Formation Energies of the Lithium Intercalations in MoS_2

First-principles calculations have been performed to study the lithium intercalations in MoS2. The formation energies, changes of volumes, electronic structures and charge densities of the lithium intercalations in MoS2 are presented. Our calculations show that during lithium intercalations in MoS2, the lithium intercalation formation energies per lithium atom are between 2.5 eV to 3.0 eV. The volume expansions of MoS2 due to lithium intercalations are relatively small

Layered Potassium Titanium Niobate/Reduced Graphene Oxide Nanocomposite as a Potassium‑Ion Battery Anode

With graphite currently leading as the most viable anode for potassium-ion batteries(KIBs),other materials have been left relatively underexamined.Transition metal oxides are among these,with many positive attributes such as synthetic maturity,longterm cycling stability and fast redox kinetics.Therefore,to address this research deficiency we report herein a layered potassium titanium niobate KTiNbO5(KTNO)and its rGO nanocomposite(KTNO/rGO)synthesised via solvothermal methods as a high-performance anode for KIBs.Through effective distribution across the electrically conductive rGO,the electrochemical performance of the KTNO nanoparticles was enhanced.The potassium storage performance of the KTNO/rGO was demonstrated by its first charge capacity of 128.1 mAh g^(−1) and reversible capacity of 97.5 mAh g^(−1) after 500 cycles at 20 mA g^(−1),retaining 76.1%of the initial capacity,with an exceptional rate performance of 54.2 mAh g^(−1)at 1 A g^(−1).Furthermore,to investigate the attributes of KTNO in-situ XRD was performed,indicating a low-strain material.Ex-situ X-ray photoelectron spectra further investigated the mechanism of charge storage,with the titanium showing greater redox reversibility than the niobium.This work suggests this lowstrain nature is a highly advantageous property and well worth regarding KTNO as a promising anode for future high-performance KIBs.

Charting the course to solid-state dual-ion batteries

An electrolyte destined for use in a dual-ion battery(DIB)must be stable at the inherently high potential required for anion intercalation in the graphite electrode,while also protecting the Al current collector from anodic dissolution.A higher salt concentration is needed in the electrolyte,in comparison to typical battery electrolytes,to maximize energy density,while ensuring acceptable ionic conductivity and operational safety.In recent years,studies have demonstrated that highly concentrated organic electrolytes,ionic liquids,gel polymer electrolytes(GPEs),ionogels,and water-in-salt electrolytes can potentially be used in DIBs.GPEs can help reduce the use of solvents and thus lead to a substantial change in the Coulombic efficiency,energy density,and long-term cycle life of DIBs.Furthermore,GPEs are suited to manufacture compact DIB designs without separators by virtue of their mechanical strength and electrical performance.In this review,we highlight the latest advances in the application of different electrolytes in DIBs,with particular emphasis on GPEs.

F-doped orthorhombic Nb_(2)O_(5) exposed with 97% (100) facet for fast reversible Liþ-Intercalation

Orthorhombic Nb_(2)O_(5)(T-Nb_(2)O_(5))is attractive for fast-charging Li-ion batteries,but it is still hard to realize rapid charge transfer kinetics for Li-ion storage.Herein,F-doped T-Nb_(2)O_(5) microflowers(F-Nb_(2)O_(5))are rationally synthesized through topotactic conversion.Specifically,F-Nb_(2)O_(5) are assembled by single-crystal nanoflakes with nearly 97%exposed(100)facet,which maximizes the exposure of the feasible Li^(+)transport pathways along loosely packed 4g atomic layers to the electrolytes,thus effectively enhancing the Li^(+)-intercalation performance.Besides,the band gap of F-Nb_(2)O_(5) is reduced to 2.87 eV due to the doping of F atoms,leading to enhanced electrical conductivity.The synergetic effects between tailored exposed crystal facets,F-doping,and ultrathin building blocks,speed up the Li^(+)/electron transfer kinetics and improve the pseudocapacitive properties of F-Nb_(2)O_(5).Therefore,F-Nb_(2)O_(5) exhibit superior rate capability(210.8 and 164.9 mAh g^(-1) at 1 and 10 C,respectively)and good long-term 10 C cycling performance(132.7 mAh g^(-1) after 1500 cycles).

