Cation Transfer Research Articles

Cellulose Derivative and Polyionic Liquid Crosslinked Network Gel Electrolytes for Sodium Metal Quasi‐Solid‐State Batteries

AbstractSodium metal batteries have gained attention as a potential solution to the low energy densities presented by current sodium‐ion batteries. However, the commonly available electrolyte systems usually fall short in safety performance. Gel polymer electrolytes, closely resembling liquid electrolytes, offer a promising balance of performance and developmental potential. A proposed polymer plastic‐crystal ionic gel composite electrolyte, featuring a polycation auxiliary chain, innovatively copolymerizes ionic liquid cations with electrolyte additives. These auxiliary chains crosslink with the main chain, attracting anions from the ionic liquid and sodium salts. Both experimental evidence and theoretical calculations affirm that this electrolyte exhibits high cation transference numbers and significant mean square displacement radii. By facilitating uniform sodium ion migration, the electrolyte has powered sodium symmetrical cells for over 550 h and has supported stable cycling of Na3V2(PO4)3 (NVP)‐sodium metal batteries at a 1 C rate for more than 800 cycles. These achievements underscore its potential in advancing the development of condensed‐state sodium metal batteries.

Nanochannel geometry-depended behaviors on ion selectivity for salinity gradient energy harvesting

Nanofluidic osmotic energy, which can be directly converted into electricity, is considered a clean and sustainable energy that effectively utilizes salinity gradients. The rational construction of nanochannel is of great significance to ion transport and osmotic energy conversion, but there is currently little attention paid to naturally formed rough and irregular channels. In this study, a model that considers the effects of nanochannel cone angle and waveform surface on interface reaction coupling was established for osmotic energy conversion. The results indicate that cone angle and waveform have a significant effect on osmotic energy conversion. It is found that the reduction of cone angle and the addition of waveform will improve ion selectivity and increase energy conversion efficiency, and ion rectification effect of corrugated cylindrical channel is the most obvious. Meanwhile, enlarging waveform dimensions leads to a significant overlap of electric double layer, resulting in a growth in cation transference number and selectivity, thereby enhancing the system's energy conversion efficiency, which can reach 49.62%. At low concentration ratios, the waveform dimensions are inversely proportional to the maximum output power, whereas at high concentration ratios, increasing the waveform dimensions and applying the waveform at channel entrance can efficiently improve the maximum output power.

Enhanced ionic conductivity and electrochemical performance of environmental friendly guar gum-based bio polymer gel electrolytes doped with Al2O3 nanofibers for Li-ion batteries.

Recently, biopolymers made from natural resources are gaining popularity as polymer electrolytes (PEs) in electrochemical devices. In the present work, a series of guar gum (GG)-based biopolymer gel electrolytes (BGEs) filled with different amounts of Al2O3 nanofibers are synthesized and tested. The BGEs containing 7.5 wt% Al2O3 nanofibers show the maximum room temperature ionic conductivity of 2.37 × 10-3 S/cm at an uptake ratio of 120 %. Given the high conductivity, this uptake ratio is low, demonstrating that Al2O3 nanofibers affect GG's ion transport characteristics. XRD reveals that the Al2O3 in GG can create conducive environment for ion conduction. FTIR and XPS analyses demonstrate that nanofibers have the ability to generate supplementary routes for ion conduction in GG. Electrochemical investigations show that BGEs with 7.5 wt% nanofibers have a broad electrochemical potential range of 4.6 V. BGEs are stable at metallic electrodes and have a cationic transference number of 0.59. The initial discharge capacity at 0.5C has been measured to be 127 mAh g-1 for Li|BGE|LiFePO4 cell in the first cycle and 116 mAh g-1 with coulombic efficiency of over 94 % after 100 cycles. Nanofiber-dispersed BGEs have high thermal and mechanical stabilities, according to TGA, DSC, and UTM tests.

