Electrolytes For Sodium-ion Batteries Research Articles

Deciphering Electrolyte Dominated Na+ Storage Mechanisms in Hard Carbon Anodes for Sodium-Ion Batteries.

Although hard carbon (HC) demonstrates superior initial Coulombic efficiency, cycling durability, and rate capability in ether-based electrolytes compared to ester-based electrolytes for sodium-ion batteries (SIBs), the underlying mechanisms responsible for these disparities remain largely unexplored. Herein, ex situ electron paramagnetic resonance (EPR) spectra and in situ Raman spectroscopy are combined to investigate the Na storage mechanism of HC under different electrolytes. Through deconvolving the EPR signals of Na in HC, quasi-metallic-Na is successfully differentiated from adsorbed-Na. By monitoring the evolution of different Na species during the charging/discharging process, it is found that the initial adsorbed-Na in HC with ether-based electrolytes can be effectively transformed into intercalated-Na in the plateau region. However, this transformation is obstructed in ester-based electrolytes, leading to the predominant storage of Na in HC as adsorbed-Na and pore-filled-Na. Furthermore, the intercalated-Na in HC within the ether-based electrolytes contributes to the formation of a uniform, dense, and stable solid-electrolyte interphase (SEI) film and eventually enhances the electrochemical performance of HC. This work successfully deciphers the electrolyte-dominated Na+ storage mechanisms in HC and provides fundamental insights into the industrialization of HC in SIBs.

Scalable Synthesis of Selenide Solid-State Electrolytes for Sodium-Ion Batteries.

Solid-state sodium-ion batteries employing superionic solid-state electrolytes (SSEs) offer low manufacturing costs and improved safety and are considered to be a promising alternative to current Li-ion batteries. Solid-state electrolytes must have high chemical/electrochemical stability and superior ionic conductivity. In this work, we employed precursor and solvent engineering to design scalable and cost-efficient solution routes to produce air-stable sodium selenoantimonate (Na3SbSe4). First, a simple metathesis route is demonstrated for the production of the Sb2Se3 precursor that is subsequently used to form ternary Na3SbSe4 through two different routes: alcohol-mediated redox and alkahest amine-thiol approaches. In the former, the electrolyte was successfully synthesized in EtOH by using a similar redox solution coupled with Sb2Se3, Se, and NaOH as a basic reagent. In the alkahest approach, an amine-thiol solvent mixture is utilized for the dissolution of elemental Se and Na and further reaction with the binary precursor to obtain Na3SbSe4. Both routes produced electrolytes with room temperature ionic conductivity (∼0.2 mS cm-1) on par with reported performance from other conventional thermo-mechanical routes. These novel solution-phase approaches showcase the diversity and application of wet chemistry in producing selenide-based electrolytes for all-solid-state sodium batteries.

Anion-derived cathode interface engineering enables ether-based electrolytes for sodium-ion batteries

High-performance sodium-ion batteries (SIBs) require not only non-aqueous electrolytes with high ion conductivity but also high interfacial compatibility with both electrodes. Ether-based electrolytes are considered one of the most promising electrolyte systems for SIBs due to the advantages of high reduction stability and weakly desolvating power. However, conventional ether-based electrolytes are easy to decompose and deteriorate on the cathode/electrolyte interface under high voltage, which greatly restricts their practical application in SIBs. Herein, a novel and effective interfacial stabilization strategy is proposed and systemically investigated. A homogeneous and compact cathode electrolyte interphase (CEI) film rich in fluorides and borides can be successfully constructed on the cathode surface by pre-cycling of NVP@C cathode in the NaODFB-DEGDME electrolyte. The ODFB anion-derived CEI film can effectively inhibit the continuous oxidation decomposition of NaPF6-DEGDME electrolytes. As a result, the Na||NVP@C half-cell can stably cycle for 1500 cycles with high average Coulombic efficiency (CE, >99.7 %) at 5C. This work illustrates the significance of the composition and structure of CEI film for improving the interfacial stability of high-voltage SIBs with ether-based electrolytes.

Research progress of organic liquid electrolyte for sodium ion battery.

