Surface-Modified LDH Nanosheets with High Dispersibility in Oil for Friction and Wear Reduction.

Surface and interfacial engineering of nanomaterials is essential for improving dispersion stability in liquids. In this study, we report that oleic acid (OA)- and stearic acid (SA)-functionalized layered double hydroxide (LDH) nanosheets as lubricant additives can achieve high dispersion and reduce friction and wear. LDH is a typical layered structure, and OA and SA are long-chain organic molecules that are not only compatible with base oils but also act as friction-reducing agents. The OA and SA molecules were branched onto ZnMgAl LDH nanosheets using dehydration condensation between the exposed OH groups on the surface of LDH and the COOH groups on the OA and SA molecules. Compared with that of the pristine ZnMgAl LDH, the dispersion of OA-ZnMgAl LDH and SA-ZnMgAl LDH was significantly improved. The surface-modified LDH exhibited superior tribological properties and great stability due to the synergistic lubrication effect between OA, SA, and LDH. Even at an ultralow concentration (0.15 wt %), the coefficient of friction and wear volume were reduced by ∼65 and ∼99%, respectively, compared to those of the base oil. Due to the green and simple synthesis method and excellent tribological properties, surface-functionalized LDH has enormous possibilities for future industrial applications.

Recent Advances in Layered-Double-Hydroxide-Based Separation Membranes.

The use of two-dimensional materials shows great promise for the development of next-generation membrane materials, thanks to their atomic thinness and the ease with which precise nanochannels can be constructed. Among these materials, layered double hydroxides (LDHs) stand out as an important class, possessing many features that make them ideal for constructing high-performance membranes. LDHs offer many advantages, such as their abundant and tunable interlayer anions, which enable the preparation of membranes with adjustable sub-nanometer pore sizes. Additionally, their hydrophilicity and positive charge characteristics afford them unique benefits. LDHs have been found to be effective in gas separation, ion sieving, and nanofiltration. This review provides a summary of the latest progress in using LDHs for membrane separation. It begins by introducing the basic properties of LDHs, followed by the assembly strategy for LDH membranes. Furthermore, the review presents the research status of LDHs membranes in various fields in a systematic manner. Lastly, the paper highlights some challenges and future prospects for preparing and applying LDHs membranes.

An MgAl layered double hydroxide as a new transition metal-free anode for lithium-ion batteries.

A carbonate intercalated magnesium aluminum layered double hydroxide is used as an anode material for lithium-ion batteries, displaying a maximum discharge specific capacity of 814 mA h g-1 at 200 mA g-1 in this work through utilizing the valence variation of Mg and the conversion between LiOH and LiH/Li2O.

Aqueous Chloride-Ion Battery within a Neutral Electrolyte Based on a CoFe-Cl Layered Double Hydroxide Anode.

Aqueous chloride-ion batteries (ACIBs) with environmental friendliness and high safety hold great potential to fulfill the green energy demand for ocean desalination. Herein, for the first time, a composite consisting of Cl--intercalated CoFe layered double hydroxides (CoFe-Cl-LDH) cross-linked with CNTs (CoFe-Cl-LDH/CNT) is synthesized and demonstrated to be a novel high-performance anode for ACIBs in a neutral NaCl aqueous solution. While exhibiting a high initial capacity of ∼190 mAh g-1 at 200 mA g-1, CoFe-Cl-LDH/CNT is capable of delivering a reversible capacity of ∼125 mAh g-1 after 200 cycles. At a high current density of 400 mA g-1, it still holds a capacity of ∼120 mAh g-1. The excellent Cl- storage performance can be contributed to the unique topochemical transformation feature that reverses intercalation/deintercalation of Cl- along with valence changes of Co2+/Co3+ and Fe2+/Fe3+ during charge/discharge and the improved electronic conductivity by hybridizing with CNTs. It is interesting that the invertible insertion/extraction of interlayer H2O was discovered, which could be beneficial to the capacity after cycles to a certain extent. The Cl--intercalated LDH material declared in this work shows its feasibility on Cl- capture/release in aqueous anion-type batteries and provides a new opportunity for future development of ACIBs or aqueous desalination technology.

