Search Results (22)

Rechargeable magnesium batteries are an attractive alternative to lithium batteries because of their higher safety and lower cost, being spinel-type materials promising candidates for their positive electrode. Herein, MgMn₂O₄ with a tetragonal structure is synthesized via a simple, low-cost Pechini methodology and tested in aqueous media. Electrochemical measurements combined with in-situ Raman spectroscopy and other ex-situ physicochemical characterization techniques show that, in aqueous media, the charge/discharge process occurs through the co-intercalation of Mg²⁺ and water molecules. A progressive structure evolution from a well-defined spinel to a birnessite-type arrangement occurs during the first cycles, provoking capacity activation. The concomitant towering morphological change induces poor cycling performance, probably due to partial delamination and loss of electrical contact between the active film and the substrate. Interestingly, both MgMn₂O₄ capacity retention and cyclability can be increased by doping with nickel. This work provides insights into the positive electrode processes in aqueous media, which is vital for understanding the charge storage mechanism and the correlated performance of spinel-type host materials. Full article

Dual-ion batteries (DIBs) are a new kind of energy storage device that store energy involving the intercalation of both anions and cations on the cathode and anode simultaneously. They feature high output voltage, low cost, and good safety. Graphite was usually used as the cathode electrode because it could accommodate the intercalation of anions (i.e., PF₆⁻, BF₄⁻, ClO₄⁻) at high cut-off voltages (up to 5.2 V vs. Li⁺/Li). The alloying-type anode of Si can react with cations and boost an extreme theoretic storage capacity of 4200 mAh g⁻¹. Therefore, it is an efficient method to improve the energy density of DIBs by combining graphite cathodes with high-capacity silicon anodes. However, the huge volume expansion and poor electrical conductivity of Si hinders its practical application. Up to now, there have been only a few reports about exploring Si as an anode in DIBs. Herein, we prepared a strongly coupled silicon and graphene composite (Si@G) anode through in-situ electrostatic self-assembly and a post-annealing reduction process and investigated it as an anode in full DIBs together with home-made expanded graphite (EG) as a fast kinetic cathode. Half-cell tests showed that the as-prepared Si@G anode could retain a maximum specific capacity of 1182.4 mAh g⁻¹ after 100 cycles, whereas the bare Si anode only maintained 435.8 mAh g⁻¹. Moreover, the full Si@G//EG DIBs achieved a high energy density of 367.84 Wh kg⁻¹ at a power density of 855.43 W kg⁻¹. The impressed electrochemical performances could be ascribed to the controlled volume expansion and improved conductivity as well as matched kinetics between the anode and cathode. Thus, this work offers a promising exploration for high energy DIBs. Full article

The idea of this work is to reduce the negative effect of ordinary Portland cement (OPC) manufacture on the environment by decreasing clinker production temperature and developing an alternative rankinite binder that hardens in the CO₂ atmosphere. The common OPC raw materials, limestone and mica clay, if they contain a higher MgO content, have been found to be unsuitable for the synthesis of CO₂-curing low-lime binders. X-ray diffraction analysis (ex-situ and in-situ in the temperature range of 25–1150 °C) showed that akermanite Ca₂Mg(Si₂O₇) begins to form at a temperature of 900 °C. According to Rietveld refinement, the interlayer distances of the resulting curve are more accurately described by the compound, which contains intercalated Fe²⁺ and Al³⁺ ions and has the chemical formula Ca₂(MgO_0.495·FeO_0.202·AlO_0.303)·(FeO_0.248·AlO·Si_1.536·O₇). Stoichiometric calculations showed that FeO and Al₂O₃ have replaced about half of the MgO content in the akermanite structure. All this means that only ~4 wt% MgO content in the raw materials determines that ~60 wt% calcium magnesium silicates are formed in the synthesis product. Moreover, it was found that the formed akermanite practically does not react with CO₂. Within 24 h of interaction with 99.9 wt% of CO₂ gas (15 bar), the intensity of the akermanite peaks does not practically change at 25 °C; no changes are observed at 45 °C, either, which means that the chemical reaction does not take place. As a result, the compressive strength of the samples compressed from the synthesized product and CEN Standard sand EN 196-1 (1:3), and hardened at 15 bar CO₂, 45 °C for 24 h, was only 14.45 MPa, while the analogous samples made from OPC clinker obtained from the same raw materials yielded 67.5 MPa. Full article