Modulating charge separation and transfer for high-performance photoelectrodes via built-in electric field

Constructing a built-in electric field has emerged as a key strategy for enhancing charge separation and transfer,thereby improving photoelectrochemical performance.Recently,considerable efforts have been devoted to this endeavor.This review systematically summarizes the impact of built-in electric fields on enhancing charge separation and transfer mechanisms,focusing on the modulation of built-in electric fields in terms of depth and orderliness.First,mechanisms and tuning strategies for built-in electric fields are explored.Then,the state-of-the-art works regarding built-in electric fields for modulating charge separation and transfer are summarized and categorized according to surface and interface depth.Finally,current strategies for constructing bulk built-in electric fields in photoelectrodes are explored,and insights into future developments for enhancing charge separation and transfer in high-performance photoelectrochemical applications are provided.

A review on anode materials for lithium/sodium-ion batteries

Since lithium-ion batteries(LIBs) have been substantially researched in recent years, they now possess exceptional energy and power densities, making them the most suited energy storage technology for use in developed and developing industries like stationary storage and electric cars, etc. Concerns about the cost and availability of lithium have prompted research into alternatives, such as sodium-ion batteries(SIBs), which use sodium instead of lithium as the charge carrier. This is especially relevant for stationary applications, where the size and weight of battery are less important. The working efficiency and capacity of these batteries are mainly dependent on the anode, cathode, and electrolyte. The anode,which is one of these components, is by far the most important part of the rechargeable battery.Because of its characteristics and its structure, the anode has a tremendous impact on the overall performance of the battery as a whole. Keeping the above in view, in this review we critically reviewed the different types of anodes and their performances studied to date in LIBs and SIBs. The review article is divided into three main sections, namely:(i) intercalation reaction-based anode materials;(ii) alloying reaction-based anode materials;and(iii) conversion reaction-based anode materials, which are further classified into a number of subsections based on the type of material used. In each main section, we have discussed the merits and challenges faced by their particular system. Afterward, a brief summary of the review has been discussed. Finally, the road ahead for better application of Li/Na-ion batteries is discussed, which seems to mainly depend on exploring the innovative materials as anode and on the inoperando characterization of the existing materials for making them more capable in terms of application in rechargeable batteries.

Li intercalation in an MoSe_(2) electrocatalyst:In situ observation and modulation of its precisely controllable phase engineering for a high-performance flexible Li-S battery

Sophisticated efficient electrocatalysts are essential to rectifying the shuttle effect and realizing the high performance of flexible lithium-sulfur batteries(LSBs).Phase transformation of MoSe_(2) from the 2H phase to the 1T phase has been proven to be a significant method to improve the catalytic activity.However,precisely controllable phase engineering of MoSe_(2) has rarely been reported.Herein,by in situ Li ions intercalation in MoSe_(2),a precisely controllable phase evolution from 2H-MoSe_(2) to 1T-MoSe_(2) was realized.More importantly,the definite functional relationship between cut-off voltage and phase structure was first identified for phase engineering through in situ observation and modulation methods.The sulfur host(CNFs/1T-MoSe_(2))presents high charge density,strong polysulfides adsorption,and catalytic kinetics.Moreover,Li-S cells based on it display capacity retention of 875.3mAh g^(-1) after 500 cycles at 1 C and an areal capacity of 8.71mAh cm^(-2) even at a high sulfur loading of 8.47mg cm^(-2).Furthermore,the flexible pouch cell exhibiting decent performance will endow a promising potential in the wearable energy storage field.This study proposes an effective strategy to precisely control the phase structure of MoSe_(2),which may provide the reference to fabricate the highly efficient electrocatalysts for LSBs and other energy systems.