A High-Nickel Layered Double Hydroxides Cathode Boosting the Rate Capability for Chloride Ion Batteries with Ultralong Cycling Life.

Chloride-ion batteries (CIBs) have drawn growing attention in large-scale energy storage applications owing to their comprehensive merits of high theoretical energy density, dendrite-free characteristic, and abundance of chloride-containing materials. Nonetheless, cathodes for CIBs are plagued by distinct volume effect and sluggish Cl- diffusion kinetics, leading to inferior rate capability and short cycling life. Herein, an unconventional Ni5 Ti-Cl LDH is reported with a high nickel ratio as a cathode material for CIB. The reversible capacity of Ni5 Ti-Cl LDH retains 127.9 mAh g-1 over 1000 cycles at a large current density of 1000 mA g-1 , which exceeds that of ever reported CIBs, with extraordinary low volume change of 1.006% during a whole charge/discharge process. Such superior Cl-storage performance is attributed to synergetic contributions consisting of high redox activity from Ni2+ /Ni3+ and pinning Ti that restrains local structural distortion of LDH host layers and enhances adsorption intensity of chloride atoms during the reversible Cl- intercalation/de-intercalation in LDH gallery, which are revealed by a comprehensive study including X-ray photoelectron spectroscopy, kinetic investigations, and DFT calculations. This work provides an effective strategy to design low-cost LDHs materials for high-performance CIBs, which are also applicable to other types of halide-ion batteries (e.g., fluoride-ion and bromide-ion batteries).

Introducing high-valence molybdenum to stimulate lattice oxygen in a NiCo LDH cathode for chloride ion batteries.

Layered double hydroxides (LDHs) have been intensively investigated as promising cathodes for the new concept chloride ion battery (CIB) with multiple advantages of high theoretical energy density, abundant raw materials and unique dendrite-free characteristics. However, driven by the great compositional diversity, a complete understanding of interactions between metal cations, as well as a synergetic effect between metal cations and lattice oxygen on LDH host layers in terms of the reversible Cl-storage capability, is still a crucial but elusive issue. In this work, we synthesized a series of chloride-inserted trinary Mox-doped NiCo2-Cl LDH (x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5) with gradient oxygen vacancies as enhanced cathodes toward CIBs. The combination of advanced spectroscopic techniques and theoretical calculations reveals that the Mo dopant facilitates oxygen vacancy formation and varies the valence states of coordinated transition metals, which can not only tune the electronic structure effectively and promote Cl-ion diffusion, but improve the redox activity of LDHs. The optimized Mo0.3NiCo2-Cl LDH delivers a reversible discharge capacity of 159.7 mA h g-1 after 300 cycles at 150 mA g-1, which is almost a triple enhancement compared to that of NiCo2Cl LDH. The superior Cl-storage of trinary Mo0.3NiCo2Cl LDH is attributed to the reversible intercalation/deintercalation of chloride ions in the LDH gallery along with the oxidation state changes in Ni0/Ni2+/Ni3+, Co0/Co2+/Co3+ and Mo4+/Mo6+ couples. This simple vacancy engineering strategy provides critical insights into the significance of the chemical interaction of various components on LDH laminates and aims to effectively design more LDH-based cathodes for CIBs, which can even be extended to other halide-ion batteries like fluoride ion batteries and bromide ion batteries.

Two-Dimensional LDH Film Templating for Controlled Preparation and Performance Enhancement of Polyamide Nanofiltration Membranes.

Tailored design of high-performance nanofiltration membranes that can be used in a variety of applications such as water desalination, resource recovery, and sewage treatment is desirable. Herein, we describe the use of layered double hydroxides (LDH) intermediate layer to control the interfacial polymerization between trimesoyl chloride (TMC) and piperazine (PIP) for the preparation of polyamide (PA) membrane. The dense surface of LDH layer and its unique mass transfer behavior influence the diffusion of PIP, and the supporting role of the LDH layer allows the formation of ultrathin PA membranes. By only changing the concentration of PIP, a series of membranes with controllable thickness from 10 to 50 nm and tunable crosslinking-degree can be prepared. The membrane prepared with a higher concentration of PIP shows excellent performance for divalent salt retention with water permeance of 28 Lm-2 h-1 bar-1 , high rejection of 95.1 % for MgCl2 and 97.1 % for Na2 SO4 . While the membrane obtained with a lower concentration of PIP can sieve dye molecules of different sizes with a flux of up to 70 Lm-2 h-1 bar-1 . This work demonstrates a novel strategy for the controllable preparation of high-performance nanofiltration membranes and provides new insights into how the intermediate layer affects the IP reaction and the final separation performance.

