NMC and LiCoO₂. However, they still suffer from lower experimental capacity as well as capacity decay, voltage fade, poor rate capability, and thermal instability. In this paper, fluorine (F)-doped Li_1.2(Mn_0.5Ni_0.2Fe_0.1)O_2(1−x)F_2x (MNF502010, x = 0, 0.025, 0.05, 0.075, 0.1) cathode materials have been synthesized in the nanoscale via sol–gel and subsequent solid-phase calcination to address some of these problems. The resulting 5% F-doped MNF502010 cathode demonstrates the advantage of fluorine doping, which makes a significant contribution to the formation of a well-ordered layer structure with a minimal LiM₂O₄ spinel phase as an impurity. This composition achieves an initial discharge capacity of 252 mAhg⁻¹ (1C = 250 mAhg⁻¹) and a 156 mAhg⁻¹ discharge capacity at 0.3 C on the 100th discharge, with an average voltage fade of 0.24 V. The optimization of fluorine composition results in an enhancement in the activation of the Li₂MnO₃-type monoclinic phase, as well as an increase in the electronic conductivity compared to the fluorine-free cathode. To understand the structural origin of this improved performance, X-ray absorption spectroscopy (XAS) measurements were carried out on pristine and cycled MNF electrodes. Full article

C276 Hastelloy/Q235 Steel cladding plates were prepared by vacuum-sealed hot rolling (VSHR) with a small hole. The effects of different Ni interlayers on the macro-morphology, microstructure, mechanical properties and corrosion resistance of the cladding plates were systematically investigated. The results indicated that without an interlayer, a large number of Mo-rich white M₆C particles formed near the C276 Hastelloy side, along with the formation of black Cr-Mn oxides at the interface. The addition of the Ni interlayer suppressed the diffusion of the C element from the Q235 Steel toward the C276 Hastelloy, consequently reducing the precipitation of M₆C carbides and Cr-Mn oxides. When the Ni interlayer thickness was 0.5 mm, the M₆C carbides on the Hastelloy side disappeared completely. The incorporation of a Ni interlayer increased the hardness of the C276 Hastelloy side and the interface layer, as well as the shear strength of the cladding plate. This was mainly because the Ni interlayer acted as a barrier to suppress the development of a Mo/Cr-depleted zone adjacent to the C276 Hastelloy and decrease interfacial Cr-Mn oxides, thus enhancing interfacial bonding. Under all three conditions, the cladding plates were bent without cracking. Moreover, the addition of a Ni interlayer also improved the corrosion resistance of the cross-section of the C276 Hastelloy. XPS analysis of the passive film revealed that the corrosion resistance was primarily attributed to the formation of Mo- and Cr-containing oxides on the surface. The corrosion resistance reached the optimal with the Ni interlayer thickness of 0.5 mm, in which Mo and Cr played a crucial role. Full article

Although halide solid electrolytes (HSEs) demonstrate a higher voltage window and superior interfacial stability toward Li-rich layered oxides (LLOs) compared to sulfide systems, HSE-based all-solid-state lithium batteries (HSE-ASSLBs) still face a fundamental trade-off between achieving high capacity and maintaining cycling stability. To resolve this issue, a rational adjustment of the depth-of-discharge (DOD) via discharge cut-off voltage control is proposed. Analysis of dQ/dV profiles and post-cycled electrodes indicates that excessive DOD (lower cut-off voltages) aggravates structural degradation and interfacial side reactions, whereas insufficient DOD (higher cut-off voltage) fails to fully utilize the compensatory capacity from low-voltage redox couples. Notably, an optimized cut-off voltage of 2.6 V activates a stable low-voltage redox reaction centered around 2.85 V, which effectively offsets high-voltage capacity loss while suppressing unfavorable interfacial evolution. As a result, the ASSLB configured with a Li_1.2Ni_0.13Mn_0.54Co_0.13O₂ cathode and a Li_2.75In_0.75Zr_0.25Cl₆ HSE delivers an initial discharge capacity of 281.6 mAh g⁻¹ at 1C and achieves significantly improved capacity retention from 71.8% to 86.1% over 300 cycles. This study confirms that DOD regulation offers a simple and effective electrochemical protocol for enabling durable high-capacity output in LLO-based ASSLBs. Full article