Characteristics of Aliphitic and Aromatic Ion-Exchange Membranes after Electrodialysis Tartrate Stabilization of Wine Materials

Color indication of anthocyanins, FTIR spectroscopy, measurement of surface contact angle values, determination of specific electrical conductivity, as well as voltammetry and parallel measurement of pH of desalted solutions were used to analyze the fouling characteristics of aliphatic (CJMA-3, CJMC-3) and aromatic (AMX-Sb, CMX-Sb) ion-exchange membranes used in electrodialysis tartrate stabilization of wine material. It has been shown that polyphenols form complexes with metal ions on the surface and in the subsurface layers of cation-exchange membranes, which do not interfere with the transfer of cations. Foulants affect the magnitude of limiting currents and enhance water splitting at the surface of all studied membranes, and also reduce the electrical conductivity of anion-exchange membranes. The use of a pulsed electric field instead of a continuous direct electric current, traditional for electrodialysis, weakens the negative impact of foulants on membranes’ electrical conductivity. These data can be useful for selecting membranes and current modes when carrying out electrodialysis tartrate stabilization of wine materials.

Anion-Anchored Polymer-in-Salt Solid Electrolyte for High-Performance Zinc Batteries.

Solid polymer electrolytes hold promise for addressing key challenges in rechargeable zinc batteries (ZBs) utilizing aqueous electrolytes. However, achieving simultaneous high ionic conductivity, excellent mechanical strength, and a high cation transference number while effectively suppressing Zn dendrites remains challenging. Herein, we design a novel polymer-in-salt solid electrolyte (PISSE) composed of polyacrylonitrile (PAN), zinc chloride (ZnCl2), and niobium pentoxide with oxygen vacancies (Nb2O5-x) with high ionic conductivity. PAN polymer matrix provides the electrolyte good mechanical properties and solubility of Zn salt. The high concentration of ZnCl2 effectively decouples the Zn2+ from polymer chain segments and provides more ionic conduction amorphous region. Moreover, incorporating Nb2O5-x filler accelerates Zn2+ desolvation by anchoring (ZnxCly)2x-y clusters and enhances the system's mechanical properties, achieving a superior Zn2+ transference number (~0.93) and interfacial stability. Consequently, the optimized PISSE demonstrates exceptional stability during prolonged cycling periods, wide temperature range operation (-40 °C to 60 °C), remarkable flexibility, and compatibility with diverse electrode materials. This study provides valuable insights into the design of solid-state electrolytes based on ZBs and elucidates their multifunctional prospects.

Anion‐Anchored Polymer‐in‐Salt Solid Electrolyte for High‐Performance Zinc Batteries

AbstractSolid polymer electrolytes hold promise for addressing key challenges in rechargeable zinc batteries (ZBs) utilizing aqueous electrolytes. However, achieving simultaneous high ionic conductivity, excellent mechanical strength, and a high cation transference number while effectively suppressing Zn dendrites remains challenging. Herein, we design a novel polymer‐in‐salt solid electrolyte (PISSE) composed of polyacrylonitrile (PAN), zinc chloride (ZnCl2), and niobium pentoxide with oxygen vacancies (Nb2O5‐x) with high ionic conductivity. PAN polymer matrix provides the electrolyte good mechanical properties and solubility of Zn salt. The high concentration of ZnCl2 effectively decouples the Zn2+ from polymer chain segments and provides more ionic conduction amorphous region. Moreover, incorporating Nb2O5‐x filler accelerates Zn2+ desolvation by anchoring (ZnxCly)2x–y clusters and enhances the system's mechanical properties, achieving a superior Zn2+ transference number (~0.93) and interfacial stability. Consequently, the optimized PISSE demonstrates exceptional stability during prolonged cycling periods, wide temperature range operation (−40 °C to 60 °C), remarkable flexibility, and compatibility with diverse electrode materials. This study provides valuable insights into the design of solid‐state electrolytes based on ZBs and elucidates their multifunctional prospects.

MnO2 Nanowires with Sub-10nm Thick Conjugated Microporous Polymers as Synergistic Triboelectric Materials.

MnO2 nanowires coated with conjugated microporous polymers (CMP) are applied as triboelectric energy harvesting materials. The tribopositive performance of the CMP shells is enhanced with the assistance of MnO2 nanowires (MnO2 NW), likely due to cationic charge transfer from the tribopositive CMP layers to the surface Mn2+ and Mn3+ species of MnO2 NW. This is supported by model studies. The MnO2@CMP-2 with sub-10nm thick CMP layers shows promising triboelectric output voltages up to 576V and a maximum power density of 1.31mWcm-2. Spring-assisted triboelectric nanogenerators fabricated with MnO2@CMP-2/PVP-3 films are used as power supplies to operate electronic devices.