A Hydrotalcite-Based PET Composites with Enhanced Properties for Liquid Milk Packaging Applications.

In the present work, the two-phase mixture (HTLc) of hydrotalcite and its oxide were used to improve the barrier properties, UV resistance and antimicrobial activity of Poly(ethylene terephthalate) (PET) for their application in liquid milk packaging. Firstly, CaZnAl-CO3-LDHs with a two-dimensional layered structure were synthesized by hydrothermal method. CaZnAl-CO3-LDHs precursors were characterized by XRD, TEM, ICP and dynamic light scattering. A series of PET/HTLc composite films were then prepared, characterized by XRD, FTIR and SEM, and a possible mechanism of the composite films with hydrotalcite was proposed. Barrier properties to water vapor and oxygen have been studied in PET nanocomposites, as well as their antibacterial efficacy by the colony technique and their mechanical properties after exposure to UV irradiation for 24 h. By the presence of 1.5 wt% HTLc in the PET composite film, the oxygen transmission rate (OTR) was reduced by 95.27%, the water vapor transmission rate was reduced by 72.58% and the inhibition against Staphylococcus aureus and Escherichia coli was 83.19% and 52.75%. Moreover, a simulation of the migration process in dairy products was used to prove the relative safety. This research first proposes a safe technique for fabricating hydrotalcite-based polymer composites with a high gas barrier, UV resistance and effective antibacterial activity.

MgAl Saponite as a Transition-Metal-Free Anode Material for Lithium-Ion Batteries.

Transition-metal compounds (oxides, sulfides, hydroxides, etc.) as lithium-ion battery (LIB) anodes usually show extraordinary capacity larger than the theoretical value due to the transformation of LiOH into Li2O/LiH. However, there has rarely been a report relaying the transformation of LiOH into Li2O/LiH as the main reaction for LIBs, due to the strong alkalinity of LiOH leading to battery deterioration. In this work, layered silicate MgAl saponite (MA-SAP) is applied as a -OH donor to generate LiOH as the anode material of LIBs for the first time. The MA-SAP maintains a layered structure during the (dis)charging process and has zero-strain characteristic on the (001) crystal plane. In the discharging process, Mg, Al, and Si in the saponite sheets become electron-rich, while the active hydroxyl groups escape from the sheets and combine with lithium ions to form LiOH in the "caves" on sheets, and the LiOH continues to decompose into Li2O and LiH. Consequently, the MA-SAP delivers a maximum capacity of 536 mA h·g-1 at 200 mA·g-1 with a good high-current discharging ability of 155 mA h·g-1 after 1000 cycles under 1 A·g-1. Considering its extremely low cost and completely nontoxic characteristics, MA-SAP has great application prospects in energy storage. In addition, this work has an enlightening effect on the development of new anodes based on extraordinary mechanisms.

A Zero-Strain Insertion Cathode Material for Room-Temperature Fluoride-Ion Batteries.

A fluoride-ion battery (FIB) is a novel type of energy storage system that has a higher volumetric energy density and low cost. However, the high working temperature (>150 °C) and unsatisfactory cycling performance of cathode materials are not favorable for their practical application. Herein, fluoride ion-intercalated CoFe layered double hydroxide (LDH) (CoFe-F LDH) was prepared by a facile co-precipitation approach combined with ion-exchange. The CoFe-F LDH shows a reversible capacity of ∼50 mAh g-1 after 100 cycles at room temperature. Although there is still a big gap between FIBs and lithium-ion batteries, the CoFe-F LDH is superior to most cathode materials for FIBs. Another important advantage of CoFe-F LDH FIBs is that they can work at room temperature, which has been rarely achieved in previous reports. The superior performance stems from the unique topochemical transformation property and small volume change (∼0.82%) of LDH in electrochemical cycles. Such a tiny volume change makes LDH a zero-strain cathode material for FIBs. The 2D diffusion pathways and weak interaction between fluoride ions and host layers facilitate the de/intercalation of fluoride ions, accompanied by the chemical state changes of Co2+/Co3+ and Fe2+/Fe3+ couples. First-principles calculations also reveal a low F- diffusion barrier during the cyclic process. These findings expand the application field of LDH materials and propose a novel avenue for the designs of cathode materials toward room-temperature FIBs.