Electrochemically triggered decoupled transport behaviors in intercalated graphite:From energy storage to enhanced electromagnetic applications

Pyrolytic graphite (PG) with highly aligned graphene layers,present anisotropic electrical and thermal transport behavior,which is attractive in electronic,electrocatalyst and energy storage.Such pristine PG could meeting the limit of electrical conductivity (~2.5×10^(4) S·cm^(−1)),although efforts have been made for achieving high-purity sp^(2) hybridized carbon.For manipulating the electrical conductivity of PG,a facile and efficient electrochemical strategy is demonstrated to enhance electrical transport ability via reversible intercalation/de-intercalation of AlCl_(4)^(-)into the graphitic interlayers.With the stage evolution at different voltages,variable electrical and thermal transport behaviors could be achieved via controlling AlCl_(4)^(-)concentrations in the PG because of substantial variation in the electronic density of states.Such evolution leads to decoupled electrical and thermal transport (opposite variation trend) in the in-plane and out-of-plane directions,and the in-plane electrical conductivity of the pristine PG (1.25×10^(4) S·cm^(−1)) could be massively promoted to 4.09×10^(4) S·cm(AlCl_(4)^(-)intercalated PG),much better than the pristine bulk graphitic papers used for the electrical transport and electromagnetic shielding.The fundamental mechanism of decoupled transport feature and electrochemical strategy here could be extended into other anisotropic conductive bulks for achieving unusual behaviors.

Synergistically coupling of graphene quantum dots with Zn-intercalated MnO2 cathode for high-performance aqueous Zn-ion batteries

Cost-effective,safe,and highly performing energy storage devices require rechargeable batteries,and among various options,aqueous zinc-ion batteries(ZIBs)have shown high promise in this regard.As a cathode material for the aqueous ZIBs,manganese dioxide(MnO_(2))has been found to be promising,but certain drawbacks of this cathode material are slow charge-transfer capability and poor cycling performance.Herein,a novel design of graphene quantum dots(GQDs)integrated with Zn-intercalated MnO_(2)nanosheets is put forward to construct a 3D nanoflower-like GQDs@ZnxMnO_(2)composite cathode for aqueous ZIBs.The synergistic coupling of GQDs modification with Zn intercalation provides abundant active sites and conductive medium to facilitate the ion/electron transmission,as well as ensure the GQDs@ZnxMnO_(2)composite cathode with enhanced charge-transfer capability and high electrochemical reversibility,which are elucidated by experiment results and in-situ Raman investigation.These impressive properties endow the GQDs@ZnxMnO_(2)composite cathode with superior aqueous Zn^(2+) storage capacity(~403.6 mAh·g^(−1)),excellent electrochemical kinetics,and good structural stability.For actual applications,the fabricated aqueous ZIBs can deliver a substantial energy density(226.8 W·h·kg^(−1)),a remarkable power density(650 W·kg^(−1)),and long-term cycle performance,further stimulating their potential application as efficient electrochemical storage devices for various energy-related fields.

Localized-domains staging structure and evolution in lithiated graphite

Intercalation provides to the host materials a means for controlled variation of many physical/chemical properties and dominates the reactions in metal‐ion batteries.Of particular interest is the graphite intercalation compounds with intriguing staging structures,which however are still unclear,especially in their nanostructure and dynamic transition mechanism.Herein,the nature of the staging structure and evolution of the lithium(Li)‐intercalated graphite was revealed by cryogenic‐transmission electron microscopy and other methods at the nanoscale.The intercalated Li‐ions distribute unevenly,generating local stress and dislocations in the graphitic structure.Each staging compound is found macroscopically ordered but microscopically inhomogeneous,exhibiting a localized‐domains structural model.Our findings uncover the correlation between the long‐range ordered structure and short‐range domains,refresh the insights on the staging structure and transition of Li‐intercalated/deintercalated graphite,and provide effective ways to enhance the reaction kinetic in rechargeable batteries by defect engineering.

