Bimetallic Anionic Organic Frameworks with Solid-State Cation Conduction for Charge Storage Applications.

A new phosphonate-based anionic bimetallic organic framework, with the general formula of A4 -Zn-DOBDP (wherein A is Li+ or Na+ , and DOBDP6- is the 2,5-dioxido-1,4-benzenediphosphate ligand) is prepared and characterized for energy storage applications. With four alkali cations per formula unit, the A4 -Zn-DOBDP MOF is found to be the first example of non-solvated cation conducting MOF with measured conductivities of 5.4×10-8  S cm-1 and 3.4×10-8  S cm-1 for Li4 - and Na4 - phases, indicating phase and composition effects of Li+ and Na+ shuttling through the channels. Three orders of magnitude increase in ionic conductivity is further attained upon solvation with propylene carbonate, placing this system among the best MOF ionic conductors at room temperature. As positive electrode material, Li4 -Zn-DOBDP delivers a specific capacity of 140 mAh g-1 at a high average discharge potential of 3.2 V (vs. Li+ /Li) with 90 % of capacity retention over 100 cycles. The significance of this research extends from the development of a new family of electroactive phosphonate-based MOFs with inherent ionic conductivity and reversible cation storage, to providing elementary insights into the development of highly sought yet still evasive MOFs with mixed-ion and electron conduction for energy storage applications.

A Phosphine-Amine-Linked Covalent Organic Framework with Staggered Stacking Structure for Lithium-Ion Conduction.

In-plane ionic conduction over two-dimensional (2D) materials is desirable for flexible electronics. Exfoliating 2D covalent organic frameworks (COFs) towards a few layers is highly anticipated, whereas most examples remain robust via π-stacking against the interlayered dislocation. Herein, we synthesize a phosphine-amine-linked 2D COF by a nucleophilic substitution reaction of phosphazene with amines. The synthesized COF is crystalline, and stacks in an AB-staggered fashion, wherein the AB dual layers are interlocked by embedding P-Cl bonds from one to another layer, and the non-interlocked layers are readily delaminated. Therefore, in situ post-quaternization over phosphazene can improve the ionization of backbones, accompanied by layered exfoliation. The ultrathin nanosheets can decouple lithium salts for fast solid-state ion transport, achieving a high conductivity and low activation energy. Our findings explore the P-N substitution reaction for COF crystallization and demonstrate that the staggered stacking 2D COFs are readily exfoliated for designing solid electrolytes.

Enabling the Operation of Highly Compatible LiI-3-Hydroxypropionitrile Small-Molecule Solid-State Electrolytes in Lithium Metal Batteries via Stepped-Amorphization Strategy.

Integrating the advantages of both inorganic ceramic and organic polymer solid-state electrolytes, small-molecule solid-state electrolytes represented by LiI-3-hydroxypropionitrile (LiI-HPN) inorganic-organic hybrid systems possess good interfacial compatibility and high modulus. However, their lack of intrinsic Li+ conduction ability hinders potential application in lithium metal batteries until now, despite containing LiI phase composition. Herein, inspired by evolution tendency of ionic conduction behaviors together with first-principles molecular dynamics simulations, we propose a stepped-amorphization strategy to break the Li+ conduction bottleneck of LiI-HPN. It involves three progressive steps of composition (LiI-content increasing), time (long-time standing), and temperature (high-temperature melting) regulations, to essentially construct a small-molecule-based composite solid-state electrolyte with intensified amorphous degree, which realizes efficient conversion from an I- to Li+ conductor and improved conductivity. As a proof, the stepped-optimized LiI-HPN is successfully operated in lithium metal batteries cooperated with Li4 Ti5 O12 cathode to deliver considerable compatibility and stability over 250 cycles. This work not only clarifies the ionic conduction mechanisms of LiI-HPN inorganic-organic hybrid systems, but also provides a reasonable strategy to broaden the application scenarios of highly compatible small-molecule solid-state electrolytes.

