Enhanced ion conductivity and electrode–electrolyte interphase stability of porous Si anodes enabled by silicon nitride nanocoating for high-performance Li-ion batteries

Silicon (Si) is a promising anode material for next-generation high-energy lithium-ion batteries (LIBs) due to its high capacity.However,the large volumetric expansion,poor ion conductivity and unstable solid electrolyte interface (SEI) lead to rapid capacity fading and low rate performance.Herein,we report Si nitride (SiN) comprising stoichiometric Si_(3)N_(4) and Li-active anazotic SiN_(x) coated porous Si (p-Si@SiN)for high-performance anodes in LIBs.The ant-nest-like porous Si consisting of 3D interconnected Si nanoligaments and bicontinuous nanopores prevents pulverization and accommodates volume expansion during cycling.The Si_(3)N_(4) offers mechanically protective coating to endow highly structural integrity and inhibit superfluous formation of SEI.The fast ion conducting Li_(3)N generated in situ from lithiation of active SiN_(x) facilitates Li ion transport.Consequently,the p-Si@SiN anode has appealing electrochemical properties such as a high capacity of 2180 mAh g^(-1)at 0.5 A g^(-1) with 84%capacity retention after 200cycles and excellent rate capacity with discharge capacity of 721 mAh g^(-1) after 500 cycles at 5.0 A g^(-1).This work provides insights into the rational design of active/inactive nanocoating on Si-based anode materials for fast-charging and highly stable LIBs.

Influence of solvent on ion conductivity of polybenzimidazole proton exchange membranes for vanadium redox flow batteries

Polybenzimidazole(PBI)is a kind of proton transport membrane material,and its ion conductivity is a key factor affecting its application in vanadium redox flow batteries(VRFBs).The casting solvent of PBI has a significant influence on the acid doping level of PBI membranes which is closely related to ionic conductivity.In this paper,3,3′-diaminobenzidine(DABz)and 4,4′-Dicarboxydiphenylether(DCDPE)were used as raw materials by solution condensation to prepare the PBI with ether bond groups.The chemical structure of PBI was determined by1H NMR and FT-IR,and the prepared PBI had good solubility which can be dissolved in a variety of solvents.The PBI proton exchange membranes were prepared by solution coating with 5 different solvents of N,N-dimethylformamide(DMF),N,N-dimethylacetamide(DMAc),dimethyl sulfoxide(DMSO),1-methyl-2-pyrrolidone(NMP),methane sulfonic acid(MSA).The effects of different solvents on the ion conductivity and physicochemical properties were discussed in detail.The results showed that the PBI membrane prepared by using MSA as solvent(the PBI+MSA membrane)exhibits high water uptake,acid doping level and low vanadium ion permeability.The VRFB assembled with the PBI+MSA membrane exhibited higher coulombic efficiency(CE)99.87%and voltage efficiency(VE)84.50%than that of the commercial Nafion115 membrane at100 m A·cm-2,and after 480 cycles,the EE value can still be maintained at 83.73%.The self-discharge time of a single battery was recorded to be as long as 1000 h.All experimental data indicated that MSA is the best solvent for casting PBI membrane.

Oxygen ion conductivity of La_(0.8)Sr_(0.2)Ga_(0.83)Mg_(0.17-x)Co_xO_(3-δ) synthesized by laser rapid solidification

Materials Lao.8Sro.2Gao.83Mgo.17_xCox03_6 with x = 0, 0.05, 0.085, 0.10, and 0.15 are synthesized by laser rapid solidification. It is shown that the samples prepared by laser rapid solidification give rise to unique spear-like or leaf-like microstructures which are orderly arranged and densely packed. Their electrical properties each show a general depen dence of the Co content and the total conductivities of Lao.8Sro.2Gao.83Mgo.085Coo.08503_6 prepared by laser rapid solidification are measured to be 0.067, 0.124, and 0.202 S.cm-1 at 600, 700, and 800 ℃, respectively, which are much higher than by conventional solid state reactions. Moreover, the electrical conductivities each as a function of the oxy gen partial pressure are also measured. It is shown that the samples with the Co content values 〈 8.5 mol% each exhibit basically ionic conduction while those for Co content values 〉 10 mol % each show ionic mixed electronic conduction under oxygen partial pressures from 10-16 atm （1 atm = 1.01325 x 105 Pa） to 0.98 atm. The improved ionic conductivity of Lao.sSro.2Gao.83Mgo.085Coo.08503 prepared by laser rapid solidification compared with by solid state reactions is attributed to the unique microstructure of the sample generated during laser rapid solidification.