Layered nickel-rich cathodes are regarded as promising cathode materials for lithium-ion batteries (LIBs) due to their higher electrochemical capacities and lower cost. However, the development and commercial application of nickel-rich cathodes are severely hindered by significant capacity fading under a high charge cut-off voltage (4.5 V), which arises from interfacial instability and bulk structural degradation during charge–discharge processes. In this study, a two-step double-coating strategy was innovatively adopted to successfully synthesize Al₂O₃/LiBO₂ co-coated LiNi_0.71Co_0.09Mn_0.2O₂ cathode material (denoted as NCM-Al/B). X-ray photoelectron spectroscopy (XPS) verified that Al existed stably in the form of Al³⁺, and B formed B-O-M covalent bonds with transition metals (Ni/Co/Mn), constructing a dual-element synergistic interface. This interface significantly reduced the surface Ni³⁺ content and enhanced the structural stability by suppressing the H₂→H₃ phase transition. The NCM-Al/B material exhibits excellent electrochemical performance: it maintains a remarkable cycling stability with a capacity retention of 91.6% after 100 cycles at 1 C and 25 °C and delivers a discharge capacity of 156.6 mAh·g⁻¹ with a capacity retention of 75.4% after 100 cycles at a high rate of 1 C. This work establishes a chemically driven double-coating strategy and provides a new paradigm for optimizing the performance of high-nickel cathode materials. Full article

Lithium-rich manganese-based cathode materials (LRMs, Li_1.2Mn_0.54Ni_0.13Co_0.13O₂) are promising prospects for subsequent-generation lithium-ion batteries owing to their elevated operating voltage, large specific capacity, and affordability. Nonetheless, their actual implementation is significantly impeded by irreversible lattice-oxygen redox reactions, surface structural disorder, and interfacial phase collapse, leading to low initial Coulombic efficiency (ICE), inadequate rate capability, and sluggish Li⁺ transport. Herein, we report a simple and mild glycolic acid-assisted surface-engineering strategy to enhance the electrochemical performance of LRM. Glycolic acid treatment induces controlled H⁺/Li⁺ ion exchange at the particle surface and anchors surface transition metals through the formation of transition metals (TM)–OH and TM–O–C=O bonds. Subsequent calcination constructs an in situ carbon layer-spinel-layered heterostructure, accompanied by the generation of coupled anionic and cationic vacancies. This reconstructed surface provides fast Li⁺ diffusion pathways and stabilized ion-transport channels, while the dual-vacancy configuration enhances lattice-oxygen reversibility and suppresses structural disorder. Consequently, the modified LRM delivers a high initial discharge capacity of 285.3 mAh⋅g⁻¹ with an ICE of 89.9%, while maintaining 81% capacity retention after 100 cycles. Notably, it exhibits a significantly suppressed voltage decay of only 1.7 mV/cycle at 3C, markedly outperforming the pristine LRM. Density Functional Theory (DFT) calculations reveal that the surface-modified sample possesses enhanced electronic conductivity, as evidenced by the improved Density of States (DOS), and achieves superior structural stability through increased binding energies. This environmentally benign surface-engineering strategy offers a practical and efficient route toward the industrial application of LRM. Full article

Observations of photoelectric conversion in Fe- and Mn-rich semiconductor mineral coatings highlight their potential role in the origin of life and the evolution of environmental conditions. However, natural silicate minerals, which make up most of the Earth’s crust, are generally considered wide-bandgap insulators and are not expected to exhibit a photoelectric effect. In this study, we experimentally confirm measurable impurity-like photoelectron activity in natural silicate minerals and explore possible regulatory mechanisms. We show that electron-active elements (e.g., structural Fe and Ti) and lattice defects in minerals such as pyroxene and mica can reduce the optical gap (E_opt) to below ~4.13 eV, producing small photocurrents ranging from 0.010 to 0.114 μA/cm² on ITO substrates (background signal excluded). The structural types of these minerals—chain, island, layer, and framework—may influence their photoelectric responses by affecting electron transport pathways. Notably, light wavelength strongly controls both the photoelectric relative activity (PRA = 3–10 for silicates) and the decay kinetics (0.002–0.021 s⁻¹) of minerals. Visible light (400–800 nm) markedly enhances photocurrent densities in low-bandgap minerals such as limonite (E_opt = 2.11 eV). In contrast, ultraviolet light (UVB, 300 nm) enhances photoelectric responses in high-bandgap minerals, including feldspar and quartz (E_opt = 4.31 and 6.08 eV, respectively). Multivariate statistical analysis further indicates that elemental composition governs spectroscopic features that influence photoelectric behavior. Among these, Fe, Al, Si, and Ti are identified as key regulatory elements. These results provide new insights into the role of natural silicates in photoelectron-driven environmental and geological processes and highlight the potential of silicate-based materials for solar energy conversion applications. Full article

