Ion Transport In Electrolytes Research Articles

Preparation of lignite-based porous carbon for high performance supercapacitor and the correlation between pore structures and electrochemical performance

Porous carbon exhibits considerable potential in energy storage field due to its remarkable electrical conductivity and adjustable pore structure. Nevertheless, the electrochemical performance of the material will be significantly impacted by its unreasonable pore structure. In this study, lignite was used as raw material to prepare lignite-based porous carbon by one-step activation method and the pore structure was optimized to improve its electrochemical performance and expand the utilization of low-rank coal. The results reveal that the porous carbon prepared at 600 °C has a higher specific surface area (940 m2 g−1) and a suitable pore structure (71 % mesopore), which enable adequate charge storage and fast transport of electrolyte ions, resulting in excellent electrochemical performance. In the three-electrode system, the lignite-based porous carbon exhibits a notable specific capacity of 331 F g−1 at the current density of 0.5 A g−1 and retains 96.4 % initial capacitance after undergoing 10,000 cycles. When assembled into a symmetrical supercapacitor, the device provides an energy density of 6.5 Wh kg−1 at a power density of 250 W kg−1. Even after 10,000 cycles, the capacitance retention rate is kept at 91 %, and the coulombic efficiency remains close to 100 %. These findings demonstrate that cost-effective porous carbon can be prepared by a simple route using lignite, hence exhibiting promise as electrode materials for high-performance supercapacitors.

Wood‐inspired High Ionic Conductivity Hydrogel Electrolytes for Flexible Supercapacitors

Hydrogel is a promising electrolyte substrate, but its ionic conductivity needs further improvement. In this paper, we propose a strategy to improve the ionic conductivity of hydrogels with flexible wood and fabricate a flexible wood‐based poly(acrylic acid‐acrylamide) composite hydrogel electrolyte (WHE) by delignification and in‐situ polymerization. The flexible wood as a porous backbone for hydrogels can regulate ion transport pathways to improve the ionic conductivity of hydrogels. The straight pores of wood confine the transport of electrolyte ions along the shortest path, resulting in a high ionic conductivity of 3.0 × 10‐2 S cm‐1, which is great in composite polymer electrolytes. We have systematically investigated the effect of the degree of delignification and the polymerization process on the overall performance of the electrolyte. The optimized supercapacitor exhibits a specific capacitance of 155.64 F g‐1 and an energy density of 7.45 W h kg‐1. The WHE is applied to flexible supercapacitor, which exhibits good flexibility under bending conditions and can maintain similar electrochemical performance at a wide range of bending angles. This work provides an effective strategy for the efficient use of wood resources and the development of low‐cost, environmentally friendly, and high‐performance hydrogel electrolyte materials.

Halogen-Bonding Nanoarchitectonics in Supramolecular Plasticizers for Breaking the Trade-Off between Ion Transport and Mechanical Strength of Polymer Electrolytes for High-Voltage Li-Metal Batteries.

The low ionic conductivity of poly(ethylene oxide) (PEO)-based polymer electrolytes at room temperature impedes their practical applications. The addition of a plasticizer into polymer electrolytes could significantly promote ion transport while inevitably decreasing their mechanical strength. Herein, we report a supramolecular plasticizer (SMP) to break the trade-off effect between ionic conductivity and mechanical properties in PEO-based polymer electrolytes. Accordingly, the SMP is constructed by tetraethylene glycol dimethyl ether (G4) and SbF3 through halogen bonds. The SMP-plasticized PEO electrolyte (PEO/SMP) presents a simultaneously enhanced ionic conductivity of 2.4 × 10-4 S cm-1 (25 °C) and a high mechanical strength of 8.1 MPa, compared to those of pristine PEO-based electrolytes. Benefiting from the halogen bonds between G4 and SbF3, the Li-O coordination in PEO/SMP is evidently weakened, and thus rapid Li+ transport is achieved. Furthermore, the PEO/SMP electrolyte possesses a wide electrochemical stability window of 4.5 V and, importantly, derives an inorganic-rich SEI with a low interfacial resistance on a lithium metal surface. By using PEO/SMP, the lithium-metal battery with the LiNi0.5Co0.2Mn0.3O2 cathode exhibits a good rate and long-term cycling performance with a capacity retention of 75.3% (500 cycles). This work offers a rational guideline for the design of polymer electrolytes suitable for high-performance lithium-metal batteries.

