Ion Transport Research Articles

Electric Field and Nanocontact Effects in Metal-Organic Framework/Li6.4La3Zr1.4Ta0.6O12 Ionic Conductors for Fast Interfacial Lithium-Ion Transport Kinetics.

The slow ion transport kinetics inside or between the nanofillers in composite polymer electrolytes (CPEs) lead to the formation of lithium dendrites for solid-state lithium batteries. To address the critical issues, CPEs (U@UNL) composed of a UIO-66@UIO-66-NH2 (U@UN) core-shell heterostructure and Li6.4La3Zr1.4Ta0.6O12 (LLZTO) filler is designed. Due to the different band structures of the U@UN heterostructure, a built-in electric field is constructed to promote the transfer kinetics of carriers. Besides, the introduction of LLZTO facilitates the formation of a close nanometer contact interface between U@UN and LLZTO, reducing interface impedance and accelerating the lithium-ion transfer rate. As a benefit from the built-in electric field and the nanometer contact interface, U@UNL exhibits a wide electrochemical window of 5.17 V, a large lithium-ion transference number of 0.76, and a high ionic conductivity of 3.50 × 10-3 S cm-1. Consequently, the U@UNL electrolyte possesses excellent interfacial stability against Li metal after 1200 h at 0.1 mA cm-2 and shows a high specific capacity of 160.2 and 152.6 mAh g-1 at 0.5 and 1 C, respectively. This work proposes a complete strategy for building high-performance solid-state lithium batteries by a built-in electric field and nanometer contact interface between U@UN and LLZTO.

Physical Origin of the Ferroelectric-Type Hysteresis in MIM Structures with Amorphous Dielectric Film.

The ferroelectric-type characteristics in metal-insulator-metal (MIM) structures with amorphous dielectrics are observed, which may open a new window for a class of new ferroelectric devices. However, the working principles of these ferroelectric devices are not well explained. It has been proposed that oxygen ion (O2-) and charged vacancy (Vo2+) migrations are associated with this ferroelectric-like behavior. In this work, a systematic experimental design is carried out to investigate the origin of O2- and Vo2+ (from the interface or bulk oxide?), the transport species (O2-, Vo2+, or both of these two species?), and the ion transport mode (long-range transport or local movement?). The experimental results answered all these questions. In addition, the role of the thickness of the dielectrics is also studied. This work sets the fundamentals of these amorphous oxide-based devices, guiding future explorations to engineer them.

Gulf toadfish (Opsanus beta) urinary bladder ion and water transport is enhanced by acclimation to higher salinity to serve water balance.

Marine teleosts experience ion gain and water loss in their natural habitats. Among other tissues, the urinary bladder epithelium of marine fishes has been shown to actively transport ions to facilitate water absorption. However, transport properties of the urinary bladder epithelium of marine fishes and its plasticity in altered ambient salinities is relatively under-investigated. We describe urinary bladder epithelium electrophysiology, water flux, and expressions of ion transporters in urinary bladder tissue of Gulf toadfish (Opsanus beta) acclimated to either 35 ppt or 60 ppt seawater. Water absorption in bladder sac preparations increased ~ 350% upon acclimation to 60 ppt. Increases in water transport coincided with a significant ~ 137% increase in urinary bladder tissue mucosal-to-serosal short circuit current (Isc) and a ~ 56% decrease in tissue membrane resistance. Collectively, these metrics indicate that an active electrogenic system facilitates water absorption via Na+ (and Cl-) transport in urinary bladder tissue. Furthermore, pharmacological inhibition of urinary bladder tissue Isc and expression of a suite of ion transporters and channels previously unidentified in this tissue provide mechanistic insights into the transport processes responsible for water flux. Analysis of water transport to overall Gulf toadfish water balance reveals a modest water conservation role for the urinary bladder of ~ 0.5% of total water absorption in 35 ppt and 1.9% in 60 ppt acclimated toadfish. These results emphasize that electrogenic ion transport facilitates water-absorptive properties of the urinary bladder in Gulf toadfish - a process that is regulated to facilitate water homeostasis.