Electrochemical energy storage technology has attracted widespread attention due to its low cost and high energy efficiency in recent years. Among the electrochemical energy storage technologies, sodium ion batteries have been widely focused due to the advantages of abundant sodium resources, low price and similar properties to lithium. In the basic structure of sodium ion battery, the electrolyte determines the electrochemical window and electrochemical performance of the battery, controls the properties of the electrode/electrolyte interface, and affects the safety of sodium ion batteries. Organic liquid electrolytes are widely used because of their low viscosity, high dielectric constant, and compatibility with common cathodes and anodes. However, there are problems such as low oxidation potential, high flammability and safety hazards. Therefore, the development of novel, low-cost, high-performance organic liquid electrolytes is essential for the commercial application of sodium ion batteries. In this paper, the basic requirements and main classifications of organic liquid electrolytes for sodium ion batteries have been introduced. The current research status of organic liquid electrolytes for sodium ion batteries has been highlighted, including compatibility with various types of electrodes and electrochemical properties such as multiplicative performance and cycling performance of electrode materials in electrolytes. The composition, formation mechanism and regulation strategies of interfacial films have been explained. Finally, the development trends of sodium ion battery electrolytes in terms of compatibility with materials, safety and stable interfacial film formation are pointed out in the future.

3D Printing of Gel Polymer Electrolytes for Sodium-Ion Batteries

In order to maximize the capabilities of existing battery chemistries, a big effort has been recently focused on manufacturing more complex battery structures, which promotes 3D lithium ion diffusion resulting in an increase in power density.1-3 The current limitation is still the manufacturing part, which is often complex and expensive for mainstream production. 3D printing appears in this context as an exceptional tool to fill the gaps for 3D battery manufacturing. Among the 3D printing processes, vat photopolymerization is especially interesting thanks to its high printing resolution through a layer-by-layer curing approach that solidifies a UV-photocurable resin. Multiple examples of functional 3D printed batteries manufactured by various methods have been reported in the literature.4-7 Most of the recent works have been focused on half-cells where only one electrode is printed, or complete cells containing printed electrodes but using a non-printed conventional separator-electrolyte couple in between. Among the alternatives to replace this couple for a functional and printable material, gel polymer electrolytes appear as an appropriate option because they possess the advantages of a liquid electrolyte, without severely compromising the mechanical integrity. In addition, they exhibit competitive ionic conductivity and enhanced safety in comparison to liquid electrolytes, and they do not require a thermal post-processing step to be manufactured. Combining the knowledge in this topic with the design freedom that 3D printing allows will certainly contribute to obtaining the next generation of 3D printed batteries. In a first instance, this work will show a brief overview about suitable UV-photocurable resin compositions that can be employed as gel polymer electrolytes in sodium-ion batteries, with a view to employ them as material feedstock in the high-resolution vat photopolymerization process. The freedom of design that 3D printing allows will be then shown through a variety of printed items that transcend the well-known tape casting method to produce conventional gel polymer electrolytes. Finally, a variety of electrochemical tests to prove stability, ionic conductivity and performance within sodium-ion batteries will be shown. Talin, A. A. et al. Fabrication, Testing, and Simulation of All-Solid-State Three-Dimensional Li-Ion Batteries. ACS Appl. Mater. Interfaces 8, 32385–32391 (2016).Liu, Y. et al. Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries. Sci Adv 3, eaao0713 (2017).Long, J. W., Dunn, B., Rolison, D. R. & White, H. S. 3D architectures for batteries and electrodes. Adv. Energy Mater. 10, 2002457 (2020).Cheng, M., Deivanayagam, R. & Shahbazian-Yassar, R. 3D printing of electrochemical energy storage devices: A review of printing techniques and electrode/electrolyte architectures. Batter. supercaps 3, 130–146 (2020).Pang, Y. et al. Additive manufacturing of batteries. Adv. Funct. Mater. 30, 1906244 (2020).Zeng, L. et al. Recent progresses of 3D printing technologies for structural energy storage devices. Materials Today Nano 12, 100094 (2020).Maurel, A. et al. Toward High Resolution 3D Printing of Shape-Conformable Batteries via Vat Photopolymerization: Review and Perspective. IEEE Access 9, 140654–140666 (2021).