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.

Charge Scaling in Classical Force Fields for Lithium Ions in Polymers.

Polymer electrolytes are of interest for applications in energy storage. Molecular simulations of ion transport in polymer electrolytes have been widely used to study the conductivity in these materials. Such simulations have generally relied on classical force fields. A peculiar feature of such force fields has been that in the particular case of lithium ions (Li+), their charge must be scaled down by approximately 20% to achieve agreement with experimental measurements of ion diffusivity. In this work, we present first-principles calculations that serve to justify the charge-scaling factor and van der Waals interaction parameters for Li+ diffusion in poly(ethylene glycol) (PEO) with bistriflimide (TFSI-) counterions. Our results indicate that a scaling factor of 0.79 provides good agreement with DFT calculations over a relatively wide range of Li+ concentrations and temperatures, consistent with past reports where that factor was adjusted by trial and error. We also show that such a scaling factor leads to diffusivities that are in quantitative agreement with experimental measurements.

Influence of Surfaces on Ion Transport and Stability in Antiperovskite Solid Electrolytes at the Atomic Scale.

Antiperovskites are generating considerable interest as potential solid electrolyte materials for solid-state batteries because of their promising ionic conductivity, wide electrochemical windows, stability, chemical diversity and tunability, and low cost. Despite this, there is a surprising lack of a systematic study of antiperovskite surfaces and their influence on the performance of these materials in energy storage applications. This is rectified here by providing a comprehensive density functional theory investigation of the surfaces of M3OX (M = Li or Na; X = Cl or Br) antiperovskites. Specifically, we focus on the stability, electronic structure, defect chemistry, and ion transport properties of stable antiperovskite surfaces and how these contribute to the overall performance and suitability of these materials as solid electrolytes. The findings presented here provide critical insights for the design of antiperovskite surfaces that are both stable and promote ion transport in solid-state batteries.

Electrochromic Covalent Organic Framework-Assembled Nanofibrous Membranes with Mimetic Chameleon Skin Architectures for Visible and Near-Infrared Camouflage Stealth.

The developments of modern surveillance technology pose great challenges to combat concealment for warfighters. Traditional camouflage suits cannot accommodate the need for camouflage stealth in complex warfare scenarios. Herein, a bidirectional diffusion-controlled in situ synthesis methodology is reported to achieve electrochromic nanofibrous membranes with mimetic chameleon skin structures (CSENs) by assembling electrochromic covalent organic frameworks on nanofibers. CSENs exhibit reversible color changes in the visible and near-infrared ranges under an applied potential with fast response times (25.8 s/26.2 s). The macro- and mesoporous structures in CSENs favored the transportation of electrolyte ions, achieving excellent color difference and coloration efficiency of 35.58 and 1053.26 cm2/C, respectively. Importantly, CSENs feature unique properties of self-standing, breathability, and flexibility, which are attributed to the micrometer pores constructed by entangled nanofibers. As a proof-of-concept study, the CSEN-based flexible electrochromic suit exhibits a dynamic camouflage function in real environments, showing promising properties as smart textiles for dynamic camouflage stealth.

High-Power Battery Electrodes Fabricated by Acupuncture-Inspired Microneedle Processing.