Controlling the Mobility of Ionic Liquids in the Nanopores of MOFs by Adjusting the Pore Size: From Conduction Collapse by Mutual Pore Blocking to Unhindered Ion Transport.

Ionic liquids (ILs) in nanoporous confinement are the core of many supercapacitors and batteries, where the mobility of the nanoconfined ILs is crucial. Here, by combining experiments based on impedance spectroscopy with molecular dynamics simulations, the mobility of a prototype IL in the nanopores of an isoreticular metal-organic framework (MOF)-series with different pore sizes is explored, where an external electric field is applied. It has been found that the conduction behavior changes tremendously depend on the pore size. For small-pore apertures, the IL cations and anions cannot pass the pore window simultaneously, causing the ions to mutually block the pores. This results in a strong concentration dependence of the ionic conduction, where the conduction drops by two orders of magnitude when filling the pores. For large-pore MOFs, the mutual hindrance of the ions in the pores is small, causing only a small concentration dependence. The cutoff between the large-pore and small-pore behavior is approximately the size of a cation-anion-dimer and increasing the pore diameter by only 0.2 nm changes the conduction behavior fundamentally. This study shows that the pore aperture size has a substantial effect on the mobility of ions in nanoporous confinement and has to be carefully optimized for realizing highly-mobile nanoconfined ILs.

Anisotropic Ion Migration and Electronic Conduction in van der Waals Ferroelectric CuInP2S6.

Van der Waals (vdW) thio- and seleno-phosphates have recently gained considerable attention for the use as "active" dielectrics in two-dimensional/quasi-two-dimensional electronic devices. Bulk ionic conductivity in these materials has been identified as a key factor for the control of their electronic properties. However, direct evidence of specific ion species' migration at the nanoscale, particularly under electric fields, and its impact on material properties has been elusive. Here, we report on direct evidence of a phase-selective anisotropic Cu-ion-hopping mechanism in copper indium thiophosphate (CuInP2S6) through detailed scanning probe microscopy measurements. A two-step Cu-hopping path including a first intralayer hopping (in-plane) and second interlayer hopping (out-of-plane) crossing the vdW gap is unveiled. Evidence of electrically controlled Cu ion migration is further verified by nanoscale energy-dispersive X-ray spectroscopy (EDS) mapping. These findings offer new insight into anisotropic ionic manipulation in layered vdW ferroelectric/dielectric materials for emergent vdW electronic device design.

Layer-by-Layer Assembly of Strong Thin Films with High Lithium Ion Conductance for Batteries and Beyond.

Polyethylene oxide (PEO) is one of the most widely used polymeric ion conductors which has the potential for a wide range of applications in energy storage. The enhancement of ionic conductivity of PEO-based electrolytes is generally achieved by sacrificing the mechanical properties. Using layer-by-layer (LbL) self-assembly with a nanoscale precision, mechanically strong and self-healable PEO/polyacrylic acid composite thin films with a high Li+ conductivity of 2.3 ± 0.8 × 10-4 S cm-1 at 30 °C, and a strength of 3.7 MPa is prepared. These values make the LbL composite among the best recorded multifunctional solid electrolytes. The electrolyte thin film withstands at least 1000 cycles of striping/plating of Li at 0.05 mA cm-2 . It is further shown that the LbL thin films can be used as separators for Li-ion batteries to deliver a capacity of 116 mAh g-1 at 0.1 C in an all-LbL-assembled lithium iron phosphate/lithium titanate battery. Finally, it is demonstrated that the thin films can be used as ion-conducting substrates for flexible electrochemical devices, including micro supercapacitors and electrochemical transistors.

Ionic-Activated Chemiresistive Gas Sensors for Room-Temperature Operation.