Intercalation of hafnium oxide between epitaxially-grown monolayer graphene and Ir(111)substrate

Intercalation of insulating materials between epitaxial graphene and the metal substrates is highly demanded to restore the intrinsic properties of graphene,and thus essential for the graphene-based devices.Here we demonstrate a successful solution for the intercalation of hafnium oxide into the interface between full-layer graphene and Ir(111)substrate.We first intercalate hafnium atoms beneath the epitaxial graphene.The intercalation of the hafnium atoms leads to the variation of the graphene moire superstructure periodicity,which is characterized by low-energy electron diffraction(LEED)and lowtemperature scanning tunneling microscopy(LT-STM).Subsequently,we introduce oxygen into the interface,resulting in oxidization of the intercalated hafnium.STM and Raman's characterizations reveal that the intercalated hafnium oxide layer could effectively decouple the graphene from the metallic substrate,while the graphene maintains its high quality.Our work suggests a high-k dielectric layer has been successfully intercalated between high-quality epitaxial graphene and metal substrate,providing a platform for applications of large-scale,high-quality graphene for electronic devices.

Fault rupture propagation in soil with intercalation using nonlocal model and softening modulus modification

Fault rupture propagation is more complex in the overlying soil with intercalation than in homogeneous soil,and it is challenging to simulate this phenomenon accurately using the finite element method.To address this issue,an improved nonlocal model that incorporates softening modulus modification is proposed.The methodology has the advantage that the solutions are independent of both mesh sizes and characteristic lengths,while maintaining objective softening rates of materials.Using the proposed methodology,a series of numerical simulations are conducted to investigate the effects of different mechanical parameters,such as elastic modulus,friction angle and dilation angle of the soil within the intercalation,as well as the impact of geometries,such as the depth and thickness of the intercalation,on the fault rupture progress.This study not only provides significant insights into the mechanisms of fault rupture propagation,specifically in relation to intercalations,but also shows a great value in promoting the current research on fault rupture.

Revealing the effect of electrolyte coordination structures on the intercalation chemistry of batteries

In-depth understanding of the electrolyte-dependent intercalation chemistry in batteries through direct operando/in situ characterizations is crucial for the development of the high-performance batteries.Herein,taking the Al/graphite battery as a model system,the effect of electrolyte coordination structure on the intercalation processes has been investigated over the batteries with either 1-hexyl-3-methylimidazolium chloride(HMICl)-AlCl_(3) or 1-ethyl-3-methylimidazolium chloride(EMICl)-AlCl_(3) ionic liquid electrolyte using operando X-ray photoelectron spectroscopy(XPS)and X-ray diffraction.With a weaker anion-cation interaction in HMI-based electrolyte,the XPS-derived atomic ratio between cointercalated N and intercalated Al is 0.9,which is lower than 1.6 for EMI-based electrolyte.Attributed to the additional de-solvation process,the batteries with the HMI-based electrolyte show a lower ionic diffusion rate,capacity,and cycling performance,which agree with the operando characterization results.Our findings highlight the critical role of the electrolyte coordination structure on the(co-)intercalation chemistry.

Water molecules and oxygen-vacancy modulation of vanadium pentoxide with fast kinetics toward ultrahigh power density and durable flexible all-solid-state zinc ion battery