Theoretical prediction of ion conductivity in solid state HfO_2

A theoretical prediction of ion conductivity for solid state HfO2 is carried out in analogy to ZrO2 based on the density functional calculation. Geometric and electronic structures of pure bulks exhibit similarity for the two materials. Negative formation enthalpy and negative vacancy formation energy are found for YSH （yttria-stabilized hafnia） and YSZ （yttria- stabilized zirconia）, suggesting the stability of both materials. Low activation energies （below 0.7 eV） of diffusion are found in both materials, and YSH＇s is a little higher than that of YSZ. In addition, for both HfO2 and ZrO2, the supercells with native oxygen vacancies are also studied. The so-called defect states are observed in the supercells with neutral and ＋1 charge native vacancy but not in the ＋2 charge one. It can give an explanation to the relatively lower activation energies of yttria-doped oxides and ＋2 charge vacancy supercells. A brief discussion is presented to explain the different YSH ion conductivities in the experiment and obtained by us, and we attribute this to the different ion vibrations at different temperatures.

Tuning the electronic conductance of REH_(x)(RE=Nd,Ce,Pr)by structural deformation

Hydride ion(H-)conductors have drawn much attention due to their potential applications in hydrideion-based devices.Rare earth metal hydrides(REH_(x))have fast H-conduction which,unfortunately,is accompanied by detrimental electron conduction preventing their application as ion conductors.Here,REH_(x)(RE=Nd,Ce,and Pr)with varied grain sizes,rich grain boundaries,and defects have been prepared by ball milling and subsequent sintering.The electronic conductivity of the ball-milled REH_(x)samples can be reduced by 2-4 orders of magnitude compared with the non-ball-milled samples.The relationship of electron conduction and miscrostructures in REH_(x)is studied and discussed based on experimental data and previously-proposed classical and quantum theories.The H-conductivity of all REH_(x)is about 10^(-4)to 10^(-3)S cm^(-1)at room temperature,showing promise for the development of H-conductors and their applications in clean energy storage and conversion.

Improving ionic conductivity of polymer-based solid electrolytes for lithium metal batteries

Because of its superior safety and excellent processability,solid polymer electrolytes(SPEs)have attracted widespread attention.In lithium based batteries,SPEs have great prospects in replacing leaky and flammable liquid electrolytes.However,the low ionic conductivity of SPEs cannot meet the requirements of high energy density systems,which is also an important obstacle to its practical application.In this respect,escalating charge carriers(i.e.Li^(+))and Li^(+)transport paths are two major aspects of improving the ionic conductivity of SPEs.This article reviews recent advances from the two perspectives,and the underlying mechanism of these proposed strategies is discussed,including increasing the Li^(+)number and optimizing the Li^(+)transport paths through increasing the types and shortening the distance of Li^(+)transport path.It is hoped that this article can enlighten profound thinking and open up new ways to improve the ionic conductivity of SPEs.

THE SCATTERING THEORY OF IONIC CONDUCTIVITY OF TERNARY GLASS

The physical expression of electrical conductivity of ternary glass can be obtained by the physical scattering theory of conducting ions by the defects in the glass. The scattering area of ion by the nucleus is given by the law of Rutherford in atomic physics. By this theory, the physical meaning of the microprocess of ionic conductivity of ternary glass is apparent.

