Electrolytes For Batteries Research Articles

Structural Engineering Developments in Sulfide Solid-State Electrolytes for Lithium and Sodium Solid-State Batteries

Solid-state batteries (SSBs), especially those derived from lithium and sodium, show great promise as the next generation of energy storage devices due to their remarkable energy density, compact electrode architecture, nonflammability, and the use of metallic anodes. The solid-state electrolytes (SSEs), a significant part of SSBs, are essential to their functionality. A family of SSEs known as sulfide-based has been extensively studied for many years as a potential SSE for sodium and lithium SSBs. It offers excellent ionic conductivity, favorable mechanical properties, and ease of manufacturing. Notwithstanding its advantages, it also presents several problems, which require careful consideration for it to be successfully commercialized. This review summarizes the recent advancements in SSEs for lithium and sodium SSBs. It explores how structural engineering strategies impact the electrochemical properties of argyrodites SSEs for lithium SSBs and Na3PS4-based SSEs for sodium SSBs. The review provides comprehensive information on successful structural engineering approaches, such as introducing vacancies, mobile ions stuffing, and doping, for both lithium and sodium SSEs. It also discusses the air stability and electrochemical stability against electrodes, offering insights for designing and synthesizing next-generation SSEs that can lead to more durable and efficient energy storage systems.

Chitosan-based gel polymer electrolytes for high performance Li-ion battery

This study explores the use of glutaraldehyde-crosslinked chitosan-based gel polymer electrolytes (GPEs) in lithium-ion batteries (LIBs). GPEs are prepared by solution casting using two different molecular weights of chitosan including 150 kDa as medium and 400 kDa as high molecular weight (MMWCS and HMWCS, respectively) with varying amounts of crosslinker. Degree of crystallinity was 25.9 and 24.1 % for HMWCS and MMWCS, respectively that was decreased to 18.3 and 22.7 % by using 5 % crosslinker and 17.8 and 21.1 % by using 10 % crosslinker, and 17.2 and 17.6 % by using 20 % crosslinker. The obtained ionic conductivity for HMWCS and MMWCS was 3.1 × 10−3 and 2.9 × 10−3 S.cm−1. After crosslinking by 5, 10, and 20 % crosslinker, the ionic conductivity was obtained to 0.9 × 10−3 and 0.3 × 10−3 S.cm−1, 6.3 × 10−3 and 5 × 10−3 S.cm−1, and 1.1 × 10−3 and 0.5 × 10−3 S.cm−1 for high and medium molecular weight, respectively. Lithium-ion transfer number was obtained between 0.34 and 0.83 and the highest t+ value was obtained for the MMWCS-GA10. Electrochemical stability window of the prepared polymer electrolytes was >5 V and samples showed no remarkable dendrite growth after cycling analyses. The symmetric cells demonstrated reliable performance, operating for over 300 h without any short-circuiting, which indicates excellent reversible cycling stability for chitosan-based lithium-ion batteries. Furthermore, the Gr/GPE cell exhibited very low voltage polarization, with the over-potential decreasing from 10 mV initially to 6 mV after 300 h at the same current density. Discharge capacity was obtained higher than 170 mAh/g at 0.2C with CE = 97 % for both HMWCS-GA20 and HMWCS-GA20.

Electroplating of Lithium-metal electrode in different electrolyte for lithium batteries

Electroplating of Lithium-metal electrode in different electrolyte for lithium batteries

La1−xSrxF3−x: A Solid-State Electrolyte for Fluoride Ion Battery with High Ionic Conductivity and Wide Electrochemical Potential Window