Two-Dimensional Beidellite/Carbon Superlattice for Boosting Lithium-Ion Storage Performance.

Two-dimensional Fe-beidellite/carbon (Fe-BEI@C) superlattice-like heterostructure was prepared by intercalation of glucose in the gallery of layered Fe-BEI followed by calcination. The interlaminar and superficial carbon coating enables Fe-BEI to have good rate performance, fast lithium-ion diffusion, and high pseudocapacitance contribution, leading to excellent lithium storage performance as anode material for lithium-ion batteries (LIBs). The Fe-BEI@C/Li half cell delivers a maximum specific capacity of 850 mAh·g-1 at 0.5 A·g-1 and has a 92.3% retention rate after 100 cycles along with a high-rate performance of 403 mAh·g-1 at 5 A·g-1. The reversible valence state change of Si2+/Si4+ and Fe0/Fex+ (0 < x < 3) in electrochemical cycles are realized without collapse of layered structure. Additionally, the Fe-BEI@C heterostructure displays a high Li+ diffusion coefficient of 10-13∼10-10 cm2 s-1, illustrating fast Li+ transfer in the interlayer of Fe-BEI@C heterostructure. Dynamic analysis reveals that the Si redox reaction is almost dominated by surface control and that of Fe is mainly diffusion-controlled. This work has exploited a novel layered silicate as anode material for LIBs and developed a molecular-level carbon hybridization method to improve their electrochemical performance, which is meaningful for the application of layered silicate in the energy-storage field.

High-efficiency CO2 separation using hybrid LDH-polymer membranes.

Membrane-based gas separation exhibits many advantages over other conventional techniques; however, the construction of membranes with simultaneous high selectivity and permeability remains a major challenge. Herein, (LDH/FAS)n-PDMS hybrid membranes, containing two-dimensional sub-nanometre channels were fabricated via self-assembly of unilamellar layered double hydroxide (LDH) nanosheets and formamidine sulfinic acid (FAS), followed by spray-coating with a poly(dimethylsiloxane) (PDMS) layer. A CO2 transmission rate for (LDH/FAS)25-PDMS of 7748 GPU together with CO2 selectivity factors (SF) for SF(CO2/H2), SF(CO2/N2) and SF(CO2/CH4) mixtures as high as 43, 86 and 62 respectively are observed. The CO2 permselectivity outperforms most reported systems and is higher than the Robeson or Freeman upper bound limits. These (LDH/FAS)n-PDMS membranes are both thermally and mechanically robust maintaining their highly selective CO2 separation performance during long-term operational testing. We believe this highly-efficient CO2 separation performance is based on the synergy of enhanced solubility, diffusivity and chemical affinity for CO2 in the sub-nanometre channels.

CoNi2S4 Nanoplate Arrays Derived from Hydroxide Precursors for Flexible Fiber-Shaped Supercapacitors.

A high-quality porous CoNi2S4 nanoplates array was in situ synthesized on carbon fibers (CFs) by a hydrothermal method via a CoNi-layered double hydroxide (LDH) precursor transformation process. The CoNi2S4@CFs electrode exhibits largely enhanced supercapacitor performance with a specific capacitance of 1724 F/g at 1 A/g, in comparison with that of the CoNi-LDH (1302 F/g) precursor. Furthermore, the CoNi2S4@CF electrode shows an extremely high rate capability with capacity retention of 79% under a charge density of 60 A/g, whereas the retention rate of CoNi-LDH@CFs is only ∼34%. The abundant pore structure, improved electrical conductivity, and lower internal resistances of CoNi2S4@CFs (1.0 Ω) compared to those of CoNi-LDH@CFs (9.5 Ω) are responsible for the enhancement of energy storage performance. By using the CoNi2S4 nanoplate array as the positive electrode, an all-solid-state asymmetric fiber-shaped supercapacitor was further obtained, which exhibits outstanding flexible, foldable, and wearable capability. In view of the component tunability for LDH materials, the hydroxide precursor transformation method with merits of mild conditions and easy operation can be extended to the synthesis of a variety of metal sulfides for broad applications in electronic devices.