Synthesis and Thermal Evaporation Deposition of Sodium Oxychloride Solid-State Electrolyte for Sodium-Ion Batteries

Sodium-ion batteries have attracted significant attention by offering an alternative option to lithium-ion batteries. Solid-state sodium oxyhalides (Na3OX, X = Cl, Br, I) have the advantage of cost-effective synthesis from raw materials in a time-effective manner. In this study, sodium oxychloride (Na3OCl) antiperovskite was synthesized using a novel approach that allowed for facile synthesis outside of an argon glovebox. The ionic conductivity of Na3OCl pellets compressed between graphite-coated copper foil was tested in the temperature range of 160˚C and 200˚C using electrochemical impedance spectroscopy (EIS). Arrhenius plots demonstrated linear behavior in the whole temperature range with a calculated activation energy of 0.98 eV. At lower temperatures, EIS data was not available likely due to high impedance from the thickness of the electrolyte pellet, high activation energy, or slow migration of sodium ions through the Na3OCl structure. To decrease electrolyte thickness, we implement physical vapor deposition (PVD) thermal evaporation to coat thin films (<100 µm) of the electrolyte onto graphite-coated copper foil and sodium-based cathodes for use in symmetric cell and half-cell configurations. The melting and crystallization temperatures were determined using differential scanning calorimetry (DSC). The purity of as-synthesized sodium oxychloride and PVD-deposited layer was evaluated using X-ray diffraction (XRD). The results on chemical composition and crystal-to-glass phase transformations are produced from in-situ X-ray diffraction (XRD) spectroscopy in the temperature range from 25˚C up to the melting point of Na3OCl. Cross-sectional SEM images of PVD-deposited sodium oxychloride showed an even distribution of sodium, oxygen, and chlorine. However, XRD analysis of deposited layers showed that sodium oxychloride had a tendency to decompose into the precursors during deposition. This work is focused on maintaining the sodium oxychloride composition and structure during PVD thermal evaporation by optimizing the PVD deposition parameters.The authors acknowledge financial support from the NSF IUCRC program for the “Center for solid-state electric power storage” (#2052631) and support from the South Dakota Board of Regents for the “Governor’s Research Center (GRC) for electrochemical energy storage”.

Low-Temperature Properties of the Sodium-Ion Electrolytes Based on EC-DEC, EC-DMC, and EC-DME Binary Solvents

Sodium-ion batteries are a promising class of secondary power sources that can replace some of the lithium-ion, lead–acid, and other types of batteries in large-scale applications. One of the critical parameters for their potential use is high efficiency in a wide temperature range, particularly below 0 °C. This article analyzes the phase equilibria and electrochemical properties of sodium-ion battery electrolytes that are based on NaPF6 solutions in solvent mixtures of ethylene carbonate and diethyl carbonate (EC:DEC), dimethyl carbonate (EC:DMC), and 1,2-dimethoxyethane (EC:DME). All studied electrolytes demonstrate a decrease in conductivity at lower temperatures and transition to a quasi-solid state resembling “wet snow” at certain temperatures: EC:DEC at −8 °C, EC:DMC at −13 °C, and EC:DME at −21 °C for 1 M NaPF6 solutions. This phase transition affects their conductivity to a different degree. The impact is minimal in the case of EC:DEC, although it partially freezes at a higher temperature than other electrolytes. The EC:DMC-based electrolyte demonstrates the best efficiency at temperatures down to −20 °C. However, upon further cooling, 1 M NaPF6 in EC:DEC retains a higher conductivity and lower resistivity in symmetrical Na3V2(PO4)3-based cells. The temperature range from −20 to −40 °C is characterized by the strongest deterioration in the electrochemical properties of electrolytes: for 1 M NaPF6 in EC:DMC, the charge transfer resistance increased 36 times, and for 1 M NaPF6 in EC:DME, 450 times. For 1 M NaPF6 in EC:DEC, the growth of this parameter is much more modest and amounts to only 1.7 times. This allows us to consider the EC:DEC-based electrolyte as a promising basis for the further development of low-temperature sodium-ion batteries.

Systematic Study of Aluminum Corrosion in Ionic Liquid Electrolytes for Sodium-Ion Batteries: Impact of Temperature and Concentration.