Advancing battery electrode performance is essential for high-power applications. Traditional fabrication methods for porous electrodes, while effective, often face challenges of complexity, cost, and environmental impact. Inspired by acupuncture, here we introduce an eco-friendly and cost-effective microneedle process for fabricating lithium iron phosphate electrodes. This technique employs commercial cosmetic microneedle molds to create low-curvature holes on electrode surfaces, significantly enhancing electrolyte infiltration and ion transport kinetics. The punctured electrodes were prepared and characterized, with comparisons to pristine electrodes conducted using scanning electron microscopy, 3D metallurgical microscopy, and detailed electrochemical evaluations. Our results show that the microneedle-processed electrodes exhibit superior rate performance and diffusion properties. Simulations and experimental data reveal that the low-curvature holes reduce Li-ion concentration polarization and improve Li-ion transport within the electrode. This enhancement leads to higher specific capacities and better rate capabilities in the punctured electrodes. The findings highlight the potential of this innovative microneedle technique for large-scale production of high-performance electrodes, offering a promising avenue for the development of high-power-density batteries.

Biomass-based three-dimensional network porous carbon anodes derived from discontinuous activation for high performance Li-ion batteries

An approach of discontinuous activation and frozon-dry pretreatment toward a three-dimensional network porous carbon was proposed by using apple as the carbon source. The porous carbon, characterized by its high surface area and abundant porosity, was optimized through the manipulation of temperature and activator quantities during the activation process. The sample obtained by first calcining at 500 °C and then at 800 °C shows ultra-high rate electrochemical performance of over 900 mA h g−1 after 100 cycles and over 500 mA h g−1 after 500 cycles under the condition of charging and discharging current density of 0.2 A g−1 due to the high porosity. It is ascribed to the unique porous structure that can make the electrolyte and lithium ion transport and path short on the surface and inside the electrode material, further enhance its fast transport ability. The described approach represents an innovative and potentially impactful method for producing porous carbon electrodes with excellent electrochemical performance, particularly in the context of high-rate capability lithium-ion batteries.

Unlocking hierarchical hollow nanoblocks of NiMo sulfide with extended interlayer spacing of Mo-S units for high-performance supercapacitor

Molybdenum sulfide (MoS2) has been investigated as electrode of supercapacitor due to its unique structure. However, the restricted availability of active sites and sluggish behavior at the basal surface impede its improvement. Here we propose an unlocking hierarchical hollow strategy to synthesis the bimetallic sulfide heterostructures loaded on the ultrathin carbon (NiS/MoS2@UC). The unlocking hierarchical hollow structure and extended S-Mo layer provide interconnected channels for rapid electrolyte ion transport, while the heterojunction interface promotes the electron transfer and redox reaction. As a result, NiS/MoS2@UC − 2 exhibits a high specific capacitance of 616.7F g−1 at the current density of 1 A/g, which is approximately 10 times higher than that of MoS2@UC and 6 times higher than that of NiS@UC. Moreover, NiS/MoS2@UC − 2 demonstrates a high energy density of 7.7 Wh kg−1 at the power density of 300 W kg−1 with excellent cycling durability.

Boosting the electrocatalytic performance of CuCo2S4 via surface-state engineering for ampere current water electrolysis applications

For the efficient production of green H2 on an industrial scale, developing durable, cost-effective electrocatalysts using earth-abundant transition-metals is crucial. Herein, we report a robust, bifunctional sulfurized CuCo2O4 (CCS/Ov) catalyst with engineered oxygen-vacancies, in which the metal catalyst is tunes to high valence state, significantly altering the intrinsic reaction kinetics and generating better catalytic activity for efficient ion transport in various electrolytes (neutral, seawater, alkaline simulated-seawater (ASW), and KOH). The optimized dual-strategy synthesized CCS/Ov catalysts with hierarchical morphology exhibits modest overpotential of 383 and 355 mV at 1000 mA cm−2 for OER and HER, respectively, in 1 M KOH. Impressively, an electrolyzer cell (CCS/Ov||CCS/Ov) demonstrates low cell-voltage of 1.487 V (6 M KOH), with excellent robustness in an ASW (1 and 2 M) environment against corrosive chlorine. The bifunctional CCS/Ov||CCS/Ov catalyst outperforms a state-of-the-art paired Pt/C||RuO2 catalyst and maintains the lowest potential response at up to 2000 mA cm−2, while demonstrating remarkably stable simultaneous O2 and H2 generation over 10 days at various current rates. Additionally, DFT calculations confirmed that CCS/Ov catalysts demonstrate significantly enhanced HER and OER activities due to reduced H2O dissociation energy and strong intermediate binding energy, which is attributed to the anionic vacancy near Co3+. The excellent bifunctional performance of the hierarchical CCS/Ov highlights its potential as non-precious catalyst with facile fabrication approach.