Fluoride ion conductors are developed for use as solid-state electrolytes in fluoride ion batteries which are one of promising candidates for next-generation storage batteries. Ba-doped LaF3 (La0.9Ba0.1F2.9: LBF) is mainly used as a solid-state electrolyte in fluoride ion batteries. However, room temperature conductivity of LBF is considerably low, on the order of 10−6 S cm−1 and it is still unclear the optimal elements to be doped to LaF3. In this study, we have explored La0.9Sr x Ba0.1−x F2.9 system (x = 0, 0.01, 0.025, 0.05, 0.1), in which Ba in LBF is substituted for Sr and investigated the composition dependence of ionic conductivity. We elucidate that the higher concentration of Sr without Ba can significantly improve the ionic conductivity, and the maximum ionic conductivity of La0.9Sr0.1F2.9 is 1.5 × 10−5 S cm−1 at room temperature, which is one order of magnitude larger than that of LBF. The higher ionic conductivity of LSF is due to the larger grain size and higher sintering density of LSF compared to LBF, which results in lower grain boundary resistance. The LSF total ionic conductivity of 10−4 S cm−1 can be achieved at 350 K, which significantly lowers operating temperature of fluoride ion batteries down to 350 K.

Advances in inorganic solid electrolytes for lithium-ion batteries

Advances in inorganic solid electrolytes for lithium-ion batteries

Regulating the Zn electrode/electrolyte interface with lactose additive for high performance Zn anode

The practical utilization of rechargeable aqueous zinc metal batteries (AZMBs) has been constrained by the formation of zinc dendrites and other associated issues. This article introduces lactose, a compound rich in hydroxyl groups, as an electrolyte additive into the aqueous solution of the electrolyte with the objective of suppressing the harmful growth of zinc dendrites. The lactose additive, with its strong zincophilicity, robust intermolecular hydrogen bonding, and a large number of exposed high electronegativity hydroxyl groups, enables lactose to effectively modulate the electrode/electrolyte interface in a dynamic manner, thereby achieving the stability and reversibility of the zinc anode. The findings presented in this work demonstrate the uniform deposition and stripping of zinc in a 2 M ZnSO4 electrolyte with the addition of lactose, thereby enhancing the cycling performance of Zn||Zn batteries. The alteration of the zinc ion environment on the surface of the zinc electrode, in conjunction with the dynamic modulation of the Gouy-Chapman-Stern (GCS) layer by lactose, increases the nucleation overpotential, thereby facilitating to a uniform deposition morphology in lieu of the formation of large-scale dendrites. Furthermore, the formation of hydrogen bonds serves to prevent the occurrence of side reactions. These factors act in concert to enhance the electrochemical performance of AZMBs. The addition of lactose to the electrolyte has resulted in a significant enhancement in the Coulombic efficiency of the card-type Zn||Cu asymmetric battery, reaching 99.7 %. The biodegradability of lactose and the sustainability of its source make this research conducive to the development of environmentally friendly battery electrolyte additives.

Self-Templated 3D Sulfide-Based Solid Composite Electrolyte for Solid-State Sodium Metal Batteries.

Rechargeable solid-state sodium metal batteries (SSMBs) experience growing attention owing to the increased energy density (vs Na-ion batteries) and cost-effective materials. Inorganic sulfide-based Na-ion conductors also possess significant potential as promising solid electrolytes (SEs) in SSMBs. Nevertheless, due to the highly reactive Na metal, poor interface compatibility is the biggest obstacle for inorganic sulfide solid electrolytes such as Na3SbS4 to achieve high performance in SSMBs. To address such electrochemical instability at the interface, new design of sulfide SE nanostructures and interface engineering are highly essential. In this work, a facile and straightforward approach is reported to prepare 3D sulfide-based solid composite electrolytes (SCEs), which utilize porous Na3SbS4 (NSS) as a self-templated framework and fill with a phase transition polymer. The 3D structured SCEs display obviously improved interface stability toward Na metal than pristine sulfide. The assembled SSMBs (with TiS2 or FeS2 as cathodes) deliver outstanding electrochemical cycling performance. Moreover, the cycling of high-voltage oxide cathode Na0.67Ni0.33Mn0.67O2 (NNMO) is also demonstrated in SSMBs using 3D sulfide-based SCEs. This study presents a novel design on the self-templated nanostructure of SCEs, paving the way for the advancement of high-energy sodium metal batteries.