The development of sodium-ion batteries utilizing sulfonylamide-based electrolytes is significantly encumbered by the corrosion of the Al current collector, resulting in capacity loss and poor cycling stability. While ionic liquid electrolytes have been reported to suppress Al corrosion, a recent study found that pitting corrosion occurs even when ionic liquids are employed. This study investigates the effects of temperature and Na salt concentration on the Al corrosion behavior in different sulfonylamide-based ionic liquid electrolytes for sodium-ion batteries. In the present work, cyclic voltammetry measurements and scanning electron microscopy showed that severe Al corrosion occurred in ionic liquids at high temperatures and low salt concentrations. X-ray photoelectron spectroscopy was employed to identify the different elemental components and verify the thickness of the passivation layer formed under varied salt concentrations and temperatures. The differences in the corrosion behaviors observed under the various conditions are ascribed to the ratio of free [FSA]- to Na+-coordinating [FSA]- in the electrolyte and the stability of the newly formed passivation layer. This work aims at augmenting the understanding of Al corrosion behavior in ionic liquid electrolytes to develop advanced batteries.

Impact of sintering temperature and ascertaining hopping bottlenecks for ions in sodium superionic conducting electrolyte for sodium-ion batteries

Recently, sodium super-ionic conducting (NASICON) type solid electrolytes have gained attention for next generation batteries because of their high ionic conductivity, low cost, excellent chemical and electrochemical stability. Therefore, in the present study, NASICON-type solid electrolyte Na3Zr2Si2PO12 is synthesized by solution assisted-solid state reaction (SA-SSR) route. The electrolytes are sintered at three different temperatures, 1200 °C, 1250 °C and 1300 °C. The sintered electrolytes are characterized by various experimental techniques. The Rietveld refinement of X-ray diffraction pattern of prepared electrolytes revealed the monoclinic crystal structure. The 3-dimension hopping channel for sodium ion migration through triangular bottleneck area is identified. From complex impedance spectroscopy measurement, the highest bulk and grain boundary conductivity are found, ∼4.05mScm−1 and ∼0.31mScm−1, respectively, for the sample sintered at 1250 °C. The optimized electrolyte shows wide electrochemical stability (∼6.5 V) which is suitable for high voltage battery application. Using optimized electrolyte, sodium half-cell is fabricated with sodium metal as anode, and Na3V2P3O12 (NVP) as cathode. The assembled cell delivers maximum discharge capacity ∼101.6 and ∼84.5mAhg−1 at the current density 10 and 40mAg−1, respectively with good capacity retention (∼95.02%) upto 50 cycles.

Altering Mechanical Properties to Improve Electrode Contacts by Organic Modification of Silica-Based Ionogel Electrolytes for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are a possible candidate to create safe, sustainable, and cost-effective batteries. Solid sodium-ion conducting organically modified ionogel electrolytes are investigated. Silica-based ionogels typically consist of an ionic liquid electrolyte (ILE) confined within a silica matrix and possess high thermal stability, good ionic conductivity, safety, and good electrochemical stability. However, they readily deteriorate when stress is applied, decreasing the electrolyte's and battery's overall performance. The mechanical characteristics of silica can be improved using organic moieties, creating Ormosils®. Silica-based ionogels with phenyl-modified silanes improve the mechanical characteristics by a reduction of their Young's modulus (from 29 to 6 MPa). This is beneficial to the charge-transfer resistance, which decreases after implementing the electrolyte in half cells, demonstrating the improved interfacial contact. Most importantly, the phenyl groups change the interacting species at the silica interface. Cationic imidazolium species pi-stacked to the phenyl groups of the silica matrix, pushing the anions to the bulk of the ILE, which affects the ionic conductivity and electrochemical stability, and might affect the quality of the SEI in half cells. In essence, the work at hand can be used as a directory to improve mechanical characteristics and modify and control functional properties of ionogel electrolytes.

Interfacial-Catalysis-Enabled Layered and Inorganic-Rich SEI on Hard Carbon Anodes in Ester Electrolytes for Sodium-Ion Batteries.