Crystallization and properties of poly(ethylene terephthalate)/layered double hydroxide nanocomposites.

Poly(ethylene terephthalate) (PET) generally suffers from low crystallization rate and long molding duration, which as a result limit its application as engineering plastics. To overcome these drawbacks, series of PET/layered double hydroxide (LDH) nanocomposites were prepared by a solution blending process. The effect of metal composition (MgAl and CaAl) and organo-modification (stearic acid intercalated) for LDH fillers on the crystallization behavior of the nanocomposites was investigated. It was revealed that, compared with PET/CaAl-LDH, the PET/MgAl-LDH nanocomposite exhibits a higher crystallization temperature and faster crystallization rate, which is associated with the superior nucleation ability of MgAl-LDH. The nucleation mechanism of PET induced by LDHs was explored by means of Avrami equation and theory of Hoffman-Lauritzen, pointing out that the incorporation of LDHs reduce the free energy of nucleation and the fold surface free energy of PET. In order to improve the compatibility between LDH and PET, stearic acid (SA) intercalated MgAl-LDH was prepared and filled into PET matrix. The resultant PET/MgAl-LDH-SA shows a further enhanced crystallization temperature and accelerated crystallization rate, in comparison with PET/MgAl-LDH nanocomposites. In addition, the thermal stability, gas barrier and mechanical properties of PET/LDH composites were improved upon incorporation of LDH fillers.

Moisture-Permeable, Humidity-Enhanced Gas Barrier Films Based on Organic/Inorganic Multilayers.

Gas barrier films with water-vapor-permeability have exhibited broad application prospects in gas separation and dehumidification. Herein, multilayer films comprised of layered double hydroxides (LDH) nanosheets and carboxymethyl cellulose sodium (CMC) were fabricated via layer-by-layer assembly. The resulting (LDH/CMC) n films show excellent gas barrier properties, which are ascribed to the significantly increased pathway for gas permeation originating from the large aspect ratio and high orientation of two-dimensional LDH nanosheets. Unlike traditional gas barrier films with nonselective blocking effect for various gases (including water vapor), the (LDH/CMC) n films exhibit an unusual moisture permselective property. The moisture-permeable property was related to the hygroscopicity of CMC and hydrophilicity of LDH, which can enrich the water molecules from the surroundings and aggrandize the osmotic pressure for water vapor, resulting in an uncommon improvement of water vapor transmission. It is interesting to find that the (LDH/CMC) n films exhibit enhanced gas (O2, CO2, CH4, and N2) barrier properties upon treatment in a humid environment, due to the formation of hydrogen bonds between the infiltrated water molecules and hydrophilic groups in CMC, thus padding the interstitial space of the CMC molecular chains and increasing the gas transmission path. The reduction of free volume and extension of the gas transmission path further enhance the gas barrier properties of (LDH/CMC) n films. Moreover, the (LDH/CMC) n films represent the water vapor permselective property in mixed gas (including O2, CO2, CH4, N2, and water vapor), while maintaining the barrier for other gases, which can be potentially applied in air dehydration and dehumidification of natural gas.

Hydroxide-ion-conductive gas barrier films based on layered double hydroxide/polysulfone multilayers.

A dual-functional organic-inorganic film with gas barrier and hydroxide ion conductivity properties was fabricated via the layer-by-layer assembly of layered double hydroxide (LDH) nanoplates and quaternary ammonium grafted polysulfone (QAPSF). By incorporating inorganic flakes with high ionic conductivity and gas barrier effects into an ion-conductive polymer matrix, this work overcomes the commonly-believed incompatibility between gas blocking and ionic conduction.

Hybrid films with excellent oxygen and water vapor barrier properties as efficient anticorrosive coatings.