Ternary Eutectic Electrolyte for Flexible Wide-Temperature Zinc-Ion Batteries from -20 °C to 70 °C.

Aqueous Zn-ion batteries (ZIBs) have attracted attention for grid applications due to their cost-effectiveness and high security. However, their lifespan decreases at high temperatures due to declining interfacial stability and increased side reactions. To address these challenges, a ternary deep eutectic solvent-based flexible electrolyte, comprised of Zn(ClO4)2 ⋅ 6H2O, butanedinitrile (BD), and LiCl in an amphoteric polymer matrix, was developed to enable wide-temperature ZIBs working from -20 °C to 70 °C. The interactions among BD, Li+, and zinc hydrate alongside the amphoteric groups on the polyelectrolyte matrix could effectively suppress the interfacial side reactions and Zn dendrites formation. Consequently, the symmetric Zn cell demonstrates exceptional stability across a wide-temperature range, with the ability to survive up to 2780 hours (1 mA cm-2) at 50 °C. Furthermore, the flexible Zn||PANI battery can operate stably over 1000 cycles at 50 °C, boasting an initial specific capacity of 124.8 mAh g-1 and capacity retention rate of 87.9 % (3 A g-1). This work presents an effective strategy for designing high-stability energy storage devices with excellent security features that can function reliably across diverse temperature conditions.

Recent Advances in Electrolytes for Magnesium Batteries: Bridging the gap between Chemistry and Electrochemistry.

Rechargeable magnesium batteries (RMBs) have the potential to provide a sustainable and long-term solution for large-scale energy storage due to high theoretical capacity of magnesium (Mg) metal as an anode, its competitive redox potential (Mg/Mg2+:-2.37 V vs. SHE) and high natural abundance. To develop viable magnesium batteries with high energy density, the electrolytes must meet a range of requirements: high ionic conductivity, wide electrochemical potential window, chemical compatibility with electrode materials and other battery components, favourable electrode-electrolyte interfacial properties and cost-effective synthesis. In recent years, significant progress in electrolyte development has been made. Herein, a comprehensive overview of these advancements is presented. Beginning with the early developments, we particularly focus on the chemical aspects of the electrolytes and their correlations with electrochemical properties. We also highlight the design of new anions for practical electrolytes, the use of electrolyte additives to optimize anode-electrolyte interfaces and the progress in polymer electrolytes.

Mechanistic Perspectives: Integration and Repairing Adaptation of Self‐Healing Electrolytes for Zinc Ion Batteries

AbstractSelf‐healing is a magical function that endows energy storage devices with extraordinary resilience and has become a promising strategy for advancing battery technology. This short review focus on the recent developments made in self‐healing chemistry for electrolytes in term of extrinsic and intrinsic dynamical concepts. Firstly, the fundamental mechanism of electrolyte self‐healing and repairing adaptation is introduced. The extrinsic self‐healing mechanism adopts capsule‐vascular networking while intrinsic self‐healing lean physical and chemical routes. The Former healing adaptation, generally follows strong physical networking and covalent linkages, which are more prevalent and practical, compared to the latter case of self‐healing. In addition to that, this review also evaluates the estimated healing capabilities and statistics using thermodynamic protocols. Finally, we propose some possible future research directions and development strategies to further apply the self‐healing phenomenon for zinc ion batteries.

