Intercalation Of Layers Research Articles

What is the potential of walnut shell-derived carbon in battery applications?

The environmental implications of utilizing walnut shells (WSs) as a material for energy storage are complex, balanced between advancing technologies and improving efficiency. This review aims to address, for the first time, environmental concerns and health effects associated with this material by conducting an in-depth analysis of carbon materials derived from waste management systems. Beginning with a reevaluation of the structural characteristics, cellular morphology, and physicochemical properties of WSs, this study explores their potential for the efficient synthesis of carbon. By examining various methods for the production of WS-derived materials such as hard carbon, we demonstrate the multifaceted nature of WS biomass as a resource. Subsequently, we shift our focus to ion storage mechanisms in the carbon source (C-S), including storage sensitivity, ion intercalation in micropores, and layer intercalation. An electrochemical analysis of the carbon source reveals its potential applications in energy storage systems. Furthermore, life cycle analysis was employed to assess the environmental impact and economic viability of WS utilization. The findings of the analysis suggest that one of the most valuable attributes of WSs is their potential for creating more environmentally sustainable materials, encouraging researchers to promote the use of green components in sodium batteries. This review underscores, for the first time, the significance of WSs in the field of carbon energy storage and their potential to enhance future prospects. The substantial opportunities in this area warrant further research and development, highlighting the relevance of WS-derived materials in advancing sustainable energy storage solutions.

Band structure database of layered intercalation compounds with various intercalant atoms and layered hosts

Here we provide a database comprising electronic band structures of 9,004 layered intercalation compounds, where atoms are intercalated into a host layered compound with different intercalant atoms, along with 468 structures related to the layered host compounds. Additionally, we provide properties derived from the electronic states such as band gap as well as stability-related properties like formation energies. Direct comparison of the band structures before and after intercalation is generally challenging due to changes in their space group and k-path. However, in this study, we developed new k-paths consistent with the host materials, allowing for the direct comparison of band structures before and after intercalation. This enables direct and quantitative discussion of the band structure changes induced by the intercalations and provides a valuable database for intercalant-driven band engineering. Layered intercalation compounds are widely used in many fields, including superconductivity and energy applications, and understanding of electronic structures is necessary. The feature of our database holds promises for the development of layered compounds with enhanced functionalities through database utilization.

Carbon nanotube intermediate layer intercalation and its influence on surface charge of thin film composite membrane

The surface charge of a separation membrane is a critical factor affecting its performance in ion separation and fouling resistance. Thin-film composite (TFC) polyamide (PA) membrane, commonly used in water treatment, often suffer from excessive surface negative charges, which significantly limits their application and fouling resistance. To address this issue, this work introduces a carbon nanotubes (CNT) intermediate layer to adjust the surface charge of TFC PA membranes, aiming to achieve a PA layer with neutral properties. Novel grazing-incidence wide-angle x-ray scattering (GIWAXS) measurements were employed to elucidate the effect of CNT on the molecular chain stacking of PA. The CNT intermediate layer was found to influence the PA cross-linking, which is related to surface negative charge, by controlling the storage and release of the m-phenylenediamine monomer during interfacial polymerization. The neutral CNT-TFC membrane demonstrated improved NH4+ retention and increased resistance to fouling by protein, surfactant, and E. coli. However, other surface properties, such as roughness and hydrophilicity, could counteract the antifouling benefits of a neutral surface. This work provides insights into additional advantages of CNT intermediate layer intercalation in TFC PA membranes, such as enhanced cross-linking and surface charge control.

Enhancing electrochemical performance of high-entropy Co/Ni-free P2/O3 hybrid-phase layered metal oxide cathode for sodium-ion batteries

Sodium-ion batteries (SIBs) have currently garnered increasing attention due to their promising applications and potential advantages. Despite the cost and performance advantages, the Co/Ni-free Fe-Mn-based cathode materials tends to undergo a large phase transition in the sodium (de)intercalation layer, which will result in the material structure damage. In this work, high entropy P2/O3-Na0.75Cu0.1Fe0.2Mg0.2Mn0.4Ti0.1O2 (NCFMMT) materials were successfully prepared by employing NaTi2(PO4)3 (NTP) as the modification layer. It can be distinctly seen that the cyclic stability of NCFMMT@NTP has been significantly improved, and the first capacity at 0.2C reaches 165.32 mAh/g and the capacity can maintain 86.73 % after 100 cycles. Moreover, the voltage hysteresis after triggering anionic redox can be clearly ameliorated. Apparently, the high-entropy strategy not only can satisfactorily optimize the lattice structure and stability of the cathode material during sodium intercalation/de-intercalation process, but also can increase the ion mobilization rate and promote further electrochemical properties. Therefore, this study provides valuable exploration for the design and preparation of cobalt/nickel-free cathodes with excellent electrochemical performance.