High-energy Ni-rich layered cathodes are critical for next-generation lithium-ion batteries yet remain limited by severe interfacial degradation and thermal vulnerability under high-voltage operation. In this work, a robust spinel-layered heterostructure is constructed by encapsulating LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) with a LiNi_0.5Mn_1.5O₄ (LNMO) spinel shell via a scalable sol–gel route. Structural characterizations confirm that the coating maintains the secondary-particle architecture, while X-ray photoelectron spectroscopy reveals a chemically reconditioned interface, achieved by the scavenging residual lithium species and suppressing of rock-salt-like surface reconstruction. Consequently, the optimized 4 wt% LNMO@NCM811 electrode demonstrates significantly enhanced high-voltage (2.8–4.4 V) stability, maintaining 41.84% of its initial capacity after 200 cycles compared to only 15.75% for the pristine sample. Crucially, thermogravimetric-differential scanning calorimetry (TG-DSC) uncovers the kinetic origin of this safety improvement: the spinel shell alters the thermal decomposition pathway, delaying the 10% mass loss temperature (T_10%) from 515.2 °C to 716.6 °C and suppressing the total exothermic heat release from 208.3 J g⁻¹ to 81.5 J g⁻¹. Collectively, these results demonstrate that the co-free spinel encapsulation is a dual-functional strategy to simultaneously stabilize surficial chemistry and intrinsically enhance the thermal safety of Ni-rich cathodes for carbon-neutral energy storage applications. Full article

As a potential strategic resource of critical metals, deep-sea cobalt-rich crusts represent one of the most promising metal reservoirs within oceanic seamount systems, and their metallogenic mechanism constitutes a frontier topic in deep-sea geoscience research. This review focuses on the cobalt-rich crusts from the Magellan Seamount region in the northwestern Pacific and synthesizes existing geological, mineralogical, and geochemical studies to systematically elucidate their mineralization processes and metal enrichment mechanisms from a microstructural perspective, with particular emphasis on cobalt enrichment and its controlling factors. Based on published observations and experimental evidence, the formation of cobalt-rich crusts is divided into three stages: (1) Mn/Fe colloid formation—At the chemical interface between oxygen-rich bottom water and the oxygen minimum zone (OMZ), Mn²⁺ and Fe²⁺ are oxidized to form hydrated oxide colloids such as δ-MnO₂ and Fe(OH)₃. (2) Key metal adsorption—Colloidal particles adsorb metal ions such as Co²⁺, Ni²⁺, and Cu²⁺ through surface complexation and oxidation–substitution reactions, among which Co²⁺ is further oxidized to Co³⁺ and stably incorporated into MnO₆ octahedral vacancies. (3) Colloid deposition and mineralization—Mn–Fe colloids aggregate, dehydrate, and cement on the exposed seamount bedrock surface to form layered cobalt-rich crusts. This process is dominated by the Fe/Mn redox cycle, representing a continuous evolution from colloidal reactions to solid-phase mineral formation. Biological processes play a crucial catalytic role in the microstructural evolution of the crusts. Mn-oxidizing bacteria and extracellular polymeric substances (EPS) accelerate Mn oxidation, regulate mineral-oriented growth, and enhance particle cementation, thereby significantly improving the oxidation and adsorption efficiency of metal ions. Tectonic and paleoceanographic evolution, seamount topography, and the circulation of Antarctic Bottom Water jointly control the metallogenic environment and metal sources, while crystal defects, redox gradients, and biological activity collectively drive metal enrichment. This review establishes a conceptual framework of a multi-level metallogenic model linking macroscopic oceanic circulation and geological evolution with microscopic chemical and biological processes, providing a theoretical basis for the exploration, prediction, and sustainable development of potential cobalt-rich crust deposits. Full article