Constructing a homogenous and inorganic-rich solid electrolyte interface (SEI) can efficiently improve the overall sodium-storage performance of hard carbon (HC) anodes. However, the thick and heterogenous SEI derived from conventional ester electrolytes fails to meet the above requirements. Herein, an innovative interfacial catalysis mechanism is proposed to design a favorable SEI in ester electrolytes by reconstructing the surface functionality of HC, of which abundant CO (carbonyl) bonds are accurately and homogenously implanted. The CO (carbonyl) bonds act as active centers that controllably catalyze the preferential reduction of salts and directionally guide SEI growth to form a homogenous, layered, and inorganic-rich SEI. Therefore, excessive solvent decomposition is suppressed, and the interfacial Na+ transfer and structural stability of SEI on HC anodes are greatly promoted, contributing to a comprehensive enhancement in sodium-storage performance. The optimal anodes exhibit an outstanding reversible capacity (379.6 mAh g-1 ), an ultrahigh initial Coulombic efficiency (93.2%), a largely improved rate capability, and an extremely stable cycling performance with a capacity decay rate of 0.0018% for 10 000 cycles at 5 A g-1 . This work provides novel insights into smart regulation of interface chemistry to realize high-performance HC anodes for sodium storage.

Exploring structural and dynamical properties of polymer-ionic liquid ternary electrolytes for sodium ion batteries

This work investigates the ion transport mechanisms in binary and ternary electrolyte systems based on polymers and ionic liquids for Na-ion batteries. Molecular dynamics (MD) simulations were performed on poly(ethylene oxide) (PEO) and ionic liquids (IL) based electrolytes, bis(trifluoromethanesulfonyl)imide (TFSI)/N-methyl-N-propylpyrrolidinium (Pyr13) and bis(fluorosulfonyl)imide (FSI)/Pyr13, varying the composition at 0, 5, 10 and 20 wt% over a range of temperatures from 313 to 400 K. The simulations could satisfactorily reproduce the experimental densities and trends in diffusivities and conductivity data. It was observed that there exists a stronger interaction between sodium ions and the FSI anions as compared to the TFSI counterparts, correlated to a difference in interaction energy between the ionic species. This controls how well the different ILs act as plasticizers for the Na-PEO system, with TFSI actually displaying lower conductivity for low IL loadings while the conductivity increases continuously for the FSI counterparts. Moreover, the simulations show that the sodium ions interact more strongly with the polymer at lower temperatures, leading to a lower polymer free volume which explains the trends in ionic transport. Thereby, these MD simulations unveil an interplay between the coordination chemistry and the dynamic properties in these ternary polymer-ionic liquid-salt electrolytes, and how the coordination strength controls the conductive properties.

Glyoxylic-Acetal-Based Electrolytes for Sodium-Ion Batteries and Sodium-Ion Capacitors.

A comprehensive study on the properties and implementation of glyoxylic-acetals in sodium-ion energy storage systems is presented. Electrolytes containing 1,1,2,2-tetramethoxyethane (tetramethoxyglyoxal, TMG), 1,1,2,2-tetraethoxyethane (tetraethoxyglyoxal, TEG) and a mixture of the latter with propylene carbonate (PC) exhibit increased thermal stabilities and higher flash points compared to classical electrolytes based on carbonates as solvents. Due to its favorable properties, 1 m NaTFSI in TEG/PC (3 : 7), has been selected and used for sodium-ion energy storage systems based on a Prussian Blue (PB) positive electrode and a hard carbon (HC) negative electrode. Compared to conventional electrolyte (based on a 1 : 1 mixture of ethylene carbonate, EC, and dimethyl carbonate, DMC), this glyoxylic-acetal electrolyte provides competitive capacity and prolonged cycle life. Postmortem XPS analysis indicates that the electrode-electrolyte interphases formed in presence of TEG are thicker and presumably more protective, inhibiting typical degradation processes of the electrodes. Furthermore, it is demonstrated that the suitable properties of TEG on the cycling stability can also be exploited for the construction of highly stable sodium-ion capacitors.

Sodium Carbazolide and Derivatives as Solid-State Electrolytes for Sodium-Ion Batteries.