Hierarchical porous self-supporting graphite carbon electrodes based on the biomimetic structure for supercapacitors

Regulating pore structure, improving conductivity, and reducing the influence of binders are considered important ways to improve the performance of carbon-based electrode materials for supercapacitors. This study successfully prepares a highly graphitized hierarchical porous self-supporting carbon electrode without the need for binders, conductive agents, and current collectors using low-cost and abundant pine wood as the precursor and K2FeO4 as the activator and catalyst. The self-supporting electrode inherits the biological structure of biomass and forms a large number of micro mesopores through activation, showing an excellent 3D interconnected pore structure, and achieves a high degree of graphitization with the ID/IG ratio of being only 0.47. The self-supporting electrode facilitates the effective transport of electrolyte ions and electrons, demonstrating excellent electrochemical performance. It achieves an area specific capacitance of 3.64 F cm−2 under a current density of 5 mA cm−2. Two identical self-supporting electrodes are employed to construct a symmetric supercapacitor. The supercapacitor exhibits an energy density of 148.61 μWh cm−2 at a power density of 1 mW cm−2, with a capacity retention rate of 89.26 % after 10,000 charge-discharge cycles.

Dynamic density functional theory of polymers with salt in electric fields.

We present a dynamic density functional theory for modeling the effects of applied electric fields on the local structure of polymers with added salt (polymer electrolytes). Time-dependent equations for the local electrostatic potential and volume fractions of polymer, cation, and anion of added salt are developed using the principles of linear irreversible thermodynamics. For such a development, a field theoretic description of the free energy of polymer melts doped with salts is used, which captures the effects of local variations in the dielectric function. Connections of the dynamic density functional theory with experiments are established by relating the three phenomenological Onsager's transport coefficients of the theory to the mutual diffusion of electrolyte, ionic conductivity, and transference number of one of the ions. The theory is connected with a statistical mechanical model developed by Bearman and Kirkwood [J. Chem. Phys. 28, 136 (1958)] after relating the three transport coefficients to friction coefficients. The steady-state limit of the dynamic density functional theory is used to understand the effects of dielectric inhomogeneity on the phase separation in polymer electrolytes. The theory developed here provides not only a way to connect with experiments but also to develop multi-scale models for studying connections between local structure and ion transport in polymer electrolytes.

Large scale atomistic and quantum mechanical study of Na+ ion transport in liquid electrolytes for batteries

Lithium–ion batteries (LIBs) have long dominated energy storage markets due to their high energy density and reliability. However, concerns over lithium scarcity and geographic distribution necessitate alternatives. Sodium-ion batteries (SIBs) offer a promising solution due to sodium's abundance, cost-effectiveness, and favorable electrochemical properties. This study investigates Na+ ion transport, aggregation, and performance in various organic electrolytes using molecular dynamics (MD) simulations and density functional theory (DFT) calculations. The electrolytes studied include ethylene carbonate (EC), propylene carbonate (PC), dimethoxyethane (DME), and dimethyl carbonate (DMC) at 320 K. We focused on conductivity, diffusivity, and survival probability of Na+ ions at different salt concentrations. Furthermore, the solvation structure and the binding energy of ions in the electrolytes are thoroughly analyzed. Key findings reveal that at 2 M salt concentration, Na+ ion diffusivity and ionic conductivity follow the order EC>PC>DME>DMC. Increasing salt concentration decreases self–diffusion coefficients of Na+ and PF6− ions across all electrolytes, affecting conductivity. EC shows the highest ionic conductivity at both 1 M and 2 M salt concentrations. These insights suggest that a 2 M NaPF6 concentration in EC optimizes ionic conductivity, making it ideal for high–performance SIBs. This study provides crucial understanding for optimizing electrolytes in SIBs, advancing their development for scalable energy storage solutions.