The compounds LiCo_1−xMn_xO₂ (x = 0.5, 0.7) were synthesized via the solid-state method and exhibited crystallization in the cubic spinel structure (space group Fd-3m). UV–Vis spectroscopy reveals strong visible-light absorption and a reduction in the indirect optical band gap from 1.85 eV (x = 0.5) to 1.60 eV (x = 0.7) with increasing Mn content, which is consistent with semiconducting behavior. This narrowing arises from Mn³⁺/Mn⁴⁺ mixed valence, which introduces mid-gap states and enhances Co/Mn 3d–O 2p orbital hybridization within the spinel framework. In contrast, the Urbach energy increases from 0.55 eV to 0.65 eV, indicating greater structural and energetic disorder in the Mn-rich composition which is attributed to the Jahn–Teller distortions and valence heterogeneity associated with Mn³⁺. Impedance and dielectric modulus analyses confirm two distinct non-Debye relaxation processes related to grains and grain boundaries. AC conductivity is governed by the Correlated Barrier Hopping (CBH) model, with bipolaron hopping identified as the dominant conduction mechanism. The x = 0.7 sample displays significantly enhanced conductivity due to increased Mn³⁺/Mn⁴⁺ mixed valence, lattice expansion, efficient 3D electronic connectivity of the spinel lattice, and reduced interfacial resistance. These findings highlight the potential of these two spinels compounds as narrow-gap semiconductors for optoelectronic applications including visible-light photodetectors, photocatalysts, and solar absorber layers extending their utility beyond conventional battery cathodes. Full article

Ni-rich layered LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) cathodes are the most promising candidates for high-energy lithium-ion batteries, but their performance is often limited by structural instability and capacity fading due to large primary particle sizes and surface degradation. Precise control of the primary particle size significantly impacts the performance of NCM622 cathodes and can mitigate fatigue mechanisms, but the underlying processes remain unclear. In this study, NCM622 cathodes with various primary particle sizes were synthesized by applying a controlled co-precipitation strategy by systematically controlling the ammonia feed rate and solution pH during precursor formation. Interestingly, higher ammonia feed rates promoted the formation of smaller, more ordered primary particles, whereas lower feed rates and reduced pH produced larger primary particles in spherical secondary structures. Electrochemical evaluation revealed that cathodes composed of smaller primary particles exhibited enhanced Li⁺ diffusion kinetics and superior electrochemical performance compared to those synthesized under lower ammonia feeding or reduced pH conditions. Moreover, the optimized NCM622 electrode demonstrated excellent rate capability and maintained a stable layered microstructure during cycling, retaining ~86% of its initial capacity. These results demonstrate that fine-tuning the ammonia feeding conditions during co-precipitation provides a simple and effective approach to control primary particle growth, thereby improving the structural integrity and electrochemical durability of NCM622 cathode materials. Full article

This work deals with the comparative analysis of fluoride coatings, i.e., 5 wt.% AlF₃ and LiF, applied as surface layer of Li-rich Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ (LNCM) layered oxides synthesized via facile and cost-effective sol–gel route. The detailed structural and morphological characterizations demonstrate that AlF₃ and LiF deposits have a pivotal role in enhancing the electrochemical properties of LNCM. These electrochemical properties include galvanostatic charge–discharge (GCD), differential capacity (dQ/dV), electrochemical impedance spectroscopy (EIS), and area-specific impedance (ASI). A much lower decay of the discharge capacity of 0.22 and 0.25 mAh g⁻¹ per cycle was obtained for AlF₃- and LiF-coated LMNC, respectively, after 100 charge/discharge cycles at 0.1 C compared with 0.42 mAh g⁻¹ per cycle for pristine LNCM. Results evidence the non-evolution of the charge transfer resistance, enhanced lithium-ion kinetics and stabilization of electrode/electrolyte interface during cycling. Full article