Synthesis and Conductivity of Oxyapatite Ionic Conductor La10-xVx（SiO4）6O3＋x

Apatite-lanthanum silicate has attracted considerable interest in recent years due to its high oxide ion conductivity.In this paper,V-doped samples La10-xVx(SiO4) 6O3+x(0≤x≤1.5) were prepared by sol-gel method and the influences of V-dopant content on calcining temperature and conductivity were reported.The samples were characterized by thermal analysis(TG-DSC) ,X-ray diffraction(XRD) and scanning electron micrograph(SEM) . The apatite was obtained at 800°C,a relatively low temperature in comparison to 1500°C with the conventional solid-state method.The ceramic pellets sintered at 1200°C for 5 h showed a higher relative density than La9.33Si6O26 pellets sintered at 1400°C for 20 h.The conductivities of samples were measured by electrochemical impedance spectroscopy.The conductivity was improved with the increase of V-dopant content on La site.

Rational Design of High-Performance PEO/Ceramic Composite Solid Electrolytes for Lithium Metal Batteries

Composite solid electrolytes(CSEs)with poly(ethylene oxide)(PEO)have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li~+solvating capability,flexible processability and low cost.However,unsatisfactory room-temperature ionic conductivity,weak interfacial compatibility and uncontrollable Li dendrite growth seriously hinder their progress.Enormous efforts have been devoted to combining PEO with ceramics either as fillers or major matrix with the rational design of two-phase architecture,spatial distribution and content,which is anticipated to hold the key to increasing ionic conductivity and resolving interfacial compatibility within CSEs and between CSEs/electrodes.Unfortunately,a comprehensive review exclusively discussing the design,preparation and application of PEO/ceramic-based CSEs is largely lacking,in spite of tremendous reviews dealing with a broad spectrum of polymers and ceramics.Consequently,this review targets recent advances in PEO/ceramicbased CSEs,starting with a brief introduction,followed by their ionic conduction mechanism,preparation methods,and then an emphasis on resolving ionic conductivity and interfacial compatibility.Afterward,their applications in solid-state lithium metal batteries with transition metal oxides and sulfur cathodes are summarized.Finally,a summary and outlook on existing challenges and future research directions are proposed.

Recent Advances on Polyoxometalate-Based Ion-Conducting Electrolytes for Energy-Related Devices

Solid-state electrolytes have attracted considerable attention in new energyrelated devices due to their high safety and broad application platform.Polyoxometalates(POMs)are a kind of molecular-level cluster compounds with unique structures.In recent years,owing to their abundant physicochemical properties(including high ionic conductivity and reversible redox activity),POMs have shown great potential in becoming a new generation of solid-state electrolytes.In this review,an overview is investigated about how POMs have evolved as ion-conducting materials from basic research to novel solid-state electrolytes in energy devices.First,some expressive POM-based ion-conducting materials in recent years are introduced and classified,mainly inspecting their structural and functional relationship.After that,it is further focused on the application of these ionconducting electrolytes in the fields of proton exchange membranes,supercapacitors,and ion batteries.In addition,some properties of POMs(such as inherent dimension,capable of forming stable hydrogen bonds,and reversible bonding to water molecules)enable these functional POM-based electrolytes to be employed in innovative applications such as ion selection,humidity sensing,and smart materials.Finally,some fundamental recommendations are given on the current opportunities and challenges of POM-based ion-conducting electrolytes.

Influence on Conductivity of Polyparaphenylene by Chemical Doping and Ion Implantation

Polyparaphenylene(PPP) is prepared by AlCl 3-CuCl 2 catalysts with benzene as the monomer and is doped by chemical method and N + ion implantation. The influences of the concentration, temperature and time of chemical doping and the dose, energy and temperature of ion implantation, on PPP conductivity are investigated. The results showed that the conductivity of PPP can be improved 4～5 orders of magnitude by ion implantation and the conductivity of PPP can reach about 0.11 S·cm -1 by chemical doping. The comparison of stability of the material conductive behavior by using the two doping methods is presented. It shows that ion implantation is better than chemical doping in stabilizing the electric conductive behavior for the material.