Large‐Area Lead Monolayers under Cover: Intercalation, Doping, and Phase Transformation

Intercalation is a promising approach for tailoring the electronic structure of epitaxial graphene on SiC. It enables the formation of otherwise unstable 2D phases of elements and allows the investigation of the interplay between the 2D materials and the substrate. Detailed studies have been conducted on the Pb intercalation process, as well as the structure and electronic properties of the 2D Pb layer using low‐energy electron microscopy and photoelectron spectroscopy. The low‐energy bands of Pb show good agreement with density‐functional theory calculations. A uniform Pb intercalation layer with (1 × 1) periodicity with respect to the SiC substrate is found. The quasifreestanding graphene is effectively screened from the doping influence of the substrate, leading to charge neutrality. Instead, the 2D Pb layer compensates for the spontaneous polarization of the substrate, allowing for the doping of a metal layer under cover. A phase transformation from the (1 × 1) intercalation phase into a bubble phase with quasi‐tenfold periodicity with respect to graphene occurs if the system is provided with sufficient energy. These results experimentally quantify the interaction between the 2D Pb layer, the substrate, and the graphene layer, demonstrating a first step toward controlling the diversity of 2D Pb phases.

Evolution and hydro-stratigraphy of the coastal aquifer in Garopaba/SC: Interpretation from georadar and tubular wells

This work analyzes the geological evolution of sedimentary deposits in the coastal aquifer of Garopaba, south Brazil, using ground penetrating radar (GPR) and data from tubular wells. The aquifer is localized in the coastal plain, where Quaternary lagoon-barrier environments are set between the Precambrian crystalline mountains and the sea. Over ten tubular wells are scattered in urbanized areas, which highlights the vulnerability of the unconfined, granular shallow aquifer. The results show that the aquifer has lithologic units of local scale. Tubular well data show the basal limit of the aquifer overlying clayey layers between 30 and 40 m deep and intercalation of sand layers up to the surface, mostly fine to very fine sand, with metric thickness, secondary lenses of clay and minor occurrence of gravel. The radarfacies interpretation shows fluvial-estuarine deposits as a local hydrostratigraphic unit, with lateral accretion bars filling a NE-axis paleochannel. The basal surface of the channel is interpreted as the sequence boundary surface of the lagoon-barrier systems III (upper Pleistocene) and IV (Holocene). The geological evolution of the aquifer is related to the upper Pleistocene marine regression (120–18 ka), that caused the aerial exposure of the continental shelf, and the development of complex drainage channels, which were superimposed during the Holocene transgression by lagoon-barrier IV deposits. After the post-glacial transgression, the lowering of the RSL to the current level promoted the silting of part of the lagoon system by continental sedimentation and aeolian deposits composing the surface.

Bi-intercalated epitaxial graphene on SiC(0001)

Abstract The intercalation of graphene with suitable atomic species is one of the most frequently applied methods to decouple the graphene layer from the substrate in order to establish the classical electronic properties of graphene. In this context, we studied the bismuth (Bi) intercalation of the (6√3×6√3)R30° reconstructed so-called "zeroth layer graphene'' on SiC(0001). 
As reported earlier by Sohn et al. [J. Korean Phys. Soc. 78, 157 (2021)], two phases are formed depending on the amount of intercalated Bi, which in turn is controlled by the annealing temperature: The α phase, showing a 1×1 periodicity with respect to the substrate, and, at higher temperatures, the √3×√3 reconstructed β phase. We characterise both phases and the transformation from the α to the β phase by photoelectron spectroscopy, normal incidence x-ray standing waves, electron diffraction and electron microscopy. We clearly see an almost complete intercalation of the graphene layers in both phases, with strong (covalent) interaction between the topmost Si atoms of the substrate and the Bi intercalant, but only weak (van der Waals) interaction between Bi and the graphene layer. The n-doping of the graphene found for the α phase decreases continuously during the phase transformation, in agreement with a reduced density of the Bi intercalating layer. Missing core level shifts of the surface species as well as the normal incidence x-ray standing waves results indicate that all surface Si atoms remain saturated during the transition and no dangling bonds are formed. Low energy electron microscopy and diffraction reveal the coexistance of both phases after annealing to intermediate temperatures and allow a quantitative analysis of island sizes and numbers.