Rational design of continuous and short-range lithium ion pathways based on polydopamine-anchored metal-organic frameworks for all-solid-state electrolytes

The immerging three dimensional (3D) metal-organic framework (MOF)-reinforced composite solid-state electrolytes have attracted great interest because of the enhanced ionic conductivity and mechanical properties. However, the defective spatial arrangement of MOFs restricted by fabrication methodology leads to insufficient lithium ion transport in electrolytes. Herein, a 3D interconnected MOF framework tailored for all-solid-state electrolytes is rationally designed by a universal polydopamine (PDA)-engineered “double-sided tape” strategy. The PDA serves as a double-sided tape, firmly adhering on the special single-layer Nylon grid as well as offering uniform nucleation sites to anchor the metal nodes to ensure continuous growth of well-ordered MOFs. Benefiting from the Lewis acid feature of MOFs and its cage effect toward TFSI−, a fast and homogeneous lithium ion transport can be achieved through the internal channels within neighboring MOFs and the continuous MOFs/polymer interfaces both along the short-range circumferential boundary of Nylon fiber. The resultant composite electrolytes exhibit high lithium ion conductivity and prominent mechanical properties, rendering excellent cyclic stability whether used in coin or pouch cells. This work demonstrates a widely applicable “double-sided tape” strategy for controllable spatial arrangement of MOF nanoparticles on optional substrates, which provides a scalable approach to rationally construct desired lithium ion pathways within composite electrolytes.

Oxygen-rich 3D hierarchical porous MXene prepared by Zn powder reduction for flexible supercapacitors

Ti3C2Tx MXene is highly compelling as an energy storage material, but 2D MXene sheets experience significant stacking due to hydrogen bonding and van der Waals forces. This blocks active sites and impedes fast electrolyte ion transport. The pseudocapacitance of MXene materials is highly reliant on their terminal groups. Therefore, an effective strategy was designed herein to prepare an oxygen-rich 3D hierarchical porous MXene (P-OR-Ti3C2Tx). First, Zn powder was used as a template to construct three-dimensional hierarchical porous structures that spanned the microporous, mesoporous, and macroporous scales. Second, Zn powder was used as a metal reducing agent in a reaction at 500 °C to eliminate most −F terminal groups on the MXene. Then, a subsequent acid washing step was used to introduce numerous −O terminal groups. The energy storage process of the prepared MXene was investigated by in situ Raman. More redox active sites (−O terminal groups) are exposed by the constructed oxygen-rich 3D hierarchical porous MXene structure, which also provides a shorter pathway for electrolyte ion transport. P-OR-Ti3C2Tx displays superb rate performance (88.19 % retention at 100Ag−1) and ultra-high capacitance (676.7F/g at 2 mV/s and 698.7Fg−1 at 1 Ag−1) when used as a supercapacitor electrode. Moreover, a symmetric flexible supercapacitor device prepared using P-OR-Ti3C2Tx and carbon cloth achieves a superb energy density of 32.8Whkg−1 at a power density of 236.5Wkg−1. This study offers insight into the design of MXenes that exhibit both high capacity and excellent rate performance.