Aqueous zinc ion battery(ZIB)with many virtues such as high safety,cost-effective,and good environmental compatibility is a large-scale energy storage technology with great application potential.Nevertheless,its application is severely hindered by the slow diffusion of zinc ions in desirable cathode materials.Herein,a technique of water-incorporation coupled with oxygen-vacancy modulation is exploited to improve the zinc ions diffusion kinetics in vanadium pentoxide(V_(2)O_5)cathode for ZIB.The incorporated water molecules replace lattice oxygen in V_(2)O_5,and function as pillars to expand interlayer distance.So the structural stability can be enhanced,and the zinc ions diffusion kinetics might also be promoted during the repeated intercalation/deintercalation.Meanwhile,the lattice water molecules can effectively enhance conductivity due to the electronic density modulation effect.Consequently,the modulated V_(2)O_5(H-V_(2)O_5)cathode behaves with superior rate capacity and stable durability,achieving 234 mA h g^(-1)over 9000 cycles even at 20 A g^(-1).Furthermore,a flexible all-solid-state(ASS)ZIB has been constructed,exhibiting an admirable energy density of 196.6 Wh kg^(-1)and impressive power density of 20.4 kW kg^(-1)as well as excellent long-term lifespan.Importantly,the assembled flexible ASS ZIB would be able to work in a large temperature span(from-20 to 70℃).Additionally,we also uncover the energy storage mechanism of the H-V_(2)O_5 electrode,offering a novel approach for creating high-kinetics cathodes for multivalent ion storage.

Er intercalation and its impact on transport properties of epitaxial graphene

Intercalation of atomic species is a practicable method for epitaxial graphene to adjust the electronic band structure and to tune the coupling between graphene and Si C substrate. In this work, atomically flat epitaxial graphene is prepared on 4H-SiC(0001) using the flash heating method in an ultrahigh vacuum system. Scanning tunneling microscopy, Raman spectroscopy and electrical transport measurements are utilized to investigate surface morphological structures and transport properties of pristine and Er-intercalated epitaxial graphene. It is found that Er atoms are intercalated underneath the graphene layer after annealing at 900℃, and the intercalation sites of Er atoms are located mainly at the bufferlayer/monolayer-graphene interface in monolayer domains. We also report the different behaviors of Er intercalation in monolayer and bilayer regions, and the experimental results show that the diffusion barrier for Er intercalated atoms in the buffer-layer/monolayer interface is at least 0.2 eV higher than that in the first/second graphene-layer interface. The appearance of Er atoms is found to have distinct impacts on the electronic transports of epitaxial graphene on SiC(0001).

New Superionic Memory Devices Can Provide Clues to the Human Memory Structure and to Consciousness

Since the work of Penrose and Hameroff the possibility is discussed that the location of human memory and consciousness could be connected with tubulin microtubules. If one would use superionic nano-materials rolled up to microtubules with an electrolyte inside the formed channels mediating fast ionic exchange of protons respectively lithium ions, it seems to be possible to write into such materials whole image arrays (pictures) under the action of the complex electromagnetic spectrum that composes these images. The same material and architecture may be recommended for super-computers. Especially microtubules with a protofilament number of 13 are the most important to note. We connected such microtubules before with Fibonacci nets composed of 13 sub-cells that were helically rolled up to deliver suitable channels. Our recent Fibonacci analysis of Wadsley-Roth shear phases such as niobium tungsten oxide , exhibiting channels for ultra-fast lithium-ion diffusion, suggests to use these materials, besides super-battery main application, in form of nanorods or microtubules as effectively working superionic memory devices for computers that work ultra-fast with the complex effectiveness of human brains. Finally, we pose the question, whether dark matter, ever connected with ultrafast movement of ordinary matter, may be responsible for synchronization between interactions of human brains and consciousness.

Incorporation of Nano-Zinc Oxide in Lamellar Zirconium Phosphate: Synthesis and Characterization