Na3Zr2Si2PO12-Polymer Composite Electrolyte for Solid State Sodium Batteries.

The integration of the flexibility of organic polymer electrolyte and high ionic conductivity of the ceramic electrolyte is attempted in search of efficient and safer battery. Composite solid polymer electrolyte (CSPE) provides high ionic conductivity with a sustainable thin film of electrolyte having the synergistic effect of ionic liquid and active inorganic filler. The CSPE is synthesized by the solution cast technique using Na3Zr2Si2PO12 (NZSP) as ceramic and poly(vinylidene fluoride-hexafluoropropylene) with Salt-Ionic liquid as polymer electrolyte. X-ray diffraction (XRD) of CSPE includes amorphous nature due to the polymer part as well as crystalline peaks of ceramic NZSP, simultaneously. The prepared CSPE sample shows homogeneous and interconnected surface morphology is observed by Scanning electron microscopy (SEM) image. Thermogravimetric analysis (TGA) shows electrolyte is thermally stable up to 200 °C and differential scanning calorimetry (DSC) reveals decrease in degree of crystallinity due to NZSP addition in the CSPE. By complex impedance spectroscopy (CIS), room temperature ionic conductivity of the prepared CSPE is found ~1.03 mS/cm. The dielectric behaviour of the prepared electrolyte is also studied to investigate the ion dynamics within the sample. The cationic transference number is 0.53 and the electrochemical stability window (ESW) of the CSPE is 4.9 V which is suitable for sodium solid-state batteries applications.

Solid-State Lithium Batteries with In Situ Polymerized Acrylate-Based Electrolytes Capable of Electrochemically Stable Operation at 100 °C.

Solid polymer electrolytes (SPEs) typically consist of salts with mobile anions that could cause instabilities and parasitic side reactions in solid-state lithium (Li) batteries. To address this challenge, single-Li-ion conducting (SLIC) SPEs, where anions of Li salts are covalently attached to the polymer backbone, have been utilized to reduce the number of mobile anions. This approach improves the cationic transference number but is accompanied by a loss of ionic conductivity. In this work, we investigate a synergetic approach of using both a polymerizable SLIC salt and a conventional Li salt in a polymer matrix by in situ polymerization of the poly(propylene glycol) acrylate (PPGA) monomer. The synthesized hybrid SPEs show a high ionic conductivity of up to ∼2 × 10-4 S cm-1 and a relatively high Li-ion transference number of ∼0.4. With a significantly reduced fraction of mobile anions in the combined salt SPE, in situ polymerized SPE cells with a LiFePO4 (LFP) cathode achieve a stable performance for over 100 cycles at temperatures as high as 100 °C, which is unattainable with conventional Li salts or electrolytes. Furthermore, solid-state nuclear magnetic resonance spectra provide additional insights into differences in Li nucleus environments and emphasize a reduction in activation energy for hybrid SPEs due to their more open structure. This study opens the path for the fabrication of high-performance solid polymer Li batteries capable of operating at high temperatures using commercial battery fabrication equipment, as in situ polymerized acrylate-based polymers provide drop-in compatibility with conventional battery production, ease of acrylate polymerization, and inexpensive, facile SPE chemistry. We expect that further tuning of the acrylate-based SPE composition may allow further increases in its conductivity without sacrificing its electrochemical stability or mechanical properties.

Generation-fusion strategy in metal-earth ionosome investigation using single-entity electrochemistry at the micro-water/trifluorotoluene interface