The development of high performance gas sensors that operate at room temperature has attracted considerable attention. Unfortunately, the conventional mechanism of chemiresistive sensors is restricted at room temperature by insufficient reaction energy with target molecules. Herein, novel strategy for room temperature gas sensors is reported using an ionic-activated sensing mechanism. The investigation reveals that a hydroxide layer is developed by the applied voltages on the SnO2 surface in the presence of humidity, leading to increased electrical conductivity. Surprisingly, the experimental results indicate ideal sensing behavior at room temperature for NO2 detection with sub-parts-per-trillion (132.3 ppt) detection and fast recovery (25.7 s) to 5 ppm NO2 under humid conditions. The ionic-activated sensing mechanism is proposed as a cascade process involving the formation of ionic conduction, reaction with a target gas, and demonstrates the novelty of the approach. It is believed that the results presented will open new pathways as a promising method for room temperature gas sensors.

Construction of 3D Electronic/Ionic Conduction Networks for All-Solid-State Lithium Batteries.

High and balanced electronic and ionic transportation networks with nanoscale distribution in solid-state cathodes are crucial to realize high-performance all-solid-state lithium batteries. Using Cu2 SnS3 as a model active material, such a kind of solid-state Cu2 SnS3 @graphene-Li7 P3 S11 nanocomposite cathodes are synthesized, where 5-10 nm Cu2 SnS3 nanoparticles homogenously anchor on the graphene nanosheets, while the Li7 P3 S11 electrolytes uniformly coat on the surface of Cu2 SnS3 @graphene composite forming nanoscaled electron/ion transportation networks. The large amount of nanoscaled triple-phase boundary in cathode ensures high power density due to high ionic/electronic conductions and long cycle life due to uniform and reduced volume change of nano-Cu2 SnS3. The Cu2 SnS3 @graphene-Li7 P3 S11 cathode layer with 2.0 mg cm-2 loading in all-solid-state lithium batteries demonstrates a high reversible discharge specific capacity of 813.2 mAh g-1 at 100 mA g-1 and retains 732.0 mAh g-1 after 60 cycles, corresponding to a high energy density of 410.4 Wh kg-1 based on the total mass of Cu2 SnS3 @graphene-Li7 P3 S11 composite based cathode. Moreover, it exhibits excellent rate capability and high-rate cycling stability, showing reversible capacity of 363.5 mAh g-1 at 500 mA g-1 after 200 cycles. The study provides a new insight into constructing both electronic and ionic conduction networks for all-solid-state lithium batteries.

Manipulation of Nanoscale Intergranular Phases for High Proton Conduction and Decomposition Tolerance in BaCeO3 Polycrystals.

In many ion-conducting polycrystalline oxides, grain boundaries are generally accepted as rate-limiting obstacles to rapid ionic diffusion, often resulting in overall sluggish transport. Consequently, based on a precise understanding of the structural and compositional features at grain boundaries, systematic control of the polycrystalline microstructure is a key factor to achieve better ionic conduction performance. In this study, we clarify that a nanometer-thick amorphous phase at most grain boundaries in proton-conducting BaCeO3 polycrystals is responsible for substantial retardation of proton migration and moreover is very reactive with water and carbon dioxide gas. By a combination of atomic-scale chemical analysis and physical imaging, we demonstrate that highly densified BaCeO3 polycrystals free of a grain-boundary amorphous phase can be easily fabricated by a conventional ceramic process and show sufficiently high proton conductivity together with significantly improved chemical stability. These findings emphasize the value of direct identification of intergranular phases and subsequent manipulation of their distribution in ion-conducting oxide polycrystals.

Synergetic Effects of Inorganic Components in Solid Electrolyte Interphase on High Cycle Efficiency of Lithium Ion Batteries.

The solid electrolyte interphase (SEI), a passivation layer formed on electrodes, is critical to battery performance and durability. The inorganic components in SEI, including lithium carbonate (Li2CO3) and lithium fluoride (LiF), provide both mechanical and chemical protection, meanwhile control lithium ion transport. Although both Li2CO3 and LiF have relatively low ionic conductivity, we found, surprisingly, that the contact between Li2CO3 and LiF can promote space charge accumulation along their interfaces, which generates a higher ionic carrier concentration and significantly improves lithium ion transport and reduces electron leakage. The synergetic effect of the two inorganic components leads to high current efficiency and long cycle stability.