Gas and moisture barrier materials are of crucial importance in various application fields, including food/drug packaging and encapsulation of electronic devices. Herein, a dual-barrier film to gas and water vapor was fabricated by a facile and cost-effective spin-coating of amphiphilic surfactant (Tween 80) modified LDH nanoplatelets (denoted as LDH-80) and polydimethylsiloxane (PDMS). The resultant (LDH-80/PDMS)15 film exhibits low O2 and H2O transmission rates with ∼0.701 and ∼0.049 cm3 m-2 d-1 atm-1, respectively, smaller than those for most of the reported barrier materials. The remarkable barrier properties are ascribed to the prolonged diffusion length for gas permeation and improved inorganic-organic interfacial compatibility between LDH-80 and PDMS. Taking advantage of this unique dual-barrier property, an aluminum foil substrate coated with (LDH-80/PDMS) n film displays an excellent anti-corrosion effect due to the inhibition of oxygen-consuming corrosion, which enables the (LDH-80/PDMS) n films to be promising candidates in metal surface protection.

Size Effect of Layered Double Hydroxide Platelets on the Crystallization Behavior of Isotactic Polypropylene.

Layered double hydroxide (LDH) platelets with nanosized and microsized level were synthesized and used as fillers in an isotactic polypropylene (PP) matrix. The nucleation and crystallization behavior of PP/LDH composites (denoted as 1-PPLx and 2-PPLx for composites containing nanosized and microsized LDH, respectively; x represents the mass percentage of LDH) was investigated by differential scanning calorimetry and polarized optical microscopy techniques. It is found that the crystallization temperature of PP/LDH composites is largely enhanced and the half crystallization time is reduced remarkably relative to pure PP, especially for 2-PPLx composite. The 2-PPLx composite exhibits stronger heterogeneous nucleating ability and faster crystallization rate than 1-PPLx samples with the same LDH loading. In addition, the crystallized PP/LDH composites possess significantly enhanced thermal stability, gas barrier, and flame-retardant properties relative to neat PP, which would show a broad application prospect in engineering plastics and packing industry.

Ultrafast switching of an electrochromic device based on layered double hydroxide/Prussian blue multilayered films.

Electrochromic materials are the most important and essential components in an electrochromic device. Herein, we fabricated high-performance electrochromic films based on exfoliated layered double hydroxide (LDH) nanosheets and Prussian blue (PB) nanoparticles via the layer-by-layer assembly technique. X-ray diffraction and UV-vis absorption spectroscopy indicate a periodic layered structure with uniform and regular growth of (LDH/PB)n ultrathin films (UTFs). The resulting (LDH/PB)n UTF electrodes exhibit electrochromic behavior arising from the reversible K(+) ion migration into/out of the PB lattice, which induces a change in the optical properties of the UTFs. Furthermore, an electrochromic device (ECD) based on the (LDH/PB)n-ITO/0.1 M KCl electrolyte/ITO sandwich structure displays superior response properties (0.91/1.21 s for coloration/bleaching), a comparable coloration efficiency (68 cm(2) C(-1)) and satisfactory optical contrast (45% at 700 nm), in comparison with other inorganic material-based ECDs reported previously. Therefore, this work presents a facile and cost-effective strategy to immobilize electrochemically active nanoparticles in a 2D inorganic matrix for potential application in displays, smart windows and optoelectronic devices.

Transparent, Ultrahigh-Gas-Barrier Films with a Brick-Mortar-Sand Structure.

Transparent and flexible gas-barrier materials have shown broad applications in electronics, food, and pharmaceutical preservation. Herein, we report ultrahigh-gas-barrier films with a brick-mortar-sand structure fabricated by layer-by-layer (LBL) assembly of XAl-layered double hydroxide (LDH, X=Mg, Ni, Zn, Co) nanoplatelets and polyacrylic acid (PAA) followed by CO2 infilling, denoted as (XAl-LDH/PAA)n-CO2. The near-perfectly parallel orientation of the LDH "brick" creates a long diffusion length to hinder the transmission of gas molecules in the PAA "mortar". Most significantly, both the experimental studies and theoretical simulations reveal that the chemically adsorbed CO2 acts like "sand" to fill the free volume at the organic-inorganic interface, which further depresses the diffusion of permeating gas. The strategy presented here provides a new insight into the perception of barrier mechanism, and the (XAl-LDH/PAA)n-CO2 film is among the best gas barrier films ever reported.