Highly Conductive Proton Selectivity Membrane Enabled by Hollow Carbon Sieving Nanospheres for Energy Storage Devices

Ion conductive membranes(ICMs)with highly conductive proton selectivity are of significant importance and greatly desired for energy storage devices.However,it is extremely challenging to construct fast proton-selective transport channels in ICMs.Herein,a membrane with highly conductive proton selectivity was fabricated by incorporating porous carbon sieving nanospheres with a hollow structure(HCSNs)in a polymer matrix.Due to the precise ion sieving ability of the microporous carbon shells and the fast proton transport through their accessible internal cavities,this advanced membrane presented a proton conductivity(0.084 S·cm^(-1))superior to those of a commercial Nation 212(N212)membrane(0.033S·cm^(-1))and a pure polymer membrane(0.049 S·cm^(-1)).The corresponding proton selectivity of the membrane(6.68×10^(5) S·min·cm^(-3))was found to be enhanced by about 5.9-fold and 4.3-fold,respectively,compared with those of the N212 membrane(1.13×10^(5) S·min·cm^(-3))and the pure membrane(1.56×10^(5) S·min·cm^(-3)).Low-field nuclear magnetic resonance(LF-NMR)clearly revealed the fast protonselective transport channels enabled by the HCSNs in the polymeric membrane.The proposed membrane exhibited an outstanding energy efficiency(EE)of 84%and long-term stability over 1400 cycles with a0.065%capacity decay per cycle at 120 mA·cm^(-2) in a typical vanadium flow battery(VFB)system.

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.

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.

Transforming a Two-Dimensional Layered Insulator into a Semiconductor or a Highly Conductive Metal through Transition Metal Ion Intercalation

Atomically thin two-dimensional(2D) materials are the building bricks for next-generation electronics and optoelectronics, which demand plentiful functional properties in mechanics, transport, magnetism and photoresponse.For electronic devices, not only metals and high-performance semiconductors but also insulators and dielectric materials are highly desirable. Layered structures composed of 2D materials of different properties can be delicately designed as various useful heterojunction or homojunction devices, in which the designs on the same material(namely homojunction) are of special interest because preparation techniques can be greatly simplified and atomically seamless interfaces can be achieved. We demonstrate that the insulating pristine ZnPS_3, a ternary transition-metal phosphorus trichalcogenide, can be transformed into a highly conductive metal and an n-type semiconductor by intercalating Co and Cu atoms, respectively. The field-effect-transistor(FET) devices are prepared via an ultraviolet exposure lithography technique. The Co-ZnPS_3 device exhibits an electrical conductivity of 8 × 10^(4) S/m, which is comparable to the conductivity of graphene. The Cu-ZnPS_3 FET reveals a current ON/OFF ratio of 1-05 and a mobility of 3 × 10^(-2 )cm^(2)·V^(-1)·s^(-1). The realization of an insulator, a typical semiconductor and a metallic state in the same 2D material provides an opportunity to fabricate n-metal homojunctions and other in-plane electronic functional devices.

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.

Laminar Composite Solid Electrolyte with Poly(Ethylene Oxide)-Threaded Metal-Organic Framework Nanosheets for High-Performance All-Solid-State Lithium Battery

Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.

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.

Preparing 3D Perovskite Li_(0.33)La_(0.557)TiO_(3)Nanotubes Framework Via Facile Coaxial Electro-Spinning Towards Reinforced Solid Polymer Electrolyte

It is of significance to construct continuous multiphase percolation channels with fast lithium-ion pathway in hybrid solid electrolytes.3D ceramic nanostructure frameworks have attracted great attention in this field.Herein,the three-dimensional perovskite Li_(0.33)La_(0.557)TiO_(3)nanotubes framework(3D-LLTO-NT)is fabricated via a facile coaxial electro-spinning process followed by a calcination process at 800°C.The hybrid polymer electrolyte of 3DLLTO-NT framework and poly(ethylene carbonate)(3D-LLTO-NT@PEC)shows improved ionic conductivity of 1.73×10^(-4)S cm^(-1)at ambient temperature,higher lithium-ion transference number(t_(Li)^(+))of 0.78 and electrochemical stability window up to 5.0 V vs Li/Li^(+).The all-solid-state cell of LiFePO_(4)/3D-LLTO-NT@PEC/Li delivers a high specific capacity of 140.2 mAh g^(-1)at 0.1 C at ambient temperature.This outstanding performance is attributed to the 3D ceramic nanotubes frameworks which provide fast lithium ion transfer pathway and stable interfaces.

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.