Ionosomes are water clusters/droplets formed in an organic phase via the spontaneous assembly of ionic bilayers by hydrated cations or anions. The ionosomes formed by monovalent ions, i.e., Li+, Na+, K+, Cl−, etc., have been thoroughly investigated. Herein, single nanowater clusters (viz. ionosomes) in organic solutions, which are formed by the transfer of metal earth cations (i.e., Mg2+, Ca2+, Ba2+) into organic lipophilic electrolytes, were discovered using single-entity electrochemistry (SEE). The generation-fusion strategy involving two-step potentiostatic chronoamperometry was applied to investigate single Mg2+-ionosomes at the water/α,α,α-trifluorotoluene (w/TFT) interface. After an exciting potential forced the hydrophilic ion into the organic phase, a train of current spikes with information on the integrated charges, frequency, and duration were recorded to gain insight into the ionosomes. Variates were thoroughly investigated, including the exciting potential, exciting time, recording potential, size of the applied w/TFT interface, ion species, and concentration. These results suggest that: (1) the size of a single Mg2+-ionosome was revealed; (2) the fleshly formed ionosomes are mainly located on the organic side of the w/TFT interfacial surface instead of diffusing into the organic bulk; (3) when the interface decreases, fewer ionosomes form, and the size of the ionosomes decreases; (4) the mean charge carried by a single ionosome is positively related to the charge density of a single cation; (5) by alternating the recording potential, the negative zeta potential of Mg2+-ionosomes was revealed; (6) Mg2+-ionosomes can form when the aqueous solution contains only 2 μmol·L−1 Mg2+. This work thoroughly investigated hydrated metal earth ion clusters in the organic phase via SEE and provides insights into the interface electric double layer from the electrochemistry perspective. In addition to promoting the understanding of ionosomes, this strategy can provide potential applications to identify high-purity water.

A Comprehensive Study on the Parameters Affecting Magnesium Plating/Stripping Kinetics in Rechargeable Mg Batteries

AbstractMg metal anode‐based battery is a more sustainable, lower cost, and higher energy density alternative to Li‐ion. However, this battery chemistry also faces several challenges associated with the high charge density of Mg2+, including achieving high reversibility and low voltage hysteresis for Mg metal plating/stripping. While significant improvements are achieved in last decades, they involve rather complex electrolyte formulations and/or Mg salts difficult to produce, and the use of unpractical substrates such as platinum. Here, significant improvement in terms of Mg plating kinetics is achieved in electrolytes containing commercial magnesium bis(trifluoromethanesulfonyl)imide salt (Mg(TFSI)2) by using titanium substrate with similar crystal structure and lattice parameter as Mg leading to lower nucleation overpotential. Low salt concentration electrolyte and addition of dibutyl magnesium (Mg(butyl)2) also enable the formation of thinner interphase, richer in solvent based decomposition products, further improving Mg plating kinetics. This work highlights the complex role of Mg(butyl)2, often considered as a simple drying agent, and how it impacts ion solvation favoring the mobility of electroactive cationic species, paving the way toward better electrolyte design with improved cation transference number.

Influence of Molecular Weight and End Groups on Ion Transport in Weakly and Strongly Coordinating Polymer Electrolytes

AbstractIn the development of polymer electrolytes, the understanding of the complex interplay of factors that affect ion transport is of importance. In this study, the strongly coordinating and flexible poly (ethylene oxide) (PEO) is compared to the weakly coordinating and stiff poly (trimethylene carbonate) (PTMC) as opposing model systems. The effect of molecular weight (Mn) and end group chemistry on the physical properties: glass transition temperature (Tg) and viscosity (η) and ion transport properties: transference number (T+), ion coordination strength and ionic conductivities were investigated. The cation transference number (T+) showed the opposite dependence on Mn for PEO and PTMC, decreasing at low Mn for PTMC and increasing for PEO. This was shown to be highly dependent on the ion coordination strength of the system regardless of whether the end group was OH or if the chains were end‐capped. Although the coordination is mainly of the cations in the systems, the differences in T+ were due to differences in anion rather than cation conductivity, with a similar Li+ conductivity across the polymer series when accounting for the differences in segmental mobility.

FFF/FDM 3D-Printed Solid Polymer Electrolytes Based on Acrylonitrile Copolymers for Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) are essential in modern electronics, particularly in portable devices and electric vehicles. However, the limited design flexibility of current battery shapes constrains the development of custom-sized power sources for advanced applications like wearable electronics and medical devices. Additive manufacturing (AM), specifically Fused Filament Fabrication (FFF), presents a promising solution by enabling the creation of batteries with customized shapes. This study explores the use of novel poly(acrylonitrile-co-polyethylene glycol methyl ether acrylate) (poly(AN-co-PEGMEA)) copolymers as solid polymer electrolytes for lithium-ion batteries, optimized for 3D printing using FFF. The copolymers were synthesized with varying AN:PEGMEA ratios, and their physical, thermal, and electrochemical properties were systematically characterized. The study found that a poly(AN-co-PEGMEA) 6:1 copolymer ratio offers an optimal balance between printability and ionic conductivity. The successful extrusion of filaments and subsequent 3D printing of complex shapes demonstrate the potential of these materials for next-generation battery designs. The addition of succinonitrile (SCN) as a plasticizer significantly improved ionic conductivity and lithium cation transference numbers, making these copolymers viable for practical applications. This work highlights the potential of combining polymer chemistry with additive manufacturing to provide new opportunities in lithium-ion battery design and function.