Replacing widely used organic liquid electrolytes with solid-state electrolytes (SSEs) could effectively solve the safety issues in sodium-ion batteries. Efforts on seeking novel solid-state electrolytes have been continued for decades. However, issues about SSEs still exist, such as low ionic conductivity at ambient temperature, difficulty in manufacturing, low electrochemical stability, poor compatibility with electrodes, etc. Here, sodium carbazolide (Na-CZ) and its THF-coordinated derivatives are rationally fabricated as Na+ conductors, and two of their crystal structures are successfully solved. Among these materials, THF-coordinated complexes exhibit fast Na+ conductivities, i.e., 1.20×10-4 S cm-1 and 1.95×10-3 S cm-1 at 90 °C for Na-CZ-1THF and Na-CZ-2THF, respectively, which are among the top Na+ conductors under the same condition. Furthermore, stable Na plating/stripping is observed even over 400 h cycling, showing outstanding interfacial stability and compatibility against Na electrode. More advantages such as ease of synthesis, low-cost, and cold pressing for molding can be obtained. In situ NMR results revealed that the evaporation of THF may play an essential role in the Na+ migration, where the movement of THF creates defects/vacancies and facilitates the migration of Na+ .

Impedance analysis of PEG plasticized PEO-based composite polymer electrolytes for sodium-ion batteries

Solid-state sodium-ion batteries (SSIBs) will be the next generation batteries due to the high safety, low price, and availability of sodium resources. Composite polymer electrolytes (CPEs) are promising electrolytes because of easy fabrication, good stability, and high flexibility facilitating a good electrolyte-electrode interface, although their ionic conductivities are still unsatisfied. In this work, a CPE made of polyethylene oxide (PEO), Na3Zr2Si2PO12, and NaClO4 has been fabricated. To further enhance the ionic conductivity and a good electrolyte–electrode interface, polyethylene glycol (PEG) is added as a plasticizer. The electrochemical impedance spectroscopy (EIS) demonstrates effect on conductivity by introducing PEG.

New Halide-Based Sodium-Ion Conductors Na3Y2Cl9 Inversely Designed by Building Block Construction.

Due to the excellent ionic conductivity and compatibility with high-voltage cathodes, halide-based superionic conductors as promising electrolytes have received widespread attention. A series of halide-based conductors, including Na3YCl6, are investigated aiming to find new solid electrolytes for sodium-ion batteries. However, Na3YCl6 with high ionic conductivity is meta-stable in thermostability while the stable phase exhibits poor ionic transport properties. In this work, we find that the coplanar formed anionic group (Y2Cl9)3- is the result of a combination of the structural features of the fast ion phase and stable phase of Na3YCl6 by systematic analysis of crystal structures. Aiming to find fast sodium-ion conductors, the three-step structure construction method using functional (Y2Cl9)3- groups as building blocks is proposed, and three new crystal structures in the composition of Na3Y2Cl9 with the space group of P63, Cc, and R32 are obtained. Na+ transport properties, thermostability, and electrochemical window of these structures with various symmetries are investigated by first-principles calculation methods. The results show that the principle to inverse design crystal structures of halides by basic blocks, e.g., anion groups and mobile cations, is proven to be effective and successful. For P63-Na3Y2Cl9 with outstanding transport properties, the simulation results indicate that its superionic behavior is attributed to the coherent diffusion connecting two directions. The synchronization of the migration pathways along the ab plane and the migration pathways along the c direction promotes the Na ion conductivity in Na3Y2Cl9. Our research will promote the understanding of the transport mechanism in halide-based electrolytes, and the structure construction method based on functional basic building blocks and special stacking modes will accelerate the inverse design of inorganic crystal structures.

Mixed ionic-electronic transport in Na2O doped glassy electrolytes: Promising candidate for new generation sodium ion battery electrolytes

In the present communication, newly developed glassy electrolytes, Na2O–ZnO–CdO, have been considered to discuss their electrical transport behavior at ambient temperature. The AC conductivity and relaxation behavior of them have been studied in the light of Almond-West formalism. The electrical conductivity (mixed conduction) is found to be a function of frequency as well as temperature. In the low-frequency range, it shows a flat conductivity owing to the diffusional motion of Na+ ions, whereas at high frequency, the conductivity shows dispersion. The DC conductivity ( σ dc ) and hopping frequency have been computed from the best fitted plots of experimental data. The AC conductivity at different concentrations and a constant temperature has been reported. The variation in the conductivity data with reciprocal temperatures indicates the dynamical behavior of charge carriers via hopping conduction in sodium oxide glassy systems. Mixed conduction in the present system may be dominated by polaron hopping in the samples with a lower Na2O content with a percolation type of motion of the electron/polaron. On the other hand, three-dimensional Na+ motion is the dominating charge carrier for the samples with a higher Na2O content. A negligible small difference in pathways in the I–V characteristics in both the directions should make the present system a promising candidate for the new generation battery electrolyte.