Navigating the Frontier Role of Electrolyte Interfaces in Dye‐Sensitized Solar Cell Technology

Recent advances in solar cell technology have been motivated by new materials and inventive engineering techniques. Dye‐sensitized solar cells (DSSCs) are becoming more widely recognized as a possible alternative for sustainable energy. Optimizing electrolytes is one of the most important variables impacting their effectiveness and durability. The electrolyte interface is critical to optimize charge separation, ion transport, and diffusion ensuring device stability and efficiency. The present investigation focuses on enhancing interface stability and investigating innovative electrolyte compositions to improve DSSC performance for sustainability in solar energy applications. Despite progress, obstacles remain in presenting core principles and research approaches in DSSC technology. Continued research is required to overcome these limitations and fully realize the potential of DSSCs in sustainable energy solutions.

Weak solvation effects and molecular-rich layers induced water-poor Helmholtz layers boost highly stable Zn anode

The advancement of aqueous Zn-based energy storage systems encounters major challenges due to the occurrence of side reactions and the growth of dendrites caused by the highly active nature of water in the aqueous electrolyte. Herein, a zwitterion additive named sulfonated amphoteric betaine (referred to as DMAPS) regulates the Zn2+ electrolyte environment through a weak solvation effect to promote highly stable Zn anodes. The inherently occurring anionic (-SO3-) and cationic (-NR4+) counterions in the DMAPS chain can be effectively separated under an external electric field to enable the creation of distinct ion migration pathways, thereby significantly enhancing the transportation of electrolyte ions. Moreover, DMAPS can be adsorbed onto the surface of Zn anode to form a H2O-poor Helmholtz layer, which can serve as a protective barrier to suppress corrosion of the Zn anode by free H2O and inhibits the formation of differential electric field to facilitate the directional deposition of Zn2+. In addition, density functional theory (DFT) and molecular dynamics (MD) further assisted in demonstrating the intrinsic mechanism of the reconstruction of the solvated sheath structure of Zn2+ by DMAPS. As a result, the Zn//Zn symmetric cell in ZnSO4+DMAPS solution can be cycled steadily for 2100 h at a current density of 1 mA cm-2 and 1 mAh cm-2. The assembled Zn ion hybrid capacitor with ZnSO4+DMAPS electrolyte was stably cycled for 20,000 cycles with 90% capacity retention at 5 A g-1.

Phase-Transition-Promoted Interfacial Anchoring of Sulfide Solid Electrolyte Membranes for High-Performance All-Solid-State Lithium Battery.

Solvent-free manufacturing is crucial for fabricating high-performance sulfide-electrolyte-based all-solid-state lithium batteries (ASSLBs), with advantages including side reaction inhibition, less contamination, and practical scalability. However, the fabricated sulfide electrolytes commonly suffer from brittleness, limited ion transport, and unsatisfactory interfacial stability due to the uncontrolled dispersion of the sulfide particles within the polymer binder matrix. Herein, a "solid-to-liquid" phase transition strategy is reported to fabricate flexible Li6PS5Cl (LPSCl) electrolytes. The polycaprolactone (PCL)-based binder (PLI) with phase-transition characteristics fills the gap of LPSCl particles and tightly grafts on the particle surface via ion-dipole interaction, bringing a thin and compact electrolyte membrane (80µm). The simultaneously high Li-ion conducting and electron insulating nature of PLI binder facilitates Li-ion transport and ensures good interfacial stability between electrolyte and anode. Consequently, the sulfide electrolyte membrane exhibits high ionic conductivity (8.5×10-4 S cm-1), enabling symmetric and full cells with 10 and 2.5 times longer cycling life compared with that of the cells with pristine LPSCl electrolyte, respectively. The demonstrated strategy is versatile and can be extended to ethylene vinyl acetate copolymer (EVA) that also brings enhanced electrochemical performance. The thin sulfide electrolyte with high interfacial stability potentially facilitates dendrite-free ASSLBs with high energy density.