Progress in Gel Polymer Electrolytes for Sodium-Ion Batteries

Sodium-ion battery is a potential application system for large-scale energy storage due to the advantage of higher nature abundance and lower production cost of sodium-based materials.However,there exist inevitably the safety problems such as flammability due to the use of the same type of organic liquid electrolyte with lithium-ion battery.Gel polymer electrolytes are being considered as an effective solution to replace conventional organic liquid electrolytes for building safer sodium-ion batteries.In this review paper,the authors present a comprehensive overview of the research progress in electrochemical and physical properties of the gel polymer electrolyte-based sodium batteries.The gel polymer electrolytes based on different polymer hosts namely poly(ethylene oxide),poly(acrylonitrile),poly(methyl methacrylate),poly(vinylidene fluoride),poly(vinylidene fluoride-hexafluoro propylene),and other new polymer networks are summarized.The ionic conductivity,ion transference number,electrochemical window,thermal stability,mechanical property,and interfacial issue with electrodes of gel polymer electrolytes,and the corresponding influence factors are described in detail.Furthermore,the ion transport pathway and ion conduction mechanism are analyzed and discussed.In addition,the advanced gel polymer electrolyte systems including flame-retardant polymer electrolytes,composite gel polymer electrolytes,copolymerization,single-ion conducting polymer electrolytes,etc.with more superior and functional performance are classified and summarized.Finally,the application prospects,development opportunities,remaining challenges,and possible solutions are discussed.

“In-N-out” design enabling high-content triethyl phosphate-based non-flammable and high-conductivity electrolytes for lithium-ion batteries

Safety issues related to flammable electrolytes in lithium-ion batteries(LIBs) remain a major challenge for their extended applications.The use of non-flammable phosphate-based electrolytes has proved the validity in inhibiting the combustion of LIBs.However,the strong interaction between Li^(+) and phosphate leads to a dominant solid electrolyte interphase(SEI) with limited electronic shielding,resulting in the poor Li^(+) intercalation at the graphite(Gr) anode when using high-phosphate-content electrolytes.To mitigate this issue and improve Li^(+) insertion,we propose an “In-N-Out” strategy to render phosphates “noncoordinative”.By employing a combination of strongly polar solvents for a “block effect” and weakly polar solvents for a “drag effect”,we reduce the Li^(+)–phosphate interaction.As a result,phosphates remain in the electrolyte phase(“In”),minimizing their impact on the incompatibility with the Gr electrode(“Out”).We have developed a non-flammable electrolyte with high triethyl phosphate(TEP) content(>60 wt.%),demonstrating the excellent ion conductivity(5.94 mS cm^(-1) at 30 ℃) and reversible Li^(+) intercalation at a standard concentration(~1 mol L^(-1)).This approach enables the manipulation of multiple electrolyte functions and holds the promise for the development of safe electrochemical energy storage systems using non-flammable electrolytes.

Moisture Detection of SF_6 Gas Instruments by Solid Electrolyte

Humidity measurement in a very low moisture atmosphere was studied by using solid electrolyte film coated with porous electrodes,considering its application to the moisture monitoring of SF_6 gas-insulated high voltage instruments such as gas-insulated switchgear (GIS) and gas circuit breakers (GCBs).Compared to the AC impedance values measured in an ambient atmosphere where the moisture atmosphere is far higher than that in these instruments,considerably large impedance values were obtained in a very low moisture atmosphere.The impedance was systematically measured in accordance with the conditions of these instruments whose moisture contents were less than 1 000×10^(-6).A good correlation was obtained between the impedance values and the moisture contents.The frequency characteristics of the impedance were analyzed based on a conventional equivalent circuit where a number of CR circuits were connected in series.Considering the dielectric relaxation of each circuit,it was found that the frequency characteristics of the impedance can be explained by the equivalent circuit. Two semicircles were clearly obtained in the Cole-Cole impedance plot which are thought to reflect the impedance characteristics of the film and the electrodes.The AC impedance can be a good indicator of the moisture content of SF_6 gas-insulated high voltage instruments.