Humidity effect on nanoscale electrochemistry in solid silver ion conductors and the dual nature of its locality.

Scanning probe microscopy (SPM) is a powerful tool to investigate electrochemistry in nanoscale volumes. While most SPM-based studies have focused on reactions at the tip-surface junction, charge and mass conservation requires coupled and intrinsically nonlocal cathodic and anodic processes that can be significantly affected by ambient humidity. Here, we explore the role of water in both cathodic and anodic processes, associated charge transport, and topographic volume changes depending on the polarity of tip bias. The first-order reversal curve current-voltage technique combined with simultaneous detection of the sample topography, referred to as FORC-IVz, was applied to a silver solid ion conductor. We found that the protons generated from water affect silver ionic conduction, silver particle formation and dissolution, and mechanical integrity of the material. This work highlights the dual nature (simultaneously local and nonlocal) of electrochemical SPM studies, which should be considered for comprehensive understanding of nanoscale electrochemistry.

Defective interfaces in yttrium-doped barium zirconate films and consequences on proton conduction.

Yttrium-doped barium zirconate (BZY) thin films recently showed surprising electric transport properties. Experimental investigations conducted mainly by electrochemical impedance spectroscopy suggested that a consistent part of this BZY conductivity is of protonic nature. These results have stimulated further investigations by local unconventional techniques. Here, we use electrochemical strain microscopy (ESM) to detect electrochemical activity in BZY films with nanoscale resolution. ESM in a novel cross-sectional measuring setup allows the direct visualization of the interfacial activity. The local electrochemical investigation is compared with the structural studies performed by state of art scanning transmission electron microscopy (STEM). The ESM and STEM results show a clear correlation between the conductivity and the interface structural defects. We propose a physical model based on a misfit dislocation network that introduces a novel 2D transport phenomenon, whose fingerprint is the low activation energy measured.

The Significance of Ion Conduction in a Hybrid Organic-Inorganic Lead-Iodide-Based Perovskite Photosensitizer.

The success of perovskite solar cells has sparked enormous excitement in the photovoltaic community not only because of unexpectedly high efficiencies but also because of the future potential ascribed to such crystalline absorber materials. Far from being exhaustively studied in terms of solid-state properties, these materials surprised by anomalies such as a huge apparent low-frequency dielectric constant and pronounced hysteretic current-voltage behavior. Here we show that methylammonium (but also formamidinium) iodoplumbates are mixed conductors with a large fraction of ion conduction because of iodine ions. In particular, we measure and model the stoichiometric polarization caused by the mixed conduction and demonstrate that the above anomalies can be explained by the build-up of stoichiometric gradients as a consequence of ion blocking interfaces. These findings provide insight into electrical charge transport in the hybrid organic-inorganic lead halide solar cells as well as into new possibilities of improving the photovoltaic performance by controlling the ionic disorder.

Stretchable and Transparent Heaters Based on Hydrophobic Ionogels with Superior Moisture Insensitivity.

Flexible and stretchable transparent heaters (THs) have been widely used in various applications, including deicing and defogging of flexible screens as well as thermotherapy pads. Ionic THs based on ionogels have emerged as a promising alternative to conventional electronic THs due to their unique advantages in terms of transparency-conductance conflict, uniform heating, and interfacial adhesion. However, the commonly used hydrophilic ionogels inevitably introduce a moisture-sensitive issue. In this work, we present a stretchable and transparent hydrophobic ionogel-based heater that utilizes ionic current-induced Joule heating under high-frequency alternating current. This ionogel-based TH exhibits exceptional multifunctional properties with low hysteresis, a fracture strain of 840%, transmittance of 93%, conductivity of 0.062 S m-1, temperature resistance up to 165 °C, voltage resistance up to 120 V, heating rate of 0.1 °C s-1, steady-state temperature at 115 °C, and uniform heating even when bent or stretched (up to 200%). Furthermore, it maintains its heating performance when it is directly exposed to water. This hydrophobic ionogel-based TH expands the range of materials available for ionic THs and paves the way for their practical applications.