Recent advances and perspectives of fluorite and perovskite-based dual-ion conducting solid oxide fuel cells

High-temperature solid-state electrolyte is a key component of several important electrochemical devices,such as oxygen sensors for automobile exhaust control,solid oxide fuel cells(SOFCs) for power generation,and solid oxide electrolysis cells for H_(2) production from water electrolysis or CO_(2) electrochemical reduction to value-added chemicals.In particular,internal diffusion of protons or oxygen ions is a fundamental and crucial issue in the research of SOFCs,hypothetically based on either oxygen-ionconducting electrolytes or proton-conducting electrolytes.Up to now,some electrolyte materials based on fluorite or perovskite structure were found to show certain degree of dual-ion transportation capability,while in available electrolyte database,particularly in the field of SOFCs,such dual-ion conductivity was seriously overlooked.Actually,few concerns arising to the simultaneous proton and oxygen-ion conductivities in electrolyte of SOFCs inevitably induce various inadequate and confusing results in literature.Understanding dual-ion transportation behavior in electrolyte is indisputably of great importance to explain some unusual fuel cell performance as reported in literature and enrich the knowledge of solid state ionics.On the other hand,exploration of novel dual-ion conducting electrolytes will benefit the development of SOFCs.In this review,we provide a comprehensive summary of the understanding of dual-ion transportation in solid electrolyte and recent advances of dual-ion conducting SOFCs.The oxygen ion and proton conduction mechanisms at elevated temperature inside oxide-based electrolyte materials are first introduced,and then(mixed) oxygen ion and proton conduction behaviors of fluorite and perovskite-type oxides are discussed.Following on,recent advances in the development of dual-ion conducting SOFCs based on fluorite and perovskite-type single-phase or composite electrolytes,are reviewed.Finally,the challenges in the development of dual-ion conducting SOFCs are discussed and future prospects are proposed.

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.

Ionic liquids for high performance lithium metal batteries

The pursuit of high energy density has promoted the development of high-performance lithium metal batteries.However,it faces a serious security problem.Ionic liquids have attracted great attention due to their high ionic conductivity,non-flammability,and the properties of promoting the formation of stable SEI films.Deeply understanding the problems existing in lithium metal batteries and the role of ionic liquids in them is of great significance for improving the performance of lithium metal batteries.This article reviews the effects of the molecular structure of ionic liquids on ionic conductivity,Li^(+)ion transference number,electrochemical stability window,and lithium metal anode/electrolyte interface,as well as the application of ionic liquids in Li-high voltage cathode batteries,Li-O_(2) batteries and Li-S batteries.The molecular design,composition and polymerization will be the main strategies for the future development of ionic liquid-based electrolytes for high performance lithium metal battery.

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.

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.

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.

Multi-objective Optimal Design of High Frequency Probe for Scanning Ion Conductance Microscopy

Scanning ion conductance microscopy（SICM） is an emerging non-destructive surface topography characterization apparatus with nanoscale resolution. However, the low regulating frequency of probe in most existing modulated current based SICM systems increases the system noise, and has difficulty in imaging sample surface with steep height changes. In order to enable SICM to have the capability of imaging surfaces with steep height changes, a novel probe that can be used in the modulated current based bopping mode is designed. The design relies on two piezoelectric ceramics with different travels to separate position adjustment and probe frequency regulation in the Z direction. To fiarther improve the resonant frequency of the probe, the material and the key dimensions for each component of the probe are optimized based on the multi-objective optimization method and the finite element analysis. The optimal design has a resonant frequency of above 10 kHz. To validate the rationality of the designed probe, microstructured grating samples are imaged using the homebuilt modulated current based SICM system. The experimental results indicate that the designed high frequency probe can effectively reduce the spike noise by 26% in the average number of spike noise. The proposed design provides a feasible solution for improving the imaging quality of the existing SICM systems which normally use ordinary probes with relatively low regulating frequency.

Highly Stretchable and Transparent Hydrogel as a Strain Sensor

The rapid developments of artificial intelligence have attracted attention in designing electronic skin(e-skin)to realize the mechanical and sensory properties of human skin.To better imitate the tactile sensing properties of human skin,a stretchable and transparent hydrogel is produced.Thus,an elastic and capacitive strain sensor was successfully produced through the as-prepared hydrogel.The sensor was elastic with a high conductive stability and could detect the strain changes in different states,which had very short response time that could be applied into the detection of large and small deformations and would shed light on its application in e-skin.

Electrochemical performance of all-solid lithium ion batteries with a polyaniline film cathode

We have prepared a high-density polyaniline（PANI） paste（50 mg/m L）, with similar physical properties to those of paints or pigments. The synthesis of PANI is confirmed by Fourier transform infrared（FT-IR） spectroscopy. The morphologies of PANI, doped PANI, and doped PANI paste are confirmed by scanning electron microscopy（SEM）. Particles of doped PANI paste are approximately 40–50 nm in diameter, with a uniform and cubic shape. The electrochemical performances of doped PANI paste using both liquid and solid polymer electrolytes have been measured by galvanostatic charge and discharge process. The cell fabricated with doped PANI paste and the solid polymer electrolyte exhibits a discharge capacity of ～87 μAh/cm2（64.0 m Ah/g） at the second cycle and～67 μAh/cm2（50.1 m Ah/g） at the 100 th cycle.

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.