Tailored PEO/PEG-PPG Polymer Electrolyte for Solid-State Lithium-Ion Battery

Abstract Solid polymer electrolytes (SPEs) offer a promising avenue for advancing the performance and safety of all-solid-state batteries. In this study, we investigated the effects of blending poly(ethylene oxide) (PEO) with amorphous poly(propylene glycol) (PPG) or poly(ethylene glycol-ran-propylene glycol) (PEG-PPG) to engineer SPEs with enhanced electrochemical properties. By blending PEO with PEG-PPG or PPG, we effectively lowered the crystallinity of PEO, facilitating the diffusion of lithium ions through the SPE and broadening its operational temperature range. This optimization strategy enhanced ionic conductivity and significantly reduced the interfacial resistance between the electrolyte and electrode, thus improving electrochemical stability. The solid-state lithium/lithium iron phosphate (LiFePO4 or LFP) with PEO blended with 7% PEG-PPG showed excellent charge/discharge cycling stability, with maximal discharge capacities of 165 mAh g-1 and 162 mAh g-1 at a current rate of 0.2 C at 60 and 125°C, respectively. The PEG-PPG-based SPE outperformed the PPG polymer-based SPE in terms of better electrochemical performance and a wider temperature range due to its longer polymer chain. This combination offered improved ionic conductivity, interface stability, and electrolyte compatibility with electrodes, making it highly suitable for high-demand applications of lithium-ion batteries.

Solid‐State Electrolytes for Lithium Metal Batteries: State‐of‐the‐Art and Perspectives

AbstractThe use of all‐solid‐state lithium metal batteries (ASSLMBs) has garnered significant attention as a promising solution for advanced energy storage systems. By employing non‐flammable solid electrolytes in ASSLMBs, their safety profile is enhanced, and the use of lithium metal as the anode allows for higher energy density compared to traditional lithium‐ion batteries. To fully realize the potential of ASSLMBs, solid‐state electrolytes (SSEs) must meet several requirements. These include high ionic conductivity and Li+ transference number, smooth interfacial contact between SSEs and electrodes, low manufacturing cost, excellent electrochemical stability, and effective suppression of dendrite formation. This paper delves into the essential requirements of SSEs to enable the successful implementation of ASSLMBs. Additionally, the representative state‐of‐the‐art examples of SSEs developed in the past 5 years, showcasing the latest advancements in SSE materials and highlighting their unique properties are discussed. Finally, the paper provides an outlook on achieving balanced and improved SSEs for ASSLMBs, addressing failure mechanisms and solutions, highlighting critical challenges such as the reversibility of Li plating/stripping and thermal runaway, advanced characterization techniques, composite SSEs, computational studies, and potential and challenges of ASS lithium–sulfur and lithium–oxygen batteries. With this consideration, balanced and improved SSEs for ASSLMBs can be realized.

Localized High-Concentration Electrolyte for All-Carbon Rechargeable Dual-Ion Batteries with Durable Interfacial Chemistry.

Lithium-based rechargeable dual-ion batteries (DIBs) based on graphite anode-cathode combinations have received much attention due to their high resource abundance and low cost. Currently, the practical realization of the batteries is hindered by easy oxidation of the electrolyte at the cathode interface, and solvent co-intercalation at the anode-electrolyte interface. Configuration of a "solvent-in-salt" electrolyte with a high concentration of Li salt is expected to stabilize the electrolyte chemistry versus both electrodes, yet inevitably reduces the mobility of the solvated working ions and increases the cost of the electrolyte. Herein, we propose to build a localized high-concentration electrolyte by adding hydrofluoroether as the diluent to reduce the salt content while improving the solvation structure, allowing more anions to enter the inner solvation sheath. The new electrolyte helps to form uniform and thin interfaces, with elevated contents of inorganic fluorides, on both electrodes, which effectively suppress electrolyte oxidation at the cathode and optimize electrolyte-electrode compatibility at the anode while facilitating charge transfer across the interface. Consequently, the DIBs with graphite as anode and cathode operate for 3000 cycles and retain a high-capacity retention of 95.7%, highlighting the importance of stable interfacial chemistry in boosting the electrochemical performance of DIBs.