Niobates are very promising anode materials for Li⁺-storage rooted in their good safety and high capacities. However, the exploration of niobate anode materials is still insufficient. In this work, we explore ~1 wt% carbon-coated CuNb₁₃O₃₃ microparticles (C-CuNb₁₃O₃₃) with a stable shear ReO₃ structure as a new anode material to store Li⁺. C-CuNb₁₃O₃₃ delivers a safe operation potential (~1.54 V), high reversible capacity of 244 mAh g⁻¹, and high initial-cycle Coulombic efficiency of 90.4% at 0.1C. Its fast Li⁺ transport is systematically confirmed through galvanostatic intermittent titration technique and cyclic voltammetry, which reveal an ultra-high average Li⁺ diffusion coefficient (~5 × 10^–11 cm² s⁻¹), significantly contributing to its excellent rate capability with capacity retention of 69.4%/59.9% at 10C/20C relative to 0.5C. An in-situ XRD test is performed to analyze crystal-structural evolutions of C-CuNb₁₃O₃₃ during lithiation/delithiation, demonstrating its intercalation-type Li⁺-storage mechanism with small unit-cell-volume variations, which results in its capacity retention of 86.2%/92.3% at 10C/20C after 3000 cycles. These comprehensively good electrochemical properties indicate that C-CuNb₁₃O₃₃ is a practical anode material for high-performance energy-storage applications. Full article

In recent years, aqueous zinc ion batteries (ZIBs) have attracted much attention due to their high safety, low cost, and environmental friendliness. Owing to the unique layered structure and more desirable layer spacing, transition metal dichalcogenide (TMD) materials are considered as the comparatively ideal cathode material of ZIBs which facilitate the intercalation/ deintercalation of hydrated Zn²⁺ between layers. However, some disadvantages limit their widespread application, such as low conductivity, low reversible capacity, and rapid capacity decline. In order to improve the electrochemical properties of TMDs, the corresponding modification methods for each TMDs material can be designed from the following modification strategies: defect engineering, intercalation engineering, hybrid engineering, phase engineering, and in-situ electrochemical oxidation. This paper summarizes the research progress of TMDs as cathode materials for ZIBs in recent years, discusses and compares the electrochemical properties of TMD materials, and classifies and introduces the modification methods of MoS₂ and VS₂. Meanwhile, the corresponding modification scheme is proposed to solve the problem of rapid capacity fading of WS₂. Finally, the research prospect of other TMDs as cathodes for ZIBs is put forward. Full article

Surface modified reduced graphene oxide (rGO) aerogels were synthesized using the hydrothermal method. Ethylene diamine (EDA) and α-cyclodextrin (CD) were used to functionalize the surface of the graphene oxide layers. The oxygen reduction and surface modification occurred in-situ during the hydrothermal self-assembly process. The chemical functionality and structure of the resulting ethylene diamine modified (rGO-EDA) and cyclodextrin modified (rGO-CD) aerogels as well as of the pristine unmodified rGO aerogel were studied using XPS, SEM, XRD, and SANS techniques. The overall surface composition showed a significant decrease in the oxygen content for all synthesized aerogels. The surface modified aerogels were characterized by a disordered stacking of the assembled rGO layers. The surface functionalities resulted in a broad distribution of the interlayer spacing and introduced structural heterogeneities. Such disordered structures can enable a better adsorption mechanism of the sodium ions. Coin cells based on the synthesized aerogels and sodium metal were assembled and tested at several charge and discharge rates. The correlation between the surface functionality of the rGO, the induced structural heterogeneities due to the disordered stacking, and the electrochemical performance of sodium-ion batteries were investigated. Operando XRD measurements were carried out during the battery cycling to investigate the adsorption or intercalation nature of the sodiation mechanism. Full article