Effect of Chemical Doping on Ion Transport in Sulfide Solid Electrolytes

Rechargeable solid-state batteries (SSBs) offer tremendous promise as a safe and energy-dense storage technology for use in electric transportation, robotics, and portable electronics. Lithium argyrodites (e.g., Li7PS6, and its halogen-doped derivatives) have emerged as a lucrative class of solid-state electrolytes (SSEs) for SSBs owing to their high Li-ion conductivity (~10-3 S/cm), good elastic stiffness (~30 GPa), and low flammability. Meanwhile, sulfide-based solid electrolytes such as Na3SbS4 (NSS) also showcase substantial potential for SSBs with their high theoretical specific capacity, enhanced safety, and abundance of resources. Despite their promise, both lithium and sodium-based SSBs remain far from commercialization due to lack of atomic-scale understanding of ion-conduction, charge transport, structural evolution, and interfacial reactions (e.g., dendrite growth, electrolyte decomposition etc.). Here we employ a combination of density functional theory calculations, ab initio molecular dynamics simulations, and nudged elastic band calculations to understand ion transport mechanism in chemically doped lithium argyrodites and NSS.In lithium-based systems, using accurate materials modeling, we design fluorine-containing argyrodite electrolytes that offers enhanced Li-ion conduction facilitated by unique Li-disorder induced by fluorine and other halogen co-dopants. Our results show the opening up of new pathways for Li inter-cage hops in these fluorine -containing argyrodite electrolytes which increases the Li-ion conductivity. In the case of sodium-based systems, we focus on atomic-scale mechanisms underlying Na-ion conduction in the presence of cation dopants. Ab initio molecular dynamics simulations reveal the significant impact of cation dopants on NSS, where the introduction of charge-compensating Na-vacancies enhances Na-ion conduction. The size of the cation dopant is found to be a critical factor, with examples such as Ca-doped NSS (rCa2+ / rNa+ = 0.98) showing a conductivity approximately 10 times that of pristine NSS, while larger Ba2+ as a dopant (rBa2+ / rNa+ = 1.35) hinders Na-ion hops due to local strain, resulting in a Na-ion conductivity ~5 times that of NSS. We will discuss these results in the context of accelerating design of novel solid-state electrolytes for long-lived, stable, and high-energy density SSBs.

The Effect of Boron Nitride Flakes on Sodium Ion Transport in PEO Electrolytes

The Effect of Boron Nitride Flakes on Sodium Ion Transport in PEO Electrolytes

CALiSol-23: Experimental electrolyte conductivity data for various Li-salts and solvent combinations

Ion transport in non-aqueous electrolytes is crucial for high performance lithium-ion battery (LIB) development. The design of superior electrolytes requires extensive experimentation across the compositional space. To support data driven accelerated electrolyte discovery efforts, we curated and analyzed a large dataset covering a wide range of experimentally recorded ionic conductivities for various combinations of lithium salts, solvents, concentrations, and temperatures. The dataset is named as ’Conductivity Atlas for Lithium salts and Solvents’ (CALiSol-23). Comprehensive datasets are lacking but are critical to building chemistry agnostic machine learning models for conductivity as well as data driven electrolyte optimization tasks. CALiSol-23 was derived from an exhaustive review of literature concerning experimental non-aqueous electrolyte conductivity measurement. The final dataset consists of 13,825 individual data points from 27 different experimental articles, in total covering 38 solvents, a broad temperature range, and 14 lithium salts. CALiSol-23 can help expedite machine learning model development that can help in understanding the complexities of ion transport and streamlining the optimization of non-aqueous electrolyte mixtures.

Recent Trends in Application of Memristor in Neuromorphic Computing: A Review

Abstract: Recently memristors have emerged as a form of nonvolatile memory that is based on the principle of ion transport in solid electrolytes under the impact of an external electric field. It is perceived as one of the key elements to building next-generation computing systems owing to its peculiar resistive switching characteristics. The switching mechanism in a memristor is mainly governed by filamentary conduction. Further, it can be employed as a memory as well as a logic element, which makes it an ideal candidate for building innovative computer architecture. Moreover, it is capable of mimicking the characteristics of biological synapses, which makes it an ideal candidate for developing a Neuromorphic system. In this review to begin with the switching mechanism of the memristor, primarily focusing on filamentary conduction, is discussed. Few SPICE models of memristor are reviewed, and their critical comparison is performed, which are widely used to build computing systems. An in-depth study on the various crossbar memory architecture augmented with memristors is reviewed. Finally, the application of memristors in neuromorphic computing and hardware implementation of Artificial Neural Networks (ANN) employing memristors is discussed.