Mechanisms of the Accelerated Li+ Conduction in MOF-Based Solid-State Polymer Electrolytes for All-Solid-State Lithium Metal Batteries.

Solid polymer electrolytes (SPEs) for lithium metal batteries have garnered considerable interests owing to their low cost, flexibility, lightweight, and favorable interfacial compatibility with battery electrodes. Their soft mechanical nature compared to solid inorganic electrolytes give them a large advantage to be used in low pressure solid-state lithium metal batteries, which can avoid the cost and weight of the pressure cages. However, the application of SPEs is hindered by their relatively low ionic conductivity. In addressing this limitation, enormous efforts are devoted to the experimental investigation and theoretical calculations/simulation of new polymer classes. Recently, metal-organic frameworks (MOFs) have been shown to be effective in enhancing ion transport in SPEs. However, the mechanisms in enhancing Li+ conductivity have rarely been systematically and comprehensively analyzed. Therefore, this review provides an in-depth summary of the mechanisms of MOF-enhanced Li+ transport in MOF-based solid polymer electrolytes (MSPEs) in terms of polymer, MOF, MOF/polymer interface, and solid electrolyte interface aspects, respectively. Moreover, the understanding of Li+ conduction mechanisms through employing advanced characterization tools, theoretical calculations, and simulations are also reviewed in this review. Finally, the main challenges in developing MSPEs are deeply analyzed and the corresponding future research directions are also proposed.

Observation of Fast Low-Temperature Oxygen Ion Conduction in CeO2/ß"-Al2O3 Heterostructure.

Semiconductor ion fuel cells (SIFCs) have demonstrated impressive ionic conductivity and efficient power generation at temperatures below 600 °C. However, the lack of understanding of the ionic conduction mechanisms associated with composite electrolytes has impeded the advancement of SIFCs toward lower operating temperatures. In this study, a CeO2/ß″-Al2O3 heterostructure electrolyte is introduced, incorporating ß″-Al2O3 and leveraging the local electric field (LEF) as well as the manipulation of the melting point temperature of carbonate/hydroxide (C/H) by Na+ and Mg2+ from ß″-Al2O3. This design successfully maintains swift interfacial conduction of oxygen ions at 350 °C. Consequently, the fuel cell device achieved an exceptional ionic conductivity of 0.019 S/cm and a power output of 85.9 mW/cm2 at 350 °C. The system attained a peak power density of 1 W/cm2 with an ultra-high ionic conductivity of 0.197 S/cm at 550 °C. The results indicate that through engineering the LEF and incorporating the lower melting point C/H, there approach effectively observed oxygen ion transport at low temperatures (350 °C), effectively overcoming the issue of cell failure at temperatures below 419 °C. This study presents a promising methodology for further developing high-performance semiconductor ion fuel cells in the low temperature range of 300-600 °C.

Solid State Ionics: from Michael Faraday to green energy-the European dimension.

Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag2S and PbF2 and coined terms such as cation and anion, electrode and electrolyte. In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an 'evolving scheme of materials science', point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987.

Facile Synthesis of Two-Dimensional Natural Vermiculite Films for High-Performance Solid-State Electrolytes.