In order to provide ultraviolet barrier, antifungal and antibacterial properties, nano-zinc oxide (ZnO) was added to lamellar zirconium phosphate (ZrP). The phosphate was synthesized via reaction of zirconium oxychloride octahydrate and phosphoric acid following its chemical modification with Jeffamine and nano-ZnO. Diffractometric, morphological, thermal, structural and relaxometric evaluations were conducted. Fourier transform infrared spectroscopy (FTIR) revealed increase of the area between 4000 - 3000 cm-1 due to the formation of ionic specie PO? +NH3-[C-(H)(CH3)-CH2-O-(C-(H)(CH3)-CH2-O)8-(CH2-CH2-O-CH3)] and nano-ZnO particles. Wide-angle X-ray diffraction indicated that intercalation of Jeffamine was successful. Thermogravimetry confirmed that nano-ZnO particle forced the expulsion of Jeffamine outside ZrP galleries. Scanning electron microscopy evidenced the Jeffamine intercalation and sample heterogeneity. Hydrogen molecular relaxation indicated the increase of molecular rigidity owing to the formation of ionic specie and the addition of nano-ZnO particles. It was postulated that a multifunctional and miscellaneous material constituted by as prepared ZrP, some delaminated ZrP platelets and nano-ZnO particles was achieved. The material has potential for usage as filler in polymeric composites.

Tungsten carbide-reduced graphene oxide intercalation compound as co-catalyst for methanol oxidation

Highly dispersed tungsten carbide（WC） nanoparticles（NPs） sandwiched between few-layer reduced graphene oxide（RGO） have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The metatungstate ion,[H2W（12）O（40）]^6-,is assembled on thiourea-modified graphene oxide（GO） by an impregnation method.The WC NPs,with a mean diameter of 1.5 nm,are obtained through a process whereby ammonium metatungstate first turns to WS2,which then forms an intercalation compound with RGO before growing,in situ,to WC NPs.The Pt/WC-RGO electrocatalysts are fabricated by a microwave-assisted method.The intimate contacts between Pt,WC,and RGO are confirmed by X-ray diffraction,scanning electron microscope,transmission electron microscope,and Raman spectroscopy.For methanol oxidation,the Pt/WC-RGO electrocatalyst exhibited an electrochemical surface area value of 246.1 m^2/g Pt and a peak current density of1364.7 mA/mg Pt,which are,respectively,3.66 and 4.77 times greater than those of commercial Pt/C electrocatalyst（67.2 m^2/g Pt,286.0 mA/mg Pt）.The excellent CO-poisoning resistance and long-term stability of the electrocatalyst are also evidenced by CO stripping,chronoamperometry,and accelerated durability testing.Because Pt/WC-RGO has higher catalytic activity compared with that of commercial Pt/C,as a result of its intercalated structure and synergistic effect,less Pt will be required for the same performance,which in turn will reduce the cost of the fuel cell.The present method is facile,efficient,and scalable for mass production of the nanomaterials.

Electrochemical investigation on kinetics of potassium intercalating into graphite in KF melt

The kinetics of potassium intercalating into graphite in molten KF at 1 163 K was investigated by means of cyclic voltammetry and chronoamperometry.Cyclic voltammetry results indicate that intercalaltion/deintercalation of potassium into/from graphite involve kinetic limitations.The intercalation process of potassium was further confirmed to be governed by both the diffusion of potassium ion in graphite bulk and the phase transition kinetics through the analyses of current-time transient curves with reversible and quasi-reversible equations.The transfer coefficient of the intercalation reaction was calculated to be 0.364 according to the parameters resulting from nonlinear fitting of the current-time transient curves with a quasi-reversible equation.Analysis with scanning electron microscope shows that graphite matrix was severely eroded by intercalation of potassium.

Preparation and Properties of Phenolic Resin/Montmorillonite Intercalation Nanocomposites

Phenolic resin/montmorillonite intercalation composites were prepared by using the methods of pressing intercalation and melt intercalation.Properties and structure of the composites were investigated by using XRD,TG and test of softening point.It is indicated that both the pressing intercalation and melt intercalation can be used to prepare the phenolic resin/organo-montmorillonite intercalation nanocomposites.Compared with phenolic resin,the intercalation nanocomposites have better heat-resistance,higher decomposition temperatures and less thermal weight-loss.However,these two intercalation methods have different effects on the softening point of the intercalation nanocomposites.Pressing intercalation almost does not affect the softening point of the intercalation nanocomposites,while melt intercalation significantly increases the softening point of the intercalation nanocomposites, probably due to the chemical actions happening in the process of melt intercalation.