The functionalization of graphene has been reported widely, showing special physical and chemical properties. However, due to the lack of surface functional groups, the poor dispersibility of graphene in solvents strongly limits its engineering applications. This paper develops a novel green “in-situ titania intercalation” method to prepare a highly dispersed graphene, which is enabled by the generation of the titania precursor between the layer of graphene at room temperature to yield titania-graphene nanocomposites (TiO₂-RGO). The precursor of titania will produce amounts of nano titania between the graphene interlayers, which can effectively resist the interfacial van der Waals force of the interlamination in graphene for improved dispersion state. Such highly dispersed TiO₂-RGO nanocomposites were used to modify epoxy resin. Surprisingly, significant enhancement of the mechanical performance of epoxy resin was observed when incorporating the titania-graphene nanocomposites, especially the improvements in tensile strength and elongation at break, with 75.54% and 176.61% increases at optimal usage compared to the pure epoxy, respectively. The approach presented herein is easy and economical for industry production, which can be potentially applied to the research of high mechanical property graphene/epoxy composite system. Full article

The dispersion mechanisms in a clay-based polymer nanocomposite (CPNC) during twin-screw extrusion are studied by in-situ rheo-optical techniques, which relate the CPNC morphology with its viscosity. This methodology avoids the problems associated with post extrusion structural rearrangement. The polydimethylsiloxane (PDMS) matrix, which can be processed at ambient and low temperatures, is used to bypass any issues associated with thermal degradation. Local heating in the first part of the extruder allows testing of the usefulness of low matrix viscosity to enhance polymer intercalation before applying larger stresses for clay dispersion. The comparison of clay particle sizes measured in line with models for the kinetics of particle dispersion indicates that larger screw speeds promote the break-up of clay particles, whereas smaller screw speeds favor the erosion of the clay tactoids. Thus, different levels of clay dispersion are generated, which do not simply relate to a progressively better PDMS intercalation and higher clay exfoliation as screw speed is increased. Reducing the PDMS viscosity in the first mixing zone of the screw facilitates dispersion at lower screw speeds, but a complex interplay between stresses and residence times at larger screw speeds is observed. More importantly, the results underline that the use of larger stresses is inefficient per se in dispersing clay if sufficient time is not given for PDMS to intercalate the clay galleries and thus facilitate tactoid disruption or erosion. Full article

Green nanocomposites from rosin-limonene (Ros-Lim) copolymers based on Algerian organophilic-clay named Maghnite-CTA⁺ (Mag-CTA⁺) were prepared by in-situ polymerization using different amounts (1, 5 and 10% by weight) of Mag-CTA⁺ and azobisisobutyronitrile as a catalyst. The Mag-CTA⁺ is an organophilic montmorillonite silicate clay prepared through a direct exchange process; the clay was modified by ultrasonic-assisted method using cetyltrimethylammonuim bromide in which it used as green nano-filler.The preparation method of nanocomposites was studied in order to determine and improve structural, morphological, mechanical and thermal properties ofsin.The structure and morphology of the obtained nanocomposites(Ros-Lim/Mag-CTA⁺) were determined using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electronic microscopy and transmission electronic microscopy. The analyses confirmed the chemical modification of clay layers and the intercalation of rosin-limonene copolymer within the organophilic-clay sheets. An exfoliated structure was obtained for the lower amount of clay (1% wt of Mag-CTA⁺), while intercalated structures were detected for high amounts of clay (5 and 10% wt of Mag-CTA⁺). The thermal properties of the nanocomposites were studied by thermogravimetric analysis (TGA) and show a significant improvement inthe thermal stability of the obtained nanocomposites compared to the purerosin-limonene copolymer (a degradation temperature up to 280 °C). Full article