Osmotic energy harvesting using acrylic acid hydrogel PET membrane

In this study, we investigated the osmotic energy harvesting using a cation-selective membrane. The cation-selective membrane was synthesized by the incorporation of acrylic acid hydrogel in a porous support membrane. FTIR analysis and SEM images confirmed the presence of the acrylic acid hydrogel rods inside the porous support material. The exposure of the acrylic acid hydrogel PET (AP) membrane to a concentration gradient culminated in the generation of electric power. The AP membrane was evaluated in regard to the following parameters: EDiff, Io, Pmax and t+. The maximum power obtained with the membrane was 1.10 μW at the 40-fold concentration gradient (test area∽ 100 mm2). Increasing the concentration gradient increased the power output. However, a decrease in power output was observed after a certain value of the concentration gradient. An enhancement in power output was noted as the fraction of acrylic acid within the membrane was augmented. Additionally, the cation transference number also increased owing to a high charge density and a reduction in the mesh size. The AP membrane was also investigated in acidic and basic media. The time-dependent study revealed the superior chemical stability of the AP membrane.

Boron Surface Treatment of Li7La3Zr2O12 Enabling Solid Composite Electrolytes for Li-Metal Battery Applications.

Despite being promoted as a superior Li-ion conductor, lithium lanthanum zirconium oxide (LLZO) still suffers from a number of shortcomings when employed as an active ceramic filler in composite polymer-ceramic solid electrolytes for rechargeable all-solid-state lithium metal batteries. One of the main limitations is the detrimental presence of Li2CO3 on the surface of LLZO particles, restricting Li-ion transport at the polymer-ceramic interfaces. In this work, a facile way to improve this interface is presented, by purposely engineering the LLZO particle surfaces for a better compatibility with a PEO:LiTFSI solid polymer electrolyte matrix. It is shown that a surface treatment based on immersing LLZO particles in a boric acid solution can improve the LLZO surface chemistry, resulting in an enhancement in the ionic conductivity and cation transference number of the CPE with 20 wt % of boron-treated LLZO particles compared to the analogous CPE with non-treated LLZO. Ultimately, an improved cycling performance and stability in Li//LiFePO4 cells was also demonstrated for the modified material.

Room-Temperature Possible Current-Induced Transition in Ca2RuO4 Thin Films Grown Through Intercalation-Like Cation Diffusion in the A2BO4 Ruddlesden-Popper Structure.

Cation deficiency tuning is a central issue in thin-film epitaxy of functional metal oxides, as it is typically more difficult than anion deficiency tuning, as anions can be readily supplied from gas sources. Here, highly effective internal deficiency compensation of Ru cations is demonstrated for Ca2RuO4 epitaxial films based on diffusive transfer of metal cations in the A2BO4 Ruddlesden-Popper lattice from solid-phase cation sources. Through detailed structural characterization of Ca2RuO4/LaAlO3 (001) thin films grown with external cation sources by solid-phase epitaxy, the occurrence of intercalation-like, interstitial diffusion of La cations (from the substrates) in the A2BO4 structure is revealed, and that of Ru cations is also suggested. Relying on the interstitial-type diffusion, an optimized Ru deficiency compensation method, which does not induce the formation of Can +1RunO3 n +1 Ruddlesden-Popper impurity phases with higher n, is proposed for Ca2RuO4 epitaxial films. In the Ca2RuO4/LaAlO3 (001) thin films grown with Ru deficiency compensation, record-high resistivity values (102-10-1 Ω cm) and a large (more than 200 K) increase in the temperature range of the nonlinear transport properties are demonstrated by transport measurements, demonstrating the possible advantages of this method in the control of the current-induced quantum phase transition of Ca2RuO4.