Construction of cellulose 3D network composite membrane supported by hydroxylated boron nitride with high surface charge density to achieve high-efficiency osmotic energy harvesting

Ion selectivity and mechanical persistence are critical properties of membranes to harvest osmotic energy. Two-dimensional nanofluidic membranes have been studied to enhance those properties, whereas they are usually constrained due to unsatisfactory mass transfer performances. Herein, a ternary three-dimensional membrane (T-CNF/PVDF/BN-OH composite membrane, abbreviated as CPBN) with distinct mechanical strength and high surface charge density (−2.65 mC·m−2) for sustainable osmotic energy harvesting is designed. In CPBN, negatively charged TEMPO-oxidized cellulose acts as a scaffold and constructs a 3D network structure together with the hydroxylated boron nitride (BN-OH) via a self-assembly process. The affluent nano-constrained ion channels effectively enhance the controllability and effectiveness of ion transport. The abundant ionized carboxyl groups extremely facilitate the selective transportation of the cations, while the BN-OH also assist this process, promoting the one-way transmission of cations in the channel. Additionally, the participation of PVDF polymer forms a network interlock structure, which significantly improves mechanical performances and stability in water. The membrane demonstrates a high power density (10.6 W/m2), measured in minimal testing areas, and an average power density around 1 W/m2 in larger areas, with an energy conversion efficiency of up to 30.7 %. This study provides a promising exploration of replacing traditional two-dimensional layered structure with three-dimensional network structure of cellulose for osmotic energy harvesting.

Yolk@shell layered NiCo hydroxide: Controllable synthesis, sulfuration and electrochemical applications for hybrid supercapacitors

Developing electrode materials with rational structures is an important strategy for constructing high-performance hybrid supercapacitors (HSCs). Herein, designing a yolk@shell structure composed of layered nickel-cobalt hydroxide with a Ni/Co feed ratio of 4:1 (denoted as layered Ni4Co1 hydroxide) and nickel-cobalt sulfide with a sulfuration duration of 2 h (labeled as Ni4Co1S-2h) to enhance the capacity and stabilize the cyclic performances of HSCs was conducted. The yolk@shell structured microspheres of layered Ni4Co1 hydroxide were synthesized using a cetyltriethylammonium bromide (CTAB) template-assisted solvothermal treatment. Subsequently, nickel-cobalt sulfide microspheres with the unique yolk@shell structure were prepared from layered Ni4Co1 hydroxide precursor. Notably, yolk@shell Ni4Co1S-2h microspheres feature a large specific surface area and an interspace between the yolk and shell, facilitating charge transfer but also effectively alleviating volume expansion during ion transport and electron transfer. The resultant Ni4Co1S-2h material demonstrates a superior capacity of 902.2 C·g−1 at 3·A g−1, while the assembled Ni4Co1S-2h//porous carbon (PC) HSC shows a relatively higher energy density (83.1 Wh·kg−1) and power density (15000 W·kg−1). The design of yolk@shell structured layered Ni4Co1 hydroxide and Ni4Co1S-2h electrode materials holds significant implications for the advancement of high-performance HSCs.

Unveiling the Resistive Switching Mechanism and Low Current Dynamics of Ru‐based Hybrid Synaptic Memristors

AbstractMobile Ru ions in oxide media have been reported as a novel species that offer extremely low switching currents for memristors. However, their bi‐stable resistive‐switching (RS) and low‐switching currents dynamics have not been quantitatively unveiled. Here, the bi‐stable RS mechanism via in‐depth field‐induced atomic migration and chemical bonding state studies is elucidated, showing that the RS of the Ru‐based hybrid memristor (RHM) is possible via the simultaneously controlled hybrid Ru cation and oxygen anion. Additionally, the Ru ion mobility is quantitatively obtained via atomic moving distance and switching time measurements, demonstrating that the lower Ru ion mobility, compared to other conventional mobile species in oxide media, can be the origin of the low‐switching currents. It is found that the current conduction mechanism of the low‐resistance‐state in RHMs has temperature‐range‐dependencies. The direct tunneling conduction mechanism is dominant in relatively low temperatures; however, the ionic transport and thermally activated hopping conduction mechanism govern the current flow in high temperatures. Owing to the low Ru ion mobility, the RHM exhibits highly linear synaptic plasticity with a low‐conductance regime, showing outstanding energy efficiency compared to other memristors in image recognition tasks. These findings can contribute to improving the feasibility of hyper‐scale synaptic cores consisting of RHMs.