SYNTHESIS AND APPLICATION AS POLYMER ELECTROLYTE OF HOMO- AND COPOLYMERS OF 3-(2-CYANO ETHOXY)METHYL- AND 3-(METHOXY(TRIETHYLENOXY))METHYL-3'-METHYLOXETANE

Two oxetane-derived monomers, 3-（2-cyano-ethoxy）methyl- and 3-（methoxy-（triethylenoxy））methyl-3＇- methyloxetane （COX and MTOX）, were prepared from 3-hydroxymethyl-3＇-methyloxetane. Their homo- and copolymerization in solution were carried out by the cationic ring-opening polymerization with BF3 · Et2O and 1,4-butanediol as co-initiator. The molecular weight and molecular weight distribution were determined using GPC so as to reveal the competition and interchange between active chain end （ACE） and activated monomer （AM） mechanism in the process. The reactivity ratios of the two monomers were calculated according to Kelen-Tudos using ^1H-NMR analysis. The influence of functional side chains in the monomers on the copolymerization behaviors was discussed in virtue of the reactivity ratio data. When doped with lithium salt LiTFSI, the ion conductivity of the homopolymer of MTOX reached 10^-3.58 S/cm at 30℃ and 10^-2.73 S/cm at 80℃, respectively, showing its potential to be used as polymer electrolyte for lithium ion battery.

Flexible ion-conducting membranes with 3D continuous nanohybrid networks for high-performance solid-state metallic lithium batteries

Polyethylene oxide(PEO)-based electrolytes are considered as one of the most promising solid-state electrolytes for next-generation lithium batteries with high safety and energy density;however,the drawbacks such as insufficient ion conductance,mechanical strength and electrochemical stability hinder their applications in metallic lithium batteries.To enhance their overall properties,flexible and thin composite polymer electrolyte(CPE)membranes with 3D continuous aramid nanofiber(ANF)–Li_(1.4)Al_(0.4)Ti_(1.6)(PO_(4))_(3)(LATP)nanoparticle hybrid frameworks are facilely prepared by filling PEO–Li TFSI in the 3D nanohybrid scaffolds via a solution infusion way.The construction of the 3D continuous nanohybrid networks can effectively inhibit the PEO crystallization,facilitate the lithium salt dissociation and meanwhile increase the fast-ion transport in the continuous LATP electrolyte phase,and thus greatly improving the ionic conductivity(~3 times that of the pristine one).With the integration of the 3D continuity and flexibility of the 3D ANF networks and the thermostability of the LATP phase,the CPE membranes also show a wider electrochemical window(~5.0 V vs.4.3 V),higher tensile strength(~4–10times that of the pristine one)and thermostability,and better lithium dendrite resistance capability.Furthermore,the CPE-based Li FePO_(4)/Li cells exhibit superior cycling stability(133 m Ah/g after 100 cycles at 0.3 C)and rate performance(100 m Ah/g at 1 C)than the pristine electrolyte-based cell(79 and 29m Ah/g,respectively).This work offers an important CPE design criteria to achieve comprehensivelyupgraded solid-state electrolytes for safe and high-energy metal battery applications.

ION CONDUCTION IN COMPLEX OF ACRYLONITRILE-COPOLYMERIZED COMB POLYETHER WITH LITHIUM PERCHLORATE

Poly (oligoether methacrylate-co-acrylonitrile) s, P (MEOn- AN), with oligoether pendants of different lengths were synthesized and the ion conduction property of their Li-salt complexes was studied as the function of polymer structure. At proper copolymer composition, lithium concentration and pendant length, the ion conductivity reaches 7.0×10^(-5)S/cm at ambient temperature, together with improved mechanical strength. The ion transport in the polymer media is assisted by segmental relaxation, which is confirmed both by the consistency between ion conductivity and T_g and by the study of TSC.