Rat Selective expression of placental MATE1 results in reduced transfer of organic cations to the fetus

Rat Selective expression of placental MATE1 results in reduced transfer of organic cations to the fetus

Simultaneous heat, moisture, and salt transfer in porous building materials considering osmosis flow: Part 1: Theoretical modeling based on nonequilibrium thermodynamics

Salt weathering is a common deterioration phenomenon that affects outdoor cultural properties, and it is important to precisely predict the heat, moisture, and salt transfer in porous materials to suppress salt weathering. Osmosis and osmotic pressure were considered in the field of soil research, especially in clay research, but not in the field of outdoor cultural properties and building materials, which are the main target of salt weathering. Osmosis in clay is supposed to be caused by its surface charge. However, it has been suggested that sandstones and bricks that constitute cultural properties and buildings also have surface charge as clay. Thus, osmosis and osmotic pressure can occur in building materials, which may lead to materials degradation. In this study, we derive basic equations, based on nonequilibrium thermodynamics, for the simultaneous heat, dry air, water vapor, liquid water, cation, and anion transfer in building materials by considering osmosis. This equation was compared with existing model for heat and moisture transfer equations as well as models that considered the salt transfer. Based on the previous research for osmosis in clay, we summarized conditions under which osmosis occurs in building materials and presented an outlook for modeling the physical properties of materials related to osmosis.

Interactions of Alkali Ions and Phospholipid Monolayers at Organic-Water Interfaces

The self-assembled phospholipids monolayers at interfaces between two immiscible electrolyte solutions (ITIES) are commonly used to study the interactions between cell membranes and species passing in and out through membrains such as ions, drugs, and other nutrients. In this study, we utilized electrochemical techniques such as open circuit potential (OCP), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) to study the pure phospholipd monolayer formed by 1,2-Dioleoyl-sn-glycero-3-phosphocholine (DOPC) and its mixture with 1,2-dioleoyl-sn-glycero-3-phospho-(1'-racglycerol) (sodium salt) (DOPG) at 1,2-dichloroethane-water interfaces. Our study has shown that at higher applied electric potentials, there seems to be no change in the facilitation of cation transfers by DOPC/DOPG monolayer compared to DOPC monolayer. However, at lower applied potentials, the DOPGs in the mixed monolayer seemed to leave the interface under the influence of the applied electric field, indicated by both the higher capacitance obtained throught the EIS measurements and the higher currents from the CV measurements compared to results obtained from the sample consisted of the pure DOPC monolayer. Furthermore, our study also showed a general rise in capacitance when incorporating heavier alkali ions in the aqueous phase for the sample with the mixture of DOPC/DOPG at higher applied electric potentials.

Solid-State Lithium Batteries with in-Situ Polymerized Acrylate-Based Electrolytes Capable of Electrochemically Stable Operation at 100 ℃

In-situ polymerized acrylate-based polymers are very appealing as solid polymer electrolytes (SPEs) in lithium (Li) batteries due to the drop-in compatibility of such in-situ polymerization with conventional battery production, the ease of acrylate polymerization and their inexpensive, facile SPE chemistry. We identified, however, that such SPEs suffer from either a low cationic transference number with dual ion conducting salts (0.12-0.2) or a low ionic conductivity with single Li-ion conducting (SLIC) salts (6·10-6 S cm-1). In this project we overcame these limitations and developed significantly improved SPE with ionic conductivity of up to 2·10-4 Scm-1 and a relatively high Li-ion transference number of 0.4. With a significantly reduced fraction of mobile anions in the hybrid SPE, in-situ polymerized SPE cells with an LiFePO4 (LFP) cathode achieve a stable performance for over 100 cycles at temperatures as high as 100 °C, which is unattainable with conventional Li salts or electrolytes. Furthermore, the motional narrowing observed in the line-shapes of solid-state nuclear magnetic resonance (SS-NMR) spectra provided additional insights of the differences in Li nucleus environments and revealed a reduced activation energy for the hybrid salt SPEs due to their more open structure. This study opens the path for the fabrication of high-performance solid polymer lithium batteries capable of operating at high temperatures using commercial battery fabrication equipment. We expect that further tuning of the acrylate based SPE composition may allow further increases in its conductivity without sacrifices in its electrochemical stability or mechanical properties.