40Ar/39Ar geochronologic and paleoenvironmental constraints to glacial termination III and MIS 7e, 7c, and 7a sea level fluctuations on the Tyrrhenian Sea coast of Italy

We provide detailed sedimentological, paleontological, and tephrochronological data on a complex sedimentary succession cropping out in the Tyrrhenian coastal area of central Italy, which was deposited in response to sea-level rise during MIS 7, coeval with the Latera phase of activity in the Vulsini Volcanic District. Diffuse intercalations of primary volcanic layers erupted during this phase and their geochronologic and chemostratigraphical characterization based on 40Ar/39Ar dating and EMP analyses, allowed for the identification of three stacked aggradational successions separated by erosive phases and their correlation with the Oxygen isotope record and phases in the relative sea-level curve. The ages of the tephra layers strictly frame the sedimentation in the interval of 253–206 ka, providing independent dating to glacial Termination III and to the three sea-level oscillations during MIS 7e, 7c, and 7a.Moreover, micro- and macrofaunal-based analyses provide information on the paleoenvironments and bathymetry during the highstands, which complement the geomorphological analysis reconstructing the inner edges of the corresponding marine terraces, allowing us to assess precise maximum sea level reached during MIS 7e and MIS 7a.The results of this multidisciplinary study enable us to establish in great detail the chronology, dynamics, relative amplitude, and effects of the sea-level fluctuations in the Tyrrhenian Sea during the whole MIS 7, providing independent, precise geochronological constraints for this period.

Desertic siliciclastic stromatolites in the Upper Jurassic Guará Formation from southwestern Gondwana: Trapping and binding in a non-marine setting

Abstract Siliciclastic stromatolites are rare in the geologic record, and their occurrence recorded in the literature is restricted to marine and coastal environments. The Upper Jurassic Guará Formation, from the Paraná Basin in southern Brazil, hosts unique non-marine siliciclastic stromatolites, providing a rare opportunity to study trapping and binding mechanisms by microbial mats in a continental setting. These microbialites occur interbedded with eolian and fluvial facies. The structural layering of the stromatolite domes is formed by the intercalation of sandy layers, resulting from trapping and binding of siliciclastic grains by microbial mats and in situ precipitation of amorphous to cryptocrystalline silica, which directly replaced the microbial colonies. The silica layers contain partially preserved spherical to ovoid bodies interpreted as colonies of coccoid microorganisms. These siliciclastic stromatolites were formed due to a specific balance of environmental factors, namely water chemistry and sediment supply, which enhanced the processes of trapping and binding and in situ precipitation. They record the presence of microbial life in a non-marine, silica-rich, fluvial-eolian environment in which there were no previous published occurrences of agglutinated stromatolites. These specimens record macroscopically identifiable evidence of microbial life in a continental environment that must be accounted for in the search for ancient life on Earth and Mars.

Out-of-Plane Electron Transport in Graphite Intercalation Compounds with Applications in Battery Anodes