Recent Advances in New-Generation Electrolytes for Sodium-Ion Batteries

Sodium-ion batteries (SIBs) are one of the recent trends in energy storage systems due to their promising properties, the high abundance of sodium in the Earth’s crust, and their low cost. However, the commercialization process of SIBs is in the early stages of development because of some challenges related to electrodes and electrolytes. Electrolytes are vital components of secondary batteries because they determine anode/cathode performance; energy density; operating conditions (electrochemical stability window, open circuit voltage, current rate, etc.); cyclic properties; electrochemical, thermal, mechanical, and dimensional stability; safety level; and the service life of the system. The performance of the battery is based on the structural, morphological, electrical, and electrochemical properties of the electrolytes. In this review, electrolytes used for SIBs are classified according to their state and material, including liquid, quasi-solid, solid, and hybrid, and recent advances in electrolyte research have been presented by considering their contributions and limitations. Additionally, future trends and recent cutting-edge research are highlighted.

Effect of SiO2 microstructure on ionic transport behavior of self-healing composite electrolytes for sodium metal batteries

Batteries matched with flexible intelligent electronic devices are required in the future to supply dense and reliable power security. In addition to energy storage performance, functionalized design of batteries with good mechanical properties and self-healing ability is critical to the development of flexible intelligent electronic devices. The polymer with quadruple hydrogen bonds can give materials the ability to repair mechanical damage and restore the original mechanical properties. The incorporation of inorganic fillers into polymer electrolytes can improve the electrochemical properties and stability of the electrolytes. Optimization of the geometry of inorganic materials could further improve the electrical conductivity of composite electrolytes. In this work, a flexible self-healing polymer electrolyte (Poly (ethylene glycol)-co-ureidopyrimidinone), PEG-UPy) was synthesized. Three different microstructures of SiO2 fillers (solid, mesoporous, and hollow mesoporous) with UPy modified were designed to improve the sodium ion transport performance of the PEG-UPy self-healing polymer electrolyte for sodium ion batteries. The PEG-UPy electrolyte filled with hollow mesoporous SiO2 (PEG-UPy@hSiO2) exhibits an excellent electrochemical performance due to its unique structure among the samples. The PEG-UPy@hSiO2 electrolyte shows the highest ionic conductivity, sodium ion transference number, and appropriate self-healing property. The discharge capacity of NVP/PEG-UPy@hSiO2-NaTFSI (HCPE)/Na cell could reach 110.5 mAh g−1 at 0.1C and the capacity retention rate could reach more than 77.6% after 200 cycles at 60 °C.

Ionic liquids as potential electrolytes for sodium-ion batteries: an overview.

In this study, we present an overview on the use of ionic liquids (ILs) as electrolytes in sodium-ion batteries (SIBs). The development of SIBs has gained traction over the last few years because Na is cheaper and more abundant than Li. In this case, although great efforts have been devoted to finding high-capacity and high cell potential materials for SIBs, electrolyte safety is an important factor in producing more competitive and reliable devices. Specifically, the intrinsic volatility of the organic solvent-based electrolytes commonly used in commercial systems is a safety risk during the operation of batteries, and thus replacing them with ILs is an alternative that should be considered. This family of electrolytes is more thermally stable than organic solvents, but they suffer from poor transport properties. Herein, we discuss these properties, considering neat ILs, effects of cations and anions, and effect of salt concentration. Moreover, the strategies to overcome the transport limitations are highlighted. Then, the recent applications of mixtures containing sodium salts and ILs as electrolytes for the negative and positive electrodes in SIBs are presented. Finally, the use of Na-IL mixtures in solid-state electrolytes is discussed.