Synthesis and characterization of MoS2-carbon based materials for enhanced energy storage applications

The article delves into the synthesis and characterization of MoS2-carbon-based materials, holding promise for applications in supercapacitors and ion batteries. The synthesis process entails the preparation of MoS2 and its carbon hybrids through exfoliation, hydrothermal treatment, and subsequent pyrolysis. Various analytical techniques were employed to comprehensively examine the structural, compositional, and morphological properties of the resulting materials. The article explores the electrochemical performance of these electrode materials in supercapacitors and ion batteries (LiB, SiB, KiB). Electrochemical measurements were conducted in aqueous electrolyte for supercapacitors and various aprotic electrolytes for ion batteries. Results highlight the impact of the synthesis process on electrochemical performance, emphasizing factors such as capacitance, rate capability, and charge/discharge cycle performance. Hydrothermally treated MoS2-carbon exhibited a specific capacitance of approximately 150 F g-1 in supercapacitors, attributed to its high surface area and efficient charge storage mechanisms. Additionally, for Li-ion battery materials without hydrothermal treatment showed impressive capacity retention of around 88% after 500 charge-discharge cycles, starting with an initial specific capacity of about 920 mAh/g. Long-term stability was demonstrated in both supercapacitors and lithium-ion batteries, with minimal capacitance degradation even after extensive charge-discharge cycles. This research underscores the potential of MoS2-based materials as effective energy storage solutions.

Investigation of the Effects of Cu and Fe/Cu Doping on ZnO Nanoparticles for Application as a Solid Electrolyte Battery

In this work, investigation is done on the effect of doping with copper (Cu) and iron/copper (Fe/Cu) on zinc oxide (ZnO) nanomaterials synthesized through a cost‐effective wet chemical precipitation method for application as a solid‐state electrolyte battery. The scanning electron microscope with energy dispersive X‐ray spectroscopy is used to investigate the morphology and elements presence in Cu and Fe/Cu‐doped ZnO nanoparticles. The X‐ray diffraction data illustrates that the crystallite sizes of pure ZnO, Cu–ZnO, and Fe/Cu–ZnO nanoparticles are 14.86, 13.35, and 10.66 nm, respectively, at the (101) plan calculated by Debye Scherrer's formula. The UV‐Vis absorption spectrum shows that the band gap energies of ZnO, Cu–ZnO, Fe–ZnO, and Fe/Cu–ZnO nanoparticles are identified as 3.382, 3.690, 3.5, and 3.465 eV, respectively. The electrical characterization revealed maximum impedance in Fe/Cu–ZnO nanoparticles with 400 Ω at 1 KHz frequency in comparison to other samples. The current–voltage (I–V) measurement shows that the current sensitivity and electrical conductivity are both enhanced for Fe/Cu–ZnO nanoparticles. Fe and Cu co‐doping improved the electrical characteristics of ZnO, and the Fe/Cu–ZnO nanoparticles are employed as a solid electrolyte in a battery, which achieved a high specific charge capacity of 657.85 mAh g−1.

Phthalocyanine-based solid-state electrolyte for high-capacity and long-life lithium-ion batteries

Phthalocyanine-based solid-state electrolyte for high-capacity and long-life lithium-ion batteries

3D-Printed Flexible Polyacrylamide/Alginate Gel Polymer Electrolyte for Zinc-Ion Batteries

Flexible and wearable electronics are increasingly popular and utilized in various forms. Batteries have become essential as an energy source for wearable electronics. To meet demands of such electronics, these batteries must remain flexible, lightweight, possess good electrochemical performance, customizable shape, and ensure safety. Zinc-ion batteries (ZIBs) have emerged as a promising energy source for these applications. However, ZIBs encounter challenges due to the lack of flexible electrolytes. Polyacrylamide (PAM) is a polymer widely used as gel polymer electrolytes (GPEs) owing to its versatile electrical conductivity and excellent flexibility. However, PAM alone lacks the mechanical strength required to support flexible and wearable electronics adequately. To address this limitation, alginate (Alg), a polysaccharide with good compatibility with PAM, is incorporated in varying concentrations (0-3 %wt.) to form interpenetrating networks (IPN) hydrogels, with a chemical network of PAM and a physical network of alginate to enhance the overall mechanical properties. Following this, the 3D-printed PAM/Alg hydrogels are immerged in a 2M ZnSO4 electrolyte to create PAM/Alg gel polymer electrolytes (PAM/Alg-GPEs). This process significantly improves the mechanical properties of PAM/Alg-GPEs. Subsequently, the ionic conductivity of these 3D-printed PAM/Alg-GPEs is evaluated using electrochemical impedance spectroscopy (EIS). The results demonstrate that PAM/Alg-GPEs exhibit the desired flexibility along with sufficient electrochemical performance, making them promising candidates for use as wearable electrolytes in zinc-ion batteries.