Graphite intercalation compounds (GICs) are commonly used as anode materials for alkali metal-ion batteries, such as Li-ion and K-ion batteries. Although typically prepared as a low-stage intercalation compound (with a high concentration of the intercalating metal), over several electrochemical cycles, the distribution of intercalate within the graphite sample is expected to be non-uniform with domains of high-stage regions where the intercalant fraction is low [1]. The mechanism of interlayer electron transport in GICs strongly depends on the intercalation staging and temperature, and is expected to vary over the lifetime of a battery.High-stage GICs and highly oriented pyrolytic graphite (HOPG), which is the upper limit of infinite-stage GIC, have an out-of-plane electrical conductivity that exponentially increases with temperature, whereas low-stage GICs have a conductivity that decreases as a function of temperature [2, 3, 4]. Although out-of-plane electron transport in low-stage GICs can be described by a metallic conduction model, the mechanism of out-of-plane electron transport in HOPG and high-stage GICs is a hitherto unresolved problem [5]. Out-of-plane electrical conductivity for HOPG and high-stage GICs increases exponentially with temperature, which cannot be described by metallic conduction, nor by conventional impurity or defect hopping mechanisms [6].We propose a new mechanism of electron transport that takes place in HOPG and high-stage GICs at temperatures relevant to battery operation. Electrons are transferred between graphite and intercalant layers through tunneling that is enhanced by large amplitude out-of-plane phonon modes in graphite layers. Due to weak interlayer interactions in adjacent graphite layers, GICs can accommodate large amplitude phonon modes in the out-of-plane direction that locally enhance the interlayer electron tunneling probability. The tunneling enhancement is temperature dependent, and exponentially depends on the population of out-of-plane phonon modes excited at a given temperature. The expression for the conductivity 𝜎 for the phonon amplitude-driven tunneling mechanism as a function of temperature T is shown in Eq. 1; the exponential dependence of conductivity with temperature qualitatively agrees with experimental observations in HOPG and high-stage GICs. On a quantitative level, we also observe from Fig.1 that the theory agrees with experimental values for out-of-plane conductivity in HOPG.The phonon amplitude-driven tunneling mechanism of electron transport is relevant in describing the kinetic over-potential in batteries that employ layered materials as anodes in ambient temperature operating conditions, and optimally sizing the anode accounting for both electron transport and ion diffusion rates.

Insights into Adsorption Behavior and Mechanism of Br- onto Nickel-Aluminum Layered Double Hydroxides Intercalated with Different Inorganic Anions.

Layered double hydroxides (LDHs) have garnered significant attention from researchers in the field of adsorption due to their unique laminated structures and ion exchange properties. LDHs with various anion intercalation showed different adsorption effects on adsorbing ions, but the corresponding adsorption mechanisms are ambiguous. In this study, three types of NiAl-LDHs were synthesized, utilizing NO3-, CO32-, or Cl- as the interlayer anions. Batch tests were conducted to study their adsorption performances for Br-. Among them, the LDH with a NO3- intercalation layer exhibited the highest adsorption capacity for Br-, reaching up to 1.40 mmol g-1. The adsorption kinetics, mechanism, and renewability of these NiAl-LDHs were systematically compared. As a result, the type of Br- adsorption by all three materials was single molecular layer chemisorption. Moreover, the thermodynamic results of adsorption suggested that the adsorption of Br- was a spontaneous exothermic process. X-ray photoelectron spectroscopy, X-ray diffraction, and point of zero charge analysis collectively indicated that the adsorption of Br- by LDHs primarily occurred through interlayer ion exchange and electrostatic interactions. Structural characterizations of the adsorbents revealed that Br- entered the interlayers of the three LDHs, causing varying degrees of reduction in the interlayer spacing. Density functional theory calculations indicated that the interlayer binding energy of LDH with NO3- intercalation was the lowest, thereby making it more susceptible NO3- to be exchanged with Br-. Finally, the stability of the NiAl-LDHs was studied. The NiAl-LDHs retains a high removal efficiency of Br- even after 5 cycles of adsorption and desorption.

NiAl LDH nanosheets based on Ag nanoparticles-decoration and alkali etching strategies for high performance supercapacitors