Nowadays, research on electrochemical storage systems moves into the direction of post-lithium-ion batteries, such as aluminum-ion batteries, and the exploration of suitable materials for such batteries. Vanadium pentoxide (V₂O₅) is one of the most promising host materials for the intercalation of multivalent ions. Here, we report on the fabrication of a binder-free and self-supporting V₂O₅ micrometer-thick paper-like electrode material and its use as the cathode for rechargeable aluminum-ion batteries. The electrical conductivity of the cathode was significantly improved by a novel in-situ and self-limiting copper migration approach into the V₂O₅ structure. This process takes advantage of the dissolution of Cu by the ionic liquid-based electrolyte, as well as the presence of two different accommodation sites in the nanostructured V₂O₅ available for aluminum-ions and the migrated Cu. Furthermore, the advanced nanostructured cathode delivered a specific discharge capacity of up to ~170 mAh g⁻¹ and the reversible intercalation of Al³⁺ for more than 500 cycles with a high Coulomb efficiency reaching nearly 100%. The binder-free concept results in an energy density of 74 Wh kg⁻¹, which shows improved energy density in comparison to the so far published V₂O₅-based cathodes. Our results provide valuable insights for the future design and development of novel binder-free and self-supporting electrodes for rechargeable multivalent metal-ion batteries associating a high energy density, cycling stability, safety and low cost. Full article

Developing an environmentally benign styrene foam is a critical environmental need. Supercritical CO₂ use in foams has proven to be a valuable path. Adding fillers to increase bubble nucleation has been pursued concurrently. A prominent filler used is high surface area fillers, such as smectic clays. However, all studies to date show a limit of 152% in compressive moduli and 260% in the compressive stress. The values, even with such gains, limit structural application. A seminal work in 1987 by Suh and Cotton proved that carbonyl linkages in calcium carbonates and CO₂ interact and impact nucleation efficiency and performance in supercritical CO₂ foams. In this paper, a high surface area clay (layer double hydroxides) which begins in an exfoliated state, then functionalized with a long chain alkyl carboxylate (stearic acid) is synthesized. The result is a remarkable multi-fold improvement to the compressive properties in comparison to polystyrene (PS); a 268% and 512% increase in compressive modulus and strength, respectively. Using a pre-delaminated approach, the higher surface area was achieved in the clays. The presence of the stearate improved the interactions between the clay galleries and PS through hydrophobic-hydrophobic interactions. The glass transition temperature of the nanocomposites was observed to shift to higher values after foaming. The results point to a new path to increase performance using a pre-delaminated clay with functional groups for environmentally benign foams. Full article

In this work, the optimum filler loading to prepare epoxy/organoclay nanocomposites by the in-situ polymerization method was studied. Bi-functionalized montmorillonite at different filler loading (0.5, 1.0, 2.0, 4.0 wt %) was dispersed in epoxy resin by using a high shear speed homogenizer. The effect on morphology, thermal, dynamic mechanical, and tensile properties of the epoxy/organoclay nanocomposites were studied in this work. Wide-angle X-ray scattering (WAXS) and field emission scanning electron microscope (FESEM) studies revealed that possible intercalated structures were obtained in epoxy/organoclay nanocomposites. Thermogravimetric analysis (TGA) shows that epoxy/organoclay nanocomposites exhibit higher thermal stability at the maximum and final decomposition temperature, as well as higher char content, compared to pristine epoxy. The dynamic mechanical analysis (DMA) indicate that storage modulus (E′), loss modulus (E″), cross-link density and glass transition temperature (T_g) of the nanocomposites were improved with organoclay loading up to 1 wt %. Beyond this loading limit, the deterioration of properties was observed. A similar trend was also observed on tensile strength and modulus. We concluded from this study that organoclay loading up to 1 wt % is suitable for further study to fabricate hybrid nanocomposites for various applications. Full article