Ceramic electrolytes hold application prospects in all-solid-state lithium batteries (ASSLB). However, the ionic conductivity of ceramic electrolytes is limited by their large thickness and intrinsic resistance. To cope with this challenge, a two-dimensional (2D) vermiculite film has been successfully prepared by self-assembling expanded vermiculite nanosheets. The raw vermiculite mineral is first exfoliated to thin sheets of several atomic layers with about 1.2 nm interlayer channels by a thermal expansion and ionic exchanging treatment. Then, through vacuum filtration, the ion-exchanged expanded vermiculite (IEVMT) sheets can be assembled into thin films with a controllable thickness. Benefiting from the thin thickness and naturally lamellar framework, the as-prepared IEVMT thin film exhibits excellent ionic conductivity of 0.310 S·cm-1 at 600 °C with low excitation energy. In addition, the IEVMT thin film demonstrates good mechanical and thermal stability with a low coefficient of friction of 0.51 and a low thermal conductivity of 3.9 × 10-3 W·m-1·K-1. This reveals that reducing the thickness and utilizing the framework is effective in increasing the ionic conductivity and provides a promising stable and low-cost candidate for high-performance solid electrolytes.

Ultrastrong and Tough Urushiol-Based Ionic Conductive Double Network Hydrogels as Flexible Strain Sensors.

Ionic conductive hydrogels have attracted increasing research interest in flexible electronics. However, the limited resilience and poor fatigue resistance of current ionic hydrogels significantly restrict their practical application. Herein, an urushiol-based ionic conductive double network hydrogel (PU/PVA-Li) was developed by one-pot thermal initiation polymerization assisted with freeze-thaw cycling and subsequent LiCl soaking. Such a PU/PVA-Li hydrogel comprises a primary network of covalently crosslinked polyurushiol (PU) and a secondary network formed by physically crosslinked poly(vinyl alcohol) (PVA) through crystalline regions. The obtained PU/PVA-Li hydrogel demonstrates exceptional mechanical properties, including ultrahigh strength (up to 3.4 MPa), remarkable toughness (up to 1868.6 kJ/m3), and outstanding fatigue resistance, which can be attributed to the synergistic effect of the interpenetrating network structure and dynamic physical interactions between PU and PVA chains. Moreover, the incorporation of LiCl into the hydrogels induces polymer chain contraction via ionic coordination, further enhancing their mechanical strength and resilience, which also impart exceptional ionic conductivity (2.62 mS/m) to the hydrogels. Based on these excellent characteristics of PU/PVA-Li hydrogel, a high-performance flexible strain sensor is developed, which exhibits high sensitivity, excellent stability, and reliability. This PU/PVA-Li hydrogel sensor can be effectively utilized as a wearable electronic device for monitoring various human joint movements. This PU/PVA-Li hydrogel sensor could also demonstrate its great potential in information encryption and decryption through Morse code. This work provides a facile strategy for designing versatile, ultrastrong, and tough ionic conductive hydrogels using sustainable natural extracts and biocompatible polymers. The developed hydrogels hold great potential as promising candidate materials for future flexible intelligent electronics.

Boosting Ion Conductivities: Light-Modulated Azobenzene-Based Ionic Liquids in Vertical Nanochannels.

Exploring stimuli-responsive ion-conductive materials is a challenging task, but it has gained increasing attention because of their enormous potential applications in actuators, sensors, and smart electronics. Here, we demonstrate a distinctive photoresponsive ion-conductive device that utilizes azobenzene-based ionic liquids ([AzoCnMIM][Br], where n = 2, 6, and 10), confined in nanochannels of anodic aluminum oxide (AAO) templates for photoisomerization. The structure of [AzoCnMIM][Br] comprises photoresponsive and hydrophobic azobenzene moieties, hydrophilic imidazolium cations, and negatively charged bromide ions. Therefore, [AzoCnMIM][Br] can form micelles and exhibit photoresponsive ion conductivities. The nanochannels of AAO templates exhibit a confinement effect on the formation of azobenzene-based ionic liquid micelles due to the pore size, thereby preventing the formation of larger micelles that could lead to a decrease in conductivity. Consequently, the ion conductivities of the azobenzene-based ionic liquids are higher in the nanochannels of the AAO templates. The effects of the length of carbon chains on the azobezene-based ionic liquids and the pore size of the AAO templates have also been investigated. Additionally, through irradiation with UV/vis light, [AzoCnMIM][Br] can undergo reversible isomerization, thereby reversibly changing the sizes of the micelles and subsequently altering the ion conductivities.