Layered double hydroxides (LDHs) represent a category of two-dimensional layered intercalation materials, showing significant potential as electrode materials for the production of high-energy-density supercapacitors due to their tunable composition, ease of synthetic modification, and low cost. Here, we constructed alkali-etched NiAl LDH-OH nanosheets/Ag nanoparticles (NPs) composite material (Ag@NiAl LDH-OH) for high-performance supercapacitors through a simple solvent-thermal reaction. The alkali treatment is employed to selectively etch some Al3+ ions, generating cation vacancies as active sites for energy storage. Additionally, under the simultaneous influence of strong alkalis and vacancies, the interlayer spacing of LDHs expands, aiding in the promotion of interlayer ion mobility. Meanwhile, the decoration of silver nanoparticles ensures excellent electron conductivity in the NiAl-LDH-OH nanosheets, thereby facilitating improved utilization of the active substance and achieving outstanding rate performance. The Ag@NiAl LDH-OH electrode, when prepared, demonstrates a significant increase in specific capacitance, reaching 1790 F g−1 at a current density of 1 A g−1. This represents approximately 7 times the specific capacitance of the pristine NiAl LDH electrode, with a capacity retention of 79 % even under a high current density of 20 A g−1. Moreover, the assembled asymmetric supercapacitor (ASC) attains a maximum energy density of 138.25 Wh kg−1 at a power density of 700 W kg−1, maintaining 81 % of its initial specific capacitance after 20000 cycles. This research introduces novel pathways for advancing high-energy-density SCs.

Sustainable utilization of phosphate mine waste rocks as sand substitutes in cement mortar production

The extraction and processing of phosphate ores from sedimentary deposits generates large quantities of mine waste rocks, raising environmental concerns and contributing to landscape disfiguration. This study proposes an eco-friendly approach by exploring the extraction of sand from phosphate waste rocks (PWR) to mitigate the environmental impact associated with the disposal of mine wastes. The investigation focuses on the feasibility of creating masonry cement mortar by incorporating sand obtained from PWR. Three types of sand, Flint (FS), dolomitic limestone (DLS), and phosphate flint (PFS), obtained from the intercalation layers of phosphate were tested as partial replacements for reference sand at varying rates (0 %, 25 %, 50 %, 75 %, and 100 %). The sands were sieved through a 4 mm sieve and characterized to assess their geotechnical, chemical, and mineralogical properties. The toxicity characteristic leaching test analysis was conducted to ensure the environmental safety of recycled sands. Consistent mortar formulations were prepared and cured under uniform conditions. Results showed that a 25 % replacement ratio for each sand type yielded the highest 28-day compressive strengths, exceeding 30.5 MPa. Moreover, the water absorption of mortars decreased from 10.65 % to 8.39 %, 7.29 %, and 5.97 % with the incorporation of 25 % of FS, PFS, and DLS, respectively. Furthermore, toxicity tests revealed that recycled sand met the specified limits for toxic elements Ag, Hg, As, Cd, Cr, Pb, and Zn, and affirmed that incorporating these wastes into MCM significantly reduced the leaching of these metal ions to levels below detection limits (DL=0.01 mg/L). This research contributes to sustainable construction practices by providing a viable solution to minimize mine waste and reduce the construction industry's reliance on natural resources, ultimately addressing both environmental and resource-related challenges.

Anisotropy in Stratified and Equivalent Media: Kinematic and Amplitude Analysis

We implemented an elastic-anisotropic seismic modeling algorithm via synthetic models to evaluate different geological scenarios, where intercalations of sandstones and shales, carbonates and shales and halite and high-speed salt were simulated. These lithologies were selected based on their abundance in the sedimentary record and the importance they have in the composition of petroleum systems. We analyzed the results relative to kinematic and dynamic aspects to broaden the understanding of how these elements act in the presence of anisotropy. Additionally, the elastic and anisotropic parameters of intercalations composed by the referred lithologies were analytically estimated, thus obtaining the characteristics of several equivalent media. The results confirm previous postulations that the intercalation of layers with different properties can generate extrinsic anisotropy, contributing to the perspective of different wavelength(λ)/thickness ratios favorable to such effects. The results indicate that λ/thickness ratios greater than 6 are propitious for extrinsic anisotropy generation and the use of equivalent media as substitutes for stratified layers are ratified for thicknesses lower than 10 meters. Also, it was observed that in most cases, intrinsic anisotropy has a main role over extrinsic anisotropy.