High-fidelity reconstruction of porous cathode microstructures from FIB-SEM data with deep learning

Accurate modeling of lithium-ion battery (LIB) electrode microstructures provides essential references for understanding degradation mechanisms and optimizing materials. Traditional segmentation methods often struggle to accurately capture the complex microstructures of porous LIB electrodes in focused ion beam scanning electron microscopy (FIB-SEM) data. In this work, we develop a deep learning model based on the Swin Transformer to segment FIB-SEM data of a lithium cobalt oxide electrode, utilizing fused secondary and backscattered electron images. The proposed approach outperforms other deep learning methods, enabling the acquirement of 3D microstructure with reduced particle elongated artifacts. Analyses of the segmented microstructures reveal improved electrode tortuosity and pore connectivity crucial for ion and electron transport, emphasizing the necessity of accurate 3D modeling for reliable battery performance predictions. These results suggest a path toward voxel-level degradation analysis through more sensible battery simulation on high-fidelity microstructure models directly twinned from real porous electrodes.

Gate-Controlled Potassium Intercalation and Superconductivity in Molybdenum Disulfide.

Intercalation of guest ions into a van der Waals (vdW) gap in layered materials is a powerful route to create novel material phases and functionalities. Ionic gating is a technique to control the motions and configuration of ions for both intercalation and surface electrostatic doping. The advance of ionic gating enables the in situ probe of dynamics of ion diffusion, carrier doping, and transport properties. Here we performed in situ resistivity and Raman experiments on the potassium ion (K+) intercalation of single-crystal MoS2 and constructed a temperature-carrier density phase diagram. The K+-intercalation induces a structural transition from the prismatically coordinated phase to the octahedrally coordinated phase, where anisotropic three-dimensional superconductivity and a possible charge density wave state were observed. The present ionic gating offers a comprehensive view of the intercalated phases and proves that the electrostatically induced superconductivity is distinct from that in the intercalated phase.

Highly Reversible Zn Anode Design Through Oriented ZnO(002) Facets.

The practical implementation of aqueous Zn-ion batteries presents formidable hurdles, including uncontrolled dendrite growth, water-induced side reactions, suboptimal Zn metal utilization, and intricate Zn anode manufacturing. Here, large-scale construction of a highly oriented ZnO(002) lattice plane on Zn anode (ZnO(002)@Zn) with thermodynamic inertia and kinetic zincophilicity is designed to address such problems. Both theoretical calculations and experiment results elucidate that the ZnO(002)@Zn possesses high Zn chemical affinity, hydrogen evolution reaction suppression, and dendrite-free deposition ability due to the abundant lattice oxygen species in ZnO(002) and its low lattice mismatch with Zn(002). These features synergistically promote ion transport and enable homogeneous Zn deposition. Consequently, the ZnO(002)@Zn anode displays a stable and prolonged cycling lifespan exceeding 500h even under a larger depth of discharge (85.6%) and realizes an impressive average Coulombic efficiency of 99.7%. Moreover, its efficacy is also evident in V2O5-cathode coin cells and pouch cells with not only high discharge capacity but also exceptional cycling stability. This integrated approach presents a promising avenue for addressing the challenges associated with Zn metal anodes, thereby advancing the prospects of aqueous Zn-ion battery technologies.

Water compression induced ionic negative differential resistance in nanopores.

The mass transport behavior through nanoscale channels, greatly influenced by the structures and dynamics of nanoconfined water, plays an essential role in many biophysical processes. However, the dynamics of nanoconfined water under an external field and its effects are still not fully understood. Here, on the basis of molecular dynamics simulations, we theoretically show that the ionic current of [Bmim][PF6] through narrow pores in graphene membrane exhibits an ionic negative differential resistance effect-the ionic current decreases as the voltage increases over a certain threshold. This effect arises from the violation of traditional fluid dynamics as the assumption of continuity and homogeneity of fluids is no longer effective in ultrathin nanopores. The gradient of electric field around the atomic-thin layer produces a strong gradient force on the polarized water inside the nanopore. This dielectrophoretically compressed water leads to a hydrostatic force that repels ions from entering the nanopore. Our findings may advance the understanding of hydrostatic mechanism, which governs ion transport through nanopores.