Functionalized Quasi-Solid-State Electrolytes in Aqueous Zn-Ion Batteries for Flexible Devices: Challenges and Strategies.

The rapid development of wearable and intelligent flexible devices has posed strict requirements for power sources, including excellent mechanical strength, inherent safety, high energy density, and eco-friendliness. Zn-ion batteries with aqueous quasi-solid-state electrolytes (AQSSEs) with various functional groups that contain electronegative atoms (O/N/F) with tunable electron accumulation states are considered as a promising candidate to power the flexible devices and tremendous progress has been achieved in this prospering area. Herein, this review proposes a comprehensive summary of the recent achievements using the AQSSE in flexible devices by focusing on the significance of different functional groups. The fundamentals and challenges of the ZIBs are introduced from a chemical view in the first place. Then, the mechanism behind the stabilization of the flexible ZIBs with the functionalized AQSSE is summarized and explained in detail. Then the recent progress regarding the enhanced electrochemical stability of the ZIBs with the AQSSE is summarized and classified based on the functional groups on the polymer chain. The advanced characterization methods for the AQSSE are briefly introduced in the following sections. Last but not least, current challenges and future perspectives for this promising area are provided from the authors' point of view.

A Computational Review on Localized High‐Concentration Electrolytes in Lithium Batteries

AbstractElectrolyte engineering plays a vital role in improving the battery performance of lithium batteries. The idea of localized high‐concentration electrolytes that are derived by adding “diluent” in high‐concentration electrolytes has been proposed to retain the merits and alleviate the disadvantages of high‐concentration electrolytes, and it has become the focus of attention in high‐voltage lithium batteries, flame‐retardant lithium batteries, and low‐temperature lithium batteries. Extensive efforts have been made to elucidate the fundamentals of localized high‐concentration electrolytes. This review provides an overview of state‐of‐the‐art computational progress in the studies of localized high‐concentration electrolytes, focusing on the application of computational techniques to analyze the redox stability, solvation structures, and interface characteristics of lithium batteries with localized high‐concentration electrolytes. Integrated with experimental approaches, complementing each other, computational methods are believed to be conducive to understanding the working mechanism and designing localized high‐concentration electrolytes for better lithium batteries in the future.

Construction of Ordered and Fast Lithium Ion Channels in Gel Electrolytes for Li-SPAN Batteries.

As one of the most promising battery systems, the lithium sulfur battery is expected to be widely used in fields of high energy density demands. Owing to the unique solid-solid conversion mechanism, there is no shuttle effect for the Li-SPAN (sulfurized polyacrylonitrile) battery. However, the compatibility between Li anode and carbonate electrolyte has not been resolved, which prevents the SPAN from practical applications. Herein, an organic-inorganic gel carbonate electrolyte is proposed to stabilize interphases and structures of both the anode and cathode, where polyimide (PI) is used for electrolyte gelation, which can assist in the uniform distribution of inorganic components at the electrolyte interface. Furthermore, ZnS nanodots loaded on two-dimensional MoS2 flakes provide abundant Li-ion diffusion paths, improve the transfer kinetic of Li ions, and induce uniform nucleation and deposition of Li. This gel electrolyte ensures Li symmetric cells a long-term cycle life of more than 900 h under the condition of deep lithium plating/stripping at 5 mAh cm-1. Li∥Cu cells exhibit a prolonged lifespan of 800 h with a CE of 98.3%. Furthermore, the Li-SPAN battery shows stability of more than 850 cycles, with the capacity retention of 85.1%. This work provides an approach for high-energy Li-SPAN batteries with carbonate-based electrolytes.