Nano Silver Imprinted Starch‐co‐Polymethylmethacrylate Sandwiched Layered Double Hydroxide Nanocomposite Films for Packaging Application

AbstractLayered double hydroxide (LDH) is a special category of layered nanomaterials that has attracted keen interest towards fabrication of hybrid materials for efficient packaging application. In the present study, starch‐co‐poly(methyl methacrylate) (St‐co‐PMMA) copolymeric matrix is sandwiched within Mg‐Al layered double hydroxides (Mg‐Al LDH) along with silver nanoparticles (AgNPs) via surfactant free in situ polymerization of MMA. The imprintment of LDH and AgNPs within the copolymeric matrix of starch and their interactions are analyzed by the Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD) study. The morphological analysis is carried out by field emission scanning electron microscopy (FESEM), which indicates the reduction of voids by the partial intercalation and exfoliation of LDH layers. This dispersive effect offered by the combination of LDH and AgNPs not only results in an eight‐fold increase in oxygen barrier properties, but also enhances the chemical resistance attributes of the St‐co‐PMMA@Ag/(Mg‐Al)LDH nanocomposite films (NFs) with increase in LDH loading. Antibacterial activity is rendered by the presence of AgNPs and is further accentuated by increasing the concentration of LDH in the nanocomposite films. This significant elevation in thermal stability, chemical resistance, barrier properties, and bactericidal nature makes the material potential for packaging applications.

Computational study on ferroelectric control over spin polarization in the bipolar magnetic semiconductor

Multiferroic van der Waals (vdW) heterostructures offer an exciting route toward the nanoelectronics and spintronics device technology. How to realize the mutual regulation between ferroelectric and magnetic materials has attracted extensive research. In this work, based on the density functional theory, we simulate a vdW multiferroic heterostructure based on the bipolar magnetic semiconductor material graphone and ferroelectric monolayer In2Te3 and further investigate its electronic properties. We find that direct contact between In2Te3 and graphone induces a transition in graphone from a ferromagnetic state to a non-magnetic state. Fortunately, the magnetic properties of graphone are preserved by using graphene as an intercalation layer, and the graphone monolayer changes from its original semiconductor to a half-metal in the graphone/graphene/In2Te3 vdW heterostructure for P↓ state. Furthermore, by adjusting the layer spacing of the heterostructure, the spin polarization states of graphone at the Fermi level (EF) are regulated between spin-up (S↑) and spin-down (S↓) with the reversal of ferroelectric polarization states. Our results not only provide a promising way to realize the half-metallicity in 2D magnetic materials but also computationally predict the ferroelectric control of the spin polarization state, which has great application potential in the next-generation nonvolatile electrically controlled spintronic devices.

Unraveling the Stability of Layered Intercalation Compounds through First-Principles Calculations: Establishing a Linear Free Energy Relationship with Aqueous Ions

Unraveling the Stability of Layered Intercalation Compounds through First-Principles Calculations: Establishing a Linear Free Energy Relationship with Aqueous Ions

Improved Ferroelectricity and Tunneling Electroresistance by Inducing the ZrO2 Intercalation Layer in La:HfO2 Thin Films

Improved Ferroelectricity and Tunneling Electroresistance by Inducing the ZrO₂ Intercalation Layer in La:HfO₂ Thin Films

Superior-performance lithium–sulfur batteries: a face-centered-cubic-structure high-entropy alloy improves the bidirectional catalytic conversion of polysulfides/sulfides

The CoCuMnMoNi high-entropy alloy constructed by thermal cracking of organic frameworks as a catalytic intercalation layer for lithium–sulfur batteries to achieve bi-directional fast catalytic conversion of polysulfides/sulfides.

Recent advances and perspectives for intercalation layered compounds. Part 2: applications in the field of catalysis, environment and health.

Intercalation compounds represent a unique class of materials that can be anisotropic (1D and 2D-based topology) or isotropic (3D) through their guest/host superlattice repetitive organisation. Intercalation refers to the reversible introduction of guest species with variable natures into a crystalline host lattice. Different host lattice structures have been used for the preparation of intercalation compounds, and many examples are produced by exploiting the flexibility and the ability of 2D-based hosts to accommodate different guest species, ranging from ions to complex molecules. This reaction is then carried out to allow systematic control and fine tuning of the final properties of the derived compounds, thus allowing them to be used for various applications. This review mainly focuses on the recent applications of intercalation layered compounds (ILCs) based on layered clays, zirconium phosphates, layered double hydroxides and graphene as heterogeneous catalysts, for environmental and health purposes, aiming at collecting and discussing how intercalation processes can be exploited for the selected applications.