Constructing high performance dry-processing oxide composite electrolyte via interfacial interactions for durable solid-state lithium batteries

Composite solid electrolytes (CSEs) have considerable combination properties, which have been considered as the most promising choice for realizing advanced solid-state lithium batteries. Yet the ionic conductivity of CSEs fails to meet the practical requirements. Herein, we develop a dry-processing CSEs based on Li1.5Al0.5Ge1.5(PO4)3 (LAGP) and succinonitrile (SN) through polytetrafluoroethylene fibrillation. On the one hand, SN can enable fast ion transport in ceramic network and serve as high-speed conducive path. On the other hand, the strong affinities of LAGP towards SN and anions can significantly improve the conductive behavior and restrict side reactions at electrolyte/Li interface. Under such regulations, the composite electrolyte exhibits high ionic conductivity (0.64 mS cm−1 at 30 °C), high transference number (0.50), and high oxidation potential (>5.0V vs. Li+/Li). The assembled lithium metal batteries demonstrate excellent stability over 300 cycles at 1.0C. This work demonstrates the ion migration mechanism and the interactions at the heterogeneous interface for SN enhanced CSEs, contributing to the development of durable solid lithium metal batteries with extended lifespan.

KOH Activated Walnut Shell Biochar Electrode of Capacitive Deionization and Its Desalination Performance

Abstract The flake biochar electrode materials with fast ion transport function were prepared by KOH activation walnut shell used as raw material. The effects of carbonization temperature and KOH-to-biochar ratio were systematically evaluated using physicochemical characterization and electrochemical performance testing. The optimized walnut shell biochar (WSC800-2), produced at 800℃ with a KOH-to-biochar ration of 2∶1, exhibited an exceptional specific surface area (2,287 m2 g-1), the highest porosity (0.824 cm3 g-1), and an excellent specific capacitance (369.51 F g-1, 10 mV s-1). Furthermore, in desalination experiments, WSC800-2 achieved a high salt adsorption capacity of 15.70 mg g-1 at 1.2V, 500 mg L-1 NaCl solution. The electrode also exhibited outstanding cycling stability, retaining 97.0% of its performance after 10 adsorption/desorption cycles. These findings highlight the potential of walnut shell-derived biochar as an effective material for capacitive deionization and future desalination technologies.

Mechanically Stable PMMA‐Based Large‐Area Nano‐Channels with Sub‐10 nm Depth

AbstractArtificial sub‐microfluidic and nanofluidic devices allow for studying mass or ion transport effects under spatial confinement. It remains challenging to fabricate large‐scale, nanofluidic channels of well‐defined thickness for fundamental studies and practical applications, especially for extreme confinement conditions (e.g., with sub‐10 nm channel height). Here, a strategy is reported to fabricate large‐scale nano‐channels with the channel height down to 5.0 nm. The fabrication is enabled by developing ultra‐flat and ultra‐thin polymethylmethaacrylate (PMMA) layers as the spacer. The ease of scaling up the channel length to a millimeter in the lateral dimensions with high mechanical stability is demonstrated. Furthermore, experimental evidence is provided of the role of the mechanical coupling between the spacer and capping materials in determining the device's mechanical properties, and how controlling the channel width and the top graphite thickness can be employed to tailor the device's mechanical properties. Finally, employing near‐field IR experiments, the decay constant is established for the near‐field absorption intensity of PMMA molecules inside the channel by increasing the top layer thickness. This work develops a novel method for fabricating large‐area, mechanically stable nano‐channels for nanofluidic devices and lays the foundation for further in situ spectroscopic studies of electrochemistry within sub‐10 nm confinement.

Driving DNA Nanopore Membrane Insertion through Dipolar Coupling.

DNA nanopores appear to be a plausible alternative to the use of transmembrane proteins. The specificity and programmability of DNA interactions allow the design of synthetic channels that insert into lipid bilayers and can regulate the ionic transport across them. In this Communication, we investigate the dependence of insertion capabilities on the electrostatic properties of the nanopore and show that the presence of a permanent electric dipole is an important factor for the nanopore to insert into the membrane. On the contrary, in the absence of such a dipole, most DNA nanopores bind to the bilayer without channel formation. We also show that this modification does not hinder the possibility of triggering a measurable conformational change with a single short oligonucleotide.