Microneedle (MN) patches comprise a promising platform for transdermal delivery of macromolecular therapeutics. However, achieving sufficient mechanical strength for skin penetration while maintaining high biocompatibility and efficient antibody loading remains a major challenge. In this study, we designed and developed a core–shell-structured hydrogel MN patch composed of a silk fibroin core and a protein-based shell layer for antibody loading and potential transdermal release. The latter was constructed using a fusion protein consisting of the B and C domains of Staphylococcus aureus protein A (BC) and a tyrosine-rich mussel adhesive protein (MAP), thereby enabling antibody binding via the BC domains. By harnessing biomimetic design strategies, the BC-MAP shell facilitates antibody immobilization via specific affinity interactions, while the silk fibroin core provides substantial mechanical strength: the MN patch demonstrated a penetration force approximately 4.2 times greater than that required to pierce porcine skin. Collectively, our core–shell-structured hydrogel MN patch is a promising platform for transdermal antibody delivery. Full article

Understanding the relationship between state-of-charge (SOC) and anisotropic lithium diffusion is essential for improving the durability of Ni-rich layered oxide cathodes. However, quantitative insights into directional lithium diffusivity and its influence on mechanical degradation remain limited. In this study, molecular dynamics (MD) simulations were performed for LiNi_xMn_yCo_zO₂ (NMC) compositions with varying nickel content and SOC levels to reveal composition- and direction-dependent lithium transport behavior. The numerical indices in NMC compositions (e.g., NMC111, NMC532, NMC811) indicate the relative molar ratios of Ni, Mn, and Co, respectively, in LiNi_xMn_yCo_zO₂. The results show that lithium diffusion is enhanced at low SOC, owing to the abundance of vacant sites, while diffusion along the out-of-plane (c-axis) direction is strongly constrained, particularly in Ni-rich systems. To bridge the atomistic and continuum scales, the SOC-dependent anisotropic diffusivities obtained from MD simulations were incorporated into a chemo-mechanical finite-element model of an NMC811 particle. The coupled analysis demonstrates that anisotropic and SOC-dependent diffusion accelerates lithium depletion and stress localization, elucidating the origin of particle cracking in Ni-rich cathodes. This multiscale framework provides quantitative parameters and mechanistic understanding critical for designing durable next-generation lithium-ion batteries. Full article

Synthesis of published and new data from the Govorov and Kocebu guyots provide geochemical and chronostratigraphic constraints on hydrogenetic cobalt-rich Fe-Mn crusts from the Western Pacific Magellan Seamount Trail (MST). The history of the crusts began about 65–60 Ma, when the relict layer R was deposited in the Campanian—Maastrichtian and Late Paleocene along the shores of guyots. The growth of the old-generation crusts continued in the Late Paleocene—Early Eocene (Layer I-1) and in the Middle—Late Eocene (Layer I-2) in a shallow-water shelf environment. The younger layers formed in the Late Oligocene—Early Miocene (Layer I-2b), Miocene (Layer II), and Pliocene—Pleistocene (Layer III) at depths about the present sea level. The precipitation of Fe and Mn oxyhydroxides from seawater was interrupted by several times, with the longest gap from 38 to 26.5 Ma between the old (R, I-1, and I-2) and young (I-2b, II, and III) layers. Fe and Mn oxyhydroxides in the crusts were affected by two global events of phosphogenesis in the Pacific: Late Eocene—Early Oligocene, from 43 to 39 Ma (Layers R, I-1, I-2) and Late Oligocene—Early Miocene, from 27 to 21 Ma (Layer I-2b). The trace element patterns in different layers of the Co-rich Fe-Mn crusts are grouped using factor analysis of principal components (varimax raw) into four factors: (1) +(all REEs except Ce and La); (2) +(Ce, La, Ba, Mo, Sr, Pb); (3) +(Zr, Hf, Nb, Rb, As)/-Pb; (4) +(U, Th, Co, As, Sb, W)/-Y. The factor score diagrams highlight fields which are especially contrasting for Layers I-1, I-2, and II + III according to factors 2 and 4. Consistent REE and Y variations in Layers I-2b → II → III of the crust from Pallada Guyot correlate with gradual ocean deepening between the Late Oligocene—Early Miocene and Present when the MST guyots were submerging. Large variations in the trace element contents across coeval layers may be due to the hydrodynamics of currents on the guyot surfaces. Furthermore, the geochemistry of the crusts bears effects from repeated episodes of Cenozoic volcanism in the MST region of the Pacific Plate. Higher contents of Nb, Zr, As, Sb, and W in the younger layers II and III may result from large-scale volcanism, including Miocene eruptions of petit-spot volcanoes. Full article