PREPARATION OF FUNCTIONAL MATERIALS BY BLENDING COPOLYESTERS WITH PVA AND METAL COMPLEX FORMATION OF POLYMER BLENDS

Copolyesters having secondary and tertiary amine salt groups in the main and side chains are prepared by chemoselective polymerization. These copolyesters are soluble in a 10% aqueous solution of poly(vinyl alcohol) (PVA) at 90 degree C and act as plasticizer in the blend films cast from the solution. Only a glass transition temperature is observed for all these blends indicating the formation of compatible blends from these polyesters with PVA. These blends exhibit manifold characteristics such as ionic conductivity, complex formation with metal ions, absorption of moisture and color changes. The electric conductivity of the copolyesters and blends is in the range of 10** minus **6 Scm** minus **1. The blends with PVA forms complexes with Cu**2** plus and Co**2** plus . The coordination structure with two chelate rings is suggested for these polymer blend/metal complexes. (Author abstract) 10 Refs.

The control and optimization of macro/micro-structure of ion conductive membranes for energy conversion and storage

Ion conductive membranes(ICMs)are frequently used as separators for energy conversion and storage technologies of fuel cells,flow battery,and hydrogen pump,because of their good ion-selective conduction and low electronic conductivity.Firstly,this feature article reviews the recent studies on the development of new nonfluorinated ICMs with low cost and their macro/micro-structure control.In general,these new nonfluorinated ICMs have lower conductivity than commercial perfluorinated ones,due to their poor ion transport channels.Increasing ion exchange capacity(IEC)would create more continuous hydrophilic channels,thus enhancing the conductivity.However,high IEC also expands the overall hydrophilic domains,weakens the interaction between polymer chains,enhances the mobility of polymer chains,and eventually induces larger swelling.The micro-scale expansion and macro-scale swelling of the ICMs with high IEC could be controlled by limiting the mobility of polymer chains.Based on this strategy,some ef ficient techniques have been developed,including covalent crosslinking,semi-interpenatrating polymer network,and blending.Secondly,this review introduces the optimization of macro/microstructure of both perfluorinated and nonfluorinated ICMs to improve the performance.Macro-scale multilayer composite is an ef ficient way to enhance the mechanical strength and the dimensional stability of the ICMs,and could also decrease the content of per fluorosulfonic acid resin in the membrane,thereby reducing the cost of the perfluorinated ICMs.Long side chain,multiple functionalization,small molecule inducing micro-phase separation,electrospun nano fiber,and organic–inorganic hybrid could construct more ef ficient ion transport channels,improving the ion conductivity of ICMs.

Comprehensively-modified polymer electrolyte membranes with multifunctional PMIA for highly-stable all-solid-state lithium-ion batteries

Polyethylene oxide(PEO)-based electrolytes have obvious merits such as strong ability to dissolve salts(e.g.,LiTFSI)and high flexibility,but their applications in solid-state batteries is hindered by the low ion conductance and poor mechanical and thermal properties.Herein,poly(m-phenylene isophthalamide)(PMIA)is employed as a multifunctional additive to improve the overall properties of the PEO-based electrolytes.The hydrogen-bond interactions between PMIA and PEO/TFSI-can effectively prevent the PEO crystallization and meanwhile facilitate the LiTFSI dissociation,and thus greatly improve the ionic conductivity(two times that of the pristine electrolyte at room temperature).With the incorporation of the high-strength PMIA with tough amide-benzene backbones,the PMIA/PEO-LiTFSI composite polymer electrolyte(CPE)membranes also show much higher mechanical strength(2.96 MPa),thermostability(4190℃)and interfacial stability against Li dendrites(468 h at 0.10 mA cm-2)than the pristine electrolyte(0.32 MPa,364℃and short circuit after 246 h).Furthermore,the CPE-based LiFePO4/Li cells exhibit superior cycling stability(137 mAh g^-1 with 93%retention after 100 cycles at 0.5 C)and rate performance(123 mAh g^-1 at 1.0 C).This work provides a novel and effective CPE structure design strategy to achieve comprehensively-upgraded electrolytes for promising solid-state battery applications.