CaMgAl-layered double hydroxides (CaMgAl-LDHs) were synthesized by a co-precipitation method to prepare sodium oleate-modified, borate-intercalated CaMgAl-LDHs (O-CaMgAl-LDHs) using in-situ intercalation and modification, and the LDHs samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), and thermal gravimetric analysis (TGA). The FESEM observations showed that the as-prepared CaMgAl-LDHs had a lamellar structure with a particle size of 200~500 nm, while the O-CaMgAl-LDHs had a plate-like structure with a particle size of about 100 nm. TGA showed that O-CaMgAl-LDHs resulted in higher thermal stability at high temperature compared to CaMgAl-LDHs. O-CaMgAl-LDHs/ABS composites were prepared by adding O-CaMgAl-LDHs to acrylonitrile-butadiene-styrene resin (ABS) to test the resulting flame retardancy and mechanical properties, and the results showed that the limiting oxygen index (LOI) could increase from 18% to 26%, while the mechanical properties decreased significantly when the added fraction was 40% (relative to ABS). O-CaMgAl-LDHs, ammonium polyphosphate (APP) and expandable graphite (EG) were added into the ABS to prepare ABS composites, and the effects of different compositions on the flame retardancy and mechanical properties of the ABS composites were investigated. The results showed that, when adding 5 g of O-CaMgAl-LDHs, 1 g of APP, and 14 g of EG into 40 g of ABS, the LOI of the ABS composite reached 28.8%, and the composite prepared could meet the V-0 grade requirements of the UL-94 combustion test, while the flexural strength decreased only 21.9% compared to pure ABS, the smallest decrease compared to all of the other composites. Full article

The effect of the counteranion of hexadecyltrimethylammonium salts on the physico-chemical properties of organoclays was investigated, using a selected natural clay mineral with a cation exchange capacity of 95 meq/100 g. The uptake amount of C₁₆ cations was dependent on the hexadecyltrimethylammonium (C₁₆) salt solution used, the organoclay prepared from C₁₆Br salt solution exhibited a value of 1. 05 mmole/g higher than those prepared from C₁₆Cl and C₁₆OH salt solutions. The basal spacing of these organoclays was in the range of 1.81 nm to 2.10 nm, indicating a similar orientation of the intercalated surfactants, and could indicated that the excess amount of surfactants, above the cation exchange capacity of 0.95 meq/g could be adsorbed on the external surface of the clay mineral sheets. These organoclays were found to be stable in neutral, acidic, and basic media. The thermal stability of these organoclays was carried out using thermogravimetric analysis and in-situ X-ray diffraction (XRD) techniques. The decomposition of the surfactant occurred at a maximum temperature of 240 °C, accompanied with a decrease of the basal spacing value close to 1.42 nm. The application of these organoclays was investigated to remove an acidic dye, eosin. The removal amount was related to the initial used concentrations, the amount of the surfactants contents, and to the preheated temperatures of the organoclays. The removal was found to be endothermic process with a maximum amount of 55 mg of eosin/g of organoclay. The value decreased to 25 mg/g, when the intercalated surfactants were decomposed. The reuse of these organoclays was limited to four regeneration recycles with a reduction of 20 to 30%. However, noticeable reduction between 35% to 50% of the initial efficiency, was achieved after the fifth cycle, depending of the used organoclays. Full article

Currently, highly demanded biodegradable or bio-sourced plastics exhibit inherent drawbacks due to their limited processability and end-use properties (barrier, mechanical, etc.). To overcome all of these shortcomings, the incorporation of lamellar inorganic particles, such as layered double hydroxides (LDH) seems to be appropriate. However, LDH delamination and homogenous dispersion in a polymer matrix without use of harmful solvents, remains a challenging issue, which explains why LDH-based polymer nanocomposites have not been scaled-up yet. In this work, LDH with intercalated ionic liquid (IL) anions were synthesized by a direct co-precipitation method in the presence of phosphonium IL and subsequently used as functional nanofillers for in-situ preparation of poly (butylene adipate-co-terephthalate) (PBAT) nanocomposites. The intercalated IL-anions promoted LDH swelling in monomers and LDH delamination during the course of in-situ polycondensation, which led to the production of PBAT/LDH nanocomposites with intercalated and exfoliated morphology containing well-dispersed LDH nanoplatelets. The prepared nanocomposite films showed improved water vapor permeability and mechanical properties and slightly increased crystallization degree and therefore can be considered excellent candidates for food packaging applications. Full article