Stable LCO Cathodes Charged at 4.6 V for High Energy Secondary Li‐ion Batteries by One‐Pot Dual Metal Fluorides Coating

AbstractLiCoO2 (LCO) has been the cathode material of choice for three decades for durable, lightweight Li‐ion storage systems. Being charged up to 4.2 V versus Li/Li+, LCO provides excellent cycling stability with a specific capacity of ≈140 mAh g−1. Raising the cut‐off voltage to 4.6 V improves capacity by up to 60% however, it leads to rapid degradation of the cathode structure. Here, a one‐pot dual coating of MgF2 and AlF3 with fluorinated electrolyte additives achieves 190 mAh g−1 at a 0.5 C rate after 400 cycles with a capacity retention of 93%. Various analytical tools are used to follow the structural and morphological changes during cycling. Synergistically, ion transport is improved, and detrimental interfacial side reactions with the electrolyte solutions are fully mitigated. Structural stability is thus improved by using this coating, with only a little loss of the active material. This work provides a brief guideline for designing dual metal‐ion‐based surface coatings in various electrolytes to develop high‐voltage cathode systems for Li and maybe also Na batteries.

Taurine is essential for mouse uterine luminal fluid resorption during implantation window via the SCNN1A and AQP8 signaling.

Uterine fluid homeostasis during peri-implantation is crucial for successful embryo implantation. Taurine (Tau) plays a crucial role in regulating osmotic pressure and ion transport. However, the precise mechanisms underlying Tau-mediated regulation of uterine fluid homeostasis during peri-implantation in mice remain unclear. In this study, we generated a Tau-deficient mouse model by administering Tau-free diet to Csad knockout (Csad-/-) mice to block endogenous Tau synthesis and exogenous Tau absorption (Csad-/--Tau free). Our findings demonstrated that Csad-/-Tau free mice with diminished level of Tau exhibited decreased rates of embryo implantation and impaired fertility. Further analysis revealed that the expression of Scnn1a was down-regulated during the implantation window, while Aqp8 was upregulated in Csad-/-Tau free mice, leading to uterine luminal fluid retention and defects in luminal closure, resulting in failed embryo implantation. Additionally, it was also found that E2 inhibited uterine Csad expression and Tau synthesis, while P4 promoted them. Therefore, our findings suggest that ovarian steroid hormones regulate Csad expression and Tau synthesis, thereby affecting release and resorption of uterine luminal fluid, ultimately impacting embryo implantation success.

Ultrafine Mo2N Quantum Dots Embedded in N-Doped Graphene Sheets Enable Efficient Adsorption-Catalytic Transformation of Polysulfides.

Because of the high theoretical energy density of 2600 Wh kg-1, lithium-sulfur batteries (LSBs) are anticipated to be among the next generation of high-energy-density storage technologies. However, the practical application of LSBs has been severely hampered by the significant shuttle effect and slow redox kinetics of polysulfides (LiPSs). To address the above problems, in this paper, the concept of quantum dots (QDs) was introduced to design and synthesize Mo2N QD-modified N-doped graphene nanosheets (marked as Mo2N-QDs@NG), which were used as separator modification materials for LSBs. The experimental results demonstrated that the introduction of Mo2N QDs avoids stacking of graphene sheets and provides more active sites for the conversion of LiPSs. Moreover, Mo2N enhances the chemical fixation and catalyzes the liquid-solid conversion of soluble LiPSs by forming Mo-S and Li-N bonds with LiPSs. Additionally, establishing Mo-C bonds with Mo2N, N-doped graphene sheets can facilitate the transport of electrons and ions and physically prevent the diffusion of LiPSs, thus creating a highly conducting carbon structure to support electrochemical reactions. Benefiting from the synergistic effect of chemical immobilization and catalysis of Mo2N QDs with the physical confinement of NG, Mo2N-QDs@NG-PP batteries exhibit enhanced electrochemical performance.